Pecvd coating using an organosilicon precursor.
Abstract
A method is provided for coating a surface of a substrate by PECVD, the method comprising generating a plasma from a gaseous reagent comprising an organosilicon precursor and optionally 02. The lubricity, hydrophobicity and / or barrier properties of the coating can be established adjusting the relationship between 02 and the organosilicon precursor in the gaseous reagent, and / or adjusting the electrical power used to generate the plasma. In particular, a lubricating coating made by said method is provided. Coated containers are also provided by said method and the use of said containers that protect a compound or composition contained or received in said coated container against mechanical and / or chemical effects of the surface of the uncoated container material.

Term
3.6 yearsleft in the term
Expires 12 May 2030.
- Priority
- Filed
- Granted
- Today
- Expires
13 claims: 8 independent, 5 dependent
- 1NOVEDAD DE LA INVENCIÓN Habiendo descrito la presente invenciófT,' 'se consT3era como una novedad y, por lo tanto, se reclama como propiedad lo contenido en las siguientes:REIVINDICACIONES 1. Un método para generar un revestimiento lubricante sobre una superficie de sustrato, el método comprende las etapas de: (a) proporcionar un reactivo gaseoso que comprende un precursor organosilícico y O2, cerca de la superficie del sustrato;y (b) generar un plasma a partir del reactivo gaseoso, para formar de esta manera un revestimiento sobre la superficie del sustrato mediante deposición química en fase vapor asistida por plasma (PECVD), en donde el revestimiento tiene las siguientes relaciones atómicas, medidas por espectroscopia fotoelectrónica de rayos X (XPS) SiwOxCy, en donde w es 1, x en esta fórmula es de 0.5 a 2.4, y es de 0.6 a 3, en donde las características de lubricidad del revestimiento se establecen ajustando la relación entre el O2 y el precursor organosilícico en el reactivo gaseoso, y/o ajustando la potencia eléctrica utilizada para generar el 573 plasma en donde el O2 está presente en una rei^eéów^voTffiñem^”’ volumen con respecto al reactivo gaseoso de 0:1 a 5:1, opcionalmente de 0:1 a 1:1, opcionalmente de 0:1 a 0.5:1, opcionalmente de 0:1 a 0.1:1, y preferiblemente en donde al menos esencialmente nada de oxígeno está presente en el reactivo gaseoso,y en donde el precursor organosilícico es un siloxano monocíclico, preferentemente octametilciclotetrasiloxano (OMCTS).
- 2El método de conformidad con la reivindicación 1, caracterizado porque el reactivo gaseoso comprende menos de un 1% en volumen de O2, más particularmente menos de 0.5% en volumen de O2, y más preferiblemente está exento de O 2 .
- 3El método de conformidad con cualquiera de las reivindicaciones anteriores, caracterizado porque el plasma es un plasma de cátodo no hueco.
- 4El método de conformidad con cualquiera de las reivindicaciones anteriores, caracterizado porque (i) el plasma se genera con electrodos alimentados con suficiente energía para formar un revestimiento sobre la superficie del sustrato, preferentemente con electrodos alimentados con una potencia eléctrica de 0.1 a 25 W, preferentemente de 1 a 22 W, más preferentemente de 3 a 17 W, IMPI 574 'NSTmnv ««ΚΑΝΟ ,¾ L. tfcÜRtrOAL' CS1 itirvmiAi ^=«-J aún más preferentemente de 5 a 14 W, más preferentemente de 7 a 11 W, en particular de 8 W;y/o (ii) la relación de la potencia de los electrodos con respecto al volumen de plasma es menor de 10 W/ml, preferentemente es de 5 W/ml a 0.1 W/ml, más preferentemente es de 4 W/ml a 0.1 W/ml, más preferentemente de 2 W/ml a 0.2 W/ml.
- 5El método de conformidad con cualquiera de las reivindicaciones anteriores, caracterizado porque el sustrato es un polímero seleccionado del grupo que consiste de un policarbonato, un polímero olefínico, un copolímero cíclico olefínico y un poliéster, y preferentemente es un copolímero cíclico olefínico, un tereftalato de polietileno o un polipropileno.
- 6El método de conformidad con cualquiera de las reivindicaciones anteriores, caracterizado porque el plasma se genera con electrodos alimentados a una radiofrecuencia, preferentemente a una frecuencia de 10 kHz a menos de 300 MHz, más preferentemente de 1 a 50 MHz, aún más preferentemente de 10 a 15 MHz, más preferentemente de 13.56 MHz.
- 7Un revestimiento lubricante obtenido mediante el método de conformidad con cualquiera de las reivindicaciones 1 a 6, en donde medido por espectroscopia de fotolelectrones 575 IMPI^ INSTITUTO MEXICANO r^*· DE LA ?«OP¡EDAI> INDUSTRIAL de rayos X (XPC) de Si w O x C y , tiene las siguientes relaciones atómicas w es 1, x en esta fórmula es de 0.5 a 2.4, y es de 0.6 a 3.
- 8El uso de un revestimiento de conformidad con la reivindicación 7 para revestir un recipiente en al menos parte de su superficie interior.
- 9El uso de conformidad con la reivindicación 8, en donde el recipiente es:i) un tubo colector de muestras, en particular un tubo de extracción de sangre;o (ii) un vial;o (iii) una jeringa o parte de una jeringa, en particular un cilindro de jeringa o un émbolo de jeringa;o (iv) una tubería;o (v) una cubeta.
- 10El uso de conformidad con la reivindicación 9, en donde dicho recipiente comprende además al menos una capa de SiOx, donde x es de 1.5 a 2.9, y en donde (i) el revestimiento de Si w O x C y está situado entre la capa de SiO x y la superficie del recipiente o viceversa, o en donde (ii) el revestimiento de Si w O x C y está situado entre dos capas de SiOx o viceversa, o en donde (iii) la capa de SiO x y el revestimiento de Si w O x C y son 576 INSTITUTO MEXICANO DE LA PROPIEDAD V»- L**_ -. , , „ . „ „ „ . „ . INDUSTRIAL ^477*^7 un compuesto escalonado de Si w O x C y a SiO x o viceversa.
- 11El uso de conformidad con cualquiera de las reivindiaciones 8 a 10, en donde el recipiente contiene un compuesto o una composición en su cavidad, preferentemente un compuesto o una composición biológicamente activo o un fluido biológico, más preferentemente (i) un citrato o una composición que contiene citrato, (ii) un medicamento, en particular insulina o una composición que contiene insulina, o (iii) sangre o células sanguíneas.
- 12Un método para generar un revestimiento lubricante sobre la superficie de un cilindro de jeringa, que comprende las etapas definidas en la reivindicación 1, en donde en la etapa (a) no se proporciona sustancialmente nada de O2 en el reactivo gaseoso.
- 13El uso de un revestimiento que tiene la fórmula molecular Si w O x C y , en donde w es 1, x es 0.5 a 2.4, y yes de 0.6 a 3, para reducir la resistencia a la fricción de la superficie revestida. 577 ÍM PJ INSTITUTO MEXICANO ' DE LA PRQHFDAI
Independent claims13
2,817 paragraphs in 104 sections, as filed
(54) Title: COATING BY PECVD USING AN ORGANOSILITICAL PRECURSOR.
(54) Title: PECVD COATING USING AN ORGANOSILICON PRECURSOR.
(57) Summary
A method is provided for coating a surface of a substrate by PECVD, the method comprising generating a plasma from a gaseous reagent comprising an organosilicon precursor and optionally 02. The lubricity, hydrophobicity and / or barrier properties of the coating can be established adjusting the relationship between 02 and the organosilicon precursor in the gaseous reagent, and / or adjusting the electrical power used to generate the plasma. In particular, a lubricating coating made by said method is provided. Coated containers are also provided by said method and the use of said containers that protect a compound or composition contained or received in said coated container against mechanical and / or chemical effects of the surface of the uncoated container material.
(57) Abstract
A method for coating a substrate surface by PECVD is provided, the method comprising generating a plasma from a gaseous reactant comprising an organosilicon precursor and optionally 02. The lubricity, hydrophobicity and / or barrier properties of the coating are set by setting the ratio of the 02 to the organosilicon precursor in the gaseous reactant, and / or by setting the electric power used for generating the plasma. In particular, a lubricity coating made by said method is provided. Vessels coated by said method and the use of such vessels protecting a compound or composition contained or received in said coated vessel against mechanical and / or Chemical effects of the surface of the uncoated vessel material are also provided.
Yes
Mexican Institute of Industrial Property
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PATENT TITLE NO. 345403
YES02 MEDICAL PRODUCTS, INC.
2250 Riley Street, Aubum, Alabama, 36832, USA
COATING BY PECVD USING AN ORGANOSILITICAL PRECURSOR.
Int.CI.8: C23C14 / 40; C23C16 / 24; C23C16 / 30; C23C16 / 50; H01L21 / 205
JOHN T. FELTS; THOMAS E. FISK; ROBERT S. ABRAMS; ROBERT J PANGBORN, PETER J. SAGONA. .....
REQUEST
International filing date:
MX / a / 2011/012038 May 2010
PRIORITY
Country:
Date:
Number:
US US US US US US May 2009 July 2009 July 2009 August 2009 November 2009 November 2009 (CONTINUED ON THE BACK)
61/177,984
61/222,727
61/213,904
61/234,505
61/261,321
61/263,289
Validity: Twenty years
Expiration Date: May 12, 2030
The reference patent is granted based on articles 1 '2<sup>or</sup> fraction V, 6<sup>or</sup> section III, and 59 of the Industrial Property Law.
In accordance with article 23 of the Industrial Property Law, this patent is valid for twenty years, non-extendable, counted from the filing date of the international application and will be subject to the payment of the fee to keep the rights in force. . .
Whoever subscribes to this title does so based on the provisions of articles 6 ° sections III and 7 ° bis 2 of the Industrial Property Law • (Official Dferio de la Federación (DOF) 06/27/1991, amended on 02 / 08/1994, 10/25/1996, 12/26/1987, 05/17/1999, 01/26/2004, 06/16/2005, 01/25/2006, 05/06/2009, 06/01 / 2010, 06/18/2010, 06/28/2010, 01/27/2012 and 04/09/2012), article I<sup>to</sup>, 3rd section V subsection a), 4 ”and 12th sections I and III of the Regulations of the Mexican Institute of Industrial Property (DOF 12/14/1999, amended on 07/01/2002, 07/15/2004, 28 / 07/2004 and 7/09/2007); items 1<sup>or</sup>, 3°, 4°, 5<sup>or</sup> fraction V paragraph a), 16 fractions I and III and 30 of the Organic Statute of the Mexican Institute of Industrial Property (DOF 12/27/1999, amended on 10/10/2002, 07/29/2004, 08/04/2004 and 09/13/2007); 1, 3 and 5 subsection a) of the Agreement that delegates powers to the Deputy General Directors, Coordinator, Divisional Directors, Heads of Regional Offices, Divisional Deputy Directors, Departmental Coordinators and other subordinates of the Mexican Institute of Industrial Property. (DOF 12/15/1999, amended on 02/04/2000, 07/29/2004, 08/04/2004 and 09/13/2007).
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T <
Issue Date: January 30, 2017
THE DIVISIONAL DIRECTOR OF PATENTS
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NAHANNY CANAL REYES
Zms-jINv 55C Floor 1
PueDic Sania María Tepepan,
MX / 2017/8905
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FIELD OF THE INVENTION
The present invention relates to the technical field of the manufacture of coated containers for storing biologically active compounds or blood. In particular, the invention relates to a container processing system for coating a container, a container processing system for coating and inspecting a container, a portable container holder for a container processing system, an apparatus from plasma-assisted chemical vapor deposition for coating the interior surface of a container, to a method of coating an interior surface of a container, to a method of coating and inspecting a container, to a method of processing a container, to the use of a container processing system, to a computational means and to a program element.
A method is provided for coating a surface of a substrate by PECVD, the method comprising generating a plasma from a gaseous reagent comprising an organosilicon precursor and optionally 02. The lubricity, hydrophobicity and / or barrier properties of the coating can be established by adjusting the relationship between
I MI 02 and the organosilicon precursor in the reac
Dt LA «OR11DAR INDUSTRIAL and / or adjusting the electrical power used to generate the plasma. In particular, a lubricating coating made by said method is provided. Coated containers are also provided by said method and the use of said containers that protect a compound or composition contained or received in said coated container against mechanical and / or chemical effects of the surface of the uncoated container material.
The present disclosure also relates to improved methods for processing containers, eg, multiple identical containers used for venipuncture and the collection of other medical samples, storage and administration of pharmaceutical preparations, and other purposes. These containers are used in large quantities for this purpose, and must be relatively inexpensive to manufacture but at the same time must be very safe during storage and use.
BACKGROUND OF THE INVENTION
For example, vacuum blood collection tubes are used to draw blood from a patient for medical tests. The tubes are sold under vacuum. The patient's blood comes into contact with the inside of a tube by inserting one end of a double-ended hypodermic needle
IMPI into the patient's blood vessel and piercing ^^ J ^^ if ^^ INDUSTRIAL vacuum blood collection tube with the other end of the double-ended needle. The vacuum of the vacuum blood collection tube draws the blood (or rather, the patient's blood pressure pushes the blood) through the needle into the vacuum blood collection tube, this causes the pressure inside the tube and, consequently, the pressure difference decreases which
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causes blood to flow. Normally, blood continues to flow until the needle tube is removed or the pressure difference is too small to maintain flow.
Vacuum blood collection tubes must have a substantial shelf life to facilitate efficient and convenient distribution and storage of tubes prior to use. For example, a shelf life of one year is desirable and progressively longer shelf lives are also desirable, such as 18 months, 24 months or 36 months in some cases. Preferably, the tube is kept completely and essentially under vacuum, at least to the extent necessary to draw enough blood for analysis (a common standard is that the tube retain at least 90% of the original collection volume), for a lifetime useful, providing very few defective tubes (optimally none).
It is likely a phlebotomist tube that is using enough blood. So he
<img file="MX345403B_D0006.tif" />
IMPI
INITITUTO MEXICANO DE LA PROPERTY INDUSTRIAL defective causing the tube to fail to extract phlebotomist may need to obtain and use one or more additional tubes to obtain an adequate blood sample.
Another example would be the common practice of preparing and selling pre-filled syringes so that it is not necessary to fill the syringe before use. For example, the syringe can be pre-filled with saline, an injection dye, or a pharmaceutically active preparation.
Typically, the distal end of the pre-filled syringe is capped, for example, with a cap, and its withdrawal plunger closes the proximal end. The pre-filled syringe can be packed in a sterile package before use. To use the pre-filled syringe, the container and cap are removed, optionally a hypodermic needle or other administration line is attached to the distal end of the barrel, the administration line or syringe is placed in a use position (such as inserting the hypodermic needle into a patient's blood vessel or into an apparatus for rinsing it with the contents of the syringe) and the plunger is pushed forward into the barrel to inject the contents of the barrel.
An important factor that must be taken into account when manufacturing pre-filled syringes the syringe will preferably have one during which it is important to isolate
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considerable shelf life, material loaded in
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syringe from the wall of the containing cylinder, to prevent the cylinder material from seeping into the pre-filled content or vice versa.
Since many of these containers are inexpensive and used in large quantities, for certain applications it will be useful to reliably obtain the required shelf life without increasing manufacturing costs to a prohibitive level. It is also convenient for certain applications to use plastic containers, which almost never break during normal use (and if they do break, no sharp fragments are formed from the remains of the container, as would happen with a glass tube) instead of containers. glass that can be broken and is expensive to manufacture. Glass containers are preferred because glass is more airtight and inert to prefilled contents than untreated plastics. Furthermore, due to its traditional use, glass is well accepted as it is known to be relatively harmless when contacted with medical samples or pharmaceutical preparations and the like. Another factor to consider regarding syringes is to ensure that the plunger can move at a speed
Constant impi and with a constant force when p
INDUSTRIAL cylinder. For these purposes, a lubricating layer on the cylinder, the piston, or both is desirable.
A non-exhaustive list of possibly relevant patents includes US Patents 6,068,884 and 4,844,986 and US Published Applications 20060046006 and 20040267194.
COMPENDIUM OF THE INVENTION
It is an object of the invention to provide improved manufacturing of lined containers.
Next, methods and devices manufactured in accordance with the methods are described, where the methods can be carried out by the container processing system described below and the devices can be manufactured by this system.
The present invention provides a method of coating a surface, eg, the inside surface of a container, with a coating applied by PECVD from an organosilicon precursor. Furthermore, the present invention provides the resulting coating, a container coated with such a coating, and the use of the coating, e.g. eg, as a lubricant coating, hydrophobic coating or barrier coating. An apparatus and various carry-on devices are also provided
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iKmVTO MJXICANO the invention into practice. The invention also inspection methods of the coating, in Ί<sup>3</sup>. a method employing degassing of volatile species from the coated surface for such inspection.
PECVD coating method
The present invention relates to a method of preparing a coating by plasma assisted chemical vapor deposition treatment (PECVD) and, for example, a method of coating the interior surface of a container.
A surface is provided, for example the inner surface of a vessel, as well as a reaction mixture comprising a gaseous organosilicon compound, optionally an oxidizing gas, and optionally a gaseous hydrocarbon.
The surface is brought into contact with the reaction mixture. Plasma forms in the reaction mixture. Preferably, said plasma is not a hollow cathode plasma, or in other words, said plasma is substantially free of hollow cathode plasma. The coating is deposited on at least a portion of the surface, e.g. eg, a portion of the inner wall of the container.
The method is carried out as follows.
β IMPIí
MEXICAN INSTITUTE
OF THE INDUSTRIAL EROMY
A precursor is provided. Preferably, said precursor is an organosilicon compound (also hereinafter referred to as organosilicon precursor), more preferably an organosilicon compound selected from the group consisting of a linear siloxane, a monocyclic siloxane, a polycyclic siloxane, a polysilsesquioxane, an alkyltrimethoxysilane type, an alkyltrimethoxysilane type of any of these precursors (i.e. a linear siloxazane, a monocyclic siloxazane, a polycyclic siloxazane or a polysilsesquioxazane) and a combination of any two or more of these precursors. The precursor is applied to a substrate under conditions effective to form a PECVD coating. In this way the precursor polymerizes, crosslinks, partially or completely oxidizes, or any combination of these phenomena.
In one aspect of the invention, the coating is a lubricating coating, that is, it forms a surface with a lower frictional resistance than the uncoated substrate.
In another aspect of the invention, the coating is a passivating coating, eg, a hydrophobic coating that produces, e.g. eg, less precipitation of the components of a composition that is in contact with the coated surface. This hydrophobic coating is the Mexican institute of property characterized by a lower wettability than its uncoated.
A lubricating coating of the present invention can also be a passivating coating and vice versa.
In another aspect of the invention, the coating is a barrier coating, eg, a SiOx coating. Normally, the barrier is against a gas or a liquid, preferably against water vapor, oxygen and / or air. The barrier can also be used to establish and / or maintain a vacuum within a container lined with the barrier coating, e.g. ex. , inside a blood collection tube.
Furthermore, the method of the invention may comprise the application of one or more additional coatings of an organosilicon precursor applied by PECVD. Another optional step is post-treatment of the SiOx coating with a process gas consisting essentially of oxygen and essentially free of a volatile silicon compound.
Lubricating coating
In a specific aspect, the present invention provides a lubricating coating.
This coating is conveniently applied by the PECVD method and using the precursors described
<img file="MX345403B_D0011.tif" />
<sup>10</sup> IMPI. msriTv »» ¡* í »cMjo previously. "^ IwMfffnAt
For example, the present invention provides a nipt-n ^ to establish the lubricity properties of a coating on the surface of a substrate, the method comprising the following steps:
(a) providing a gaseous reagent, comprising an organosilicon precursor and optionally 02, near the surface of the substrate; and (b) generating a plasma from the gaseous reagent, to thereby form a coating on the substrate surface by plasma-assisted chemical vapor deposition (PECVD), where the lubricity-related properties of the coating are set by adjusting the relationship between 02 and the organosilicon precursor in the gaseous reagent, and / or adjusting the electrical power used to generate the plasma.
A preferred precursor for the lubricant coating is a monocyclic siloxane, for example, octamethylcyclotetrasiloxane (OMCTS).
The resulting coated surface has a lower frictional resistance than the untreated substrate. For example, when the coated surface is inside the barrel of a syringe and / or the plunger of a syringe, the coating
IMPH, INSTITUTE '^ ίϋΐίϋίί The lubricant effectively provides a start-up or plunger displacement force (s) less than the corresponding force required in the absence of the lubricating coating.
The article coated with the lubricant coating may be a container with the lubricant coating on a wall, preferably on the inner wall, e.g. ex. , the barrel of a syringe, or a part of a container or a lid of a container with said coating on the contact surface with the container, e.g. ex. , the plunger of a syringe or the cap of a container.
The lubricating coating can in one aspect have the formula SiwOxCyHz, for example, where w is 1, x is w is 1, x is from about 0.5 to about 2.4, and is from about 0.6 to about 3, and z is about 2 to about 9, preferably where w is 1, x is about 0.5 to 1, and is about 2 to about 3, and z is about 6 to about 9.
Passivation, for example hydrophobic coating
The passivating coating according to the present invention is, for example, a hydrophobic coating.
A preferred precursor for passivation, eg, the hydrophobic coating, is a linear siloxane, eg, hexamethyldisiloxane (HMDSO). <sup>Dt</sup>^ NDurnuAi
A passivating coating according to coa-<sup>1</sup> = invention prevents or reduces the mechanical and / or chemical effects of the uncoated surface on a compound or a composition contained in the container. For example, precipitation and / or coagulation or platelet activation of a compound or component of a composition that is in contact with the surface are prevented or reduced, e.g. ex. , blood clotting or platelet activation or insulin precipitation, or wetting of the uncoated surface of an aqueous fluid is prevented.
A particular aspect of the invention is a surface with a hydrophobic coating of the formula SiwOxCyHz, for example, where w is 1, x is from about 0.5 to about 2.4, and is from about 0.6 to about 3, and z is from about 2 to about 9, preferably where w is 1, x is about 0.5 to 1, y is about 2 to about 3, and z is 6 to about 9.
The article coated with the passivating coating may be a container with the passivating coating on a wall, preferably on the inner wall, e.g. ex. , a tube, or a part of a container or a lid of a container with said coating on the contact surface with the container, e.g. e.g., the
Lining a container
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When a container is coated by the above coating method using PECVD, the method comprises several steps. A container is provided having an open end, a closed end, and an inner surface. At least one gaseous reagent is introduced into the container. Plasma is formed within the container under conditions effective to form a reaction product of the reagent, ie, a coating, on the interior surface of the container.
Preferably, the method is carried out by seating the open end of the container in a container holder as described herein, thereby establishing sealed communication between the container holder and the interior of the container. In this preferred aspect, the gaseous reagent is introduced into the container through the container holder. In a particularly preferred aspect of the invention, a plasma-assisted chemical vapor deposition (PECVD) apparatus, comprising a vessel holder, an internal electrode, an external electrode and a power source, is used for the method of coating according to the present invention.
I ΜΡ I
MEXICAN INSTITUTE
The container holder has a port for a container in a seated position for payment. The internal electrode is positioned to be inserted into a container seated on a container holder. The outer electrode has an inner portion positioned to receive a container seated in the container holder. The power supply supplies alternating current to the inner / outer electrode to form a plasma in the container seated on the container holder.
Normally, the power supply supplies alternating current to the outer electrode while the inner electrode is grounded. In this embodiment, the container defines the plasma reaction chamber.
In a particular aspect of the invention, the PECVD apparatus described in the preceding paragraphs comprises a gas outlet, which does not necessarily include a vacuum source, to transfer the gas from and to the interior of a container seated in the port to define a closed chamber.
In another particular aspect of the invention, the PECVD apparatus includes a container holder, a first clamping tool, a seat on the container holder, a reagent supply, a plasma generator, and a container release mechanism.
The container holder is configured
<img file="MX345403B_D0013.tif" />
the open end of a container. The first holding tool is configured to selectively hold and release the closed end of a container and, while holding the closed end of the container, transporting the container into proximity to the container holder. The container support has a seat configured to establish sealed communication between the container support and the interior space of the first container.
The reagent supply is operatively connected to introduce at least one gaseous reagent into the first container through the container holder. The plasma generator is configured to form plasma within the first container under conditions effective to form a reaction product of the reagent on the interior surface of the first container.
The container release mechanism is provided to release the first container from the container holder. A holding tool that is the first holding tool or another holding tool is configured to transport the first container axially away from the container holder and subsequently release the first container.
In a particular aspect of the invention, the method is <sup>16</sup> IMPI ^ tNSTITUT · MEXICAN to line the internal surface of an aperture ^ l ^^ liKSda ^^ C! of a container, for example, a container- · 98ηοκ ·; Ε1ΐ! η »ΏίΒ. tubular, using PECVD. The container includes an outer surface, an inner surface that defines a cavity, a larger opening with an inner diameter and a limited opening defined by an inner surface and having an inner diameter smaller than the inner diameter of the larger opening. A processing container is provided with a cavity and an opening in the processing container. The opening of the processing container is connected with the limited opening of the container to establish communication between the cavity of the container to be processed and the cavity of the processing container through the limited opening. At least a partial vacuum is created in the cavity of the container to be processed and the cavity of the processing container. A PECVD reagent is introduced through the first opening, through the cavity of the container to be processed and then through the limited opening to the cavity of the processing container. Plasma is generated next to the limited aperture under conditions effective to deposit a coating of a PECVD reaction product on the inner surface of the limited aperture.
1 'IMPI ^
MEXICAN INSTITUTE
HEARD THE FSONEOAD
Coated bowl and hoostrial bowl parts' ***.
The present invention further provides a coating resulting from the method described above, a surface coated with said coating and, for example, a container coated with said coating.
The surface coated with the coating, e.g. For example, the wall of the container or part of it can be glass or a polymer, preferably a thermoplastic polymer, more preferably a polymer selected from the group consisting of a polycarbonate, an olefinic polymer, a cycloolefinic copolymer and a polyester. For example, it is a cycloolefinic copolymer, a polyethylene terephthalate, or a polypropylene.
In a particular aspect of the invention, the wall of the container has an inner polymeric layer covered by at least one outer polymeric layer. The polymers can be the same or different. For example, one of the polymeric layers of a cycloolefinic copolymeric resin (COC) (eg, defining a barrier against water vapor) and another polymeric layer is a layer of a polyester resin. This container can be manufactured by a process that includes introducing layers of polyester resin and COC into an injection mold through concentric injection nozzles.
<sup>18</sup> IMPI ΐΝΚ'πτυτο Mexican
The lined container of the invention is empty, under vacuum or (pre) filled with a <-ητηρπο <-ι-η n mi.i 'composition.
A particular aspect of the invention is a container having a passivating coating, for example a hydrophobic coating as defined above.
Another particular aspect of the invention is a surface with a lubricating coating as defined above. It can be a container with the lubricant coating on a wall, preferably on the inner wall, e.g. eg, the barrel of a syringe, or a part of a container or a lid of a container with said coating on the contact surface with the container, eg. ex. , the plunger of a syringe or the cap of a container.
A particular aspect of the invention is a syringe that includes a plunger, a syringe barrel and a lubricant coating as defined above on one or both parts of this syringe, preferably on the inner wall of the barrel of the syringe. The barrel of the syringe includes a barrel with an interior surface on which the plunger slides. The lubricant coating can be applied to the inner surface of the syringe barrel or to the surface of the plunger that is in contact
IMPIAS with the cylinder, or on both surfaces. He
INDUSTRIAL lubricant effectively reduces the breakout force or plunger sliding force required to move the plunger within the cylinder.
Another particular aspect of the invention is a syringe barrel coated with the lubricant coating defined in the previous paragraph.
In a specific aspect of such a coated syringe barrel, the syringe barrel comprises a barrel defining a cavity and having an interior surface through which the plunger slides. The syringe barrel is preferably made of thermoplastic material. A lubricating coating is applied to the inner surface of the cylinder, plunger, or both by plasma-assisted chemical vapor deposition (PECVD). A solute retainer is applied to the lubricant coating by surface treatment, e.g. eg, an amount effective to reduce leakage of the lubricating coating, thermoplastic material, or both into the cavity. The lubricating coating and the solute retainer are compounded and present in relative amounts so as to be effective to provide a breakout force, a plunger sliding force, or both, less than the corresponding force required in <sup>20</sup> IMPI ^
INSTITUTO MÍXICANO absence of lubricant coating and the & ftWíñSÍMAL of<sup>1 </sup>solute retention. ... - —————
Yet another aspect of the invention is a syringe that includes a plunger, a syringe barrel, and inner and outer liners. The cylinder has an inner surface on which the plunger slides and an outer surface. On the inside surface there is a lubricating coating and an additional SiOX barrier coating, where x is from about 1.5 to about 2.9, can be provided on the inside surface of the cylinder. A barrier coating is provided, e.g. ex. , of a resin or an additional SiOx coating, on the outer surface of the cylinder.
Another aspect of the invention is a syringe that includes a plunger, a syringe barrel, and a Luer-type connector. The syringe barrel has an inside surface on which the plunger slides. The Luer-type connector includes a conical luer-type fitting with an internal passage defined by an internal surface. The Luer-type connector is formed as a separate piece from the syringe barrel and attached to the syringe barrel by coupling. The inner passage of the Luer taper fitting has a SiOx barrier coating, where x is from about 1.5 to about
2.9.
MEXICAN INSTITUTE OF LA PEONEDAt <sup>Γ</sup>- L-Λ ΓΕΜΓΙΙΙΛΜ l>
Another aspect of the invention is a pafa plunger<sup>,? T</sup>»A syringe, which includes a piston and a push rod —— The piston has a front face, a generally cylindrical side face, and a rear portion, the side face being configured to be movably seated within a syringe barrel. The plunger has a lubricating coating according to the present invention on its side face. The push rod engages the rear portion of the piston and is configured to advance the piston in a syringe barrel. The plunger may further comprise a coating of SiOx.
Another aspect of the invention is a container with only one opening, that is, a container for collecting or storing a compound or composition. Said container is in a specific aspect a tube, e.g. eg a sample collection tube, eg. ex. , a blood collection tube. Said tube can be closed with a closure, e.g. eg, a cap or plug. Said cap or plug may comprise a lubricating coating according to the present invention on its surface that is in contact with the tube and / or it may contain a passivating coating according to the present invention on its surface facing the tube cavity. In a specific aspect, said plug or a part of it can be made of an elastomeric material.
<sub>22</sub> IMPI
MEXICAN INSTITUTE
M THE PROPERTY _. . . „. ,, Industrial
This type of plug can be prepared as follows: The plug is in a chamber substantially under vacuum. A reaction mixture is provided that includes a gaseous organosilicon compound, optionally an oxidizing gas, and optionally a gaseous hydrocarbon. Plasma forms in the reaction mixture, which is brought into contact with the plug. A coating is deposited on at least a portion of the plug.
Another aspect of the invention is a container having a barrier coating in accordance with the present invention. The container is generally tubular and made of thermoplastic material. The container has a mouth and a cavity joined at least in part by a wall. The wall has an internal surface that interconnects with the cavity. In a preferred aspect, an at least essentially continuous barrier coating made of SiOx as defined above is applied to the inner surface of the wall. The barrier coating is effective in maintaining within the container at least 90% of its initial vacuum level, optionally 95% of its initial vacuum level, for a useful life of at least 24 months. A closure is provided that covers the mouth of the container and isolates the container cavity from air
<img file="MX345403B_D0014.tif" />
environmental.
<img file="MX345403B_D0015.tif" />
The PECVD-applied coatings and the PECVD-coating methods using an organosilicon precursor described in this disclosure are also useful for coating catheters or trays to form a barrier coating, a hydrophobic coating, a lubricating coating, or more than one of these. . A cuvette is a small tube of circular or square cross-section, sealed at one end, made of molten polymer, glass, or quartz (for UV light) and designed as a sample holder for spectroscopic experiments. The best cuvettes are as transparent as possible, with no impurities that can affect the spectroscopic reading. Like test tubes, cuvettes can be exposed to the atmosphere or have a stopper to seal them. The PECVD applied coatings of the present invention can be very thin, transparent and optically flat so that they do not interfere with the optical analysis of the cuvettes or their contents.
Lined container (pre) filled
A specific aspect of the invention is a lined container such as those described above that is pre-filled or used to fill it with a compound or composition in its cavity. Said compound or composition
<img file="MX345403B_D0016.tif" />
can be
IMPI
MEXICAN INSTITUTE
BE THE INDUSTRIAL PROPERTY (i) a biologically compound or composition — ctet4va-r preferably a medicament, more preferably insulin or a composition comprising insulin; or (ii) a biological fluid, preferably a body fluid, more preferably blood or a fraction of the blood (eg, blood cells); or (iii) a compound or composition that can be combined with another compound or composition directly in the container, e.g. eg, a compound to prevent blood clotting or platelet activation in a blood collection tube, such as citrate or a citrate-containing composition.
Generally, the coated container of the present invention is particularly useful for collecting or storing a compound or composition that is sensitive to mechanical and / or chemical effects from the surface of the coated container material, preferably to prevent or reduce precipitation and / or the coagulation or platelet activation of a compound or a component of the composition that is in contact with the interior surface of the container.
For example, a cell preparation tube having a hydrophobic coated wall of the present invention and containing a citrate reagent is suitable for drawing blood and preventing or reducing blood clotting. An effective amount of the aqueous sodium citrate reagent is introduced into the cavity of the tube to inhibit clotting of the blood introduced into the tube.
A specific aspect of the invention is a container for drawing / receiving blood or a container containing blood. The container has a wall. The wall has an internal surface that defines a cavity. The inner surface of the wall has an at least partial hydrophobic coating of the present invention. The coating can be thin with a monomolecular thickness or with a thickness of about 1000 nm. Preferably, blood drawn or stored in the container cavity that is in contact with the liner can be returned to the vascular system of a patient. The coating effectively reduces coagulation or platelet activation of blood exposed to the inner surface, compared to the same type of uncoated wall.
Another aspect of the invention is a container that contains insulin and has a wall with an internal surface defining a cavity. The inner surface has at least a partial hydrophobic coating of the present
<img file="MX345403B_D0017.tif" />
ΝΤΤΙΤυΤΟ MEXICAN invention. The coating may have a ™ in the thickness range mnnomolecq] ar .., a. approximately 1000 nm thick on the inner surface. Insulin or a composition comprising insulin is introduced into the cavity that is in contact with the coating. Optionally, the coating effectively reduces the formation of a precipitate with the insulin that is in contact with the inner surface, compared to the same surface without coating.
The present invention therefore provides the following embodiments with regard to coating methods, coated products, and use of such products:
(1) A method for establishing the lubricity properties of a coating on the surface of a substrate, the method comprising the following steps:
(a) providing a gaseous reagent, comprising an organosilicon precursor and optionally 02, near the surface of the substrate; and (b) generating a plasma from the gaseous reagent, thus forming a coating on the substrate surface by plasma-assisted chemical vapor deposition (PECVD), where the lubricity properties of the coating
<img file="MX345403B_D0018.tif" />
IMPI, iNsTmno Mty<sup>SPOUT</sup> They can be established by adjusting the ratio of the organosilicon precursor in the gaseous reagent, __;
adjusting the electrical power used to generate the plasma.
(2) A method for preparing a hydrophobic coating on a substrate, the method comprising the following steps:
(a) providing a gaseous reagent, comprising an organosilicon precursor and optionally 02, near the surface of the substrate; and (b) generating a plasma from the gaseous reagent, thus forming a coating on the surface of the substrate by plasma-assisted chemical vapor deposition (PECVD), where the hydrophobic properties of the coating can be established by adjusting the ratio between 02 and the organosilicon precursor in the gaseous reagent, and / or adjusting the electrical power used to generate the plasma.
(3) The method of (1) or (2), which results in a coating that is characterized by a molecular formula where the C: O atomic ratio increases and / or the Si: O atomic ratio decreases compared to the formula molecular structure of the organosilicon precursor.
<img file="MX345403B_D0019.tif" />
IMPI
INSTITUTO MEXICANO (4) The method according to any where 02 is present in a volume-volume ratio with respect to the gaseous reagent from 0: 1 to 5: 1, optionally from 0: 1 to 1: 1, optionally from 0: 1 to 0.5: 1, optionally 0: 1 to 0.1: 1, preferably when essentially no oxygen is present in the gaseous reagent.
(5) The method according to any of (1) to (4), wherein the gaseous reagent comprises less than 1% v of 02, more particularly less than 0.5% v of 02 and even more preferably is free of 02 .
(6) The method according to any of (1) to (5), where the plasma is not a hollow cathode plasma.
(7) The method according to any of (1) to (6), where the substrate is the inner wall of a container with a cavity, the cavity having a volume when empty of 0.5 to 50 mL, preferably 1 to 10 mL, more preferably 0.5 to 5 mL, even more preferably 1 to 3 mL.
(8) The method according to any of (1) to (7) (i) wherein the plasma is generated with electrodes supplied with sufficient energy to form a coating on the surface of the substrate, preferably with electrodes supplied with an electrical power of 0.1 to 25 W, preferably 1 to 22 W, more preferably 3 to 17 W,
<img file="MX345403B_D0020.tif" />
even more preferably 5 to 14
IMPI
INDUSTRIAL preferably 7 to 11 W, in particular 8 W; and / or (ii) where the ratio of the power of the electrodes to the plasma volume is less than 10 W / mL, preferably it is 5 W / mL to 0.1 W / mL, more preferably it is 4 W / mL at 0.1 W / mL, even more preferably 2 W / mL to 0.2 W / mL.
(9) A method for preparing a coating on the surface of a substrate, the method comprising the following steps:
(a) providing a gaseous reagent, comprising an organosilicon precursor and optionally 02, near the surface of the substrate; and (b) generating a plasma other than a hollow cathode plasma from the gaseous reagent under reduced pressure, thereby forming a coating on the substrate surface by plasma-assisted chemical vapor deposition (PECVD), where the properties Physical and chemical coating can be established by adjusting the ratio of 02 to the organosilicon precursor in the gaseous reagent, and / or adjusting the electrical power used to generate the plasma.
(10) A method for preparing a barrier coating on a substrate, the method comprising the following steps:
(a) providing a gaseous reagent, comprising a. __ organosilicon precursor and 02, near the surface of the substrate; and (b) generating a plasma other than a hollow cathode plasma from the gaseous reactant under reduced pressure, thereby forming a coating on the substrate surface by plasma-assisted chemical vapor deposition (PECVD), where the properties Barrier coatings can be established by adjusting the ratio of 02 to the organosilicon precursor in the gaseous reagent, and / or adjusting the electrical power used to generate the plasma.
(11) The method according to (10) (i) where the plasma is generated with electrodes supplied with sufficient energy to form a coating on the surface of the substrate, preferably with electrodes supplied with an electrical power of 8 to 500 W, preferably 20 to 400 W, more preferably 35 to 350 W, even more preferably 44 to 300 W, still more preferably 44 to 70 W; and / or (ii) the ratio of the power of the electrodes to the plasma volume is greater than or equal to 5 W / mL, preferably
IMPI 'WTVTO MEXICANO Df IA PROHIBIT O is from 6 W / mL to 150 W / mL, more preferably it is 7<sup>, N</sup>'Wf7WL
100 W / mL, even more preferably 7 W / mL to 20 w / mL7 ~ <sup>:</sup> (12) The method according to (10) or (11), where 02 is present in a volume: volume ratio relative to the gaseous reagent of 1: 1 to 100: 1 relative to the silicon-containing precursor, preferably in a ratio from 5: 1 to 30: 1, more preferably in a ratio of 10: 1 to 20: 1, even more preferably in a ratio of 15: 1.
(13) The method of any of (1) to (12), where the organosilicon precursor is selected from the group consisting of a linear siloxane, a monocyclic siloxane, a polycyclic siloxane, a polysquioxane, a linear silazane, a monocyclic silazane, a Polycyclic silazane, a polysilsesquiazane, an alkyltrimethoxysiloxane, and a combination of any two or more of these compounds, preferably it is a linear or monocyclic siloxane.
(14) The method of (1) or (2), where the organosilicon precursor is a monocyclic siloxane, preferably OMCTS.
(15) The method of (2) or (10), where the organosilicon precursor is a linear siloxane, preferably HMDSO.
(16) The method according to any of (1) to (15), where PECVD is carried out with an organosilicon precursor flux less than or equal to 6 sccm, preferably less
2.5 sccm, more preferably less ®sTTiiu®MeicAia> <sup>Γ</sup> CETA WOFIEDAO industrial more preferably less than or equal to 1.25 sccm.
The method according to any of (1) to (16), substrate is a polymer selected from the group or equal to sccm, yet (17) where the one consisting of a polycarbonate, an olefinic polymer, a cycloolefinic copolymer and a polyester, and preferably it is a cycloolefinic copolymer, a polyethylene terephthalate or a polypropylene.
(18) The method according to any of (1) to (17), where the surface of the substrate is part or all of the inner surface of a container with at least one opening and one inner surface, and where the gaseous reagent fills the interior cavity of the container and plasma is generated in part or all of the interior cavity of the container.
(19) The method according to any of (1) to (18), where the plasma is generated with electrodes fed to a radio frequency, preferably with a frequency of 10 kHz to less than 3 00 MHz, more preferably 1 to 5 0 MHz, even more preferably 10 to 15 MHz, even more preferably 13.56 MHz.
(20) The method according to any of (1) to (19), where the plasma is generated under reduced pressure and the reduced pressure is less than 300 mTorr, preferably less than 200 mTorr, even more preferably less than 100 mTorr.
<img file="MX345403B_D0021.tif" />
(21) where the
IMPI Mexican institute DE LA non W * D industrial
The method according to any of (1) to (20), PECVD deposition time is 1 to 30 seconds, preferably 2 to 10 seconds, more preferably 3 to 9 seconds.
(22) The method according to any of (1) to (21), wherein the resulting coating has a thickness in the range of 1 to 100 nm, preferably in the range of 20 to 50 (23) A coating that can obtained by the method according to any of the preceding claims.
(24) The coating (23), which is a lubricating and / or hydrophobic coating.
(25) The coating of (24), where the atomic ratio between carbon and oxygen increases compared to the organosilicon precursor, and / or where the atomic ratio between oxygen and silicon decreases compared to the organosilicon precursor.
(26) The coating of any of (23) to (25), where the precursor is octamethylcyclotetrasiloxane and where the coating has a density that is higher than the density of a coating made of HMDSO under the same reaction conditions for PECVD.
(27) Coating in accordance with any of (24)
4* <sup>34</sup> IMPI *, ^^ τιτυτο, ΜεχιοΑΝΟι ya (26), where the coating (i) has a lesser friction resistettoiBiwBAKlsl · 'INDUSTRIAL' than the surface without re ves.tir, where preferably the friction resistance is reduced by at least 25 %, more preferably at least 45%, even more preferably at least 60% compared to the uncoated surface.
(28) The coating according to any of (24) to (27), where (i) has a lower wettability than the uncoated surface, preferably a wettability of 20 to 72 dynes / cm, more preferably a wettability of 30 to 60 dynes / cm, more preferably a wettability of 30 to 40 dynes / cm, preferably 34 dynes / cm; and / or (iv) is more hydrophobic than the uncoated surface.
(29) A container coated at least in part of its inner surface with the coating according to any of (23) to (28), preferably a container that is (i) a sample collection tube, in particular a tube of blood draw; or (ii) a vial; or (iii) a syringe or a part of a syringe, in particular the barrel of a syringe or the plunger of a syringe; or
<img file="MX345403B_D0022.tif" />
(iv) a pipe; or (v) a bucket.
IMPI
MEXICAN INSTITUTE
OF THE HDUSTBIAL CURRENCY (30) The container coated according to (29), further comprising at least one SiOx layer, where x is from 1.5 to 2.9, where (i) the coating is located between the SiOx layer and the surface of the substrate or vice versa, or where (i) the coating is located between two layers of SiOx or vice versa, or where (iii) the layers of SiOx and the coating are a compound graduated from SiwOxCyHz to SiOx or vice versa.
(31) The container coated according to any of (29) to (30), containing at least one more layer on its outer surface, preferably one more barrier layer consisting of plastic or SiOx, where x is 1.5 to 2.9.
(32) The container lined according to any of (29) to (31), containing a compound or composition in its cavity, preferably a biologically active compound or composition or a biological fluid, more preferably (i) a citrate or a citrate-containing composition, (ii) a medicament, in particular insulin or an insulin-containing composition, or (iii) blood or blood cells.
(33) The coated container in accordance with any
IMPI of (29) to (32), which is the barrel of a syringe according to the method of claim 1, the precursor is a siloxane, more preferably it is a monocyclic siloxane, even more preferably it is octamethylcyclotetrasiloxane, and where in step (a) practically no 02 gas is provided in the gaseous reactant, where the force to move the plunger through said coated cylinder is reduced by at least 25%, more preferably at least 45%, even more preferably 60% compared to the barrel of an uncoated syringe.
(34) Using a coating having the molecular formula SiwOxCyHz, where w is 1, xesde0.5a2.4, and is 0.6 to 3, yzesde2a9 as a (i) lubricating coating with a frictional resistance less than uncoated surface; and / or (ii) a hydrophobic coating that is more hydrophobic than the uncoated surface.
(35) The use of (34), where the cladding is a cladding as defined in any of (24) to (28).
(36) The use of (34) or (35), where the coating prevents or reduces precipitation of a compound or component of a composition that is in contact with the coating, in particular prevents or reduces insulin precipitation or coagulation of 1
<img file="MX345403B_D0023.tif" />
comparison with the uncoated surface and / or a coated surface according to the method of (1) using HMDSO as a precursor.
(37) The use of the coated container according to any of (29) to (33) to protect a compound or composition contained or received in said coated container against mechanical and / or chemical effects of the surface of the container material without coating, preferably to prevent or reduce precipitation and / or coagulation of a compound or a component of the composition that is in contact with the interior surface of the container.
(38) The use of (37), where the compound or composition is (i) a biologically active compound or composition, preferably a drug, more preferably insulin or a composition comprising insulin where insulin precipitation is reduced or prevented ; or (ii) a biological fluid, preferably a body fluid, more preferably blood or a fraction of the blood where blood clotting and / or platelet activation is reduced or prevented.
(3 9) A medical or diagnostic kit comprising a <sup>38 </sup>'NSTnyro mekicaní coated container according to the present ίηνεπόνόΚ-ί- ^ ιιε may further comprise: a medicament or diagnostic agent --- · .—— which is contained in said coated container; and / or a hypodermic needle, a double ended water or other administration conduit; and / or a prospectus.
The present invention further provides the following embodiments:
VESSEL PROCESSING SYSTEM HAS MULTIPLE PROCESSING STATIONS AND MULTIPLE VESSEL STANDS
In accordance with one aspect of the present invention, there is provided a container processing system for lining a container, the system comprising a first processing station, a second processing station, a container holder, and a conveyor device. The first processing station is configured to carry out a first processing, for example an inspection or coating, of the interior surface of the container. The second processing station is based on the first processing station and is configured to carry out a second processing, for example an inspection or coating, of the inner surface of the container. The vessel holder comprises a vessel port configured to receive and seat
IMF the opening of the container to process (inspect ^^^ pj ^ / ó ^ * '1 v * ·' * coat and / or inspect) the inner surface of the container seated through the container port at the first processing station and at the second processing station. The conveyor device is adapted to transport the container holder and the container seated after the first processing from the first processing station to the second processing station for the second processing of the inner surface of the container seated in the second processing station.
The definition of containers in this description is very broad and includes containers of all types including, but not limited to, sampling tubes for collecting or storing blood, urine or other samples; syringes for storing or administering a biologically active compound or composition; vials for storing biological materials or biologically active compounds or compositions; catheters for transporting biological materials or biologically active compounds or compositions; and sample cells for biological materials or compounds or biologically active compositions.
The vessels described below are all processed with one of the
<img file="MX345403B_D0024.tif" />
processing described below. That is, the features described below with respect to a processing apparatus or system can also be implemented as method steps and can affect the container processed in this way.
A cuvette is a small tube of circular or square cross-section, sealed at one end, made of molten plastic, glass, or quartz (for UV light) and designed as a sample holder for spectroscopic experiments. The best cuvettes are as transparent as possible, with no impurities that can affect the spectroscopic reading. Like test tubes, cuvettes can be exposed to the atmosphere at the top or have a lid to seal them.
The term "container interior" refers to the empty space within the container that can be used to store blood or, according to another embodiment, a biologically active compound or composition.
The term processing may comprise a coating step and / or an inspection step or a series of coating and inspection steps, for example an initial inspection step, followed by a coating step which is then followed by a second or even a third or fourth inspection. The second, tere
<img file="MX345403B_D0025.tif" />
<img file="MX345403B_D0026.tif" />
inspection can be carried out in a
INSTITUTO MEXICANO DE LA PROPERTY s imul t áneát<sup>1</sup>?<sup>05</sup>™<sup>1</sup>*'
<img file="MX345403B_D0027.tif" />
According to an exemplary embodiment of the invention, the container support comprises a vacuum conduit for extracting gas from the interior space of the seated container, where the container support is adapted to maintain the vacuum inside the seated container, so that no additional vacuum chamber is required to process the container. That is, the container support forms, together with the seated container, a vacuum chamber which is adapted to provide the vacuum in the interior space of the container. This vacuum is important for certain processing steps, such as plasma assisted chemical vapor desorption (PECVD) and other chemical vapor deposition steps. In addition, the vacuum within the container may be important to carry out some inspection of the container wall, in particular the coating of the inner surface of the container wall, for example, by measuring the rate of degassing of the wall or the conductivity electric from the wall.
According to another embodiment of the present invention, the first processing is carried out for 30 seconds or less. Also, the second processing is carried out for 30 seconds ^ Tu®> * íM®ere
Thus, a container processing system is provided for lining containers which enables the containers to be manufactured quickly.
According to another exemplary embodiment of the present invention, the first processing and / or the second processing comprise an inspection of the interior surface of the container and then a coating of the interior surface.
According to another embodiment of the present invention, the container support comprises a gas inlet port for transporting gas into the container.
According to another embodiment of the present invention, the system is adapted to automatically reprocess the container if a coating defect is detected. For example, the container processing system and in particular the container support may comprise a mounting with different detectors, for example optical detectors, pressure probes, gas detectors, electrodes for electrical measurements, etc.
Furthermore, according to another embodiment of the present invention, the processing system of
IMPW containers, for example, one or more of the processing tests, comprises one or more holding tools for transporting the container to the container support and / or for removing the container from the container support.
According to another embodiment of the present invention, the container support comprises a gas inlet port for transporting gas into the container.
According to another embodiment of the present invention, the container processing system is adapted to automatically reprocess the container if a coating defect is detected.
The gas conveyed to the interior of the container can be used to coat the interior surface of the container with PECVD.
According to another exemplary embodiment of the present invention, the first processing and / or the second processing comprise a coating of the inner surface of the container.
According to another embodiment of the present invention, the first processing station and / or the second processing station comprise a PECVD apparatus for coating the interior surface of the container.
According to another example of
<img file="MX345403B_D0028.tif" />
In the invention, the system further comprises an external electrode surrounding at least the upper part of the seated container.
According to another exemplary embodiment of the present invention, the container holder comprises an electroconductive probe to provide a counter electrode within the container.
According to another exemplary embodiment of the present invention, the first processing and / or the second processing comprise an inspection of the interior surface of the container.
According to another embodiment of the present invention, the system further comprises a first detector adapted to be inserted into the container through the container port of the first processing station and / or the second processing station to inspect the surface. inside the container for defects.
According to another embodiment of the present invention, the container processing system further comprises a second detector located outside the container to inspect the interior surface of the container for defects.
In accordance with the invention, another example of
<img file="MX345403B_D0029.tif" />
reali
INSTITUTO MEXICANO DE LA r * OMSDAt> INDUSTRIAL
<img file="MX345403B_D0030.tif" />
the first detector and / or the second detector are coupled to the container holder.
According to another example of embodiment of the present invention, the container support comprises a mold for forming the container.
In accordance with another aspect of the present invention, the use of a container processing system described above and below is established to manufacture a blood collection tube for storing blood, a syringe for storing a compound or a biologically active composition, a vial for storing a biologically active compound or composition, a catheter for transporting biologically active compounds or compositions, or a pipette for pipetting a biologically active compound or composition.
The container processing system may also be adapted to inspect a container and may also be particularly adapted to carry out a first inspection of the container for defects, to apply a first coating on the interior surface of the container, followed by a Second inspection of the inner surface of the coated container for defects. Furthermore, the system may be adapted to evaluate the data acquired during
<img file="MX345403B_D0031.tif" />
inspections, where the second inspection and data evaluation require less than 30 seconds.
In accordance with another aspect of the invention, there is provided a container processing system for lining and inspecting a container, the system comprising an assembly of processing stations configured to perform a first inspection of the container for defects, applying a first coating to the inside surface of the container, carry out a second inspection of the inside surface of the coated container for defects and evaluate the data acquired during the inspection, where the second inspection and data evaluation require less than 30 seconds.
Applying the first coating may also be referred to as the first or second processing and carrying out the second inspection of the inner surface of the coated container may be referred to as the second processing.
According to another exemplary embodiment of the present invention, the processing station assembly comprises a first processing station to carry out the first inspection, apply the first coating to the inside surface of the seated container and carry out the second inspection. . In addition, the assembly of stations
<img file="MX345403B_D0032.tif" />
<img file="MX345403B_D0033.tif" />
<img file="MX345403B_D0034.tif" />
processing comprises a support comprising a container port configured for<sup>wv</sup>¥<sup>,</sup>Select and seat a container opening to apply the first coating to the inside surface of the seated container through the container port at the first processing station.
According to another embodiment of the present invention, the assembly of processing stations further comprises a second processing station separate from the first processing station and configured to carry out the second inspection, apply a second coating and carry out a third inspection after the second coating. Furthermore, the container processing system comprises a conveyor device for conveying the container holder and the seated container after the first coating has been applied from the first processing station to the second processing station to apply the second coating on the inner surface. of the container seated in the second processing station. The container port of the container holder is configured to receive and seat the container opening to line and inspect the interior surface of the container seated through the container port at the first station.
<img file="MX345403B_D0035.tif" />
and in the second processing station.
According to another embodiment of the present invention, the container support comprises a vacuum conduit for extracting gas from the inside of the seated container, where the container support is adapted to maintain the vacuum inside the seated container, in such a way that no additional vacuum chamber is required to line or inspect the vessel.
According to another embodiment of the present invention, each inspection is carried out for 30 seconds or less.
According to another embodiment of the present invention, the container processing system is adapted to automatically reprocess the container if a coating defect is detected.
According to another embodiment of the present invention, the first processing station and / or the second processing station comprise a PECVD apparatus for applying the coating on the interior surface of the container.
According to another embodiment of the present invention, the first coating is a barrier coating, where the system is
<img file="MX345403B_D0036.tif" />
confirm
Of
<img file="MX345403B_D0037.tif" />
According to another embodiment of the present invention, the second coating is a lubricating coating, where the system is adapted to confirm whether the lubricating coating (ie the lubricating layer) is present or absent.
According to another embodiment of the present invention, the first coating is a barrier coating, where the second coating is a lubricating coating and where the system is adapted to confirm whether the barrier layer and the lubricating layer are present or absent. .
According to another exemplary embodiment of the present invention, the system is adapted to confirm whether the lubricating layer and the barrier layer are present or absent to at least a six sigma level of certainty.
According to another embodiment of the present invention, the first inspection and / or the second inspection comprise at least one of the following operations: measurement of the gas degassing rate of the coated container, optical monitoring of the coating application, measurement of the optical parameters of the inner surface of the coated container and measurement of the electrical properties of the coated container.
I prevented
<img file="MX345403B_D0038.tif" />
The corresponding measurement data can be subsequently analyzed by a processor.
According to another example of embodiment of the present invention, the processing system further comprises a first detector to measure the degassing rate and / or a second detector to measure the diffusion rate and / or a third detector to measure the optical parameters. and / or a fourth detector to measure electrical parameters.
According to another embodiment of the present invention, the first coating and / or the second coating have a thickness of less than 10 nm.
According to another embodiment of the present invention, the container processing system further comprises a processor to evaluate the data acquired during the inspection.
One aspect of the invention is a container processing system comprising a first processing station, a second processing station, a multiplicity of container holders, and a conveyor. The first processing station is configured to process a container having an opening and a wall defining an interior surface. The
IMPI second processing station is separatediNdeuT ^ jjgJÍ ^ fi.
<img file="MX345403B_D0039.tif" />
<img file="MX345403B_D0040.tif" />
container having an opening and a wall defining an interior surface.
At least some, optionally all, container holders include a container port configured to receive and seat the opening of a container for processing the interior surface of a container seated through the container port at the first processing station. The conveyor is configured to transport a series of container holders and seated containers from the first processing station to the second processing station to process the interior surface of a seated container through the container port in the second processing station.
II. CONTAINER SUPPORTS
II.A. Vessel support without mentioning any specific sealing mechanism
The portable container holder of the container processing system may be adapted to support a container while the interior surface of the container is coated and inspected for defects and while the container is transported from a first
<img file="MX345403B_D0041.tif" />
<img file="MX345403B_D0042.tif" />
processing station up to a second, <sup>OF 1</sup> industrial container processing system processing, the container holder comprising a container port configured to seat an opening of the container and to process the interior surface of the container seated through the container port in the first processing station and in the second processing station.
The portable container support further comprises, according to another embodiment of the present invention, a second port for receiving a gas supply or external ventilation and a conduit for the passage of gas between the opening of the container seated in the port. of the vessel and the second port.
According to another embodiment of the present invention, the portable container holder weighs less than 2.25 kg.
According to another embodiment of the present invention, the portable container support further comprises a vacuum conduit and an outer vacuum port to extract gas from the interior of the seated container through the container port, where the container support is adapted to maintain a vacuum inside the seated container, so that no container vacuum chamber is required.
According to another additional for
<img file="MX345403B_D0043.tif" />
exemplary embodiment of the present invention, the portable container support further comprises a vacuum conduit and an outer vacuum port for extracting gas from the interior of the seated container through the container port, where the container support is adapted to maintain the vacuum inside the seated container so that no additional vacuum chamber is required to process the container.
According to another embodiment of the present invention, the outer vacuum port also incorporates a gas inlet port, contained within the vacuum port, to transport gas into the seated container.
According to another embodiment of the present invention, the processing of the container comprises a coating of the inside surface of the seated container.
According to another embodiment of the present invention, the container support is made essentially of thermoplastic material.
According to another embodiment of the
<img file="MX345403B_D0044.tif" />
present invention, the container carrier]!
INSTITUTO MEXICANO DE LA PROPERTY also comprises a cylindrical internal surface.<sup>1</sup>™ ^^ receiving the cylindrical wall of the container, a first annular groove in the cylindrical inner surface and which is coaxial therewith, an O-ring arranged in the first annular groove to provide a seal between the container seated in the container holder.
According to another embodiment of the present invention, the portable container holder further comprises an axially extending stop adjacent to the round cylindrical inner surface against which the open end of the seated container can be secured.
According to another embodiment of the present invention, the portable container support further comprises a second annular groove in the cylindrical inner surface, which is coaxial with respect to this and is axially spaced from the first annular groove. In addition, the container holder comprises a second O-ring arranged in the second annular groove to provide a seal between the container seated in the container holder.
According to another embodiment of the present invention, the portable container support further comprises a first detector for examining the interior space of the container through the industrial port - in order to inspect the interior surface of the seated container for defects.
According to another embodiment of the present invention, the portable container support comprises a mold for forming the container.
According to another embodiment of the present invention, the container processing system for lining a container comprises the container support described above and below.
In accordance with another aspect of the present invention, the portable container holder includes a container port, a second port, a conduit, and a transportable housing. The container port is configured to seat an opening of the container in a mutually communicating relationship. The second port is configured to receive a gas supply or external vent. The conduit is configured for the passage of one or more gases between a container opening seated in the container port and the second port. The container port, the second port, and the conduit are attached in a substantially rigid relationship to the transportable housing. Optionally, the portable container holder weighs less than five pounds.
jvl F1B
Another aspect of the present invention is a portable container system that includes a container port, a vacuum conduit, a vacuum port, and a transportable housing. The container port is configured to receive a container opening in a sealed and mutually communicating relationship. The vacuum conduit is configured to draw a gas through the container port of a container seated in the container port. The vacuum port is configured to communicate the vacuum conduit and an external vacuum source. The vacuum source can be a pump or a ballast or reserve tank with a pressure lower than the vacuum line. The container port, the vacuum conduit and the vacuum port may be attached in a substantially rigid relationship to the transportable housing. Optionally, the portable container holder weighs less than five pounds.
II. B. Container holder including a sealing mechanism.
Yet another aspect of the invention is a container holder for receiving the open end of a container having a substantially cylindrical wall adjacent its open end. The container holder may have a generally cylindrical inner surface (for example, a round cylindrical inner surface), an annular groove, and
- IMPI?
INSTITUTO MEXICANO V DE LA MONEDAD (an O-ring. It will be understood that the description of the containers that is specified <sup>1</sup> that having round or circular openings or cross sections are merely examples and do not limit the scope of the description or claims. If the container has an opening or cross section that is not round, which is common, for example when the container is a bucket, the round cylindrical surface of the container holder may not be round and can be sealed using a sealing element that it is not round, such as a gasket or a shaped seal to seal the non-round cross section, unless specifically required otherwise. Furthermore, cylindrical does not mean a cylinder with a round section and contemplates cross sections with other shapes, for example, squares with rounded edges.
The generally cylindrical inner surface is shaped to receive the cylindrical wall of the container.
The annular groove is arranged on the generally cylindrical inner surface and is coaxial with it. The first annular groove has an opening in the generally cylindrical inner surface and a bottom wall radially spaced from the generally cylindrical inner surface.
The O-ring is arranged on the first annular groove.
The O-ring is shaped properly,
<img file="MX345403B_D0045.tif" />
with the first annular groove, to normally extend ...... _ radially through the opening and to be pressed radially outward by a container received by the generally cylindrical inner surface. This installation forms a seal between the container and the first annular groove.
In accordance with another aspect of the present invention, there is provided a method for coating and inspecting a container, wherein a first inspection of the interior surface of the container for defects is carried out after which a coating is applied to the surface. inside the container. This is followed by a second inspection of the inside surface of the coated container for defects, followed by evaluation of the data acquired during the first and second inspection, where the second inspection and evaluation of the data requires less. 30 seconds.
In accordance with another aspect of the invention, there is provided a method of processing a container, wherein a container opening is seated in the container port of a container holder, after which the interior surface of the container is coated through the container port. Thereafter, the<sub>Ί</sub> _ J, ___ _, _ π INSTITUTO MEXICANO- J coating looking for defects through the nsüeabfliuAde ' <sup>x</sup> fwniimi ai containers. After which, the container is transported from the first processing station to a second processing station, where the container holder holds the seated container during coating, inspection, and transportation.
III. METHODS FOR TRANSPORTING CONTAINERS Processing of containers seated on container racks
III .A. Transport of container supports to processing stations
Another aspect of the invention is a method of processing a container. A first processing station and a second processing station separate from the first processing station are provided for processing containers. A container is provided having an opening and a wall defining an interior surface. A container holder is provided comprising a container port. The container opening is seated over the container port. The inside surface of the seated container is processed through the container port at the first station
IΜΡΙ 6 processing. The container holder and<sup>N</sup>^ S ^^ iD8intXi ^ settled are transported from the first processing station to the second processing station. The inner surface of the seated container is further processed through the container port at the second processing station.
III.B. Transport of processing devices to container supports or vice versa.
Another aspect of the invention is a method of processing a container that includes several parts. A first processing device and a second processing device are provided for processing containers. A container is provided having an opening and a wall defining an interior surface. A container holder is provided comprising a container port. The container opening is seated over the container port.
The first processing device moves functionally coupled to the container holder or vice versa. The inside surface of the seated container is processed through the container port using the first processing device.
The second processing device is subsequently moved functionally coupled to the container holder or vice versa.
The surface
INDUSTRIAL seated vessel is then processed through the vessel port using the second processing device.
III. C. Using a clamping tool to transport tubes to and from the processing station
Yet another aspect of the invention is a method of plasma-assisted chemical vapor deposition (PECVD) treatment of a first vessel that includes several stages. A first container is provided having an open end, a closed end, and an inner surface. At least one first holding tool is configured to selectively hold and release the closed end of the first container. The closed end of the first container is clamped with the first clamping tool and, using the first clamping tool, is transported close to the container holder configured to seat the open end of the first container. The first clamping tool is then used to axially advance the first container and seat its open end in the container holder, thereby establishing a sealed communication between the container holder and the interior of the first container.
At least one gaseous reagent is introduced into the <sup>62</sup> IMPIí
INSTITUTO MEXICANO 'first container through the holder of recipiefft ^' ^^ S forms plasma within the first container in — xxmdiciqnes. effective to form a reaction product of the reagent on the interior surface of the first container.
The first container is then removed from the container holder and, using the first clamping tool or other clamping tool, the first container is transported axially away from the container holder. Subsequently, the first container is released from the clamping tool used to transport it axially away from the container holder.
IV. PECVD APPARATUS TO MAKE CONTAINERS
IV .A. PECVD apparatus including a vessel holder, an internal electrode and a vessel as a reaction chamber
In accordance with another aspect of the invention, a plasma assisted chemical vapor deposition (PECVD) apparatus is provided for coating the interior surface of a container. The PECVD apparatus may form part of the container processing system and comprises a container holder, such as the holder described above and below, comprising a container port configured to receive and seat a first container opening for processing the inner surface
IMPI ^
MEXICAN INSTITUTE,. . ,,, PELAFAOHÍOAI 'of the container seated through the port of recipieirt> ess <iA <In addition, the PECVD apparatus comprises an electrode ~ ± rrber<sup>></sup>no-- ~ · ^ which must be inserted into the interior space of the seated container and an external electrode that has an inner portion to receive the seated container. A power source is also provided for creating a plasma within the container, where the seated container and the container holder are adapted to define a plasma reaction chamber.
According to another embodiment of the present invention, the PECVD apparatus further comprises a vacuum source for evacuating the interior space of the seated container, where the container port and the seated container are adapted to define a vacuum chamber. .
According to another embodiment of the present invention, the PECVD apparatus further comprises a gas supply for supplying a reactive gas from a reactive gas source to the interior space of the container.
In accordance with another exemplary embodiment of the present invention, the gas feed is located at a distal portion of the inner electrode.
According to another example of embodiment of the present invention, the internal electrode is a
<img file="MX345403B_D0046.tif" />
distal portion positioned to extend concentrically to the seated container.
According to another embodiment of the present invention, the external electrode has a cylindrical section and extends concentrically with respect to the seated container.
According to another embodiment of the present invention, the PECVD apparatus further comprises a holding tool for selectively holding and releasing the closed end of the container and, while holding the closed end of the container, transporting the container close to the container support. .
According to another exemplary embodiment of the present invention, the PECVD apparatus is adapted to form a plasma in the interior of the container that is substantially free of hollow cathode plasma.
In accordance with another exemplary embodiment of the present invention, the PECVD apparatus further comprises a detector for examining the interior space of the container through the container port in order to inspect the interior surface of the container for defects.
According to another embodiment of the present invention, the PECVD apparatus further comprises a
INSTIlVro MEXICANO processing vessel having an opening ^^ j ^^^ VAVe ^ ñ ^ a ^ y ^ processing vessel to connect nnn a spgundg ....... limited opening of the vessel to allow a reagent gas to flow from the interior space of the container to the processing container.
According to another embodiment of the present invention, a distal end of the inner electrode is positioned at a distance that is less than half the distance from the second limited opening to the first larger opening of the seated container.
According to another exemplary embodiment of the present invention, the distal end of the inner electrode is positioned outside the first larger opening of the seated container.
In addition, a method is provided for coating the interior surface of a container, wherein an opening of the container is received and seated in a container port of a container holder to process the interior surface of the seated container. Subsequently, an inner electrode is introduced into the interior space of the seated container after which a gas feed is placed at the distal portion of the inner electrode. Furthermore, the seated container is inserted into an inner portion of an outer electrode. The container seated in the container holder is defining a plasma reaction chamber.
<img file="MX345403B_D0047.tif" />
In particular, a vacuum chamber can be defined by the container port and the seated container, and gas is drawn from the interior space of the seated container, so that no external vacuum chamber is required for coating.
In another step, a plasma is formed in the interior space of the container and a coating material is deposited on the interior surface of the seated container.
In accordance with another exemplary embodiment of the present invention, an opening of the processing vessel is connected with a limited opening of the vessel to allow a reactive gas to flow from the interior of the vessel to the processing vessel.
According to another aspect of the invention, the use of a PECVD apparatus described above and below is established to manufacture a blood collection tube for storing blood, a syringe for storing a biologically active compound or composition, a vial for storing a biologically active compound or composition, a catheter for transporting biologically active compounds or compositions, or a cuvette as a sample holder of a biologically active compound or composition.
MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY
Another aspect of the invention is a PECVD apparatus comprising a container holder, an inner electrode, an outer electrode, and a power source.
The container holder has a port to receive a container in a seated position for processing. The inner electrode is positioned to be inserted into a container seated in a container holder. The outer electrode has an inner portion positioned to receive a container seated in the container holder. The power supply supplies alternating current to the inner and outer electrode to form a plasma in the container seated on the container holder. The vessel defines a plasma reaction chamber.
Yet another aspect of the invention is a PECVD apparatus described in the preceding paragraphs, where a gas outlet, which does not necessarily include a vacuum source, is provided to transfer the gas to and from a container seated in the port. to define a closed camera.
IV. B. PECVD apparatus that uses a clamping tool to transport tubes to and from a coating station
Another aspect of the invention is an apparatus for
IMPI. . . INSTITUTO MEXICANO treatment by PECVD of a first container with an open end, a closed end and an interior space. The apparatus includes a container holder, a first holding tool, a seat on the container holder, a reagent supply, a plasma generator, and a container release mechanism.
The container holder is configured to seat the open end of a container. The first holding tool is configured to selectively hold and release the closed end of a container and, while holding the closed end of the container, transporting the container into proximity to the container holder. The container support has a seat configured to establish sealed communication between the container support and the interior space of the first container.
The reagent supply is operatively connected to introduce at least one gaseous reagent into the first container through the container holder. The plasma generator is configured to form plasma within the first container under conditions effective to form a reaction product of the reagent on the interior surface of the first container.
The canister release mechanism is provided iMPie to release the first canister from the v holder.
INDUSTRIAL 'A holding tool that is the first holding tool or another holding tool is configured to transport the first container axially away from the container holder and subsequently release the first container.
V. PECVD METHODS
In accordance with another aspect of the present invention, there is provided a method of coating (and / or inspecting) the interior surface of a container, where an opening of the container is received and seated in a container holder to process the interior surface of the container. settled. It should be noted that the term "process" can refer to a coating stage or several coating stages or even a series of coating and inspection stages.
In addition, a first processing of the interior surface of the seated container is carried out through the container port of the container holder in a first processing station. Subsequently, the container holder and the seated container are transported to a second processing station after the first processing in the first processing station. Subsequently, in the second processing station, a second processing of the
<img file="MX345403B_D0048.tif" />
inside surface of seated container
INDUSTRIAL canister port of the canister stand.
VA PECVD to apply a SiOx barrier coating using plasma that is substantially free of hollow cathode plasma
Another aspect of the invention is a method of applying a SiOx barrier coating, where x in this formula is from about 1.5 to about 2.9, alternatively from about 1.5 to about 2.6, alternatively from about 2, to one surface, preferably on the inside of a container. The method includes several stages.
A surface is provided, e.g. g., the wall of a vessel, as well as a reaction mixture comprising a plasma-forming gas, ie, a gaseous organosilicon compound, optionally an oxidizing gas, and optionally a gaseous hydrocarbon.
Plasma is formed in the reaction mixture that is substantially free of hollow cathode plasma. The vessel wall is contacted with the reaction mixture and the SiOx coating is deposited on at least a portion of the vessel wall.
VB PECVD coating of the limited opening of
<img file="MX345403B_D0049.tif" />
7ΐ IMPI
MEXICAN INSTITOTE
OWNED a ndwtrial container (syringe capillary)
Another aspect of the invention is a method for i'éJébLir · an internal surface of a limited opening of a generally tubular container to be processed by PECVD. The method includes the following stages.
A generally tubular container is provided that must be processed. The container includes an outer surface, an inner surface that defines a cavity, a larger opening with an inner diameter and a limited opening defined by an inner surface and having an inner diameter smaller than the inner diameter of the larger opening.
A processing container is provided with a cavity and an opening in the processing container. The opening of the processing container is connected with the limited opening of the container to establish communication between the cavity of the container to be processed and the cavity of the processing container through the limited opening.
At least a partial vacuum is created in the cavity of the container to be processed and the cavity of the processing container. A PECVD reagent is introduced through the first opening, through the cavity of the container to be processed and then through the opening
<img file="MX345403B_D0050.tif" />
limited to the cavity of the prqL container <sup>Γ c</sup> ΊΝΪΤΠρΤΪ) MEXICAN
M INDUSTRIAL PROPERTY
<img file="MX345403B_D0051.tif" />
limited aperture in conditions
Plasma is generated alongside effective ones to deposit a coating of a PECVD reaction product on the inner surface of the limited aperture. ,
V .C. Method of applying a lubricating coating
Yet another aspect of the invention is a method of applying a lubricant coating on a substrate. The method is carried out as follows.
A precursor is provided. The precursor is preferably an organosilicon compound, more preferably a linear siloxane, a monocyclic siloxane, a polycyclic siloxane, a polysilsesquioxane or a combination of any two or more of these precursors. Other precursors are also contemplated, e.g. ex. , organometallic precursors that contain metals of group III and IV of the periodic system. The precursor is applied to a substrate under conditions effective to form a coating. The coating is polymerized or lattice, or both, to form a lubricated surface with a lower sliding force or plunger pullout force, as defined in this description, than the untreated substrate.
' SAW. INSPECTION OF THE CONTAINER
VI .A.
Container processing including
<img file="MX345403B_D0052.tif" />
IMPI pre-coating and post-coating inspection
INSTITUTO MEXICANO Oí LA non IDAD INDUSTRIAL
Even plastic processing another aspect of the invention is a container method for processing a container that has an opening and a wall that defines an interior surface. The method is carried out by inspecting the inner surface of the obtained container for defects; applying a coating on the inside surface of the container after inspecting the obtained container; and inspecting the coating for defects.
Another aspect of the invention is a container processing method in which a barrier coating is applied to the container after inspecting the molded container and the interior surface of the container is inspected for defects after applying a barrier coating.
SAW . B. Inspection of the container by detecting outgassing of the container wall, for example, through barrier layer
Another aspect of the invention is a method of inspecting a coating by measuring the outgassing of a volatile species from the coated article (outgassing method). Such a method can be used to inspect the product of a coating process where a coating has been applied over the top surface to form a coated surface. In particular, the method can be used as an online process control for a coating process to identify and remove coated products that do not meet a predetermined standard or defective coated products.
Generally, the volatile species is a gas or vapor under test conditions, preferably it is selected from the group consisting of air, nitrogen, oxygen, water vapor, volatile coating components, volatile substrate components, and a combination of these, most preferably is air, nitrogen, oxygen, water vapor, or a combination of these. The method can be used to measure only one or a few volatile species, but preferably a plurality of different volatile species are measured in step (c) and more preferably substantially all volatile species released by the inspection object are measured in step ( c).
The degassing method comprises the following stages:
(a) provide the product as an object of inspection;
(c) measuring the release of at least one volatile species from the inspection object into the gaseous space adjacent to the
<img file="MX345403B_D0053.tif" />
(d) comparing the result of step (c) with the result of step (c) for at least one reference object measured under the same test conditions, in this way the presence or absence of the coating and / or a physical and / or chemical property of the coating.
In said degassing method, the physical and / or chemical property of the coating to be determined can be selected from the group consisting of its barrier effect, its wettability and its composition, and is preferably its barrier effect.
Conveniently, step (c) is carried out by measuring the mass flow rate or volumetric flow rate of at least one volatile species in the gas space adjacent to the coated surface.
Preferably, the reference object (i) is an uncoated substrate; or (ii) is a substrate coated with a reference coating. This will depend, for example, on whether the degassing method is used to determine the presence or absence of a coating (then the reference object can be an uncoated substrate) or to determine the properties of the coating, for example, compared to a coating with known properties. To determine the identity of the coating with a <sup>76</sup> impi
MEXICAN INSTITUTE '
DI THE SPECIFIC COATING, the reference coating is also a typical choice. The degassing method may also comprise, as an additional step between steps (a) and (c), step (b) consisting of changing the atmospheric pressure in the gas-occupied space adjacent to the coated surface so that it You get a pressure difference across the coated surface and a higher mass flow rate or volumetric flow rate of the volatile species can be produced than without the pressure difference. In this case, the volatile species will migrate in the direction of the side, less than the pressure difference. If the coated object is a container, the pressure difference is established between the cavity of the container and the exterior to measure the degassing of volatile species from the wall of the coated container. The pressure difference can be obtained, for example, by at least partially emptying the gaseous space in the container. In this case, the volatile species that is degassed in the container cavity can be measured.
If vacuum is applied to create a pressure difference, the measurement can be carried out using a measurement cell interposed between the coated surface of the substrate and a vacuum source.
In one aspect, the inspection object ^ ued ^ Mjysmi ^ contact with a volatile species in step (a), preferably a volatile species selected from the group consisting of air, nitrogen, oxygen, water vapor, and a combination of these, preferably to allow adsorption or absorption of said volatile species on or in the material of the inspection object. Next, the subsequent release of said volatile species from the inspection object is measured in step (c). Because different materials (such as the coating and the substrate) have different adsorption and absorption characteristics, this can simplify determining the presence and characteristics of a coating.
The substrate can be a polymeric compound, preferably it is a polyester, a polyolefin, a cycloolefinic copolymer, a polycarbonate or a combination of these.
In the context of the present invention, the coating characterized by the degassing method is usually a coating prepared by PECVD from, for example, an organosilicon precursor such as those described herein. In particular aspects of the invention, (i) the coating is a barrier coating, preferably it is a SiOx layer where x is<sup>78</sup> _ x-yü ϊ ι ^ ΑΡΛ about 1.5 to about 2.9; T ^ irro coating is a coating that modifies the lubricity and / or surface tension of the coated substrate, preferably it is a layer of SiwOxCyHz, where w is 1, x is approximately 0.5 to 2.4, and is approximately 0.6 to approximately 3, and z it is from 2 to about 9.
When the coating process whose product is inspected by the degassing method is a PECVD coating carried out under vacuum conditions, the measurement of subsequent degassing can be carried out without breaking the vacuum used for PECVD.
The volatile species measured can be a volatile species released by the coating, a volatile species released by the substrate, or a combination of both. In one aspect, the volatile species is a volatile species released by the coating, preferably it is a component of the volatile coating, and inspection is carried out to determine the presence, properties, and / or composition of the coating. In another aspect, the volatile species is a volatile species released by the substrate and inspection is carried out to determine the presence of the coating and / or the barrier effect of the coating.
The degassing method of the present invention is. IMPIí particularly suitable for determining the prq ^ ft ©> i * axic ^ o li ^ industrial characteristics of a coating applied on a wall
<img file="MX345403B_D0054.tif" />
of a container. Accordingly, the coated substrate can be a container having a wall whose inner or outer surface is at least partially coated during the coating process. For example, the liner is disposed on the inner surface of the container wall.
Effective conditions to distinguish the presence or absence of the coating and / or to determine a physical and / or chemical property of the coating may include a test lasting less than one hour or less than a minute, or less than 50 seconds, or less. 40 seconds, or less than 30 seconds, or less than 20 seconds, or less than 15 seconds, or less than 10 seconds, or less than 8 seconds, or less than 6 seconds, or less than 4 seconds, or less than 3 seconds, or less than 2 seconds, or less than 1 second.
To increase the difference between the reference object and the inspection object with respect to the release rate and / or type of the measured volatile species, the release rate of the volatile species can be modified by modifying the pressure and / or temperature and / or or environmental humidity.
In a specific aspect, outgassing is measured using a micrometer measurement technique. For example, the measurement can be carried out as irKf! Íí ^<sup>L</sup> performance: - (i) (a) providing at least one micro bracket having the ability, when in the presence of a degassed material, to move or change shape;
(b) exposing the micro-bracket to the degassed material under conditions effective to cause the micro-bracket to move or change shape; and (c) detecting movement or change in shape, preferably reflecting an energetic incident beam, eg, a laser beam, from a portion of the micro-bracket that changes shape before and after exposing the micro-bracket to degassing, and measuring the resulting deflection of the reflected beam at a point off the bracket; or (ii) (a) providing at least one micrometer that resonates at a different frequency when in the presence of a degassed material;
(b) exposing the micro-bracket to the degassed material under conditions effective to cause the micro-bracket to resonate at a different frequency; and (c) detecting the different resonant frequency, e.g. ex. , using a harmonic vibration sensor.
It is also considered to employ an apparatus for carrying out the degassing method, for example, an apparatus comprising such a micro-bracket above.
Using the degassing method of the present invention, for example, a barrier layer applied on a material that degasses a vapor can be inspected, where the inspection method has several stages. A sample of material is provided that degasses a gas and has at least a partial barrier layer. In a specific aspect of the invention, a pressure difference is provided across the barrier layer, so that at least part of the material that is degassed is on the higher pressure side of the barrier layer. The degassed gas that passes through the barrier layer is measured. If there is a pressure difference, the measurement is optionally carried out on the lower pressure side of the barrier layer.
VII. PECVD TREATED VESSELS
VII.A.1.ai Deposited hydrophobic coating of an organosilicon precursor
Another aspect of the invention is a deposited hydrophobic coating of an organosilicon precursor, e.g. ex. , in a container with a hydrophobic coating on the inner wall. The coating is of the prepared type
<img file="MX345403B_D0055.tif" />
through the following stages.
A precursor is provided which is organometallic, preferably a compound »ι ·· ιι
<img file="MX345403B_D0056.tif" />
organosilicon, more preferably a compound selected from a group consisting of a linear siloxane, a monocyclic siloxane, a polycyclic siloxane, a polysilsesquioxane, an alkyltrimethoxysilane, a linear silazane, a monocyclic silazane, a polycyclic silazane, a polysilsesiane combination, a polysilsesiane combination or any more of these precursors. Alternatively, organometallic compounds containing a metal from the group
III or IV as precursors.
The precursor is applied to a substrate under conditions effective to form a coating. The coating is polymerized or lattice, or both, to form a hydrophobic surface with a higher contact angle than the untreated substrate.
The resulting coating can have the molecular formula: SiwOxCyHz, where w is 1, x is from about 0.5 to about 2.4, and is from about 0.6 to about 3, and z is from about 2 to about 9, preferably where w is 1, x is about 0.5 to 1, and is about 2 to about 3, and z is about 6 to about 9.
The values of w, x, y and z ^ iJij ^ | [oP INSTITUTO MEXICANO DE LA PROPIEDAD description should be interpreted as proportions ©?) ®! ^<sup>1</sup>· In * —ure empirical formula (eg for a coating); in Ve¿ give as a limit of the number of atoms in a molecule. For example, octamethylcyclotetrasiloxane, with the molecular formula SÍ4O4C8H24, can be described by the following empirical formula [expression modified by us], which is obtained by dividing each of w, x, y and z in the molecular formula by 4, the greatest common divisor: SÍ1O1C2H6. The values of w, x, y, and z are also not limited to whole numbers. For example, octamethyltrisiloxane (acyclic), of molecular formula SÍ3O2C8H24, can be reduced to SilOO.67C2.67H8.
V II.Alb Citrated blood tube having a wall lined with a deposited hydrophobic layer of an organosilicon precursor
Another aspect of the invention is a cell preparation tube having a wall provided with a hydrophobic coating and containing an aqueous sodium citrate reagent.
The wall is made of thermoplastic material with an internal surface that defines a cavity.
The hydrophobic coating is provided on the inner surface of the tube. The hydrophobic coating is prepared by providing an organometallic compound, preferably a compound
<img file="MX345403B_D0057.tif" />
preferably a compound selected from a gmpn.
made up of a linear siloxane, a monocyclic siloxane, a polycyclic siloxane, a polysilsesquioxane, an alkyltrimethoxysilane, a linear silazane, a monocyclic silazane, a polycyclic silazane, a polysilsesquiazane, or a combination of any two or more of these precursors. PECVD is used to form a coating on the inner surface. The resulting coating can have the structure: SiwOxCyHz, where w is 1, x is from about 0.5 to about 2.4, and is from about 0.6 to about 3, and z is from about 2 to about 9, preferably where w is 1, x is from about 0.5 to 1, and is from about 2 to about 3, and z is from about 6 to about 9.
An effective amount of the aqueous sodium citrate reagent is introduced into the cavity of the tube to inhibit clotting of the blood introduced into the tube.
V II.Alc Double-walled plastic container lined with a SiOx barrier- layers of COC, PET, SiOx Another aspect of the invention is a container having a wall that contains at least partially a cavity. The wall has an inner polymeric layer contained in an outer polymeric layer. One of a layer of at least 0.1 mm cycloolefinic copolymeric (COC)
<img file="MX345403B_D0058.tif" />
against water vapor. Another of the polymeric layers is a layer at least 0.1 mm thick of a polyester resin.
The wall includes a SiOx oxygen barrier layer, where x in this formula is from about 1.5 to about 2.9, alternatively about 1.5 to about 2.6, alternatively about 2, with a thickness of about 10 to about 500 angstroms.
V II.Ald Method of preparation of a double-walled plastic container - COC, PET, SiOx layers
Another aspect of the invention is a method of preparing a container having a wall with an inner polymeric layer contained in an outer polymeric layer, one layer made of COC and the other of polyester. The container is manufactured by a process that includes introducing layers of COC and polyester resin into an injection mold through concentric injection nozzles.
An optional additional step is to apply an amorphous carbon coating to the container by PECVD, as an internal coating and an external coating or as a
<img file="MX345403B_D0059.tif" />
<img file="MX345403B_D0060.tif" />
intermediate lining located between the two INDUSTRIAL
An optional additional step is to apply a SiOx barrier layer to the inside of the vessel wall, where SiOx is defined as above. Another optional additional step consists in the post-treatment of the SiOx layer with a process gas consisting essentially of oxygen and essentially free of a volatile silicon compound.
Optionally, the SiOx coating can be formed at least partially from a silazane feed gas.
V II.Ale Barrier coating made of glass
Another aspect of the invention is a container that includes a container, a barrier liner, and a closure. The container is generally tubular and made of thermoplastic material. The container has a mouth and a cavity joined at least in part by a wall having an internal surface interconnected with the cavity. There is at least one essentially continuous barrier cladding made of glass on the inner surface of the wall. A closure covers the mouth and isolates the container cavity from ambient air.
A related aspect of the invention is a container as described in the previous paragraph, in which the barrier coating is made of
<img file="MX345403B_D0061.tif" />
calcium, borosilicate glass or other type of glass
V II.A.2. Plugs
V II.A.2.a. Method of applying a lubricant coating on a plug in a vacuum chamber
Another aspect of the invention is a method of applying a coating, for example a lubricating coating as defined above, on an elastomeric plug. For example, the plug is in a substantially vacuum chamber. A reaction mixture is provided that includes a plasma-forming gas, ie, a gaseous organosilicon compound, optionally an oxidizing gas, and optionally a gaseous hydrocarbon. Plasma forms in the reaction mixture, which is brought into contact with the plug. A lubricating coating, e.g., is deposited on at least a portion of the plug. ex. , a coating of SiwOxCyHz, preferably where w is 1, x in this formula is from about 0.5 to 2.4, and is from about 0.6 to about 3, and z is from 2 to about 9, preferably where w is 1, x is about 0.5 to 1, y is from about 2 to about 3, and z is from 6 to about 9.
V II.A.2.b. PECVD application of a coating of a group III or IV element and carbon on a plug<sup>38</sup> IMPIf ^<sup>if</sup>*<sup>ST</sup>^ y »« M «i<sup>AC</sup>No
Another aspect of the invention is a method of coating a composition that ..... included? ^ arhnno and one or more elements of groups III or IV on an elastomeric plug. To carry out the method, a plug is introduced into a deposition chamber.
A reaction mixture is introduced into the deposition chamber, which includes a plasma-forming gas with a gaseous source of a group III element (for example, Al), a group IV element (for example, Si, Sn) or a combination of two or more of these. The reaction mixture optionally contains an oxidizing gas and optionally contains a gaseous compound with one or more CH bonds. Plasma forms in the reaction mixture and the stopper is contacted with the reaction mixture. A coating of a Group III element or compound, a Group IV element or compound, or a combination of two or more of these is deposited on at least a portion of the plug.
VII.A.3. Plastic container covered with a barrier coating effective to provide 95% vacuum retention for 24 months
Another aspect of the invention is a container that includes a container, a barrier liner, and a closure. The container is generally tubular and made of thermoplastic material. The container has a mouth and<sup>89</sup> IMPI ^ a cavity united at least in part by a pair ^ dní ^^ filL pSW ^ S has an inner surface which is intPrpnTipni-a 1-a. cavity. An at least essentially continuous barrier coating is applied on the inner surface of the wall. The barrier coating is effective in maintaining within the container at least 90% of its initial vacuum level, optionally 95% of its initial vacuum level, for a useful life of at least 24 months. A closure is provided which covers the mouth of the container and isolates the container cavity from ambient air.
Vil.B.1.a. Cylinder syringe lined with a deposited lubricating coating of an organometallic precursor
Yet another aspect of the invention is a container with a lubricating coating made of an organosilicon precursor. An organometallic precursor other than that defined herein can also be contemplated.
The coating can be of the type prepared by the following process.
A precursor is provided which is an organometallic precursor, preferably an organosilicic precursor, more preferably a linear siloxane, a monocyclic siloxane, a polycyclic siloxane, a polysilsesquioxane, a linear silazane, a monocyclic silazane, a silazane <sup>90 </sup>. . . . . .... polycyclic, a polysilsesquiazan, or any one or more of these precursors. . -
The precursor is applied to a substrate under conditions effective to form a coating. The coating is polymerized or lattice, or both, to form a lubricated surface with a lower sliding force or plunger pull-out force than the untreated substrate.
Another aspect of the invention is a syringe that includes a plunger, a syringe barrel, and a lubricating layer. The syringe barrel has an inside surface on which the plunger slides. The lubricant layer is disposed on the inner surface of the syringe barrel and includes a coating of a lubricant layer of SiwOxCyHz made of organosilicon precursor as defined in this description. The lubricating layer is less than 1000 nm thick and is effective in reducing the breakout force or plunger sliding force necessary to move the plunger within the cylinder.
Another aspect of the invention is a lubricating coating on the inner wall of a syringe barrel. The coating is produced by a PECVD process using the following materials and conditions. A cyclic precursor selected from a monocyclic siloxane, a polycyclic siloxane or a combination of two or more of these is used.
At least it is not added
<img file="MX345403B_D0062.tif" />
to the process. Sufficient input power is provided to generate plasma to induce the formation of a coating. The materials and conditions employed are effective in reducing the sliding force or the breakout force of the syringe plunger moving through the syringe barrel by at least 25 percent relative to an uncoated syringe barrel.
The resulting coating can have the formula: SiwOxCyHz, where w is 1, x is from about 0.5 to about 2.4, and is from about 0.6 to about 3, and z is from about 2 to about 9, preferably where w is 1, x is from about 0.5 to 1, and is from about 2 to about 3, and z is from about 6 to about 9.
V II.B.1.ai Lubricant coating: SiOx barrier, lubricant layer, surface treatment
Another aspect of the invention is a syringe comprising a barrel defining a cavity and having an interior surface through which the plunger slides. The syringe barrel is made of thermoplastic base material. A lubricating coating is applied, e.g. ex. , to the inner surface of the cylinder, to the plunger, or to both using PECVD. The lining lu
INSTITUTE MEX ^ YEAR ¥ ^ “8 OS l A EROWDAI?
be made of an organosilicon precursor and may be less than 1000 nm thick. A surface treatment is carried out on the lubricant coating in an amount effective to reduce leakage of the lubricant coating, the thermoplastic base material, or both into the cavity, that is, effective to form a solute retention element on the surface. . The lubricating coating and the solute retainer are compounded and present in relative amounts so as to be effective to provide a breakout force, a plunger sliding force, or both, less than the corresponding force necessary in the absence of the lubricant. lubricant coating and solute retainer.
V II.Blb Syringe with a barrel whose interior has a SiOX coating and whose exterior has a barrier coating
Yet another aspect of the invention is a syringe barrel that includes a plunger, barrel, and inner and outer barrier liner. The cylinder is made of a thermoplastic base material that defines a cavity. The cylinder has an inner surface on which the plunger slides and an outer surface. A
<img file="MX345403B_D0063.tif" />
INSTITUTE MüXiCANt
Μ LA mannfi e
<img file="MX345403B_D0064.tif" />
SiOx barrier coating, where x eii from about 1.5 to about d ^ alternative from about 1.5 to about 2. alternatively from about 2, on the inside surface of the cylinder. A barrier coating of a resin is provided on the outer surface of the cylinder.
V II.Blc Method of preparing a syringe having a barrel with the interior lined with SiOx and the exterior lined with a barrier
Still another aspect of the invention is a method of preparing a syringe that includes a plunger, a barrel, and an inner and outer barrier coating. A cylinder is provided with an inner surface on which the plunger slides and an outer surface. A SiOx barrier coating, where x in this formula is from about 1.5 to about 2.9, alternatively from about 1.5 to about 2.6, alternatively from about 2, is provided on the inner surface of the cylinder by PECVD. A barrier coating of a resin is provided on the outer surface of the cylinder. The plunger and cylinder are assembled to provide a syringe.
V II.B.2. Plungers
VII.Β.2.a.
With the face
<img file="MX345403B_D0065.tif" />
with a barrier
Another aspect of the invention is a plunger for a syringe, which includes a piston and a push rod. The piston has a front face, a generally cylindrical side face, and a rear portion, the side face being configured to movably seat within a syringe barrel. The front face has a barrier coating.
The push rod is coupled to the rear portion and is configured to advance the piston in a syringe barrel.
V II.B.2.b. With lubricant coating interconnected with the side face
Yet another aspect of the invention is a plunger for a syringe, which includes a piston, a lubricating coating, and a push rod. The piston has a front face, a generally cylindrical side face, and a rear portion. The side face is configured to movably seat within a syringe barrel. The lubricant coating is interconnected with the side face. The push rod is coupled to the rear portion of the piston and is configured to advance the piston in a syringe cylinder.
V II.B.3. Two-piece syringe and Luer connector
Another aspect of the invention is a j eriñg ^ £ | j ^<sub>TO</sub>My®W $ i heard INDUSTRIAL CURRENCY --- a plunger, a syringe barrel, and a Luer-type connector. The syringe barrel includes an interior surface on which the plunger slides. The Luer-type connector includes a conical luer-type fitting with an internal passage defined by an internal surface. The Luer-type connector is formed as a separate piece from the syringe barrel and attached to the syringe barrel by coupling. The luer taper fitting liner has a SiOx barrier coating, where x in this formula is about 1.5 to about 2.9, alternatively about 1.5 to about 2.6, alternatively about 2.
V II.B.4. Lubricating coating obtained by polymerizing an organosilicon precursor in situ
V il.B.4.a. Product obtained through the process and lubricity
Yet another aspect of the invention is a lubricating coating made from an organosilicon precursor. This coating is of the type prepared by the following process.
A precursor selected from an organometallic precursor, preferably an organosilicon precursor, preferably a linear siloxane, a monocyclic siloxane, a polycyclic siloxane, a
IMPI® polysilsesquioxane, a monocyclic industrial, linear silazane, a polycyclic silazane, a polysilsesquioxane, or a combination of any two or more of these precursors. The precursor is applied to a substrate under conditions effective to form a coating. The coating is polymerized or lattice, or both, to form a lubricated surface with a lower sliding force or plunger pull-out force than the untreated substrate.
The resulting coating can have the structure: SiwOxCyHz, where w is 1, x is from about 0.5 to about 2.4, and is from about 0.6 to about 3, and z is about 2 to about 9, preferably where w is 1, x is from about 0.5 to 1, and it's about 2 to about 3, and z is about 6 to about 9.
V II.B.4.b. Product obtained through the process and analytical properties
Yet another aspect of the invention is a PECVD-deposited lubricating coating of an organometallic precursor, preferably a precursor <sup>97</sup> IMPI
INSTITUTO MEXICANO - j- ____-, _ DJ LA-PTOmOAD. Organosilicic material, more preferably of a tbairáeeílΛ · 5Π siloxane !! monocyclic siloxane, a hairy siloxane। polysilsesquioxane, a linear silazane, a monocyclic silazane, a polycyclic silazane, a polysilsesquioxane, or a combination of any two or more of these precursors. The coating has a density between 1.25 and 1.65 g / cm3 determined by X-ray reflectivity (XRR).
The use of an organometallic precursor containing a group III metal, i.e. boron, aluminum, gallium, indium, thallium, scandium, yttrium or lanthanum, or group IV, i.e. silicon, germanium, tin, can also be contemplated. lead, titanium, zirconium, hafnium, thorium, or combinations of two or more of these. Other volatile organic compounds can also be contemplated. However, organosilicon compounds are preferred for carrying out the present invention.
Yet another aspect of the invention is a PECVD-deposited lubricating coating of a feed gas comprising an organometallic precursor, preferably an organosilicon precursor, more preferably a linear siloxane, a monocyclic siloxane, a polycyclic siloxane, a polysilsesquioxane.
a linear silazane, a monocyclic silazane, a silazane
<img file="MX345403B_D0066.tif" />
polycyclic, a polysilsesquiazan, or any one or more of these precursors. The use of a precursor containing a Group III or IV metal can also be contemplated.
The coating has a degassing component, one or more oligomers containing repeating - (Me) 2SiO moieties, as determined by gas chromatography / mass spectrometry. Optionally, the liner meets the limitations of either embodiment VII.B.4.a or VII.B.4.b.
Another aspect of the invention is a PECVD-deposited lubricating coating of a feed gas comprising an organometallic precursor, preferably an organosilicon precursor, more preferably a linear siloxane, a monocyclic siloxane, a polycyclic siloxane, a polysilsesquioxane, a silazane linear, a monocyclic silazane, a polycyclic silazane, a polysilsesquiazane, or a combination of any two or more of these precursors. The coating has normalized atomic concentrations to 100% carbon, oxygen, and silicon, as determined by X-ray photpelectron spectroscopy (XPS), less than 50% carbon and greater than 25% silicon. Optionally, the cladding meets the limitations of any of Embodiments VII.B.4.ao
VII.
<img file="MX345403B_D0067.tif" />
<img file="MX345403B_D0068.tif" />
INDUSTRIAL _______MEXICANO Di LA FROHtDAD
<img file="MX345403B_D0069.tif" />
The use of an organometallic precursor containing a Group III or IV metal can also be contemplated.
Another aspect of the invention is a PECVD-deposited lubricating coating of a feed gas comprising an organosilicon precursor, preferably a monocyclic siloxane, a monocyclic silazane, a polycyclic siloxane, a polycyclic silazane, or a combination of two or more of these. The coating has an atomic concentration of carbon, normalized to 100% carbon, oxygen, and -silicon, as determined by X-ray photoelectron spectroscopy (XPS), greater than the atomic concentration of carbon in the atomic formula for the feed gas . Optionally, the liner meets the limitations of Embodiments VII.B.4.a or VII.B.4.b.
A further aspect of the invention is a PECVD-deposited lubricant coating of a feed gas comprising an organosilicon precursor, preferably a monocyclic siloxane, a monocyclic silazane, a polycyclic siloxane, a polycyclic silazane, or a combination of two or more of these. The cladding has an atomic concentration of silicon, normalized to 100% carbon, oxygen and silicon, as
100 determined by
<img file="MX345403B_D0070.tif" />
(XPS), photoelectron spectroscopy inferior to the atomic concentration of silicon in the
<img file="MX345403B_D0071.tif" />
atomic formula for feed gas. Optionally, the coating meets the limitations of the embodiments
VII.B.4.ao VII.B.4.b.
V II.Cl Vessel containing viable blood with a deposited coating of an organosilicon precursor
Yet another aspect of the invention is a container that contains blood. The container has a wall. The wall has an internal surface that defines a cavity. The inner surface of the wall has an at least partial hydrophobic coating as defined above, preferably a SiwOxCyHz hydrophobic coating, preferably where w is 1, x in this formula is from about 0.5 to 2.4, and is from about 0.6 to about 3 , and z is from 2 to about 9, more preferably where w is 1, x is from about 0.5 to 1, and is from about 2 to about 3, and z is from 6 to about 9. The coating can be thin with a monomolecular thickness or with a thickness of about 1000 nm. The container contains viable blood in its cavity that is in contact with the SiwOxCyHz coating, which can be returned to the vascular system of a patient.
V II.C.2. A deposited coating of an organosilicon precursor that reduces
<img file="MX345403B_D0072.tif" />
101 coagulation or
<img file="MX345403B_D0073.tif" />
<img file="MX345403B_D0074.tif" />
platelet on the vessel wall
Another aspect of the invention is a container that has a wall. The wall has an internal surface that defines a cavity and has a passivating coating, e.g. ex. , hydrophobic, at least partially made of an organosilicon precursor by PECVD, preferably a SiwOxCyHz coating, preferably where w is 1, x in this formula is from about 0.5 to 2.4, and is from about 0.6 to about 3, and z is 2 at about 9, more preferably where w is 1, x is from about 0.5 to 1, and is from about 2 to about 3, and z is from 6 to about 9. The coating has a thickness that is between a monomolecular thickness and a thickness of approximately 1000 nm on the inner surface. The coating effectively reduces platelet activation of blood plasma treated with a sodium citrate additive and exposed to the inner surface, compared to the same type of uncoated wall. The coating effectively reduces coagulation of blood exposed to the inner surface, compared to the same type of uncoated wall.
V II.C.3. Container containing viable blood coated with a Group III or IV metallic element
102
Another aspect of the invention is a network containing blood and having a wall with an internal surface defining a cavity. The inner surface is at least partially coated with a composition that includes carbon, one or more Group III metals, one or more Group IV metals, or a combination of two or more of these. The coating has a thickness that. it ranges from a monomolecular thickness to a thickness of approximately 1000 nm, inclusive, on the inner surface. The container contains in its cavity blood that is in contact with the lining, which can be returned to the vascular system of a patient.
V II.C.4. Coating of a group III or IV element that reduces blood clotting or platelet activation in the container
Optionally, in the container of the preceding paragraph, the coating of the group III or IV element effectively reduces coagulation or platelet activation of blood exposed to the inner surface of the container wall.
V II.Dl Container containing insulin with a deposited coating of an organosilicon precursor
Another aspect of the invention is a container containing insulin and having a wall with a surface
103 internal that defines a cavity.
<img file="MX345403B_D0075.tif" />
an at least partial passivating coating made of an organosilicon precursor by PECVD, preferably a SiwOxCyHz coating, preferably where w is 1, x in this formula is from about 0.5 to 2.4, and is from about 0.6 to about 3, and z is 2 at about 9, more preferably where w is 1, x is from about 0.5 to 1, and is from about 2 to about 3, and z is from 6 to about 9. The coating can have a thickness in the range of monomolecular thickness to about 1000 nm thick on the inner surface. Insulin is disposed within the cavity in contact with the SiwOxCyHz coating.
V II.D.2. Deposited coating of an organosilicon precursor that reduces precipitation of insulin in the container
Optionally, in the container from the previous paragraph, the SiwOxCyHz coating effectively reduces the formation of a precipitate with the insulin that is in contact with the inner surface, compared to the same surface without the SiwOxCyHz coating.
V II.D.3. Container containing insulin with a coating of a Group III or IV element
Another aspect of the invention is a container that
104
<img file="MX345403B_D0076.tif" />
contains insulin and has a wall with unatL-AHa <aisÉ¿f <DÍ
Internal INDUSTRIAL DEGTOOHEDAD that defines a cavity. The inner surface is at least partially coated with a composition comprising carbon, one or more group III elements, one or more group IV elements, or a combination of two or more of these. The coating can have a thickness in the range of monomolecular thickness to about 1000 nm thick on the inner surface. Insulin is arranged within the cavity in contact with the coating.
V II.D.4. Coating of a group III or IV element that reduces the precipitation of insulin in the container
Optionally, in the container of the previous paragraph, coating a composition, comprising carbon, one or more elements of group III, one or more elements of group IV, or a combination of two or more of these, effectively reduces the formation of a precipitate with the insulin that is in contact with the inner surface, compared to the same surface without the coating.
V II.E. Buckets
The coating applied by PECVD, etc., described in this description is also useful for coating trays to form a barrier coating, a hydrophobic coating, a lubricating coating or more than
INDUSTRIAL
A cuvette is a small tube of circular or square cross-section, sealed at one end, made of molten plastic, glass, or quartz (for UV light) and designed as a sample holder for spectroscopic experiments. The best cuvettes are as transparent as possible, with no impurities that can affect the spectroscopic reading. Like test tubes or sample collection tubes, the cuvettes can be exposed to the atmosphere or have a lid to seal them. The PECVD applied coatings of the present invention can be very thin, transparent and optically flat so that they do not interfere with the optical analysis of the cuvettes or their contents.
vil.f. vials
The PECVD coating methods, etc., described in this disclosure are also useful for coating vials to form a coating, eg, a barrier coating or a hydrophobic coating, or a combination of these coatings. A vial is a container or a small bottle, especially used to store medication such as lyophilized liquids, powders or powders. They can also be sample containers, for example for use in sampling devices
106 automatic in analytical chromatography.
tubular shape or a shape similar to
A vial DE¿A ÉáorlEDAP INDUSTRIAL
<img file="MX345403B_D0077.tif" />
a bottle with a neck. The bottom is generally flat, unlike test tubes or sample collection tubes that generally have a rounded bottom. The vials can be made, for example, of plastic (for example, polypropylene, COC, COP).
Computational medium and program element
In addition, a computational means is provided, in which a computer program for coating and / or inspecting a container is stored, which when executed by a processor of a container processing system, causes the processor to perform the steps of method mentioned above or below.
In addition, a program item is provided for coating and / or inspecting a container, which when run by a processor of a container processing system, causes the processor to perform the method steps mentioned above or below. .
Other aspects of the invention will be apparent from this disclosure and the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic diagram showing a container processing system according to a
107 realization of the description.
IMPI t ^ STITUTO MEXICANO
OF THE INDUSTRIAL PHOHSDAD
<img file="MX345403B_D0078.tif" />
FIG. 2 is a cross-sectional view of the container support at a coating station in accordance with one embodiment of the disclosure.
FIG. 3 is a view similar to FIG. 2 of an alternative embodiment of the description.
FIG. 4 is a diagrammatic plan view of an alternative embodiment of the container holder.
FIG. 5 is a diagrammatic plan view of another alternative embodiment of the container holder.
FIG. 6 is a view similar to FIG. 2 of a container inspection apparatus.
FIG. 7 is a view similar to FIG. 2 of an alternative container inspection apparatus.
FIG. 8 is a section taken along the lines of section A-A of FIG. 2.
FIG. 9 is an alternative embodiment of the structure shown in FIG. 8.
FIG. 10 is a view similar to FIG. 2 of a container holder in a coating station according to another embodiment of the disclosure, employing a CCD detector.
FIG. 11 is a detailed view similar to FIG. 10 from a light source and detector that are inverted in
FIG. 12 is a view similar to FIG. 2 of a container holder in a coating station according to yet another embodiment of the disclosure, which uses microwave energy to generate the plasma.
FIG. 13 is a view similar to FIG. 2 of a container holder at a coating station according to yet another embodiment of the description, where the container can be seated on the container holder at the processing station.
FIG. 14 is a view similar to FIG. 2 of a container holder in a coating station according to still another embodiment of the description, where the electrode can be configured as a coil.
FIG. 15 is a view similar to FIG. 2 of a container holder in a coating station according to another embodiment of the disclosure, employing a tube conveyor to move a container to and from the coating station.
FIG. 16 is a diagrammatic view of the operation of a container transport system, such as that shown in FIG. 15, for placing and supporting a container in a processing station.
FIG. 17 is a diagrammatic view of a mold and a<sup>109</sup> ΙΜΡΙ6, INSTITUTO MEXICANO cavity of a mold to form a container of aeu ^ ggg ^ A'po'S 'an aspect of the present description. ..
FIG. 18 is a diagrammatic view of the mold cavity of FIG. 17 provided with a container liner device in accordance with one aspect of the present disclosure.
FIG. 19 is a view similar to FIG. 17 provided with an alternative container liner device in accordance with one aspect of the present disclosure.
FIG. 2 0 is a longitudinal cross-sectional exploded drawing of a syringe and a cap adapted for use as a pre-filled syringe.
FIG. 21 is a view generally similar to FIG. 2 showing a capped syringe barrel and container holder in a coating station according to one embodiment of the disclosure.
FIG. 22 is a view generally similar to FIG. 21 showing an uncapped syringe barrel and a container holder at a coating station in accordance with yet another embodiment of the invention.
FIG. 23 is a perspective view of a blood collection tube assembly having a closure in accordance with yet another embodiment of the invention.
110
FIG. 24 is a fragmentary section of the Fll? Blood collection and closure tube assembly.<sup>1</sup> 23 .
FIG. 25 is an isolated section of an elastomeric insert of the closure of FIGS. 23 and 24.
FIG. 26 is a view similar to FIG. 22 of another embodiment of the invention for processing syringe barrels and other containers.
FIG. 27 is an enlarged detail view of a processing vessel of FIG. 26.
FIG. 28 is a schematic view of an alternative processing vessel.
FIG. 29 is a schematic view showing degassing of a material through a coating.
FIG. 30 is a schematic cross-sectional view of a test setup for causing the wall of a container to degas into the container and for measuring degassing using a measuring cell interposed between the container and a vacuum source.
FIG. 31 is a graph of the degassing mass flow rate measured in the test assembly of FIG. 30 for multiple containers.
FIG. 32 is a bar chart showing a statistical analysis of the parameters shown in the
FIG. 31.
lll <sup>υ</sup> industrial
FIG. 33 is a longitudinal section of a syringe barrel and a volume for receiving gas nailed according to another embodiment of the invention.
FIG. 34 is a view similar to FIG. 34 of another embodiment of the invention that includes an electrode extension.
FIG. 35 is a view taken along section lines 35-35 of FIG. 34, showing the distal gas supply openings and the extension electrode of FIG. 3. 4.
FIG. 36 is a perspective view of a double walled blood collection tube assembly in accordance with yet another embodiment of the invention.
FIG. 37 is a view similar to FIG. 22 showing another embodiment.
FIG. 38 is a view similar to FIG. 22 showing yet another embodiment.
FIG. 39 is a view similar to FIG. 22 showing yet another embodiment.
FIG. 40 is a view similar to FIG. 22 showing yet another embodiment.
FIG. 41 is a plan view of the embodiment of FIG. 40.
FIG. 42 is a fragmentary longitudinal section in
INSTITUTO MEXICANO DE LA MONEDAD detail of an alternative sealing mechanism to be used, for example, in the realizations of “the FlUS. IT 2, 3, 6-10, 12-16, 18, 19, 33 and 37-41 to seat a container on a container stand. FIG. 42 also shows an alternative construction of a syringe barrel that can be used, for example, in the embodiments of FIGS. 2, 3, 6-10, 12-22, 26-28, 33-34 and 37-41.
FIG. 43 is a further enlarged detail view of the sealing arrangement shown in FIG. 42.
FIG. 44 is a view similar to FIG. 2 of an alternative internal electrode / gas delivery tube that can be used, for example, with the embodiments of FIGS. 1, 2, 3, 8, 9, 12-16, 18-19, 21-22, 33, 37-43, 46-49 and 52-54.
FIG. 45 is an alternative container support construction that can be used, for example, in the embodiments of FIGS. 1, 2, 3, 6-10, 12-16, 18, 19, 21, 22, 26, 28, 33-35 and 37-44.
FIG. 46 is a schematic cross-sectional view of a gas supply tube arrangement and a mechanism for inserting and removing gas supply tubes from a container holder, showing a gas supply tube.<sup>113</sup> IMPI ^
INSTITUTO MEXICANO gas in its fully advanced position. <sup>say</sup>* nous ™ a '
FIG. 47 is a view similar to ftg -4 6, qwe · shows a gas supply tube in an intermediate position.
FIG. 4 8 is a view similar to FIG. 46, showing a gas supply tube in a retracted position. The gas supply tube arrangement of FIGS. 46-48 can be used, for example, in the embodiments of FIGS. 1, 2, 3, 8, 9, 12-16, 18-19, 2122, 26-28, 33-35, 37-45, 49 and 52-54. The mechanism of FIGS. 46-48 can be used, for example, in the gas supply tube embodiments of FIGS. 2, 3, 8, 9, 12-16, 18-19, 21-22, 26-28, 33-35, 37-45, 49 and 52-54, as well as with the probes of the vessel inspection apparatus of FIGS. 6 and 7.
FIG. 49 is a view similar to FIG. 16 showing a supply mechanism for vessels to be treated and a cleaning reactor for a PECVD coating apparatus. The mechanism of FIG. 4 9 can be used with the container inspection apparatus of FIGS. 1, 9, 15 and 16, for example.
FIG. 50 is an exploded drawing of a two-piece syringe barrel and a Luer-type safety connector. The syringe barrel can be used in the apparatus
114
IMPIAS for treatment and inspection of containers of
26-28, 33-35, 37-39, 44 and 53-54.
FIG. 51 is an assembled view of the two-piece syringe barrel and Luer-type safety connector of FIG. fifty.
FIG. 52 is a view similar to FIG. 42 showing a syringe barrel being treated that does not have clamps or manual stops 440. The syringe barrel can be used in the container inspection and treatment apparatus of FIGS. 1-19, 27, 33, 35, 44-51 and 53-54.
FIG. 53 is a schematic view of an assembly for treating containers. The assembly can be used in the apparatus of FIGS. 1-3, 8-9, 12-16, 18-22, 26-28, 33-35 and 37-49. .
FIG. 54 is a diagrammatic view of the embodiment of FIG. 53.
FIG. 55 is a diagrammatic view similar to FIG. 2 of an embodiment of the invention that includes a plasma screen.
FIG. 56 is a schematic cross-sectional view of a gas supply tube arrangement, having separate gas supplies and a mechanism for inserting and removing gas supply tubes from a container holder.
FIG. 57 is a graph of the most ico flow rate of
115
<img file="MX345403B_D0079.tif" />
degassing measured in Example 19.
FIG. 58 shows a linear rack, otherwise similar to FIG. Four.
FIG. 59 shows a schematic representation of a container processing system according to an embodiment of the present invention.
FIG. 60 shows a schematic representation of a container processing system according to another embodiment of the present invention.
FIG. 61 shows a processing station of a container processing system according to an exemplary embodiment of the present invention.
FIG. 62 shows a portable container holder according to an embodiment of the present invention.
The following reference characters are used in the figures of the drawings:
<img file="MX345403B_D0080.tif" />
116
<td> 20</td><td>Container Processing System</td>
<td> 22</td><td>Injection molding machine</td>
<td> 24</td><td>Visual inspection station</td>
<td> 26</td><td>Inspection station (precoating)</td>
<td> 28</td><td>Coating station</td>
<td> 30</td><td>Inspection station . (post-coating)</td>
<td> 32</td><td>Optical source transmission station (thickness)</td>
<td> 34</td><td>Optical source transmission station (defects)</td>
<td> 36</td><td>Departure</td>
<td> 38</td><td>Container support</td>
<td> 40</td><td>Container support</td>
<td> 42</td><td>Container support</td>
<td> 44</td><td>Container support</td>
<td> 46</td><td>Container support</td>
<td> 48</td><td>Container support</td>
<td> 50</td><td>Container support </td>
<td> 52</td><td>Container support</td>
<td> 54</td><td>Container support</td>
<td> 56</td><td>Container support</td>
<td> 58</td><td>Container support</td>
<td> 60</td><td>Container support</td>
<td> 62</td><td>Container support</td>
<td> 64</td><td>Container support</td>
<td> 66</td><td>Container support</td>
<td> 68</td><td>Container support</td>
MBXiCANU
<td> 70</td><td>__________________________ pt: Transported ^,</td>
<td> 72</td><td>Mechanism of 'transfer (switched on) " </td>
<td> 74</td><td>Transfer mechanism (off)</td>
<td> 80</td><td>Container</td>
<td> 82</td><td>Opening</td>
<td> 84</td><td>Closed end</td>
<td> 86</td><td>Wall</td>
<td> 88</td><td>Inner surface</td>
<td> 90</td><td>Barrier coating</td>
<td> 92</td><td>Container port</td>
<td> 94</td><td>Vacuum duct</td>
<td> 96</td><td>Vacuum port</td>
<td> 98</td><td>Vacuum source</td>
<td> 100</td><td>O-ring (of 92)</td>
<td> 102</td><td>O-ring (of 96)</td>
<td> 104</td><td>Gas inlet port</td>
<td> 106</td><td>O-ring (of 100)</td>
<td> 108</td><td>Probe (counter electrode)</td>
<td> 110</td><td>Gas supply port (of 108)</td>
<td> 112</td><td>Container support (Fig. 3)</td>
<td> 114</td><td>Housing (of 50 or 112)</td>
<td> 116</td><td>Ring</td>
<td> 118</td><td>External surface (of 80)</td>
<td> 120</td><td>Container support (arrangement)</td>
<td> 122</td><td>Container port (Fig. 4, 58)</td>
<img file="MX345403B_D0081.tif" />
117
<td> 130</td><td>Frame (Fig. 5)</td>
<td> 132</td><td>Light source</td>
<td> 134</td><td>Side channel</td>
<td> 136</td><td>Shut-off valve</td>
<td> 138</td><td>Probe port</td>
<td> 140</td><td>Vacuum port</td>
<td> 142</td><td>Gas inlet port PECVD</td>
<td> 144</td><td>PECVD gas source</td>
<td> 146</td><td>Vacuum line (to 98)</td>
<td> 148</td><td>Shut-off valve</td>
<td> 150</td><td>Flexible line (out of 134)</td>
<td> 152</td><td>Pressure gauge</td>
<td> 154</td><td>Container interior 80</td>
<td> 160</td><td>Electrode</td>
<td> 162</td><td>Power supply</td>
<td> 164</td><td>Side wall (of 160)</td>
<td> 166</td><td>Side wall (of 160)</td>
<td> 168</td><td>Closed end (from 1'60)</td>
<td> 170</td><td>Light source (Fig. 10)</td>
<td> 172</td><td>Detector</td>
<td> 174</td><td>Pixel (out of 172)</td>
<td> 176</td><td>Interior surface (out of 172)</td>
<td> 182</td><td>Orifice (of 186)</td>
<td> 184</td><td>Wall (of 186)</td>
<td> 186</td><td>Integration sphere</td>
<td> 190</td><td>Microwave power supply</td>
<td> 192</td><td>Waveguide</td>
<td> 194</td><td>Microwave cavity</td>
<td> 196</td><td>Separation</td>
<td> 198</td><td>Top End (of 194)</td>
<td> 200</td><td>Electrode</td>
<td> 202</td><td>Tube transport</td>
<td> 204</td><td>Sucker</td>
<td> 208</td><td>Mold core</td>
<td> 210</td><td>Mold cavity</td>
<td> 212</td><td>Mold cavity liner</td>
<td> 22 0</td><td>Support surface (Fig. 2)</td>
<td> 222</td><td>Support surface</td>
<td> 224</td><td>Support surface (Fig. 2)</td>
<td> 226</td><td>Apoyo surface (Fig. 2)</td>
<td> 228</td><td>Support surface (Fig. 2)</td>
<td> 230</td><td>Support surface (Fig. 2)</td>
<td> 232</td><td>Support surface (Fig. 2)</td>
<td> 234</td><td>Support surface (Fig. 2)</td>
<td> 236</td><td>Support surface (Fig. 2)</td>
<td> 238</td><td>Support surface (Fig. 2)</td>
<td> 240</td><td>Support surface (Fig. 2)</td>
<td> 250</td><td>Syringe barrel</td>
<td> 252</td><td>Syringe</td>
<td> 254</td><td>Interior surface (of 250)</td>
<td> 256</td><td>Rear end (of 250)</td>
<td> 258</td><td>Plunger (of 252)</td>
<td> 260</td><td>Front end (out of 250)</td>
<td> 262</td><td>Top</td>
<td> 264</td><td>Interior surface (out of 262)</td>
<td> 266</td><td>Connector</td>
<td> 268</td><td>Container</td>
<td> 270</td><td>Closing</td>
<td> 272</td><td>Inward facing surface</td>
<td> 274</td><td>Cavity</td>
<td> 276</td><td>Surface that is in contact with the wall</td>
<td> 278</td><td>Internal surface (out of 280)</td>
<td> 280</td><td>Vessel wall</td>
<td> 282</td><td>Plug</td>
<td> 284</td><td>Protection</td>
<td> 286</td><td>Lubricating layer</td>
<td> 288</td><td>Barrier layer</td>
<td> 290</td><td>Apparatus for coating, for example, 250</td>
<td> 292</td><td>Inner surface (out of 294)</td>
<td> 294</td><td>Limited opening (of 250)</td>
<td> 296</td><td>Processing vessel</td>
<td> 298</td><td>External surface (of 250)</td>
<td> 300</td><td>Cavity (of 250)</td>
<td> 302</td><td>Larger opening (of 250)</td>
<img file="MX345403B_D0082.tif" />
118
<img file="MX345403B_D0083.tif" />
MEXICAN INSTITUTE OF THE «OREDAD INDUST1IAI
<td> 304</td><td>Processing vessel cavity</td>
<td> 306</td><td>Processing vessel opening</td>
<td> 308</td><td>Internal electrode</td>
<td> 310</td><td>Inside passage (of 308)</td>
<td> 312</td><td>Proximal end (of 308)</td>
<td> 314</td><td>Distal end (of 308)</td>
<td> 316</td><td>Distal opening (of 308)</td>
<td> 318</td><td>Plasma</td>
<td> 320</td><td>Vessel support</td>
<td> 322</td><td>Port (out of 320)</td>
<td> 324</td><td>Processing vessel (conduit type)</td>
<td> 326</td><td>Vessel opening (of 324)</td>
<td> 328</td><td>Second opening (of 324)</td>
<td> 330</td><td>Vacuum port (receiving 328)</td>
<td> 332</td><td>First Connector (Male Luer Tapered Fitting)</td>
<td> 334</td><td>Second connector (female taper luer fit)</td>
<td> 336</td><td>Safety Ring (of 332)</td>
<td> 338</td><td>First stop (of 332)</td>
<td> 340</td><td>Second stop (out of 332)</td>
<td> 342</td><td>O-ring</td>
<td> 344</td><td>Hook</td>
<td> 346</td><td>Wall</td>
<td> 348</td><td>Siding (out of 346)</td>
<td> 350</td><td>Permeation trajectory</td>
<td> 352</td><td>Empty</td>
<td> 354</td><td>Gaseous molecule</td>
<td> 355</td><td>Gaseous molecule</td>
<td> 356</td><td>Interface (between 346 and 348)</td>
<td> 357</td><td>Gaseous molecule</td>
<td> 358</td><td>PET container</td>
<td> 359</td><td>Gaseous molecule</td>
<td> 360</td><td>Stamp</td>
<td> 362</td><td>Measure cell</td>
<td> 364</td><td>Vacuum pump</td>
<td> 366</td><td>Arrows</td>
<td> 368</td><td>Conical pitch</td>
<td> 370</td><td>Inner wall</td>
<td> 372</td><td>Inner wall</td>
<td> 374</td><td>Camera</td>
<td> 376</td><td>Camera</td>
<td> 378</td><td>Diaphragm</td>
<td> 380</td><td>Diaphragm</td>
<td> 382</td><td>Conductive surface</td>
<td> 384</td><td>Conductive surface</td>
<td> 386</td><td>Detour</td>
<td> 390</td><td>Graphic (glass tube)</td>
<td> 392</td><td>Graphic (uncoated PET)</td>
<td> 3 94</td><td>Main graph (coating with SiO<sub>2</sub>)</td>
<td> 396</td><td>Outliers (SiO coating<sub>2</sub>)</td>
<td> 398</td><td>Inner electrode and gas supply tube</td>
<td> 400</td><td>Distal opening</td>
<td> 402</td><td>Extension counter electrode</td>
<td> 404</td><td>Ventilation (Fig. 7)</td>
<td> 406</td><td>Valve</td>
<td> 408</td><td>Internal wall (Fig. 36)</td>
<td> 410</td><td>External wall (Fig. 36)</td>
<td> 412</td><td>Inner surface (Fig. 36)</td>
<td> 414</td><td>Plate electrode (Fig. 37)</td>
<td> 416</td><td>Plate electrode (Fig. 37)</td>
<td> 418</td><td>Vacuum duct</td>
<td> 420</td><td>Container support</td>
<td> 422</td><td>Vacuum chamber</td>
<td> 424</td><td>Container support</td>
<td> 426</td><td>Counter electrode</td>
<td> 428</td><td>Container support (Fig. 39)</td>
<td> 430</td><td>Electrode mount</td>
<td> 432</td><td>Volume locked by 430</td>
<td> 434</td><td>Pressure control valve</td>
<td> 436</td><td>Vacuum chamber duct</td>
<td> 438</td><td>Syringe barrel (Fig. 42)</td>
<td> 440</td><td>Clamp (of 438)</td>
<td> 442</td><td>Rear opening (of 438)</td>
<td> 444</td><td>Cylinder wall (of 438)</td>
<td> 450</td><td>Container support (Fig. 42)</td>
<img file="MX345403B_D0084.tif" />
119
<td> 452</td><td>Annular edge</td>
<td> 454</td><td>Side wall generally cylindrical (out of 438)</td>
<td> 456</td><td>Generally cylindrical inner surface (from 450)</td>
<td> 458</td><td>Stop</td>
<td> 460</td><td>Hole</td>
<td> 462</td><td>O-ring</td>
<td> 464</td><td>External wall (out of 460)</td>
<td> 4 66</td><td>Bottom wall (out of 460)</td>
<td> 4 68</td><td>Top wall (out of 460)</td>
<td> 470</td><td>Inner electrode (Fig. 44)</td>
<td> 472</td><td>Distal portion (of 470)</td>
<td> 474</td><td>Porous side wall (of 472)</td>
<td> 476</td><td>Internal passage (of 472)</td>
<td> 478</td><td>Proximal portion (out of 470)</td>
<td> 480</td><td>Distal end (of 470)</td>
<td> 482</td><td>Support body containers</td>
<td> 484</td><td>Top portion (of 482)</td>
<td> 486</td><td>Base portion (of 482)</td>
<td> 488</td><td>Board (between 484 and 486)</td>
<td> 490</td><td>O-ring></td>
<td> 4 92</td><td>Annular gap</td>
<td> 494</td><td>Radially extending stop surface</td>
<td> 4 96</td><td>Extending wall radially</td>
<td> 4 98</td><td>Screw</td>
<td> 500</td><td>Screw</td>
<td> 502</td><td>Container port</td>
<td> 504</td><td>Second o-ring</td>
<td> 506</td><td>Inner diameter (from 490)</td>
<td> 508</td><td>Vacuum duct (of 482)</td>
<td> 510</td><td>Internal electrode</td>
<td> 512</td><td>Internal electrode</td>
<td> 514</td><td>Insertion mechanism and removal</td>
<td> 516</td><td>Flexible hose</td>
<td> 518</td><td>Flexible hose</td>
<td> 520</td><td>Flexible hose</td>
<td> 522</td><td>Valve</td>
<td> 524</td><td>Valve</td>
IMPI
MEXICAN INSTITUTE
OF THE INDUSTRIAL PKOWEtKAO
<td> 526</td><td>Valve</td>
<td> 528</td><td>Station -<sup>-</sup>give electrode</td>
<td> 530</td><td>Electrode drive internal</td>
<td> 532</td><td>Cleaning reactor</td>
<td> 534</td><td>Vent valve</td>
<td> 536</td><td>Second clamping tool</td>
<td> 538</td><td>Conveyor</td>
<td> 539</td><td>Solute retainer</td>
<td> 540</td><td>Open End (of 532)</td>
<td> 542</td><td>Interior space (out of 532)</td>
<td> 544</td><td>Syringe</td>
<td> 546</td><td>Plunger</td>
<td> 548</td><td>Body</td>
<td> 550</td><td>Cylinder</td>
<td> 552</td><td>Interior surface (of 550)</td>
<td> 554</td><td>Coating</td>
<td> 556</td><td>Luer type connector</td>
<td> 558</td><td>Tapered luer fit</td>
<td> 560</td><td>Internal passage (of 558)</td>
<td> 562</td><td>Inner surface</td>
<td> 564</td><td>Coupling</td>
<td> 566</td><td>Male part (of 564)</td>
<td> 568</td><td>Female part (of 564)</td>
<td> 570</td><td>Barrier coating</td>
<td> 572</td><td>Safety ring</td>
<td> 574</td><td>Main vacuum valve</td>
<td> 576</td><td>Vacuum line</td>
<td> 578</td><td>Manual diverter valve</td>
<td> 580</td><td>Diversion line</td>
<td> 582</td><td>Vent valve</td>
<td> 584</td><td>Main reagent gas valve</td>
<td> 586</td><td>Main reagent feed line</td>
<td> 588</td><td>Fluid reservoir organosilicon</td>
<td> 590</td><td>Power line organosilicon (capillary)</td>
<td> 592</td><td>Shut-off valve Organs i1i ci o</td>
<td> 5 94</td><td>Oxygen tank</td>
<img file="MX345403B_D0085.tif" />
120
<img file="MX345403B_D0086.tif" />
MEXICAN INSTITUTE OF INDUSTRIAL TOOWeDAD
<td> 596</td><td>Oxygen feed line</td>
<td> 598</td><td>Mass flow controller</td>
<td> 600</td><td>Oxygen shutoff valve</td>
<td> 602</td><td>Barrier coating outside of syringe</td>
<td> 604</td><td>Cavity</td>
<td> 606</td><td>Outer surface of cylinder</td>
<td> 610</td><td>Plasma screen</td>
<td> 612</td><td>Plasma screen cavity</td>
<td> 614</td><td>Free space</td>
<td> 616</td><td>Pressure source</td>
<td> 618</td><td>Pressure line</td>
<td> 620</td><td>Capillary connection</td>
<td> 630</td><td>Graphics for COC without coating</td>
<td> 632</td><td>Graphics for SiOx Coated COC</td>
<td> 634</td><td>Graphics for glass</td>
<td> 5501</td><td>First station prosecution</td>
<td> 5502</td><td>Second station prosecution</td>
<td> 5503</td><td>Third station prosecution</td>
<td> 5504</td><td>Fourth station prosecution</td>
<td> 5505</td><td>Processor</td>
<td> 5506</td><td>User interface</td>
<td> 5507</td><td>Manifold</td>
<td> 5701</td><td>PECVD apparatus</td>
<td> 5702</td><td>First detector</td>
<td> 5703</td><td>Second detector</td>
<td> 5704</td><td>Detector</td>
<td> 5705</td><td>Detector</td>
<td> 5706</td><td>Detector</td>
<td> 5707</td><td>Detector</td>
<td> 7001</td><td>Output arm conveyor</td>
<td> 7002</td><td>Output arm conveyor</td>
<td> 7003</td><td>Output arm t ransporter</td>
<td> 7004</td><td>Output arm conveyor</td>
121
MEXICAN INSTITUTE
DETAILED DESCRIPTION OF THE REALIZATIONS
The present invention will be described below in more detail with reference to the accompanying drawings, in which various embodiments are shown. This invention, however, can be carried out in many different ways and the embodiments described herein should not be construed as limiting it in any way. Rather, these embodiments are examples of the invention, the full scope of which is indicated in the claims. Like numbers refer to the same or corresponding items from start to finish.
In the context of the present invention, the following definitions and abbreviations are employed:
RF is radio frequency; sccm is standard cubic centimeters per minute.
The term at least, in the context of the present invention, means greater than or equal to the integer that follows the expression. The word comprises does not exclude other elements or stages and the indefinite article one or one does not exclude a plurality unless otherwise indicated.
First and second or similar references to, for example, processing stations or processing devices refer to the minimum number of stations
122 or processing devices that are pres¿WBek, necessarily represent the order or the total number of stations and processing devices. '* These ”terms do not limit the number of processing stations or the particular processing that takes place in the stations respective.
For the purposes of the present invention, an organosilicon precursor is a compound that has at least one bond:
| —0 — Si — C — H which is a tetravalent silicon atom connected to an oxygen atom and an organic carbon atom (an organic carbon atom being a carbon atom linked to at least one hydrogen atom). A volatile organosilicon precursor, defined as a precursor that can be delivered as a vapor in a PECVD apparatus, is a preferred organosilicon precursor. Preferably, the organosilicon precursor is selected from the group consisting of a linear siloxane, a monocyclic siloxane, a polycyclic siloxane, a polysilsesquioxane, an alkyltrimethoxysilane, a linear silazane, a monocyclic silazane, a polycyclic silazane plus an oxycyclic combination, and a polysilic acid silazane plus a polysilic acid combination. any of these precursors.
L_- - H ΊΓ ~ Τ- "Ί"
IMPI ^
In the context of the present invention, I®g ^ n <§ | ^ S 'industrial ^ * ^ 2 = essentially no oxygen or (interchangeably) substantially no oxygen to the gaseous reactant in some embodiments. This means that some residual atmospheric oxygen may be present in the reaction space and that residual oxygen fed in a previous stage may be present and not completely depleted in the reaction space, this is defined herein as essentially nothing. oxygen present. Essentially there is no oxygen present in the gaseous reagent particularly if the gaseous reagent comprises less than 1 vol% 02, more particularly less than 0.5 vol% 02 and even more particularly if it is free of 02, if not adds no oxygen to the gaseous reagent or if no oxygen is present during PECVD, this is also within the scope of essentially no oxygen.
A container in the context of the present invention can be any type of container with at least one opening and a wall defining an interior surface. The term at least, in the context of the present invention, means greater than or equal to the integer that follows the expression. Accordingly, a container in the context of the present invention has one or more openings.
<sup>124</sup> IMPI One or two ports are preferred, such as the IHÜUSTOAL sampling tube (one port) or a syringe barrel (two ports). If the container has two openings, these can be the same or different sizes. If there is more than one opening, one of the openings can be used for gas inlet for a PECVD coating method according to the present invention, while the other openings are plugged or open. A container according to the present invention can be a sampling tube, for example, for collecting or storing biological fluids such as blood or urine, a syringe (or a part thereof, for example a syringe barrel) for storing or administering a biologically active compound or composition, for example a drug or pharmaceutical composition, a vial for storing biological materials or biologically active compounds or compositions, a tubing, for example, a catheter for transporting biological materials or biologically active composites or compositions, or a cup for containing fluids, for example, for containing biological materials or biologically active composites or compositions.
A container can be of any shape, a container having a substantially cylindrical wall adjacent to at least one of its open ends is preferred.
<img file="MX345403B_D0087.tif" />
125
IMPI
Generally, the inner wall of the container Nsi ^^^ S ^ inwistwal cylindrical, as for example in a sampling tube or a syringe cylinder. Sampling tubes and syringes or parts thereof (eg, syringe barrels) are particularly preferred.
A hydrophobic coating in the context of the present invention means that the coating decreases the wettability of a surface coated with said coating compared to the corresponding uncoated surface. Hydrophobicity, therefore, is a function of the uncoated substrate and the coating. The same applies to appropriate alterations in other contexts where the term hydrophobic is used. The term "hydrophilic" means the opposite, that is, that the wettability increases compared to the reference sample. A particular hydrophobic coating in the context of the present invention may be a coating of the empirical or molecular formula SiwOxCyHz, where w is 1, x is from about 0.5 to about 2.4, and is from about 0.6 to about 3, and z is 2 to about 9.
Wettability is a specific measure for the hydrophobicity or hydrophilicity of a surface. The preferred wettability measurement method in the context of
<img file="MX345403B_D0088.tif" />
method described in ASTM D 2578. This method uses solutions with standard wettability (called dyne solutions) to determine the solution that comes closest to wetting the plastic film surface for exactly two seconds. This is the wettability of the film. The procedure used is modified herein from ASTM D 2578 in that the substrates are not flat plastic films, but are tubes made according to the protocol for forming PET tubes and (except controls) coated according to with the protocol for coating the inside of tubes with a hydrophobic coating (refer to Example 9).
A lubricating coating according to the present invention is a coating that has a lower frictional resistance than an uncoated surface. In other words, it reduces the frictional resistance of the coated surface compared to the reference surface that is uncoated. The friction resistance can be the resistance to static friction and / or the resistance to kinetic friction. One of the preferred embodiments of the present invention is a part of a syringe, for example a barrel or a syringe plunger, coated with a lubricant coating. In this
<img file="MX345403B_D0089.tif" />
INSTITUTE MLXK> N <.____ _ friccie ^ aiSN ^: ^
127 Preferred embodiment, the resistance to pullout in the context of the present invention as defined herein and the resistance to kinetic friction in the context of the present invention is the sliding force of the plunger as defined. defined in the present. For example, the plunger sliding force as defined and determined herein is suitable for determining the presence or absence and the lubricity characteristics of a lubricating coating in the context of the present invention as long as the coating is applied to any syringe or part of a syringe, for example, to the inner wall of the barrel of a syringe. Breakout force is of particular relevance for the evaluation of the coating effect on a pre-filled syringe, that is, a syringe that is filled after coating and can be stored for some time, for example several months or even years, before moving again the plunger (has to separate).
Plunger sliding force in the context of the present invention is the force necessary to maintain movement of a plunger in a syringe barrel, for example, during aspiration or administration. It can be conveniently determined using the ISO 78861: 1993 test described herein and known in the art. A
128 synonymous with the sliding force of the piston rod ^ 'jui ^ industry * usually in the art is sliding force or thrust force.
<img file="MX345403B_D0090.tif" />
Breakout force in the context of the present invention is the initial force necessary to move the plunger in a syringe, for example a pre-filled syringe.
Plunger sliding force and breakout force and methods for measuring them are described in more detail later in this description.
Slidable means that it allows the plunger to slide into a syringe barrel.
In the context of this invention, "substantially rigid" means that the assembled components (the ports, the conduits, and the housing, explained in detail below) can be moved as a unit by manipulating the housing, without significant deflection of any of the components. mounted with respect to the others. Specifically, none of the components are connected by hoses or the like that allow substantial relative movement between the parts in normal use. The provision of a substantially rigid relationship between these parts allows the location of the container seated in the container holder to be almost as well known and precise as the location of these parts attached to the housing.
129
KTrfi ^ Ma® ^ ató & 'OF THE PROPERTY will be described first below
INDUSTRIAL to carry out the present invention, then the coating methods, liners and coated vessels and uses in accordance with the present invention.
I. Container Processing System with Multiple Processing Stations and Multiple Container Stands
I. A container processing system is contemplated comprising a first processing station, a second processing station, a multiplicity of container holders, and a conveyor. The first processing station is configured to process a container having an opening and a wall defining an interior surface. The second processing station is separate from the first processing station and is configured to process a container having an opening and a wall defining an interior surface.
I. At least some, optionally all, container holders include a container port configured to receive and seat the opening of a container for processing the interior surface of a container seated through the container port at the first processing station. The conveyor is configured to
130 carry a series of supports
<img file="MX345403B_D0091.tif" />
Containers seated from the first processing to the second processing station to process the inner surface of a container seated through the container port at the second processing station.
I. Referring first to FIG. 1, a container processing system is shown generally indicated 20. The container processing system may include processing stations that are more widely contemplated as processing devices. The container processing system 20 of the illustrated embodiment may include an injection molding machine 22 (which can be thought of as a processing station or device), additional processing stations or devices 24, 26, 28, 30, 32 and 34 , and an outlet 36 (which can be thought of as a processing station or device). At a minimum, system 20 has at least a first processing station, eg, station 2-8, and a second processing station, eg, 30, 32, or 34.
I. Any of the processing stations 22-36 in the illustrated embodiment may be a first processing station, any other processing station may
<img file="MX345403B_D0092.tif" />
131 be a second station of ¿MPI • Ντπτυτο MU.r-Δ proce s ami at t &
successively.
I. The embodiment illustrated in FIG. 1 can include eight processing stations or devices: 22, 24, 26,
28, 30, 32, 34 and 36. The example container processing system 20 includes an injection molding machine 22, a post-mold inspection station 24, a pre-coat inspection station 26, a coating station 28, a post-coat inspection station 30, a transmission station of optical source 32 to determine coating thickness, an optical source transmitting station 34 for examining the coating for defects and an exit station 36.
I. The system 20 may include a transfer mechanism 72 for moving containers from the injection molding machine 22 to a container holder 38. The transfer mechanism 72 may be configured, for example, as a robotic arm that positions, moves , holds, transfers, orients, seats, and releases the containers 80 for removal from the container forming machine 22 and installing them on the container supports such as 38.
I. System 20 may also include a transfer mechanism in processing station 74 to
132 remove the container from one or more supports such as 66, with
INSTITUTO MEXICANO DE LA MtOMSDAD ..... JNOUSTXIAl.
further processing ae
<img file="MX345403B_D0093.tif" />
inside surface of the seated container such as 80 (FIG.
1) . The containers 80 can therefore be moved from the container support 66 to the packaging, storage, or other suitable zone or process stage, generally indicated 36. The transfer mechanism 74 can be configured, for example, as a robotic arm that positions, moves, holds, transfers, orients, seats, and releases containers 80 for removal from container holders such as 38 and onto other equipment at station 36.
I. Processing stations or devices 32, 34, and 36 shown in FIG. 1 optionally perform one or more suitable steps after coating and inspection system 20, after removing individual containers 80 from container holders such as 64. Some non-limiting examples of the functions of these stations or devices 32, 34 and 36 include:
placing the treated and inspected containers 80 on a conveyor to further processing apparatus;
add chemical agents to containers;
133 cover the containers;
place containers in racks
<img file="MX345403B_D0094.tif" />
adequate processing;
pack the containers; and sterilizing the packaged containers.
I. The container processing system 20 illustrated in FIG. It may also include a multiplicity of container holders (or pucks, as in some embodiments they resemble a hockey puck) respectively 38 to 68, and a conveyor generally indicated as an endless belt 70 to transport one or more of the holders of containers 38-68 and, consequently, containers such as 80, from or to the processing stations 22, 24, 26, 28, 30, 32, 34 and 36.
I. Processing station or device 22 may be a container forming device 80. A contemplated device 22 may be an injection molding machine. Another contemplated device 22 may be a blow molding machine. Also contemplated are vacuum molding machines, stretch molding machines, cutting or grinding machines, glass drawing machines for glass or other materials that can be drawn by stretch or other types of container forming machines. Optionally, the
134 iMP! » Containers 22 can be omitted, since the re
INDUSTRIAL be obtained already trained. '
--------------- t ~ ti - i tr ib un. · »
II. CONTAINER SUPPORTS
II. A. Portable container holders 38-68 are provided to support and transport a container having an opening while the container is being processed. The container holder includes a container port, a second port, a conduit, and a transportable housing.
II.A. The container port is configured to seat an opening of the container in a mutually communicating relationship. The second port is configured to receive a gas supply or external vent. The conduit is configured for the passage of one or more gases between a container opening seated in the container port and the second port. The container port, the second port, and the conduit are attached in a substantially rigid relationship to the transportable housing. Optionally, the portable container holder weighs less than five pounds. An advantage of a lightweight container holder is that it can be more easily transported from one processing station to another.
II. A. In certain embodiments of the vessel holder, the conduit is more specifically a vacuum conduit and the second port is more specifically a port.
135 of emptiness.
The vacuum line is configured ^
INDUmtAL a gas through the vessel port of 'a vessel seated in the vessel port. The vacuum port is configured to communicate the vacuum conduit and an external vacuum source. The container port, the vacuum conduit and the vacuum port may be attached in a substantially rigid relationship to the transportable housing.
II.A. The container supports of Embodiments II.A and II.A. 1 are shown, for example, in FIG. 2. The container holder 50 has a container port 82 configured to receive and seat the opening of a container 80. The interior surface of the seated container 80 can be processed through the container port 82. Container support 50 may include a conduit, eg, vacuum conduit 94, for drawing a gas from container seated 8 or in container port 92. Container support may include a second port, eg, port. 96 connecting the vacuum conduit 94 and an external vacuum source, such as the vacuum pump 98. Vessel port 92 and vacuum port 96 may have sealing elements, for example, O-ring type butt seals, respectively 100 and 102, or side seals between a
136 inner or outer cylindrical wall of the port? NsgfijbTdK ^ i & ^
0t THE industrial FKOPIITY and an internal or external cylindrical wall of the container 80 to receive and form a seal with the container 80 or the external vacuum source 98 while facilitating communication through the port. Gaskets and other sealing mechanisms can also be used.
II. A. The container holder, such as 50, may be made of any material, eg, thermoplastic material and / or non-electroconductive material. Or the vessel holder, such as 50, may be made partially or even primarily of electroconductive material and lined with non-electroconductive material, particularly in the channels defined by vessel port 92, vacuum conduit 94 and vacuum port 96 . Examples of suitable materials for the container support 50 are: a polyacetal, for example, Delrin® acetal material available from EI du Pont De Nemours and Company, Wilmington Delaware; polytetrafluoroethylene (PTFE), e.g. PTFE Teflon® available from EI du Pont De Nemours and Company, Wilmington Delaware; ultra high molecular weight polyethylene (UHMWPE); high-density polyethylene (HDPE); or other materials known in the art or recently discovered.
II. A. FIG. 2 also illustrates that the container holder, for example,<sup>137</sup> IMPI
MUICANO INSTITUTE
50, may have a
<img file="MX345403B_D0095.tif" />
Center Vessel 80 when approaching Ji. seated in port 92.
Arrangement of container supports
II. A. Another way to treat, inspect and / or move parts through a production system can be to use a container rack arrangement. The array can comprise individual disks, or it can be a solid array in which devices are placed. An arrangement may allow more than one device, optionally many devices, to be tested, transported or treated / coated simultaneously. The arrangement can be one-dimensional, for example, grouped together to form a linear or two-dimensional rack, similar to a bucket or tray.
II. A. FIGS. 4, 5 and 58 show three types of arrangement. FIG. 4 shows a solid array 120 in which (or on top of) the devices or containers 80 are placed. In this case, the devices or containers 80 can be moved through the production process as a solid array, although they can be removed during the process. production process and transferred to individual container holders. A simple container holder 120 has multiple container ports, such as 122, for carrying an array of seated containers, such as 80,
- · Ν that move as a unit. In this reál ^^^^ jg
INDUSTRIAL can provide multiple individual vacuum ports, such as 96, to receive an array of 98 vacuum sources. Or a single vacuum port connected to all vessel ports such as 96 can be provided. Multiple probe probes can also be provided. gas inlet 108 in one arrangement. The gas inlet probe arrays or vacuum sources can be mounted to move as a unit to process many vessels, such as 80, simultaneously. Or the multiple container ports, such as 122, can be treated in one or more rows at a time or individually at a processing station. The number of devices in the array can be related to the number of devices that are molded in a single stage or to other tests or stages that can improve efficiency during operation. In the case where an array is involved, the electrodes can be coupled together (to form a large electrode) or they can be individual electrodes each with its own power supply. All of the above methods can be applied (from the point of view of electrode geometry, frequency, etc.).
II. A. In FIG. 5, individual container discs or supports are grouped (as noted above) in an arrangement, as if surrounding them
139 with a frame ι
<img file="MX345403B_D0096.tif" />
Installation provides the advantages of Ja solid arrangement.
FIG. 4, when this is desired, and also allows the array to be disassembled for other processing steps in which the containers 80 are treated in different arrangements or individually.
II.A. FIG. 58 shows a linear rack, otherwise similar to FIG. 4. If using a linear rack, another option, in addition to those explained above, is to transport the rack in rows through the processing station, processing the vessels in series.
II.B. Container holder including a set of O-rings
II. B. FIGS. 42 and 43 are a fragmentary detailed longitudinal cross-sectional view and a detailed view, respectively, of a container support 450 provided with an alternative sealing arrangement, usable, for example, with the container support embodiments of FIGS. 2, 3, 6, 7, 19, 12, 13, 16, 18, 19, 30 and 4 3 to seat a container in a container holder. Referring to FIG. 42, the container, eg, the barrel of a syringe 438, seated in the container holder 450 has a rear opening 442 defined by a generally annular edge 452
IMPI tNJTiTUTO MtXICANO (and usually beveled or rounded), as well as a generally cylindrical side wall 454. A medical fluid collection tube usually has the same type of rim 452 but without the clamp 440 and therefore can be instead seat in the container support 450.
II.B. Container support 450 in the illustrated embodiment includes a generally cylindrical inner surface 456 which in the illustrated embodiment serves as a guide surface for receiving generally cylindrical side wall 454 of syringe barrel 438. The well is further defined by a generally annular stop 458 against which annular edge 452 bears when syringe barrel 438 is seated in container holder 450. A generally annular recess or groove 460 formed in internal surface 456 is provided to retain the sealing element, for example, an O-ring 462. The radial depth of the recess 460 is less than the radial cross section of the sealing element, for example. For example, an O-ring 462 (as illustrated in FIG. 42), and the inner diameter of the O-ring 462 is preferably slightly less than the outer diameter of the annular edge 452.
II.B. These relative dimensions cause the radial cross section of the O-ring 462 to compress horizontally between at least the outer wall 464 of the
<img file="MX345403B_D0097.tif" />
141 hollow 460 and the generally cylindrical syringe barrel side wall 438, as shown in FIG. 42, when a container, such as 438, is seated as shown in FIG. 42. This compression flattens the bearing surfaces of the O-ring 462 forming a seal between at least the outer wall 464 of the bore 460 and the generally cylindrical side wall 454 of the syringe barrel.
438 .
II.B. The gap 460 can optionally be constructed, relative to the dimensions of the O-ring 462, to form two more seals between the lower and upper wall 466 and 468, and the side wall 454, spacing the upper and lower wall 468 and 466 approximately. the same distance as the corresponding radial transverse diameter of the O-ring 462. When the O-ring 462 is compressed between the outer wall 464 and the generally cylindrical side wall 454 of the gap 460, its resilience will cause it to expand up and down as shown in FIG. 43, this causes it to also face the upper and lower wall 466 and 464 and flatten against them. Therefore, the O-ring 462 will optionally deform both vertically and horizontally, tending to square its normally round cross-section. Additionally, annular edge 452 seated on stopper 458 will limit the flow of reagents from
IMPI process of PECVD and other gases and materials intíSSSaanSMBAo to ^ CTSu ^ through or adjacent to posterior opening 442.
II. B. As a result of this optional construction, only the space in the lower right corner of the O-ring 462, as shown in FIG. 43, is on the outside of the O-rings and is therefore exposed to process gases, plasma, etc. introduced into or into the generated container 438. This construction protects O-ring 462 and adjacent surfaces (such as the outer surface of side wall 438) against the unwanted build-up of PECVD deposits and attack by activated chemical species in the plasma. Additionally, the container 438 is more positively located by the hard surface of the stop 458, as opposed to the resilient surface which would butt seal the annular edge 452 directly against the O- ring, as illustrated in some of the other Figures. . Additionally, the forces on the respective portions around the main circumference of the O-ring 462 are more evenly distributed, as the container is constrained 438 against any substantial rocking.
II.B. Or the gap 460 may be formed with its bottom wall 466 above the stop 458 shown in FIG. 43. In another embodiment, more than
143 an axially spaced gap 460 to provide
<img file="MX345403B_D0098.tif" />
higher or double level to further restrict container 438 against rocking when seated against stop 458.
II.B. FIG. 45 is an alternative construction of a container holder 482 than the embodiments of FIGS. 21, 22, 26, 28, 33-35 and 37-44.
can be used, for example, with
1, 2, 3, 6-10, 12-16, 18, 19,
The container support 482 comprises an upper portion 4 84 and a base 486 joined in the gasket 488. A sealing element, for example, an O-ring 490 (its right side is sectioned to describe the hollow that retains it) is captured between the upper portion
484 and base 486 in gasket 488. In the illustrated embodiment, O-ring 490 is received in an annular gap
492 to locate the O-ring when the upper portion
484 joins base 486.
II.B. In this embodiment, the O-ring 490 is captured and supported against a radially extending abutment surface 494 and the radially extending wall 496 that partially defines the gap 492 when the top portion 484 and the base 486 are joined, at this case by screws 498 and 500. O-ring 490 therefore sits between upper portion 484 and base 486. O-ring 490 captured between upper portion
144
<img file="MX345403B_D0099.tif" />
<img file="MX345403B_D0100.tif" />
484 and the base included in this features)
86 also receives the recipi ^ INSTITUTO MEXICANO DE LA MOMDAD industrial figure to more clearly illustrate others and forms a first container port O-ring seal 502 around container opening 80, analogous to the installation of O-ring seal around the rear opening of the container 442 in FIG: 42.
II.B. In this embodiment, although not a requirement, the vessel port 502 has both a first O-ring seal 490 and a second axially spaced O-ring seal 504, each having an inside diameter, such as 506, of the appropriate size. to receive the outer diameter (analogous to side wall 454 in FIG. 43) of a container such as 80 to seal the container port 502 and a container such as 80. The space between the O-rings 490 and 504 provides support for a container, such as 80, at two axially spaced points, which prevents the container such as 80 from tilting relative to the O-rings 490 and 504 or the container port 502 In this embodiment, although not a requirement, the radially extending abutment surface 494 is located near the O-ring seals 490 and 506 and surrounds the vacuum conduit 508.
145
III. METHODS TO TRANSPORT
Processing of vessels seated vessels
IMPI
RECIPT ^^^^ cano
INDUSTRIAL
<img file="MX345403B_D0101.tif" />
in supports of
III.A. Transport of container supports to processing stations
III.A. FIGS. 1, 2 and 10 show a method for processing a container 80. The method can be carried out as follows.
III.A. A container 80 may be provided with an opening 82 and a wall 86 defining an interior surface 88. As one embodiment, the container 80 may be formed in a mold, such as 22, and then removed from it. Optionally, 60 seconds, or 30 seconds, or 25 seconds, or 20 seconds, or 15 seconds, or 10 seconds, or 5 seconds, or 3 seconds or 1 second after removing the container from the mold, or as soon as the container 80 can be moved without disturbing it during processing (assuming it is manufactured at an elevated temperature, from which it cools progressively), the container opening 82 can be seated in the container port 92. Moving container 80 rapidly from mold 22 to container port 92 reduces dust or other impurities that may reach surface 88 and occlude or impede adhesion of barrier or other coating 90. In addition, how much
146
I — I · H the faster the vacuum is created in the container KTrgrg ^ ¡ggo
INDUSTRIAL manufactured, the less chance any particulate impurities will have to adhere to the interior surface 88.
III.A. A container holder, such as 50, may be provided comprising a container port 92. The opening 82 of the container 80 can be seated in the container port 92. Previously, during or after seating the opening 82 of the container 80 in container port 92, container holder, such as 40, (eg, in FIG. 6) may be transported coupled to one or more of the bearing surfaces 220-240 to position the container holder 40 relative to the device or processing station such as 24.
III.A. One or more than one or all of the processing stations, such as 24-34, as illustrated by station 24 in FIG. 6, may include a bearing surface, such as one or more of bearing surfaces 220, 222, 224, 226, 228, 230, 232, 234, 236, 238 or 240, to hold one or more container supports, such as 40, in a predetermined position while the inner surface 88 of the seated container 80 is processed in the station or the processing device such as 24. These support surfaces can form part of a stationary or mobile structure, for example, tracks or rails that guide and position the container support, such as 40, while the container !.
indicted. For example, the downward facing bearing surfaces 222 and 224 secure the vessel holder 40 and act as a reaction surface to prevent the vessel holder 40 from moving upward when the probe 108 is inserted into the vessel holder. 40. Reaction surface 236 secures vessel holder and prevents vessel holder 40 from moving to the left while seating a vacuum source 98 (as in FIG. 2) at vacuum port 96. Bearing surfaces 220, 226, 228, 232, 238, and 240 similarly secure container support 40 and prevent it from moving horizontally during processing. Bearing surfaces 230 and 234 similarly secure the container support, such as 40, and prevent it from moving vertically out of position. Accordingly, a first bearing surface, a second bearing surface, a third bearing surface or more may be provided at each of the processing stations such as 24-34.
III.A. The inner surface 88 of the seated container 80 may be further processed through the container port 92 in the first processing station, which may be, for example, the application of a barrier or it may be another type of station. . <· RLM-rn —-— - »* · *
148 _ _ - τΓ I MP I of cladding 28 shown in FIG. 2. <3ΰΒ ^^ ί * Μ industrial containers 50 and the settled container 80 are transported from the first processing station 28 to the second processing station, for example, the processing station 32. The inner surface 88 of the settled container 80 may be processed through the container port 92 at the second processing station such as 32.
III.A. Any of the above methods may include the additional step of removing the container 80 from the container holder, such as 66, by subsequently processing the inner surface 88 of the seated container 80 at the second processing station or device.
III.A. Any of the above methods may include, after the removal step, the additional step of providing a second container 80 with an opening 82 and a wall 86 defining an interior surface 88. The opening 82 of the second container, such as 80, It may be seated in the container port 92 of another container holder such as 38. The inner surface of the second seated container 80 may be processed through the container port 92 at the first processing station or device such as 24. The container support, such as
149 as 38, and transporting the second seated container from the first station or
<img file="MX345403B_D0102.tif" />
processing device 24 to the second station or processing device such as 26. The second seated container 80 may be processed through the container port 92 at the second processing station such as 26.
III.B. Transport of processing devices to container supports or vice versa.
III.B. 0 processing stations can be more widely processing devices and media supports
<td>containers</td><td>can be transported</td><td>with</td><td>about</td><td>the</td>
<td>devices</td><td>processing or</td><td>the</td><td>devices</td><td>from</td>
<td>prosecution</td><td>can be transported</td><td>with</td><td>about</td><td>the</td>
<td>supports of</td><td>containers or part of</td><td>each</td><td colspan="2">installation can</td>
be provided in a given system. In another installation, the container holders can be transported to one or more stations and more than one processing device can be installed at or near at least one of the stations. Therefore, there is not necessarily a correspondence
0 one by one between the processing devices and the processing stations.
III.B. A multi-part method of processing a container is contemplated. A first processing device is provided, such as probe 108 (FIG. 2),
150 Mexican iNSTn-ura Dt THE INOUSTTIAL FKOriiDAD and a second processing device, light source 170 (FIG. 10), for processing containers such as 80. A container 80 is provided with an opening 82 and a wall 86 defining an interior surface 88. A container holder 50 is provided comprising a container port 92. The opening 82 of the container 80 is seated in the container port 92.
III.B. The first processing device, such as probe 108, moves functionally coupled to container holder 50 or vice versa. The interior surface 88 of the seated container 80 is processed through the container port 92 using the first processing device or probe 108.
III.B. The second processing device, such as 170 (FIG. 10), then moves functionally coupled to the container holder 50 or vice versa. The interior surface 88 of the seated container 80 is processed through the container port 92 using the second processing device such as the light source 170.
III.B. Optionally, any number of additional processing steps can be provided. For example, a third processing device 34 may be provided to process containers 80. The third processing device 34 may be moved to create a
151 coupling vice versa.
operational with the support of
<img file="MX345403B_D0103.tif" />
The interior surface of the seated container 80 can be processed through the container port 92 using the third processing device 34.
III.B. In another method of processing a container, a container 80 may be provided with an opening 82 and a wall 86 defining an interior surface 88. A container holder, such as 50, may be provided comprising a container port 92. The Opening 82 of container 80 can be seated in container port 92. The inner surface 88 of the seated container 80 can be processed through the container port 92 in the first processing device, which can be, for example, the barrier or other type of coating device 28 shown in FIG. 2. Container support 50 and seated container 80 are transported from first processing device 28 to second processing device, eg, processing device 34 shown in FIGS. one and 10. The inner surface 88 of the seated container 80 may be further processed through the container port 92 in the second processing device such as 34.
III. C. Using a clamping tool to transport pipe to and from a coating station
152
<img file="MX345403B_D0104.tif" />
III.C. Yet another embodiment is a method<sup>1</sup> by PECVD a first container including several stages. A first container is provided having an open end, a closed end, and an inner surface. At least one first holding tool is configured to selectively hold and release the closed end of the first container. The closed end of the first container is clamped with the first clamping tool and, using the first clamping tool, is transported close to the container holder configured to seat the open end of the first container. The first clamping tool is then used to axially advance the first container and seat its open end in the container holder, thereby establishing a sealed communication between the container holder and the interior of the first container.
III.C. At least one gaseous reagent is introduced into the first container through the container holder. Plasma is formed within the first container under conditions effective to form a reaction product of the reagent on the interior surface of the first container.
III.C. The first container is then removed from the container holder and, using the first holding tool or other holding tool, the
<img file="MX345403B_D0105.tif" />
153 first container axially away from the container. Subsequently, the first container is released from the clamping tool used to transport it axially away from the container holder.
III.C. Referring again to FIGS. 16 and 49, a serial conveyor 538 may be used to hold and transport multiple clamping tools, such as 204, through the apparatus and process as described herein. The clamping tools 204 are functionally connected to the serial conveyor 538 and are configured to successively transport a series of at least two containers 80 to near the container holder 48 and carry out the other steps of the cleaning method as described in the present.
IV. PECVD APPARATUS TO MAKE CONTAINERS
IV. A. PECVD apparatus including a vessel holder, an internal electrode, and a vessel as a reaction chamber
IV. A. Another embodiment is a PECVD apparatus that includes a container holder, an inner electrode, an outer electrode, and a power supply. A vessel seated in a vessel holder defines a plasma reaction chamber which can optionally be a vacuum chamber. Optionally, a power supply can be supplied
154
<img file="MX345403B_D0106.tif" />
a combination of two or more of these. Optionally, a gas drain, which does not necessarily include a vacuum source, is provided to transfer gas from or into a container seated in the port to define a closed chamber.
IV.A. The PECVD apparatus can be used for PECVD at atmospheric pressure, in which case it is not necessary for the plasma reaction chamber to function as a vacuum chamber.
IV. A. In the embodiment illustrated in FIG. 2, the container holder 50 comprises a gas inlet port 104 for conveying a gas to the container seated in the container port. Gas inlet port 104 has a sliding seal provided by at least one O-ring 106, or two O-rings in series, or three O-rings in series, which can seat against a cylindrical probe 108 when probe 108 is inserted through through gas inlet port 104. Probe 108 may be a gas inlet conduit that extends to a gas supply port at its distal end 110. The distal end 110 of the illustrated embodiment may be inserted deep into container 80 to provide one or more reagents for PECVD and other process gases.
<sup>155</sup> WICKED
INSTnUTOMJXlCANC '
IV.A. Optionally, in the illustrated realization £ ^ rtj | ^ 5§ | ^
FIG. 2 or more generally in any described implementation, such as in the embodiments of FIGS. 1-5, 8, 9, 12-16, 18, 19, 21, 22, 26-28, 33-35, 37-49 or 52-55, and that specifically described in FIG. 55, a plasma screen 610 may be provided to confine the plasma formed in the container 80 generally to the volume greater than the plasma screen 610. The 610 plasma display is a porous, conductive material, several examples of which are steel wool, porous sintered metal, or ceramic material coated with conductive material, or a foraminous plate or disc of metal (eg, brass) or other conductive material. . An example is a pair of metal discs that have center holes set to pass the gas inlet 108 and that have holes 0.02 inches (0.5 mm) in diameter separated by 0.04 inches (1 mm), center to center, providing the holes 22% open area as a proportion of the surface area of the disc.
IV.A. Plasma screen 610, particularly for embodiments where probe 108 also functions as a counter electrode, can make intimate electrical contact with gas inlet 108 near or at opening 82 of the tube, syringe barrel, or other container 80 that is is processing. Alternatively, the 610 plasma display
156 can be grounded,
IMPI
<img file="MX345403B_D0107.tif" />
INDUSTRIAL
<img file="MX345403B_D0108.tif" />
potential common with gas inlet 108. Plasma screen 610 reduces or eliminates plasma in vessel holder 50 and its internal passageways and connections, eg, vacuum conduit 94, gas inlet port 104, surrounding O-ring 106, vacuum port 96, O-ring 102, and other apparatus adjacent to gas inlet 108. At the same time, the porosity of the plasma screen allows process gases, air and the like to escape from the container 80 to the vacuum port 96 and the subsequent apparatus.
IV.A. At coating station 28 illustrated in FIG. 3, the container holder 112 comprises a gas inlet port and a composite vacuum port 96 in communication with the container port 92, respectively for conveying a gas to a container 80 seated in the container port 92 (via probe 108) and withdrawing a gas from a container seated in container port 92 (via vacuum source 98). In this embodiment, the gas inlet probe 108 and the vacuum source 98 can be provided as a composite probe. The two probes can advance as a unit or separately, as desired. This installation eliminates the need for a third seal 106 and allows the use of butt seals throughout. A butt seal allows the application of an axial force,
15, IMPI®
INSTITUTO MEXICANO DE LA NOFTEDAD V · ». ,. INDUSTRIAL for example, by emptying the container 80, to positively seat the container 80 and the vacuum source 98 by deforming the O-rings, tending to close any gaps caused by irregularities in the sealing surface on either side of the O-ring. In the embodiment of FIG. 3, the axial forces applied by container 80 and vacuum source 98 on container holder 112 are opposite, tending to hold container 80 and container holder 112 together and the respective butt seals. ·
IV.A. FIG. 13 is a view similar to FIG. 2 of a container holder 48 at a coating station according to yet another embodiment of the disclosure, where the container 80 can be seated on the container holder 48 at the processing station. This can be used to process a container 80 that does not move with a container support, such as 48, or it can be used in a barrier or other type of coating station 28 that first seats container 8 or in a container support, such as at 48, before the seated container 80 is transported to another apparatus by system 20.
IV.A. FIG. 13 shows a cylindrical electrode 16 0 suitable for frequencies from 50 Hz to 1 GHz, as an alternative to the U-shaped electrode of FIGS. 2 and 9.
158
The vessel holder (or the electrode) can be <®Dao®ai ^ ef ^^ <J * Í®SS position before activation by moving the.-Elecrr®d ^<sup>K</sup>The movement of the container support and the electrode in the vertical plane can be avoided by creating an electrode 160 constructed as a shell (two halves of cylinders that are joined from opposite sides when the container support is in position and ready for treatment / coating). IV.A. Optionally, at coating station 28 the vacuum source 98 creates a seal with the disk or container holder 50 that can be retained during the movement of the container holder, if the process is a continuous process in which the tube moves throughout the coating station, such as 28, while creating a vacuum and introducing gas through probe 108. Or a stationary process can be employed in which the disk or container holder 50 is placed in a stationary position, at which point the probe 108 is pushed up into the device and subsequently the pump or vacuum source 98 is attaches to vacuum port 96 and is activated to create a vacuum. Once the probe 108 is in position and a vacuum is created, the plasma can be established within the tube or container 80 with an external fixed electrode 160 that is independent of the disk or container holder.
159
IMPI ^ _ „π. . . . . _ _ INSTITUTO MEXICANO and the tube or other container 80. delamomíoad, INDUSTRIAL ™
IV.A. FIG. 53 shows additional optional details about coating station 28 that can be used, for example, in the embodiments of FIGS. 1, 2, 3, 6-10, 12-16, 18, 19, 21, 22, 26-28, 30, 33-35, 37-44 and 52. Coating station 28 may also have a vacuum valve main 574 in its vacuum line 576 leading to pressure sensor 152. A manual bypass valve 578 is provided in bypass line 580. A vent valve 582 controls flow in vent 404.
IV.A. The outflow from the PECVD gas source 144 is controlled by a main reagent gas valve 584 that regulates flow through the main reagent feed line 586. One component of the gas source 144 is the gas reservoir. organosilicon liquid 588. The contents of reservoir 588 are drawn through organosilicon capillary line 590, which is provided to a suitable length to obtain the desired flow rate. Organosilicon vapor flow is controlled by the organosilicon shutoff valve 592. Pressure is applied to the free space 614 of the liquid reservoir 588, for example, a pressure in the range of 0-15 psi (0 to 78 cm.Hg) , from a pressure source 616, such as pressurized air
160
IMPI ^ connected to free space 614 by a line ^ M ^ ro® »» ®! ® * 618, to establish a supply of liquid ^ organ ^<sup>0</sup>·· <sup>1</sup> repeatable that does not depend on atmospheric pressure (and fluctuations in it). Reservoir 588 is sealed and capillary connection 620 is at the bottom of reservoir 588 to ensure that only clean organosilicon liquid (not pressurized gas from headspace 614) flows through capillary tube 590. The organosilicon liquid can optionally be heated to a temperature above room temperature, if necessary or desirable, to cause the organosilicon liquid to evaporate and form an organosilicon vapor. Oxygen is provided from an oxygen tank 594 through an oxygen feed line 596 controlled by a mass flow controller 598 and fitted with an oxygen shutoff valve 600.
IV.A. In the embodiment of FIG. 7, station or device 26 may include a vacuum source 98 adapted to seat in vacuum port 96, a side channel 134 connected to probe 108, or both (as illustrated). In the illustrated embodiment, side channel 134 includes a shutoff valve 136 that regulates flow between a probe port 138 and a vacuum port 140. In the illustrated embodiment, the selector valve 136 has at least two states: an evacuation state in which ports 138 and
161
140 are connected, thus providing two more toxic inputs for the gas flow (which increases the rate <y¿r> uK £ ftSbL ^ * decreases the pumping effort) and a disconnection state .____ in which the ports 138 and 140 are isolated.
Optionally, selector valve 136 may have a third port, such as a PECVD gas inlet port 142, to introduce PECVD process and reactive gases from a gas source 144. This facility allows the same supply of The vacuum and probe 10 8 can be used both for leak detection or permeation tests and to apply the barrier or other type of coating.
IV. A. In illustrated embodiments, the vacuum line, such as 146, to the vacuum source 98 may also include a shutoff valve 14 8. Shut-off valves 136 and 14 8 can be closed when probe 108 and vacuum source 98 are not connected to a vessel holder, such as 44, so side channel 134 and vacuum line 14 do not need to be emptied 6 on the side of valves 13 6 and 14 8 away from container 8 0 as they move from one container support 44 to another. To facilitate removal of the probe 108 axially from the gas inlet port 104, a flexible line 150 may be provided to allow axial movement of the probe.
<img file="MX345403B_D0109.tif" />
<img file="MX345403B_D0110.tif" />
108 independent of line position
INDUSTRIAL regarding port 96.
IV.A. FIG. 7 also shows another optional feature that can be used in any embodiment - a vent 404 to ambient air controlled by a valve 406. The valve 406 can be opened to break the vacuum quickly after processing the container 80, either to release the container 80 from container holder 44, to release container holder 44 at vacuum port 96 from vacuum source 98 or optionally both.
IV.A. In the illustrated embodiment (still referring to FIG. 7), probe 108 can also be connected to a pressure valve 152 and can communicate with the interior 154 of container 80, allowing pressure within container 80 to be measured.
IV. A. In the apparatus of FIG. 1, the vessel coating station 28 may be, for example, a PECVD apparatus such as that described in detail below, which operates under conditions suitable to deposit a SiOx barrier or other type of coating 90 on the inner surface 88 from a container 80, as shown in FIG. 2.
IV.A. Referring especially to FIGS. 1 and 2, processing station 28 may include an electrode
160 powered by a radio frequency source 162 to provide an electric field that generates a plasma within container 80 during processing. In this embodiment, probe 108 is also electrically conductive and grounded, thereby providing a counter electrode within container 80. Alternatively, in either embodiment, external electrode 160 may be grounded and probe 108 is directly connected. to power supply 162.
IV. A. In the embodiment of FIG. 2, the outer electrode 160 may be generally cylindrical as illustrated in FIGS. 2 and 8 or as a generally elongated U-shaped channel as illustrated in FIGS. 2 and 9 (FIGS. 8 and 9 being alternative embodiments of the section taken along section line A-A of FIG. 2). Each illustrated embodiment has one or more side walls, such as 164 and 166, and optionally a top end 168, all of which are arranged closely around container 80.
IV.A., IV.B. FIGS. 12-19 show other variants of the container coating station or device 28 as previously described. One or more of these variants may be substituted for a vessel coating station or device 28 shown
<img file="MX345403B_D0111.tif" />
164 f Ό1
L J'Ví λ in FIG. 1-5. Institute
IV.A. FIG. 12 shows an electrode system
<img file="MX345403B_D0112.tif" />
alternative that can be used (in the same way as discussed above using the same canister holder and gas inlet) at frequencies above 1 GHz. At these frequencies, electrical energy from the power supply can be transferred into the tube through one or more waveguides that are connected to a cavity that absorbs energy or resonates energy. Resonating the energy allows it to couple to the gas. Different cavities can be provided for use with different frequencies and vessels, such as 80, as vessel 80 will interact with the cavity altering its resonance point, creating plasma for coating and / or for treatment.
IV.A. FIG. 12 shows that coating station 28 may include a microwave power source 190 that directs microwaves through a waveguide 192 to a microwave cavity 194 that at least partially surrounds container 80 within which plasma can be generated. Microwave cavity 194 can be adjusted with respect to microwave frequency and partial pressures and gas selection, to absorb microwaves and couple to plasma generating gas. In FIG.
<img file="MX345403B_D0113.tif" />
13, as well as in
<img file="MX345403B_D0114.tif" />
165
Φί illustrated, there may be a small gap .19 & MJ &
container 80 and cavity 194 (or the electrJSU, ti detootjaÍ ... or other surrounding structure) to avoid scraping or other damage to the container 80. Furthermore, in FIG. 13, microwave cavity 194 has a flat rear wall 198, such that space 196 does not have a uniform width, particularly opposite the circular edge of rear wall 198. Optionally, end 198 can be curved to provide substantially uniform 196. IV.A. FIG. 44 is a view similar to FIG. 2 of an alternative gas / electr supply tube: internals 470 that may be used, for example, in the embodiments of FIGS. 1, 2, 3, 8, 9, 12-16, 18-19, 2122, 33, 37-43, 46-49 and 52-54. As shown in FIG. 44, the distal portion 472 of the inner electrode 470 comprises an elongated porous side wall 474 that contains at least one inner passage 476 within the inner electrode. Inner passage 476 is connected to gas supply 144 through proximal portion 478 of inner electrode 470 extending outward of container 80. Distal end 480 of inner electrode 470 may also optionally be porous. The porosity of the porous side wall 474 and, if present, the porous distal end 480
166
<img file="MX345403B_D0115.tif" />
allows at least a portion of the food »OF the <sub>hpUSTMA</sub>i reagent from the W feed. 144 laterally escapes from passage 476 to supply reactive gas to the adjacent portion of inner surface 88 of container 80. In this embodiment, the porous portion of porous side wall 474 extends the full length of inner electrode 470 within container 80, although the porous portion may be less extensive, extending only a portion of the length of the inner electrode 470. As indicated elsewhere in this description, the inner electrode 470 may also be longer or shorter, relative to the length of the container 80, than is shown in FIG. 44, and the porous portion can be continuous or discontinuous.
IV. A. The outer diameter of the inner electrode 470 may be at least 50% or at least 60% or at least one
70% or at least 80% or at least 90% or at least 95% of the laterally adjacent internal diameter of the container. The use of a larger diameter inner electrode 470, relative to the inner diameter of container 80, particularly if electrode 470 is concentric with container 80, reduces the distance between the outside of inner electrode 470 and the adjacent inner surface 88 of the container 80 isolating the plasma in a region more<sup>167</sup> I Thousand $ small within which can be more uniform than a larger diameter inner electrode 470 as well, provides a more uniform distribution of reactive gas and / or carrier gas along inner surface 80, as gases are introduced new to the plasma at closely spaced points along the inner surface 88, very close to the site of the initial reaction, as opposed to flowing from a single point relative to the inner surface 88 to be formed.
IV.A. In one contemplated installation, shown in solid lines, power supply 162 has a power connection to electrode 200, which can be anywhere along electrode 200 and probe 108 can be grounded. In this configuration, a capacitive charge can be used to generate the plasma in the container 80. In another contemplated installation, shown in virtual lines (and eliminating the connections shown in solid lines), the respective power outlets of power supply 162 are connected to the respective ends of coil 200, which for convenience may again referred to as an electrode in this description. In this configuration, an inductive load can be used to generate the plasma in container 80. Inductive and capacitive loads can also be used in
168 an alternative embodiment.
IV.A. FIGS. 46-48 show an arrangement of two or more gas supply tubes, such as 108 (also shown in FIG. 2), 510 and 512, which are also internal electrodes. The arrangement can be linear or carousel. A carousel arrangement allows the electrodes to be reused periodically.
IV.A. FIGS. 46-48 also show an internal electrode extender and retractor 514 for inserting and removing internal electrode / gas supply tubes 108, 510, and 512 from and to one or more container holders such as 50 or 48. These features are resources. optional to use gas supply tubes.
IV.A. In an illustrated embodiment, referring to FIGS. 46-48, as well as 53, internal electrodes 108, 510, and 512 are respectively connected by flexible hoses 516, 518, and 520 to a common gas supply 144 via shut-off valves 522, 524, and 526 (hoses hoses are shortened in FIGS. 46-48 by omitting the clearance portions). Briefly referring to FIG. 56, flexible hoses 516, 518, and 520 may alternatively be connected to separate gas sources 144. A mechanism 514 is provided to extend or retract an internal electrode such as 108. The
169
IMPI
INSTITUTO MEXICANO DE LA MONEDAD internal electrode extender and retractor are confi ^ ffi ^ Bos to move an internal electrode between Uñá ' <sup>1</sup> 'βδδΙ'δΓδϊΓ fully advanced, an intermediate position and a retracted position relative to the container support.
IV.A. In FIGS. 46 and 56, the inner electrode 108 extends to its functional position within the container holder 50 and container 80, and its shutoff valve 522 is opened. Also in FIG. 46, the inactive inner electrodes 510 and 512 retract and their shutoff valves 524 and 526 close. In the illustrated embodiment, one or more of the inactive internal electrodes 510 and 512 are disposed in an electrode cleaning device or station 528. One or more electrodes can be cleaned and others can be replaced at station 528, optionally. As non-exhaustive examples, cleaning operations may involve chemical reaction or solvent treatment to remove deposits, grinding to physically remove deposits, or plasma treatment to burn accumulated deposits.
IV.A. In FIG. 47, internal inactive electrodes 510 and 512 are the same as above, while internal working electrode 108 has retracted into container 80, its distal end remaining within container holder 50, and its valve 522 has been closed.
170
<img file="MX345403B_D0116.tif" />
<sub>π</sub> , · · - -1 · · -1 MEXICAN INSTITUTE
In this condition, the container 8 0 can be removed and a new container can be seated on the container support.
without there being any risk of touching the electrode 108 with the containers 80 which are removed and replaced. After replacing the container 80, the inner electrode 108 can advance to the position of FIGS. 46 and 56 and the shutoff valve 522 can be reopened to begin coating the new container 80 using the same internal electrode 108 that was used previously. Accordingly, in an installation where a series of containers 80 are seated and removed from the container holder 50, the inner electrode 108 may partially extend and retract numerous times as the container 80 is installed or removed from the container holder. containers 50 at the station where the inner electrode 108 is in use.
IV.A. In FIG. 48, the container support 50 and its container 80 have been replaced with a new container support 48 and another container 80. Referring to FIG. 1, in this type of embodiment each container 80 remains in its container holder, such as 50 or 48, and an internal electrode, such as 108, is inserted into each container when its container holder reaches the coating station.
IV.A. Additionally in FIG. 48, the inner electrodes 108, 510 and 512<sup>171</sup> IMPI are completely rerf ^^> sb
<img file="MX345403B_D0117.tif" />
internal electrode arrangement 108,
<img file="MX345403B_D0118.tif" />
offset to the right relative to the container holder 48 and the electrode cleaning station 528, compared to the positions of each in FIG. 47, such that the inner electrode 108 has been removed from position, and the inner electrode 510 has been placed in position relative to the container holder 48.
IV. A. It should be understood that the movement of the internal electrode array may be independent of the movement of the vessel holders. They can be moved together or independently, to simultaneously or independently switch to a new vessel holder and / or a new internal electrode.
IV.A. FIGS. 46-48 show an arrangement of two or more gas supply tubes, such as 108 (also shown in FIG. 2), 510 and 512, which are also internal electrodes. The arrangement can be linear or carousel. A carousel arrangement allows the electrodes to be reused periodically.
IV.A. FIGS. 46-48 also show an internal electrode extender and retractor 514 for inserting and removing the internal electrode / gas supply tubes 108, 510 and 512 from and to one or more container holders such
<img file="MX345403B_D0119.tif" />
<img file="MX345403B_D0120.tif" />
packets <sup>ηϊ</sup> 'fWSTMAL referencing the electrodes
172 such as 50 or 48. These features are for using the gas supply tubes.
IV.A. In an illustrated embodiment, FIGS. 4 6-48, as well as trim 108, 510, and 512 are respectively connected by flexible hoses 516, 518, and 520 to a common gas supply 144 through shut-off valves 522, 524, and 526 (flexible hoses are shortened in FIGS. 46-48 omitting the clearance portions). A mechanism 514 is provided to extend or retract an internal electrode such as 108. The inner electrode extender and retractor are configured to move an inner electrode between a fully advanced position, an intermediate position, and a retracted position with respect to the container holder.
IV.A. In FIGS. 46 and 56, the inner electrode 108 extends to its functional position within the container holder 50 and container 80, and its shutoff valve 522 is opened. Furthermore, in FIGS. 4, 6 and 56, the inactive internal electrodes 510 and 512 retract and their shutoff valves 524 and 526 close. In the illustrated embodiment, the inactive internal electrodes 510 and 512 are arranged in an electrode cleaning station 528. Some electrodes can be cleaned and others can be replaced at the 528 station, optionally. As non-exhaustive examples,
173
IMPI® cleaning operations can involve an industrial - * or solvent treatment to remove deposits, grinding to physically remove deposits or plasma treatment to essentially burn off accumulated deposits.
'IV.A. In FIG. 47, internal inactive electrodes 510 and 512 are the same as above, while internal working electrode 108 has retracted into container 80, its distal end remaining within container holder 50, and its valve 522 has been closed. In this condition, the container 80 can be removed and a new container can be seated in the container holder 50 without there being any risk of touching the electrode 108 with the containers 80 that are removed and replaced. After replacing the container 80, the inner electrode 108 can advance to the position of FIGS. 46 and 56 and the shutoff valve 522 can be reopened to begin coating the new container 80 using the same internal electrode 108 as previously used. Accordingly, in an installation where a series of containers 80 are seated and removed from the container holder 50, the inner electrode 108 may partially extend and retract numerous times as the container 80 is installed or removed from the container holder. vessels 50 at the station where the inner electrode 108 is at usWMpmoxg
IV.A. In FIG. 48, the container holder ^ SO and its container 80 have been replaced with a new container holder 48 and another container 80. Referring to FIG. 1, in this type of embodiment each container 80 remains in its container holder, such as 50 or 48, and an internal electrode, such as 108, is inserted into each container when its container holder reaches the coating station.
IV. A. Additionally in FIG. 48, the inner electrodes 108, 510, and 512 are fully retracted and the inner electrode array 108, 510, and 512 has shifted to the right relative to the vessel holder 48 and the electrode cleaning station 528, compared to the positions of each in FIG. 47, such that the inner electrode 108 has been removed from position, and the inner electrode 510 has been placed in position relative to the container holder 48.
IV.A. It should be understood that the movement of the internal electrode array may be independent of the movement of the container holders. They can be moved together or independently, to simultaneously or independently switch to a new vessel holder and / or a new internal electrode.
175
IV.A. An arrangement of one or more electrod®®m * slsrn5bs ^ 0M ^ \ 5YES 510 and 512 is useful because the supply tubes of ga ^ -T<sup>5 </sup>Combined individual internal electrodes 108, 510, and 512 "some instances will tend to accumulate polymerized reactive gases or some other type of deposit as they are used to line a series of vessels such as 80. Deposits can accumulate to the point where they decrease the coating rate or uniformity produced, which may not be desirable. To maintain a smooth process, the internal electrodes can be periodically removed from operation, replaced or cleaned, and a new or clean electrode can be put into operation. For example, from FIG. 46 to FIG. 48, the inner electrode 108 was replaced with a new or reconditioned inner electrode 510, which is ready to be extended into the container holder 48 and container 80 to apply an inner coating to the new container.
IV. A. Accordingly, an internal electrode actuator 530 may be operated in conjunction with the internal electrode extender and retractor 514 to move a first internal electrode 108 from its extended position to its retracted position, replacing a second internal electrode 510 with the first. inner electrode 108 and, moving the second inner electrode 510 to its extended position (analogous to<sup>176</sup> IMPIAS
JNSTnVTO H * ^ **<sup>1</sup>^ FIGS. 46 and 56 except for the substitution αθ1 · ^ 3 ^ ί ^ α & 3Γ3Ε · IV.A. The supply tube arrangement of. qn ^ lm
FIGS. 46-48 and internal electrode driver 530 can be used, for example, in the embodiments of FIGS. 1, 2, 3, 8, 9, 12-16, 18-19, 21-22, 26-28, 33-35, 37-45, 49 and 52-54. The extension and retraction mechanism 514 of FIGS. 46-48 can be used, for example, in the gas supply tube embodiments of FIGS. 2, 3, 8, 9, 12-16, 18-19, 21-22, 26-28, 33-35, 37-45, 49 and 52-54, as well as with the probes of the vessel inspection apparatus of FIGS. 6 and 7.
IV.A Electrode 160 shown in FIG. 2 may be in the shape of a U channel with its length on the page and the disk or container holder 50 may move across the activated (driven) electrode during the treatment / coating process. It should be noted that because internal and external electrodes are used, this apparatus can employ a frequency between 50Hz and 1GHz applied from a power source 162 to the U-channel-shaped electrode 160. Probe 108 may be grounded to complete the electrical circuit, allowing current to flow through the low pressure gas or gases within vessel 80. The current creates plasma to allow selective treatment and / or coating of
177 the inner surface 88 of the device.
<img file="MX345403B_D0121.tif" />
οβττιυτο MKICANC Di LA ΙΚΗΜΛΠ
L INDUSTRIAL. J &. ',
IV.A The electrode of FIG. 2 tamble® 'can be powered by a pulsed power source. Pulsation allows the depletion of the reactive gases and subsequently the removal of by-products prior to activation and the depletion (again) of the reactive gases. Pulsed power systems are typically characterized by their duty cycle which determines the amount of time that the electric field (and therefore the plasma) is present. The power on time is relative to the power off time. For example, a 10% duty cycle might correspond to a 10% power on time for a cycle where the power was off 90% of the time. As a specific example, the power can be on for 0.1 second and off for 1 second. Pulsed power systems reduce the effective input power for a given power source 162, since the power off time causes the processing time to increase. When the system is pulsed, the resulting coating can be very pure (without by-products or contaminants). Another result of pulsed systems is the possibility of achieving atomic layer deposition (ALD). In this case, the duty cycle can be adjusted so that the industrial power-on time produces the single layer of a desired material.
Of this form.
It contemplates that a single atomic layer is deposited in each cycle. This method can result in very pure and highly structured coatings (although at the temperatures necessary for deposition on polymeric surfaces, temperatures are preferably kept low (<100 ° C) and low-temperature coatings can be amorphous).
IV. A. An alternative coating station is described in FIG. 12 that employs a microwave cavity instead of an external electrode. The applied energy can be a microwave frequency, for example 2.45 GHz.
IV.B. PECVD apparatus that uses a clamping tool to transport tubes to and from a coating station
IV. B. Another embodiment is an apparatus for PECVD treatment of a container employing a holding tool as previously described. FIGS. 15 and 16 show apparatus generally indicated at 202 for PECVD treatment of a first container 80 having an open end 82, a closed end 84, and an interior space defined by surface 88. This embodiment includes a container holder 48, at least
<img file="MX345403B_D0122.tif" />
<img file="MX345403B_D0123.tif" />
179 iNsTmrrc) Mexican
INDUSTRIAL PROPERTY a first holding tool 204 (in this embodiment, for example, a suction cup), a seat defined by the container port 92 on the container holder 48, a reagent supply 144, a plasma generator represented by electrodes 108 and 160, a container release, which can be a vent valve, such as 5 34, and the same holding tool 2 04 or a second (in fact, optionally a second holding tool 204).
IV.B. The first holding tool 204, and as illustrated by any of the holding tools 204, is configured to selectively support and release the closed end 84 of a container 80. While holding the closed end 84 of the container, the first holding tool 204 can transport the container to near the container holder 48. In the illustrated embodiment, the transport function is facilitated by a serial conveyor 53 8 to which the holding tools 204 are attached in series.
IV.B. Container support 48 has been previously described in connection with other embodiments and is configured to seat open end 82 of container 80. The seat defined by container port 92 has been previously described in connection with
IMPI ^ other embodiments and sealed communications are configured between the container support 48 and the interior space 88 of the first container and, in this case, any of the containers 80. The reagent supply 144 has been previously described in connection with other embodiments. and is operatively connected to introduce at least one gaseous reagent into the first container 80 through the container holder 48. The plasma generator defined by electrodes 108 and 160 has been previously described in connection with other embodiments and is configured to form plasma within the first container under conditions effective to form a reaction product of the reagent on the interior surface of the first container.
IV.B. The container release mechanism 534 or other resources, such as introducing into the seated container 80 a reactive gas, a carrier gas, or an inexpensive gas, such as nitrogen or compressed air, can be used to remove the first container 80 from the holder. containers 48.
IV. B. The clamping tools 204 are configured to axially transport the first container 80 away from the container holder 48 and subsequently release the first container 80, such as by releasing the suction, from between the clamping tool 48 and the end.
181 of the container 84.
IV. B. Treatment in several stages.
FIGS. 15 and 16 also mués turiWlu £ Industrial ----- PECVD of a first container comprising
A first "Container 80 is provided having an open end 82, a closed end 84, and an interior surface 88. At least one first holding tool 204 is configured to selectively grip and release the closed end 84 of first container 80. The closed end 84 of the first container 80 is clamped with the first clamping tool 204 and carried in use near the container holder 48 configured to seat the open end of the first container. In the embodiment of FIG. 16, two container supports 48 are provided which allow containers 80 to advance and seat in container supports 48 two at a time, thereby doubling the effective production rate. Next, the first holding tool 204 is used to axially advance the first container 80 and seat its open end 82 in the container support 48 to establish sealed communication between the container support 48 and the interior of the first container. Next, at least one gaseous reagent is introduced into the first container through the container holder, optionally as explained for previous embodiments.
IV.B. Subsequently, plasma is formed within the first container under conditions effective to form a reaction product of the reagent on the inner surface of the first container, optionally as explained for previous embodiments. The first container is removed from the container holder, optionally as explained for previous embodiments. The first clamping tool or other clamping tool, optionally as explained for previous embodiments, is used to axially transport the first container away from the container holder. The first container can then be released from the holding tool used to transport it axially away from the container holder, optionally as explained for previous embodiments.
IV.B. Additional optional steps that may be carried out in accordance with this method include providing a reaction vessel other than the first vessel, the reaction vessel having an open end and an interior space, and seating the open end of the reaction vessel in the holder. of vessels to establish sealed communication between the vessel holder and the interior space of the reaction vessel.
183
MEXICAN WSTiTUTO
A reagent conduit may be provided from the interior space. The plasma can fn-warre Hpntrn interior space of the reaction vessel under conditions effective to remove at least a portion of a deposit of a PECVD reaction product from the reagent line. These reaction conditions have been explained in connection with a previously described embodiment. Subsequently, the reaction vessel can be removed from the vessel holder and transported away from the vessel holder.
IV. B. Additional optional steps that can be carried out in accordance with any embodiment of this method include:
providing at least a second holding tool;
functionally connecting at least the first and second clamping tools to a serial conveyor;
providing a second container having an open end, a closed end, and an interior surface;
providing a holding tool configured to selectively hold and release the closed end of the second container;
clamping the closed end of the second container with the clamping tool;
Using the holding tool, transport the
184 second container until it is located near dasTriu »Msi & Q] ^: BjM DE LA PRONEVXn
INDUSTRIAL T * vessels configured to seat the open end of the second vessel;
using the clamping tool, advancing the second container axially and seating its open end in the container support to establish sealed communication between the container support and the interior of the second container;
introducing at least one gaseous reagent into the second container through the container holder;
forming plasma within the second container under conditions effective to form a reaction product of the reagent on the interior surface of the second container;
releasing the second container from the container holder; and using the second clamping tool or another clamping tool, axially transporting the second container away from the container holder; and releasing the second container from the holding tool used to transport it axially away from the container holder.
IV. B. FIG. 16 is an example of using a suction cup device to support the end of a sample collection tube (in this example) that can be
185
IMPI
INSTITUTO MEXICANO DE LA PROPIEDAD _ INDUSTRIAL moving along a production line / system. The specific example shown herein is one possible step (of many possible steps as explained above and below) of coating / treatment. The tube can move in the coating stage / area and the tube can move down into the vessel holder and (in this example) the cylindrical electrode. Subsequently, the vessel holder, sample collection tube, and suction cup can be moved together to the next stage where the electrode is actuated and treatment / coating takes place. Any of the types of electrodes mentioned above can be used in this example.
IV.B. Therefore, FIGS. 15 and 16 show a container holder 48 at a coating station 28 similar to FIG. 13, which employs a container transport indicated generally at 202 to move container 80 to and from coating station 28. Container transport 202 may be provided with a holding tool 204, which in the illustrated transport 202 can be a sucker. An adhesive backing, an active vacuum source (with a pump to draw air from the clamping tool, which actively creates a vacuum), or another resource can be used as a clamping tool. He
186
IMPI ^
INSTITUTO MEXICÁN · Container Transport 202 can be used, by eji®iwpíi <», ^ S3K to move container 80 downward while seated in container port 92 to position container 80 for coating. Container transport 202 can also be used to remove container 80 from container port 92 by lifting it up after processing at station 28. Container transport 202 can also be used to seat container 80 before container 80 and container transport 48 advance together to a station. Container transport can also be used to hold container 80 in its seat in container port 92. Additionally, although FIG. fifteen it may be oriented to show the vertical elevation of container 80 from above, an inverted orientation may exist or may be contemplated in which container transport 202 is below container 80 and holds it from below.
IV.B. FIG. 16 shows an embodiment of a method in which container transports 202, such as suction cups 204, transport containers 80 horizontally, for example, from one station to the next, as well as (or instead of) vertically in and out of a station such as 28. Containers 80 can be lifted and transported in any orientation. Therefore, FIG.
187 represents a method of treatment per container 80 comprising several steps.
<img file="MX345403B_D0124.tif" />
IV. B. In the embodiment of FIG. 13, the outer electrode 160 may be generally cylindrical with open ends and may be stationary. Container 80 can be advanced through outer electrode 160 until opening 82 seats in container port 96. In this embodiment, probe 108 may optionally be permanently molded or otherwise secured in gas inlet port 104, rather than a sliding seal that allows relative movement between port 104 and probe 108.
IV.B. FIG. 14 shows an additional alternative for coupling electrical power to plasma at 50Hz - 1GHz. This can consist of a coil that can be moved down into position or the container holder (with device) can be pushed up into position. Helical electrodes are called inductive coupling devices and can transmit a magnetic component into the device where plasma can be created.
IV.B. A probe 108 can still be used as indicated in FIG. 2 and in FIG. 13. Other aspects of the container support or container support 48
-θ IMPI
MEXICAN INSTITUTE. - ,. , ________ __π __ OELAfSeNTOAD listed above may remain the same HroswAL
<img file="MX345403B_D0125.tif" />
IV. B. As shown, for example, FI-G. -'- dO, can provide a reaction vessel 532 different from the first vessel 80, which also has an open end 540 and an interior space defined by interior surface 542. Like vessels 80, reaction vessel 532 may have its open end 540 on vessel holder 48 and establish sealed communication between vessel holder 48 and the interior space 542 of the reaction vessel .
IV.B. FIG. 49 is a view similar to FIG. 16 showing a mechanism for supplying vessels 80 to treat them and a cleaning reactor 532 for a PECVD coating apparatus. In this embodiment, the inner electrode 108 can optionally be cleaned without removing it from the container holder 48.
IV.B. FIG. 49 shows that the PECVD reagent conduit 108 as described above is positioned to be inserted into the interior space 542 of the reaction vessel 532 when the reaction vessel is seated in the vessel holder 48 instead of a vessel 80 being provides to coat as described above. FIG. 49 shows reagent line 108 in this configuration, although line 108
189 It has an outer portion as well as an inner distal portion. For these purposes and claims it is enough if the conduit
<img file="MX345403B_D0126.tif" />
for the presents of reagent 108 it extends at least partially into container 80 or 532.
IV.B. The mechanism of FIG. 4 9 as illustrated can be used with the embodiments of at least FIGS. 1 and 15-16, for example. Cleanup reactor 532 can also be provided as a simple vessel seated and carried on a vessel holder, such as 48, in an alternative embodiment. In this configuration, cleaning reactor 532 can be used with the apparatus of at least FIGS. 1-3, 8, 9, 12-15, 18, 19, 21, 22, 26-28, 3335, 37-48 and 52-54, for example.
IV. B. The plasma generator defined by electrodes 108 and 160 is configured to form plasma in the interior space of reaction vessel 532 under conditions effective to remove at least a portion of a deposit of a PECVD reaction product from the reagent line 108. It is previously contemplated that the internal electrode and gas source 108 may be a conductive tube, for example, a metal tube, and that the reaction vessel 532 may be made of any suitable, preferably heat resistant material, such as ceramic, quartz, glass or other materials that can <sup>190 </sup>withstand more heat than a thermopSiglí ^^ Reaction vessel material + Γ * i MinU-Uln may preferably be resistant to chemicals or plasma under the conditions used in the reaction vessel to remove deposits from reaction products . Optionally, the reaction vessel 532 can be made of electroconductive material and in turn serve as a special external electrode for removing deposits from the reagent conduit 108. As yet another alternative, reaction vessel 532 may be configured as a lid that sits on outer electrode 160, in which case outer electrode 160 would preferably be seated on vessel holder 48 to define a closed cleaning reaction chamber. .
IV.B. Effective reaction conditions for removing at least a portion of a deposit of a PECVD reaction product from the reagent line are contemplated
108 include the introduction of a substantial portion of an oxidizing reagent, such as oxygen or ozone (generated separately or by the plasma apparatus), a power level higher than that used for coating deposition, a longer cycle time than used for deposition of coatings or other known resources to remove the type of unwanted deposit
191 found in reaction line 108.
Mechanical grinding can also be used to remove unwanted deposits.
Or solvents or other agents can be drawn through reagent line 108 to remove clogs. These conditions may be more aggressive than the vessels 80 to be coated can withstand, as the reaction vessel 532 need not be suitable for the normal uses of vessel 80. However, optionally, a vessel 8 0 can be used as the reaction vessel and, if the deposit removal conditions are too aggressive, the vessel 80 used as the reaction vessel may be discarded, in an alternative embodiment.
PECVD METHODS FOR MAKING CONTAINERS
Vl Precursors for PECVD coating
The precursor for PECVD coating of the present invention is broadly defined as an organometallic precursor. An organometallic precursor is defined in the present description as one that comprises compounds of metal elements from group III and / or group IV of the periodic table with organic residues, for example, hydrocarbon, aminocarbon or oxycarbon residues. Organometallic compounds defined herein include any precursor that has organic moieties attached to
192
<img file="MX345403B_D0127.tif" />
directly or optionally linked via oxygen or nitrogen atoms. The relevant elements of group III of the periodic table are boron, aluminum, gallium, indium, thallium, scandium, yttrium and lanthanum, with aluminum and boron being preferred. The relevant elements of group IV of the periodic table are silicon, germanium, tin, lead, titanium, zirconium, hafnium and thorium, with silicon and tin being preferred. Other volatile organic compounds can also be contemplated. However, organosilicon compounds are preferred for carrying out the present invention.
An organosilicon precursor is contemplated, where an organosilicon precursor is defined in this disclosure more broadly as a compound with at least one of the linkages:
| —O — Si — C — H | —NH — Si — C — H
The first structure immediately above is a tetravalent silicon atom connected to an oxygen atom
193
<img file="MX345403B_D0128.tif" />
and to an organic carbon atom (being an organic £ áf ^ ioj ^ lj INSTITUTO MEXICANO bonded to at least one hydrogen atom) '.NDusTfaa.
The immediately preceding structure is mT — ι iw · ji - tetravalent u rium connected to an -NH- bond and to an organic carbon atom (an organic carbon atom being attached to at least one hydrogen atom). Preferably, the organosilicic precursor is selected from the group consisting of a linear siloxane, a monocyclic siloxane, a polycyclic siloxane, a polysilsesquioxane, a linear silazane, a monocyclic silazane, a polycyclic silazane, one more polysilsesquiazane, and a combination of these two or more. precursors. An alkyltrimethoxysilane is also contemplated as a precursor ', although not within the two immediately preceding formulas.
If an oxygen-containing precursor (eg. g., a siloxane), a representative predicted empirical formula as a result of PECVD under conditions to form a hydrophobic or lubricating coating would be SiwOxCyHz, where w is 1, x for this formula is from about 0.5 to about 1, and is about 2 at about 3, and z is from 6 to about 9, while a representative predicted empirical composition as a result of PECVD under conditions to form a barrier coating would be SiOx, where x in this formula
194
<img file="MX345403B_D0129.tif" />
uses a nitrogen-containing precursor (eg a silazane), the predicted composition would be Siw * Nx * Cy * Hz *, that is, in SiwOxCyHz according to the present invention O is replaced by N and the indices are adapted to the higher valence of N compared to O (3 instead of 2). The latter adaptation will generally follow the relationship of w, x, y, and z in a siloxane with the corresponding indices in its aza counterpart. In a particular aspect of the invention, Siw * Nx * Cy * Hz * in which w *, x *, y *, and z * are defined the same as for the siloxane counterparts, but for an optional deviation in the hydrogen number .
One type of precursor starting material having the above empirical formula is a linear siloxane, for example a material having the following formula:
RR
R - Yes — O - YES — R
RR in which each R is independently selected from alkyl, eg, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, vinyl, alkyne, or others, and n is 1, 2, 3, 4 or greater, preferably greater than or equal to two. Several examples of contemplated linear siloxanes are
195
<img file="MX345403B_D0130.tif" />
hexamethyldisiloxane (HMDSO), octamethyltrisiloxane, decamethyltetrasiloxane, dodemethylpentasiloxane, or combinations of two or more of these. Analogous silazanes in which -NH- is substituted by the oxygen atom of the above structure are also useful for making analogous coatings. Several examples of contemplated linear silazanes are octamethyltrisilazane, decamethyltetrasilazane, or combinations of two or more of these.
VC Another type of precursor starting material is a monocyclic siloxane, for example, a material having the following structural formula:
R
<img file="MX345403B_D0131.tif" />
in which R is defined as for linear structure and is 3 to about 10 or the analogous monocyclic silazanes. Several examples of contemplated heterosubstituted and unsubstituted monocyclic siloxanes and silazanes include
1,3,5-trimethyl-l, 3,5-tris (3,3,3-trifluoropropyl) methyl] cyclotrisiloxane <sup>196</sup> IMPI
INSTITUTO MEXICANO ϊχ * OE LA WOWLQAI '
2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetriaphth'riiexanbT pentamethylcyclopentasiloxane, , 3-trifluoropropyl) cyclosiloxane, Cyclic organosilazanes are also contemplated, such as octamethylcyclotetrasilazane,
1,3,5,7-tetravinyl-l, 3,5,7-tetramethylcyclotetrasilazane hexamethylcyclotrisilazane, octamethylcyclotetrasilazane, decamethylcyclopentasilazane, dodecamethylcyclohexasilazane, or combinations of any two or more of these.
VC Another type of precursor starting material is a polycyclic siloxane, for example, a material having one of the following structural formulas:
<img file="MX345403B_D0132.tif" />
in which Y can be oxygen or nitrogen, E is silicon and Z is a hydrogen atom or an organic substituent, for example, alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, vinyl, alkyne or others. When each Y is oxygen, the respective structures, from left to right, are a silatran, a silcuasilatran, and a silproatran. When Y is nitrogen, the respective structures are an azasilatran, an azasylquasiatran, and an azasylproatran.
VC Another type of polycyclic siloxane precursor starting material is a polysilsesquioxane, with the empirical formula RSiOl, 5 and the structural formula:
<img file="MX345403B_D0133.tif" />
T<sub>8</sub> cube <sup>198</sup> IMPI®a
INSTITUTO MEXICANO in which each R is a hydr% ^ «fe organic substituent atom, for example, alkyl, ΐττί — egmr m-?<sup>1-Ί</sup>'<sup>1</sup> . ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, vinyl, alkyne or others. Two commercial materials of this class are SST-eMOl poly (methylsilsesquioxane), in which R is methyl, and SST-3MH1.1 poly (methylhydridosylsesquioxane), in which 90% of the R groups are methyl and 10% are hydrogen atoms. This material is available in a 10% solution in tetrahydrofuran, for example. Combinations of two or more of these are also contemplated. Other examples of a contemplated precursor are methylsilatran, CAS No. 2288-13-3, in which each Y is oxygen and Z is methyl, methylazasilatran, SST-eMOl poly (methylsilsesquioxane), in which each R can optionally be methyl, SST -3MH1.1 poly (methylhydridosylsesquioxane), in which 90% of the R groups are methyl and 10% are hydrogen atoms or a combination of any two or more of these.
VC Analogous polysilsesquiazanes in which NH- is substituted for the oxygen atom in the above structure are also useful for making analogous coatings. Examples of contemplated polysilsesquiazanes are a poly (methylsilsesquiazane), in which each R is methyl, and a poly (methylhydridosylsesquiazane), in which 90% of the R groups are methyl and 10% are hydrogen atoms.
<img file="MX345403B_D0134.tif" />
of these.
VC A particularly contemplated precursor for the lubricant coating according to the present invention is a monocyclic siloxane, for example, octamethylcyclotetrasiloxane.
A particularly contemplated precursor for the hydrophobic coating according to the present invention is a monocyclic siloxane, for example, octamethylcyclotetrasiloxane.
A particularly contemplated precursor for the barrier coating according to the present invention is a linear siloxane, eg, HMDSO.
VC In any of the coating methods according to the present invention, the application step can optionally be carried out by vaporizing the precursor and providing it close to the substrate. For example, OMCTS is generally vaporized by heating it to approximately 50 ° C before applying it to the PECVD apparatus.
V.2 General PECVD method
In the context of the present invention, the following PECVD method is generally applied, which contains the following steps:
200
<img file="MX345403B_D0135.tif" />
(a) providing a gaseous reagent, which precursor as defined herein, preferably an organosilicon precursor and optionally 02, near the surface of the substrate; and (b) generating a plasma from the gaseous reagent, to thereby form a coating on the substrate surface by plasma-assisted chemical vapor desorption (PECVD).
In such a method, the characteristics of the coating are conveniently established by one or more of the following conditions: the properties of the plasma, the pressure at which the plasma is applied, the power applied to generate the plasma, the presence and relative amount of 02 in the gaseous reagent, the plasma volume and the organosilicon precursor. Preferably, the characteristics of the coating are established by the presence and relative amount of 02 in the gaseous reagent and / or the power applied to generate the plasma.
In all embodiments of the present invention the plasma, in an optional aspect, is not a hollow cathode plasma.
In another preferred aspect, the plasma is generated under reduced pressure (compared to ambient pressure or atmospheric pressure). Preferably, the reduced pressure is lower
201 300 mTorr, more preferably less than
<img file="MX345403B_D0136.tif" />
more preferably less than 100 mTorr.
PECVD is preferably carried out by activating the gaseous reagent containing the precursor with electrodes fed at a frequency that is a radio frequency or microwave frequency and preferably a radio frequency. The preferred radio frequency for carrying out an embodiment of the invention will also be referred to as the RF frequency. A typical radio frequency range for carrying out the present invention is a frequency of 10 kHz to less than 300 MHz, more preferably 1 to 50 MHz, even more preferably 10 to 15 MHz. A frequency of 13.56 MHz is preferred, being This is a government authorized frequency to carry out PECVD work.
Using an RF power supply offers several advantages compared to a microwave source: Since RF operates at a lower power, there is less heating of the substrate / container. Because the present invention focuses on the application of a plasma coating on plastic substrates, lower processing temperatures are desirable to avoid melting / deformation of the substrate. To prevent the substrate from overheating when using microwave PECVD, the microwave PECVD <sup>202</sup> IMPI ^
INSTITUTO MEXICANO 1¾ is applied in short bursts, in power pulses, power pulses extend the cycle time to e / 1. coating, which is undesirable in the present invention. Higher frequency microwaves can also cause the degassing of volatile substances such as waste water, oligomers and other materials in the plastic substrate. This outgassing can interfere with the PECVD coating. One of the main problems with using microwaves for PECVD is the delamination of the coating from the substrate. Delamination occurs because microwaves modify the surface of the substrate before depositing the coating layer. To mitigate the possibility of delamination, interface coating layers have been developed for microwave PECVD to achieve a good bond between the coating and the substrate. Such an interface coating layer is not necessary with RF PECVD since there is no risk of delamination. Finally, the lubricating coating and the hydrophobic coating according to the present invention are advantageously applied using less power. RF power operates at a lower power and provides more control over the PECVD process than microwave power. However, microwave power, although less preferred, is useful under suitable process conditions.
...... IMPIí ^
Likewise, for all methods of PECV¡EKn-dfis «dí: iÁ £ oa ^^ a
DI! .A MtOEISOAD INDUSTRIAL herewith, there is a specific correlation between the power (in watts) used to generate the plasma and the volume of the cavity in which the plasma is generated. Generally, the cavity is the cavity of a container lined in accordance with the present invention. The RF power should be graduated according to the volume of the container if the same electrode system is used. Once the composition of a gaseous reagent has been set, for example the ratio of precursor to 02, and all other parameters of the PECVD coating method except for potency, they will generally not change when the geometry of a container is changed. hold and just vary its volume. In this case, the power will be directly proportional to the volume. Therefore, starting from the relationships between energy and volume provided by the present description, one can easily determine the power that must be applied in order to achieve the same or similar coating in a container with the same geometry but of different size. The influence of container geometry on the power to be applied is illustrated by the results of the Examples for tubes compared to the Examples for syringe barrels.
For any coating of the present invention,
204 plasma is generated with powered electrodes
<img file="MX345403B_D0137.tif" />
INDUSTRIAL power to form a coating on the surface of the substrate. For a lubricating or hydrophobic coating, in the method according to an embodiment of the invention, the plasma is preferably generated (i) with electrodes supplied with an electrical power of 0.1 to 25 W, preferably 1 to 22 W, more preferably of 3 to 17 W, even more preferably 5 to 14 W, still more preferably 7 to 11 W, for example 8 W; and / or (ii) where the relationship between the power of the electrode and the plasma volume is less than 10 W / mL, preferably it is from 5 W / mL to 0.1 W / mL, more preferably it is from 4 W / mL to 0.1 W / mL, even more preferably 2 W / mL to 0.2 W / mL. For a barrier or SiOx coating, the plasma is preferably generated (i) with electrodes supplied with an electrical power of 8 to 500 W, preferably 20 to 400 W, more preferably 35 to 350 W, even more preferably 44 at 300 W, even more preferably 44 to 70 W; and / or (ii) the relationship between the power of the electrode and the plasma volume is less than or equal to 5 W / mL, preferably it is from 6 W / mL to 150 W / mL, more preferably it is 7 W / mL to 100 W / mL, even more preferably 7 W / mL to 20 W / mL.
The geometry of the container can also influence the
205 IMPI ^ ίΝβτιτυτ · MEXICAN
OWNERSHIP I ^^ J choice of gas inlet used for reverse ^ SMienropor PECVD. In a particular aspect, a yuytltí TS'í'Tfiga · 'is lined with an open tube inlet, and a tube can be lined with a gas inlet with small holes extending into the tube.
The power (in watts) used for PECVD also influences the properties of the coating. Generally, an increase of. the potency will increase the barrier properties of the coating and a decrease in the potency will increase the lubricity and hydrophobicity of the coating. For example, for a coating on the inner wall of a syringe barrel that has a volume of approximately 3 mL, a power of less than 30 W will produce a coating that is predominantly a barrier coating, while a power of more than 30 W will produce a coating that is predominantly a lubricating coating (refer to Examples).
A further parameter that determines the coating properties is the ratio of 02 (or other oxidizing agent) to the precursor (eg, organosilicon precursor) in the gaseous reagent used to generate the plasma. Generally, an increase in the 02 content in the gaseous reagent will increase the barrier properties of the coating, and a decrease in the 02 content
<img file="MX345403B_D0138.tif" />
206
IMJJ.
will increase the lubricity and hydrophobicity of the ré ^^ jgg ^ tit
Therefore, the PECVD dp J-rt coating method of the present invention can be used to set the lubricity properties of a coating, the hydrophobicity properties of a coating and the barrier properties of a coating prepared by said method.
If a lubricating coating is desired, then the 02 is preferably present in a volume-volume ratio to the gaseous reactant of 0: 1 to 5: 1, more preferably 0: 1 to 1: 1, even more preferably 0: 1 to 0.5: 1 or even 0: 1 to 0.1: 1. More advantageously, there is essentially no oxygen present in the gaseous reagent. Therefore, the gaseous reagent should comprise less than 1 vol% 02, more particularly less than 0.5 vol% 02, and more preferably free from 02. The same is true for the hydrophobic coating.
If, on the other hand, a barrier coating or SiOx is desired, then the 02 is preferably present in a volume: volume relation to the gaseous reactant of 1: 1 to 100: 1 relative to the silicon-containing precursor, preferably in a ratio of 5: 1 to 30: 1, more preferably in a ratio of 10: 1 to 20: 1, even more preferably in a ratio of 15: 1.
<sup>207</sup> ΙΜΡΙί * 5 ^
MEXICAN INSTITUTE
GOES. PECVD to apply a coating ^ e ^ Ntfeaaí ^ eráElHg: SiOx using plasma that is substance-Ímonteo ·· exempt · 'da hollow cathode plasma
GOES. One specific embodiment is a method of applying a SiOx barrier coating, defined in this description (unless otherwise specified in a particular instance) as a coating containing silicon, oxygen, and optionally other elements, where x , the ratio of oxygen to silicon atoms is about 1.5 to about 2.9, or 1.5 to about 2.6, or about 2. These alternative definitions of x apply to any use of the term SiOx in this description. The barrier coating is applied to the inside of a container, such as a sample collection tube, syringe barrel, or other type of container. The method includes several stages.
GOES. A vessel wall is provided, as is a reaction mixture containing a plasma-forming gas, ie, a gaseous organosilicon compound, optionally an oxidizing gas, and optionally a gaseous hydrocarbon.
VA Plasma is formed in the reaction mixture that is substantially free of hollow cathode plasma. The vessel wall is brought into contact with the reaction mixture and the SiOx coating
208 is deposited so
<img file="MX345403B_D0139.tif" />
portion of the container wall.
VA In certain embodiments, it is preferred to generate
<img file="MX345403B_D0140.tif" />
a uniform plasma throughout the portion of the container to be coated, as has been found in certain instances to generate a SiOx coating that provides a better barrier against oxygen. A uniform plasma means a regular plasma that does not include a considerable amount of hollow cathode plasma (which has a higher emission intensity than regular plasma and manifests as a localized area of greater intensity that interrupts the more uniform intensity of regular plasma ).
VA The hollow cathode effect is generated by a pair of opposite conductive surfaces with the same negative potential with respect to a common anode. If a separation is maintained (depending on pressure and gas type) such that the spaced charged shells overlap, the electrons begin to oscillate between the reflection potentials of the opposing wall shells, resulting in multiple collisions since electrons are accelerated by the potential gradient in the sheath region. Electrons are confined in the overlapping of spaced charged shells resulting in very high ionization and high plasmas.
IMPIS ionic density. This phenomenon is described comc?<sup>N</sup>^ HE ^ HE ^ Kb INDUSTRIAL hollow cathode. Those skilled in the art can change the processing conditions, such as the power level and the feed rates or pressure of the gases, to form a completely uniform plasma or to form a plasma that includes various levels of hollow cathode plasma.
VA In an alternative method, using, for example, the apparatus of FIG. 12 previously described, microwave energy can be used to generate plasma in a PECVD process. However, these processing conditions may be different since microwave energy applied to a thermoplastic container will stimulate (vibrate) the water molecules. Because there is a small amount of water in all plastic materials, microwaves will heat the plastic. As the plastic heats up, the large driving force created by the vacuum inside the device relative to atmospheric pressure outside the device will easily release and desorb the materials towards the inner surface 88 where they will become volatile or weakly bond to the surface. The loosely bonded materials will then create an interface that can prevent subsequent coatings (deposited by plasma) from adhering to the inner plastic surface 88 of the device.
VA One way to override this effect<sup>51</sup>^^^^^! The first of the coating consists of depositing a coating at a very low power (in the example above 5 to 20 watts at 2.45 GHz) that creates a cover on which subsequent coatings can adhere. This results in a two-stage coating process (and two coating layers). In the example above, the initial gas flows (for the protective layer) can be changed to 2 sccm (standard cubic centimeters per minute) of HMDSO and 20 sccm of oxygen with a process power of 5 to 20 watts for approximately 2-10 seconds. The gases can then be adjusted to the flows in the example above and the power level can be increased up to e.g. ex. , 35 to 50 W, so that a coating of SiOx can be deposited, where x in this formula is from about 1.5 to about 2.9, alternatively from about 1.5 to about 2.6, alternatively about 2. Notably, the cover layer may provide little to no functionality in certain embodiments, except to prevent migration of materials to the interior surface of container 88 during deposition of the higher strength SiOx coating. It should also be noted that the migration of easily desorbed materials on the walls of the device
<img file="MX345403B_D0141.tif" />
211
<img file="MX345403B_D0142.tif" />
generally does not occur
INSTITUTO MEXICANO at lower frequencies tjaa'STXPtB most of the RF range, since lower frequencies do not stimulate (vibrate) the molecular species.
VA Another way to override the blocking effect of the coating described above is to dry the container 80 to remove the soaked water before applying the microwave energy. Desiccation or drying of container 80 can be accomplished, for example, by thermally heating container 80, for example, using an electric heater or heating with pressurized air. Desiccation or drying of container 80 can also be accomplished by exposing the interior of container 80 or the gas in contact with the interior of container 80 to a desiccant. Other resources can also be used to dry the container, such as vacuum drying. These resources can be applied at one or more of the illustrated stations or devices or by means of a separate station or device.
VA Additionally, the coating-blocking effect described above can be addressed by selecting or processing the resin from which the containers 80 are cast to minimize the water content of the resin.
VB PECVD coating of the limited opening of
212
<img file="MX345403B_D0143.tif" />
<img file="MX345403B_D0144.tif" />
. . ., .... . . . INSTITUTO MEXICANA a container (capillary of -syringe) of the λονεοαο
V .B. FIGS. 26 and 27 show a method and apparatus indicated generally at 290 for PECVD coating an internal surface 292 of a limited opening 294 of a generally tubular container 250 to be processed, for example, the limited front opening 294 of a cylinder of syringe 250. The process described above is modified by connecting limited port 294 to processing vessel 296 and optionally making certain other modifications.
V .B. The generally tubular container 250 to be processed includes an outer surface 298, an inner or inner surface 254 that defines a cavity 300, a larger opening 302 that has an inner diameter, and a limited opening 294 defined by an inner surface 292 and with a inner diameter smaller than the inner diameter of the largest opening 302.
V .B. Processing vessel 296 has a cavity 304 and a processing vessel opening 306, which is optionally the only opening, although in other embodiments a second opening may be provided which is optionally closed during processing. The opening of the processing vessel
306 is connected to the limited opening 294 of the container
250 what has been <sup>213</sup> IMPI • ΝΪΤΤΤυΤΟ MEXICAN to process for est & t ^^ rí ^ t
<img file="MX345403B_D0145.tif" />
Communication between the cavity 300 of the reningent 2 50 em to be processed and the cavity of the processing vessel by means of the limited opening 294.
VB At least a partial vacuum is created in cavity 300 of vessel 250 to be processed and cavity 304 of process vessel 296. A flow of PECVD reagent is introduced from gas source 144 (refer to FIG. 7) through the first opening 3 02, then through the cavity 300 of the container 250 to be processed, then through the limited opening 294 to the cavity 304 of the processing container 296.
VB The PECVD reagent can be introduced through the larger opening 302 of the container 250 providing an internal generally tubular electrode 308 having an inner passage 310, a proximal end 312, a distal end 314 and a distal opening 316, in an alternative embodiment. Multiple distal openings may be provided adjacent to distal end 314 and communicating with interior passage 310. The distal end of the electrode 308 may be positioned adjacent to or within the larger opening 3 02 of the container 250 to be processed. A reactive gas can be fed through distal opening 316 of electrode 308<sup>214</sup> IMPI 6¾
INSTITUTO MEXICANO in cavity 300 of container 250 that has been
The reagent will flow through the limiting aperture 294 and then into well 3 04, as long as the PECVD reagent is delivered at a pressure higher than the vacuum initially created before introducing the PECVD reagent.
VB Plasma 318 is generated adjacent to limited aperture 294 under conditions effective to deposit a coating of a PECVD reaction product on inner surface 292 of limited aperture 294. In the embodiment shown in FIG. 26, the plasma is generated by feeding RF energy to the generally U-shaped outer electrode 160 and grounding the inner electrode 308. The power and ground connections of the electrodes can also be reversed, although this reversal can lead to complexity if the container 250 to be processed, and thus also the inner electrode 308, are moved through the outer electrode in a manner. of U while plasma is being generated.
VB Plasma 318 generated in vessel 250 during at least a portion of the processing may include hollow cathode plasma generated within limited opening 294 and / or cavity of processing vessel 304. Generation of hollow cathode plasma 318 may
<img file="MX345403B_D0146.tif" />
contribute to
215 ability to apply
IMPI
MF.MatNt + reoSTO / m<sup>1</sup>'inbusteial barrier coating to limited aperture 294, although the invention is not limited according to the accuracy or applicability of this theory of operation. Therefore, in a contemplated mode of operation, processing may be carried out partially under conditions that generate a uniform plasma throughout the vessel 250 and the gas inlet and partially under conditions that generate a hollow cathode plasma, for example, adjacent to limited opening 294.
VB The process is desirably operated under conditions, as explained herein and shown in the drawings, in which the plasma 318 extends substantially throughout the syringe cavity 300 and the limited opening 294. Conveniently, the plasma 318 preferably it also extends substantially through syringe cavity 300, limited opening 294, and cavity 304 of processing vessel 296. It is assumed that a uniform coating of the interior 254 of the container 250 is desired. In other embodiments, a non-uniform plasma may be desired.
V .B. It is generally desired that the plasma 318 have a substantially uniform color throughout the syringe cavity 300 and the limited opening 294 during processing and preferably a substantially uniform color throughout the entire
216 syringe cavity 300, limited opening 294
304 of the processing vessel 296. Preferably, the plasma is substantially stable in the syringe cavity 300 and the limited opening 294, and preferably also throughout the cavity 304 of the processing vessel 296.
V .B. The order of the stages of this method is not considered fundamental.
V .B. In the embodiment of FIGS. 26 and 27, the limited opening 294 has a first connector 332 and the processing container opening 306 has a second connector 334 adapted to fit the first connector 332 in order to establish communication between the cavity 3 04 of the processing container 2 96 and cavity 3 00 of container 250 to be processed.
V .B. In the embodiment of FIGS. 26 and 27, the first and second connectors are male and female Luer-type connectors 332 and 334, respectively integrated into the structure defining the limited opening 294 and the processing vessel opening 306. One of the connectors, in this case the male Luer type connector 332, comprises a safety ring 336 with an internal threaded surface and defining a first generally axially-oriented annular stop 338 and the other connector 334 comprises a second generally axially annular stop. oriented 340 opposite
217
IM Pifé first stopper 338, when the connectors 332 mated. _ -
V .B. In the illustrated embodiment, a seal, eg, an O-ring 342, may be positioned between the first and second connectors 332 and 334. For example, an annular seal may be engaged between the first and second stoppers 338 and 340. The female luer connector 334 also includes hooks 344 that engage the threaded internal surface of the circlip 336 to capture the O-ring 342 between the first and second connectors 332 and 334. Optionally, the communication established between the cavity 300 of the container 250 to be processed and the cavity 304 of the processing container 296 through the limited opening 294 is at least substantially leak-proof.
V .B. As another option, one or both of the Luer-type safety connectors 332 and 334 can be made of electroconductive material, eg, stainless steel. This material of construction that forms or is adjacent to a limited opening 294 can contribute to the formation of the plasma in the limited opening 294.
V .B. The desirable volume of cavity 304 of process vessel 296 is viewed as a balance between a small volume that will not divert much of the reagent flow away from product surfaces.
<img file="MX345403B_D0147.tif" />
what do you want
218 veneer and large volume
IMPI
Say LA * «Industrial OHETY that will allow a generous reactive gas flow rate to be maintained through limited opening 294 before filling cavity 304 sufficiently to reduce the flow rate to a less desirable level (reducing the pressure difference to through limited aperture 294). The contemplated volume of cavity 304, in one embodiment, is less than three times the volume of cavity 300 of container 250 to be processed, or less than two times the volume of cavity 300 of container 250 to be processed. process, or less than the volume of the cavity 300 of the container 250 to be processed, or less than 50% of the volume of the cavity 300 of the container 250 to be processed, or less than 25% of the volume of the cavity 300 of the container 250 to be processed. Other effective relationships between the volumes of the respective cavities are also contemplated.
V .B. The inventors have discovered that coating uniformity can be improved in certain embodiments by repositioning the distal end of electrode 308 with respect to container 250 so that it does not penetrate as much into cavity 300 of container 250 as the position of the internal electrode shown in the Previous figures. For example, although in certain embodiments distal opening 316 may be positioned adjacent to limited opening 294,
219 in others
IMPIí
INSTITUTO MEXICANO I realizations, IS ^ r ^^ u:
distal 316 can be positioned less than 7 / r, optionally less than% distance, optionally less than half the distance to the limited opening 294 of the larger opening 3 02 of the container to be processed while feeding the reactive gas. Or the distal opening 316 can be positioned less than 40%, less than 30%, less than 20%, less than 15%, less than 10%, less than 8%, less than 6%, less than 4%, less than 2% or less than 1% of the distance to the limited opening 294 of the largest opening of the container to be processed while feeding the reactive gas.
VB O the distal end of the electrode 308 may be positioned slightly in or out of or at the level of the larger opening 3 02 of the container 250 to be processed while communicating with the container 250 and feeding reagent gas into it. The positioning of the distal opening 316 relative to the container 250 to be processed can be optimized for particular dimensions and other treatment conditions by testing it in various positions. One particular position of the electrode 308 contemplated for treating syringe barrels 250 is with the distal end 314 penetrating approximately one-quarter inch (approximately 6 mm) into the cavity of the container 300 by
220 above the larger opening 302.
<img file="MX345403B_D0148.tif" />
VB The inventors contemplate herein. what - && advantageous to place at least the distal end 314 of the electrode 308 within the container 250 so that it functions properly as an electrode, although this is not necessarily a requirement. Surprisingly, the plasma 318 generated in the container 250 can be made more uniform, extending through the limited opening 294 into the cavity of the processing container 304, with less permeation of the electrode 308 in the cavity 300 than previously employed. With other facilities, such as closed-end container processing, the distal end 314 of the electrode 308 is typically positioned closer to the closed end of the container than to its inlet.
VB O distal end 314 of electrode 308 may be positioned in limited opening 294 or beyond limited opening 294, eg, within the cavity of processing vessel 304 as illustrated, for example, in FIG. 33. Various features such as molding the processing vessel 296 may optionally be provided to improve gas flow through the limited opening 294.
VB As another alternative, illustrated in FIGS. 3435, the internal composite electrode and gas supply tube 3 98 may have gas supply openings.<sup>0</sup> INDUSTRIAL such as 400, optionally located near the larger aperture 302 and an extension electrode extending distally 402 with respect to the distal gas supply apertures 400, optionally extending to a distal end adjacent the limited aperture 294 and , optionally, also extending into processing vessel 324. This construction is contemplated to facilitate plasma formation within internal surface 292 adjacent limited aperture 294.
VB In yet another contemplated embodiment, inner electrode 308, as in FIG. 26, may be moved during processing, for example, first extending into the cavity of the processing container 304 and then progressively and proximally withdrawn as the process progresses. This resource is particularly contemplated if the container 250, under the selected processing conditions, is long and the movement of the inner electrode facilitates uniform treatment of the inner surface 254. Using this resource, the processing conditions, such as the gas feed rate, the vacuum creation rate, the electrical power applied to the outer electrode 160, the removal rate of the inner electrode 308, or other factors may vary as the process advances. <sup>222</sup> IMPIra
INSTITUTE * 255 ^ $ process, which customizes the process for<sup>0£</sup>{ϊϊ £ & βΐΜβιη1 are parts of a container to be processed. ..... VB Conveniently, as in the other processes described in this description, the larger opening of the generally tubular container 250 to be processed can be placed on a container support 320, the larger opening 302 of the container seating. 250 to be processed at a port 322 of the vessel holder 320. The inner electrode 308 can then be positioned within the container 250 seated in the container holder 320 prior to creating at least a partial vacuum within the cavity 300 of the container 250 to be processed.
VB In an alternative embodiment, illustrated in FIG. 28, the processing vessel 324 may be provided in the form of a conduit having a first opening 306 attached to the vessel 250 to be processed, as shown in FIG. 26, and a second opening 328 that communicates with a vacuum port 33 0 in the container holder 320. In this embodiment, the PECVD process gases can flow into container 250, then through limited opening 294 in process container 324, and can subsequently return through vacuum port 330. Optionally, container 250 is
223
<img file="MX345403B_D0149.tif" />
INDUSTRIAL can evacuate through both openings 294 and i apply the PECVD reagents.
<img file="MX345403B_D0150.tif" />
VB Or, an uncapped syringe barrel 250 may be provided, such as that shown in FIG. 22, with an interior coating of SiOx, where x in this formula is from approximately 1.5 to approximately 2.9, alternatively from approximately 1.5 to approximately 2.6, alternatively approximately 2, or another type of coating by PECVD or barrier introducing the reagents of the source
144 through the opening at the rear end 256 of the cylinder 250 and creating the vacuum with a vacuum source 98 through the opening at the front end 260 of the cylinder. For example, the vacuum source 98 can be connected through a second connector 266 seated at the front end 260 of the syringe barrel 250. Using this facility, reagents can flow through the barrel 250 in a single direction (upward as shown in FIG. 22, although orientation is not critical), and there is no need to transport the reagents through a probe that separates the gas feed from the withdrawn gas in the syringe barrel 250. The front and rear ends 260 and 256 of the syringe barrel Syringe 250 can also be reversed relative to the coating apparatus in an alternative setup. Probe 108 can simply act as a
<img file="MX345403B_D0151.tif" />
<img file="MX345403B_D0152.tif" />
electrode and can be tubular or a rod SW »INDUSTRIAL realization. As before, the spacing between inner surface 254 and probe 108 can be uniform for at least most of the length of syringe barrel 250.
V .B. FIG. 37 is a view similar to FIG. 22 showing another embodiment in which connector 266 is independent and is not coupled to plate electrodes 414 and 416. Connector 266 may have a Luer-type safety connector adapted to be attached to the corresponding connector on syringe barrel 250. This embodiment allows vacuum conduit 418 to pass over electrode 416 while container holder 420 and seated container 250 are moved between electrodes 414 and 416 during a coating step.
V .B. FIG. 38 is a view similar to FIG. 22 showing yet another embodiment in which the front end 260 of the syringe barrel 250 is open and the syringe barrel 250 is closed by a vacuum chamber 422 seated in the container holder 424. In this embodiment the pressures Pl in the syringe barrel 250 and in the vacuum chamber 422 are approximately identical and the vacuum in the vacuum chamber 4 22 is optionally created through the front end 260 of the syringe barrel 250. When the
<img file="MX345403B_D0153.tif" />
225 Process gases flow into the barrel 250 through the front end 260 of the syringe barrel 20. until a stable composition is provided within the syringe barrel 250, at which point the electrode 160 is activated to form the coating. It is contemplated that, because the volume of the vacuum chamber 422 is greater relative to the syringe barrel 250 and because of the location of the counter electrode 426 within the syringe barrel 250, the passage of process gases through the end front 260 will not form significant deposits on the walls of the vacuum chamber 422.
V .B. FIG. 3 9 is a view similar to FIG. 22 showing yet another embodiment in which the rear flange of the syringe barrel 250 is clamped between a container holder 428 and an electrode assembly 430 to which a cylindrical electrode or a pair of plate electrodes indicated 160 and a plate are attached. vacuum source 98. The closed volume generally indicated 432 outside the syringe barrel 250 is relatively small in this embodiment to minimize the pumping required to evacuate the volume 432 and the interior of the syringe barrel 250 to carry out the PECVD process.
V .B. FIG. 4 0 a view similar to FIG. 22 and FIG. 41 is a horizontal projection showing yet another
<img file="MX345403B_D0154.tif" />
<img file="MX345403B_D0155.tif" />
embodiment as an alternative to FIG. 38 in which the ratio of the pressures P1 / P2 is maintained at a desired level by providing a pressure control valve 434.
It is contemplated that P1 may be a lower vacuum, i.e. * 20 higher pressure, than P2 during a PECVD process, so that process waste gases and by-products will pass through the front end 260 of the syringe barrel. 250 and will be expelled. Also, a separate vacuum chamber conduit 436 to serve vacuum chamber 422 allows the use of a separate vacuum pump to empty the larger contained volume 432 more quickly.
V .B. FIG. 41 is a plan view of the embodiment of FIG. 40, which also shows the removed electrode 160 of FIG. 40.
V .C. Method of applying a lubricating coating
V .C. Another embodiment is a method of applying a lubricating coating derived from an organosilicon precursor. A lubricating coating or any similar term is generally defined as a coating that reduces the frictional resistance of the coated surface, relative to the uncoated surface. If the coated object is a syringe (or part of a syringe, for example a syringe barrel) or any other item that generally contains a plunger or movable part in
ΙΜΡΙ «sliding contact with the surface friction resistance has two fundamental aspects: breakout force and sliding force of the plunger.
The plunger sliding force test is a specialized test of the sliding friction coefficient of the plunger within a syringe, representing the fact that the normal force associated with the sliding friction coefficient, as generally measured on a surface flat, it is counteracted by standardizing the fit between the plunger or other sliding element and the tube or other container into which it slides. The parallel force associated with a coefficient of sliding friction as generally measured is comparable to the sliding force of the plunger measured as described in this description. Plunger sliding force can be measured, for example, as indicated in the ISO 7886-1: 1993 test.
The plunger sliding force test can also be adapted to measure other types of frictional resistance, for example, the friction that a plug retains within a tube, through suitable variations in apparatus and procedure. In one embodiment, the plunger can be replaced by a closure and the extraction force to remove or insert the closure can be measured as the
228 IMPI®
MEXICAN INSTITUTE
OF THE PROPERTY OR counterpart of the sliding force of the plunger.
Instead of or in addition to the sliding force of the piston, the breakout force can be measured. Breakout force is the force necessary for a stationary plunger to begin to move within a syringe barrel or the comparable force required to unseat a seated stationary seal and begin to move it. The breakout force is measured by applying a force to the plunger starting at zero or low and increasing until the plunger begins to move. Breakout force tends to increase with storage of a syringe, after the pre-filled syringe plunger has driven the lubricant interposed or adhered to the barrel due to breakdown of the lubricant between the plunger and the barrel. Breakout force is the force required to overcome stickiness, an industry term used for the adhesion between the plunger and cylinder, which needs to be overcome to start the plunger and start moving.
V .C. One utility of coating a container in whole or in part with a lubricating coating, such as selectively on surfaces that are in sliding contact with other parts, is to facilitate the insertion or removal of a plug or the passage of an element. slide such as a piston in a syringe or a plug in a sampling tube. The container may be made of glass or a polymeric material, such as polyethylene terephthalate (PET), a cycloolefinic copolymer (COC), an olefin such as polypropylene, or other materials. The application of a lubricating coating by PECVD can avoid or reduce the need to coat the wall or the closure of the container with a sprayed, dipped or otherwise applied organosilicon or other lubricant that is commonly applied in a much greater quantity than is I would deposit with a PECVD process.
V .C. In any of the above VC embodiments, a plasma, optionally a non-hollow cathode plasma, may be formed, optionally close to the substrate.
V .C. In any of the VC embodiments, the precursor can optionally be provided in the substantial absence of oxygen. VC In any of the VC embodiments, the precursor may optionally be provided in the substantial absence of carrier gas. VC In any of the VC embodiments, in which the precursor may optionally be provided in the substantial absence of nitrogen. VC In any of the VC embodiments, where the precursor may optionally be provided at less than 1 Torr absolute pressure.
<sup>230 </sup>, Mexican jNJTiTyro
V .C. In any of the realizations% ^^ gg'i<sup>i</sup>g. Precursor may optionally be provided close to plasma emission.
V .C. In any of the VC embodiments, the coating can optionally be applied to the substrate with a thickness of 1 to 5000 nm, or 10 to 1000 nm, or 10-200 nm or 20 to 100 nm in thickness. The thickness of this and other coatings can be measured, for example, by transmission electron microscopy (TEM).
V .C. TEM can be carried out, for example, in the following way. Samples can be prepared for Focused Ion Beam Cross Section (FIB) in two ways. Samples can be coated first with a thin layer of carbon (50-100nm thick) and then coated with an electronically deposited layer of platinum (50-100nm thick) using an Emitech K575X coating system or, samples can be coated directly with the electronically deposited Pt protective layer. Coated specimens can be placed in an FEI FIB200 FIB system. An additional layer of platinum can be deposited on FIB by injecting an organometallic gas while sweeping the 30kV gallium ion beam over the area of interest. The area of interest for each sample can be chosen to be a
<img file="MX345403B_D0156.tif" />
<sup>231</sup> IMPI. . , .. ,,,,,,,. INSTITUTO MITIGAN; i location mid-length of cylinder of ί erin ^ SAPdonaSife<sup>3</sup> J □ industrial thin cross sections measuring --—, - - approximately 15 pm (micrometers) long, 2 pm wide and 15 pm deep from the die surface using an in situ FIB extraction technique. . Cross sections can be attached to a 200 mesh copper TEM grating using FIB deposited platinum. One or two windows in each section, measuring ~ 8 pm wide, can be made thinner to electron transparency using the FIB FEI gallium ion beam.
VC Cross-sectional image analysis of prepared samples can be performed using a transmission electron microscope (TEM), or a transmission scanning electron microscope (STEM), or both. All imaging data can be recorded digitally. For STEM imaging, the grid with the thinnest metal foils can be transferred to a specialized Hitachi HD2300 STEM. Transmitted scanning electron images can be acquired at suitable amplifications in atomic number contrast (ZC) and transmitted electron (TE) mode. The following instrument settings can be used.
<img file="MX345403B_D0157.tif" />
<img file="MX345403B_D0158.tif" />
MEXICAN INSTITUTE
- □ x --------- -------- rsr .. -. ^ Al.ru. INDUSTRIAL
Scanning electron microscope for ___________ Instrument ____________________ transmission _________________________________
Manufacturer / Model ___________________________ Hitachi HD2300_________________ '~ _________2
Acceleration voltage 200kV
Lens aperture ______________________ # 2___________________________________________
1.672 Condenser Lens 1 Adjustment
Condenser Lens 2 Adjustment _______ 1,747 __________________________________________
Approximate Objective Lens Adjustment 586___________________________________________
I, projector entity in ZC mode 1,149
Projector head in TE_____________0 7____________________________________________ mode
Image acquisition _________________________________________________________________
Resolution in pixels 1280x960
Acquisition time 20 s (x4)
VC For TEM analysis, sample grids can be transferred to a Hitachi HF2000 transmission electron microscope. The transmitted electronic images can be acquired at appropriate magnifications.
The relevant instrument settings used during image acquisition may be as provided below.
<td>Instrument</td><td>Electronic microscope transmission</td><td>from</td>
<td>Manufacturer / Model</td><td>Hitachi HF2000</td><td></td>
<td>Acceleration voltage</td><td>200 kV</td><td></td>
<td>Condenser lens 1</td><td> 0.78</td><td></td>
<td>Condenser lens 2</td><td> 0</td><td></td>
<td>Objective lens</td><td> 6.34</td><td></td>
<td>Condenser lens aperture</td><td> #1</td><td></td>
<td>Objective lens aperture for imaging</td><td> #3</td><td></td>
<td>Opening of the selective area for SAD</td><td>N / C</td><td></td>
IMPI
VC In any of the embodiments®> ™ Ty * ^ c ^ {g 'eíDUSTllAL substrate may comprise glass or a polymer, for example, a polycarbonate polymer, an olefinic polymer, a cycloolefinic copolymer, a polypropylene polymer, a polymer of polyester, a polyethylene terephthalate polymer, or a combination of two or more of these.
<img file="MX345403B_D0159.tif" />
VC In any of the VC embodiments, PECVD can optionally be performed by activating the gaseous reagent containing the precursor with electrodes fed at a frequency of RE as defined above, for example, a frequency of 10 kHz to less than 3 00 MHz, plus preferably 1 to 50 MHz, even more preferably 10 to 15 MHz, even more preferably at a frequency of 13.56 MHz.
VC In any of the VC embodiments, plasma can be generated by activating the gaseous reagent comprising the precursor with electrodes supplied with sufficient electrical power to form a lubricating coating. Optionally, the plasma is generated by activating the gaseous reagent containing the precursor with electrodes supplied with an electrical power of 0.1 to 25 W, preferably 1 to 22 W, more preferably 3 to 17 W, even more preferably 5 to 14 W , even more preferably 7 to 11 W, in particular 8 W. The ratio between the power of
<img file="MX345403B_D0160.tif" />
2. 3. 4 plasma can from 5 W / mL to
W / mL to 0.1 to 0.2 W / mL. These levels of to apply coatings to the electrodes and the volume W / mL, preferably is preferably 4, preferably 2 W / mL power, lubricants are suitable for syringes, sampling tubes and containers of similar geometry with a vacuum volume of 1 to 3 mL in which plasma is generated by PECVD. It is contemplated that for larger or smaller objects, the applied power should therefore be increased or decreased to suit the process to the size of the substrate.
V .C. A contemplated product may optionally be a syringe having a barrel treated by the method of one or more of any of the VC embodiments.
VD Coatings applied as a liquid
VD. Another example of a barrier or other suitable coating type usable in conjunction with coatings applied by PECVD or other PECVD treatment, such as those described herein, can be a liquid barrier, a lubricant, surface energy adaptation or another type of coating 90 applied to the inside surface of a container directly or with one or more interposing coatings applied by PECVD of SiwOxCyHz, SiOx, a lubricating coating, or both.
<sup>235</sup>
VD Liquid or other types of coatings 90 can also optionally be applied aULi for example, applying a liquid monomer or other polymerizable or curable material to the interior surface of container 80 and curing, polymerizing or crosslinking the liquid monomer to form a solid polymer. A liquid barrier or other suitable coatings 90 may also be provided by applying a polymer dispersed in a solvent to surface 88 and removing the solvent.
VD Any of the above methods may include as a step the formation of a liner 90 on the interior 88 of a container 8 or through the container port 92 at a processing station or device 28. One example is applying a liquid coating, eg, a curable polymeric, prepolymer or monomeric dispersion, to the interior surface 88 of a container 80 and curing it to form a film that physically isolates the contents of the container 80 from its interior surface 88. Prior art describes polymeric coating technology as suitable for coating plastic blood collection tubes. For example, acrylic and polyvinylidene chloride (PVdC) coating materials can optionally be used and the methods of
236
<img file="MX345403B_D0161.tif" />
coatings described in United States Patent 6,165,566, which is incorporated herein by reference.
V .D. Any of the above methods may also include as a step the formation of a coating on the outer outer wall of a container 80. The coating may optionally be a barrier coating, optionally an oxygen barrier coating, or optionally a barrier coating. against the water. An example of a suitable coating is polyvinylidene chloride, which functions as a barrier against water and a barrier against oxygen. Optionally, the barrier coating can be applied as an aqueous coating. The coating can optionally be applied by dipping the container into it, spraying it onto the container or other resources. A container having an exterior barrier coating as described above is also contemplated.
SAW . INSPECTION OF THE CONTAINER
SAW. A station or device shown in FIG. 1 is the processing station or device 30 that may be configured to inspect the interior surface of a container 80 for defects, for example, by measuring air pressure loss, mass flow rate, or volumetric flow rate at through the
<img file="MX345403B_D0162.tif" />
237 wall of a container, or the
WiTiwiTa m «ican <»
For example, the degassing of a pSíéíi container. Device 30 can operate from tOHna'Slmilerr to device 26, except that it may require the container to perform better (less leakage or permeation under given process conditions) to pass the inspection of device 30, since in the Illustrated embodiment station or device 28 has applied a barrier or other coating prior to arriving at station or device 30. In one embodiment, this inspection of the coated container 80 can be compared to the inspection of the same container 80 at the device or station 26. Less leakage or less permeation at the station or device 30 indicates that the barrier coating works at least to some degree measure.
SAW. The identity of a container 80 measured at two different stations or by two different devices can be established by assigning individual identifying characteristics, such as a barcode, other markings, or a marker or radio frequency identifier (RFID) device, to each of the container supports 38-68 and match the identity of the containers measured at two or more different points on the continuous conveyor shown in FIG. 1. Because canister holders can be reused, they can be registered to a
238 computer database or other structure of a
<img file="MX345403B_D0163.tif" />
of data when they arrive at the position of the holder of containers 40 of FIG. 1, just after a new container 80 has been seated in the container holder and has been removed from the data logger during or near the end of the process, for example, upon reaching or after reaching the position of the container holder 66 in FIG. 1 and the processed container 80 is removed by the transfer mechanism 74.
V I. Processing station or device 32 may be configured to inspect a container, eg, a barrier or other type of coating applied to the container, for defects. In the illustrated embodiment, station or device 32 determines the coating's optical source transmission as a measure of coating thickness. The barrier or other type of coating, if properly applied, can make the container 80 more transparent, even if additional material has been applied, as it provides a more uniform surface.
V I. Other measurements of coating thickness are also contemplated, such as using interference measurements to determine the difference in distance traveled between an energy wave bouncing inside the container liner 154) and an energy wave bouncing off the interior surface 88 of container 80 (interconnecting with the exterior of liner 90). It is known that the difference in distance traveled can be determined directly, as for example, by measuring the arrival time of the respective waves with high precision, or indirectly, as for example, by determining which wavelengths of the incident energy are reinforced or canceled in relation to the test conditions.
V I. Another measurement technique that can be used to verify the integrity of the coating is an ellipsometric measurement on the device. In this case, a polarized laser beam can be projected from the inside or outside of the container 80. In the case of a laser beam projected from inside, the laser beam can be pointed orthogonally to the surface and subsequently can be measure the transmitted or reflected beam. The change in beam polarity can be measured. Since a coating or treatment on the surface of the device will have an effect on (change) the polarization of the laser beam, changes in polarity may be the desired result. Changes in polarity are a direct result of the existence of a
240 «ÍSTOUTO MEXICANO coating or treatment on the surface and the magnitude of the changes is related to the amount of treatment or coating.
V I. If the polarized beam is projected from the outside of the device, a detector can be positioned inside to measure the transmitted component of the beam (and the polarity determined as before). Alternatively, a detector can be placed outside the device in a position that may correspond to the point of reflection of the beam from the treatment / coating interface (inside the device). Changes in polarity can be determined as indicated above.
V I. In addition to measuring optical properties and / or leak rates as described above, other probes and / or devices can be inserted into the device and measurements can be made with a detector apparatus. This apparatus is not limited by technique or method of measurement. Other test methods that employ mechanical, electrical, or magnetic properties, or any other physical, optical, or chemical properties may be used.
V I. During assembly for plasma treatment, an optical detection system can optionally be used to record the plasma emission spectrum (wavelength and intensity profile), which corresponds to the unique
241 chemical signature of the plasma environment.
<img file="MX345403B_D0164.tif" />
characteristic emission applied and treated. The confirm that the coating has been system also offers a measure of the precision in real time and a tool for the archiving of data for each part processed.
V I. Any of the above methods may include as a step inspecting the interior surface 88 of a container 80 for defects at a processing station such as 24, 26, 30, 32, or 34. Inspection can be carried out, such as at stations 24, 32 and 34, by inserting a sensing probe 172 into container 80 through container port 92 and detecting the condition of the interior surface of container 88 or a barrier or another type of coating 90 using probe 172. Inspection can be carried out, as shown in FIG. 11, radiating energy inward through the wall of the container 86 and the interior surface of the container 88, and sensing the energy with the probe 172. Or the inspection can be carried out by reflecting the radiation from the interior surface of the container 88 and sensing the energy with a detector located within the container 80. 0 Inspection can be accomplished by detecting the condition of the interior surface of the container 88 at many closely spaced positions on the interior surface of the container.
242 container.
V I. Any of the above methods may include conducting the inspection step at a sufficient number of locations across the entire interior surface of the container 88 to determine whether the barrier or other type of liner 90 effectively prevents pressure within The container, when initially emptied and its wall exposed to the ambient atmosphere, increases to more than 20% ambient atmospheric pressure over a one-year service life.
V I. Any of the above methods may include carrying out the inspection step in a period of less than or equal to 30 seconds per container, or less than or equal to 25 seconds per container, or less than or equal to 20 seconds per container, or less than or equal to 15 seconds per container, or less than or equal to 10 seconds per container, or less than or equal to 5 seconds per container, or less than or equal to 4 seconds per container, or less than or equal to 3 seconds per. container, or less than or equal to 2 seconds per container, or less than or equal to 1 second per container. This can be achieved, for example, by measuring the effectiveness of the barrier or other type of coated container wall, as shown in FIG. 7, which may involve a measurement for the entire container 8 0, or by inspecting many or even all inspection plinths in parallel, such as using a load-coupled dispense such as detector 172 shown or replaceable in FIGS. 6, 10 and 11. The last stage can be used to detect the condition of the barrier or other type of coating at numerous closely spaced positions on the interior surface of container 88 in a very short total time.
V I. In any embodiment of the method, inspection of the container at multiple points can be further expedited, if desired, by collecting data with a load-coupled device 172, transporting the container 80 just inspected and processing the data. collected shortly thereafter, while container 80 advances through the processing line. If it is later determined by data processing that there is a defect in the container 80, the defective container 80 may be removed from the line at a point after the detection station such as 34 (FIG. 10).
V I. In any of the above embodiments, the inspection step can be carried out at a sufficient number of locations throughout the interior surface 88 of the container 80 to determine whether the barrier or other type of coating 90 effectively prevents the initial vacuum level (i.e., initial pressure drop vs. ambient) in vessel 80, when '^ SJV & ^^ fjA<sup>1</sup>^ initially and its wall 86 is exposed to ambierrtd-L atmosphere ^ decrease more than 20%, optionally more than 15%, optionally more than 10%, optionally more than 5%, optionally more than 2%, during a shelf life of at least 12 months or at least 18 months or at least two years.
V I. The initial vacuum level can be a high vacuum, that is, a remaining pressure of less than 10 Torr, or a lower vacuum such as less than 20 Torr of positive pressure (that is, excess pressure over at full vacuum) or less than 50 Torr or less than 100 Torr or less than 15 0 Torr or less than 200 Torr or less than 250 Torr or less than 30 0 Torr or less than 3 50 Torr or less than 380 Torr pressure positive. The initial vacuum level of vacuum blood collection tubes, for example, is determined in many cases by the type of test for which the tube is used, and therefore the type and appropriate amount of a reagent to be used. it is added to the tube when it is manufactured. The initial vacuum level is usually set to draw the correct volume of blood to be combined with the reagent load in the tube.
V I. In any of the above embodiments, the inspection step of the barrier or other type of coating 90 can be carried out in a number
245 Enough of positions on the entire surface iciq ^ - ^^^ iwoc
INDUSTRIAL CONFIDENCE vessel 88 to determine whether barrier or other coating 90 effectively prevents the pressure within vessel 80, when initially emptied and its wall exposed to ambient atmosphere, from increasing to more than 15% or more than 10% of ambient atmospheric pressure during a useful life of at least one year.
V IA Container processing including precoat and postcoat inspection
V IA Still another embodiment is a container processing method for processing a molded plastic container having an opening and a wall defining an interior surface. The method is carried out by inspecting the interior surface of the container as it is being molded or just prior to coating for defects; applying a coating to the interior surface of the container after inspecting the container as it is molded; and inspecting the coating for defects.
V IA Another embodiment is a container processing method in which a barrier coating is applied to the container after inspecting the container as it is molded and the interior surface of the container is inspected for defects after
246 apply a barrier coating.
IMPI iNruiSTnixt.
<img file="MX345403B_D0165.tif" />
V IA In one embodiment, the station or device 26
<img file="MX345403B_D0166.tif" />
(which can also function as the station or device for applying a coating) can be used in the following way to inspect a container barometrically. With one or both valves 136 and 148 open, container 80 can be emptied to a desired degree, optionally at a very low pressure such as less than 10 Torr, optionally less than 1 Torr. Any of the valves 13 6 and 14 8 that are initially open can be subsequently closed, isolating the vacuum interior 154 of the container 80 and the pressure gauge 152 from ambient conditions and the source of vacuum 98. The pressure change over a measurement time, either due to gas ingress through the vessel wall or degassing of the wall material and / or a coating on the vessel wall, can be sensed and used to Calculate the ambient gas inlet rate into the container 80 mounted on the container holder 44. For the purposes herein, degassing is defined as the release of adsorbed or entrapped gases or water vapor from the wall of the container, optionally in at least partial vacuum.
V IA Another optional modification may be to provide the ambient gas at a pressure greater than the
247
INSTITUTE MSXtCANO atmospheric pressure. This again can increase gas transfer through a barrier or other layer t-ip, which provides a measurable difference in less time than if a lower ambient pressure had been provided. Alternatively, gas may be introduced into container 80 at a pressure higher than atmospheric pressure, which causes the transfer rate through wall 86 to increase again.
V IA Optionally, the inspection of the container at the station or by means of the device 26 can be modified by providing an inspection gas, such as helium, on a side anterior to the substrate, inside or outside the container 80, and detecting it on the side later. A low molecular weight gas, such as hydrogen, or a less expensive or more available gas, such as oxygen or nitrogen, can also be used as the inspection gas.
V IA Helium is viewed as an inspection gas that can increase the rate of leak detection 'or permeation, as it will pass through an imperfect barrier or other type of coating, or pass through a leaking seal, much more quickly than usual ambient gases such as nitrogen and oxygen in ordinary air. Helium has a high transfer rate through many solid substrates or small gaps
ΙΝΓΠΤΙΓΓΟ MEXICANO DÉ LA MONEDAD because: (1) it is inert, so it is not adsorbedW'áb<sup>TO THE</sup>po?<sup>M </sup>the substrate to a great extent, (2) does not ionize Γ á C TI ¡RUI ft'é, 'thus<sup>1 </sup>that molecules are very compact due to the high level of attraction between their electrons and nucleus, and (3) has a molecular weight of 4, as opposed to nitrogen (molecular weight 28) and oxygen (molecular weight 32), again making the molecules are more compact and easily pass through a porous substrate or separation. Due to these factors, helium will pass through a barrier with a given permeability much more quickly than many other gases. Furthermore, the atmosphere contains an extremely small proportion of helium naturally, so the presence of additional helium can be relatively easy to detect, particularly if helium is introduced into container 80 and detected outside of container 80 to measure the leakage and permeation. Helium can be detected by a pressure drop before the substrate or by other means, such as a spectroscopic analysis of the gas after it has passed through the substrate.
V IA Below is an example of barometric inspection of the container determining the oxygen concentration from the detection of fluorescence in the presence of 02.
V IA An excitation source is used (Ocean
249
<img file="MX345403B_D0167.tif" />
Optics USB-LS-450 Pulsed Blue LED), a mount (Ocean Optics QBIF6000-VIS-NIR), an eepertrometer (USB4000-FL fluorescence spectrometer), an oxygen detector probe (Ocean Optics FOXY-R) and a power supply vacuum through an adapter (such as VFT-1000-VIS-275) connected to a vacuum source. A vacuum can be applied to remove ambient air and when the container is at a defined pressure, the oxygen content that has leaked or penetrated to fill the container with ambient air can be determined using the detection system. A coated tube replaces the uncoated tube and the 02 concentration can be measured. The coated tube will exhibit a reproducibly different atmospheric oxygen content than the uncoated sample due to the absorption of the differential 02 surface on the coated tube (a SiOx surface versus an uncoated glass or PET surface) and / or the change in diffusion rate of 02 from the surface. The detection time can be less than one second.
V IA These barometric methods should not be considered to be limited to a specific perceived gas (detection with helium or other gases may be considered) or a specific apparatus or arrangement.
V IA The station or processing device 34
250
INSTITUTO MEXICANO can also be configured to inspect uFf ^ is ^ 'S'Éer or other type of coating in search of def .................-— In the embodiment of FIGS . one and 10, the processing station or device 34 may be another optical inspection, this time designed to separately scan or measure the properties of at least a portion of the barrier or other type of coating 90, or substantially the entire barrier or other type. liner 90, in numerous closely spaced positions on the barrier or other liner 90. The many closely spaced positions may be spaced, for example, about 1 micron, or about 2 microns, or about 3 microns, or about 4 microns, or about 5 microns, or about 6 microns or about 7 microns, in either each case or on average at least part of the surface, in this way some or all small portions of the barrier or other type of coating 90 are measured separately. In one embodiment, a separate scan of each small area of the liner may be useful to detect individual perforations or other defects and to distinguish local effects of defects that are perforations from more general defects, such as a large area with a coating that is too fine or porous.
V IA Inspection of the station or device 34
251 can be carried out by inserting a source of
IMPI
<img file="MX345403B_D0168.tif" />
light 170 or any other suitable source of radio frequency microwave, infrared, visible light, ultraviolet, X-ray or electron beam, for example, into container 80 through the container port 92 and sensing the condition of the interior surface of the container, for example, barrier coating 90, detecting transmitted radiation from the radiation source using a detector.
V IA The above vessel support system can also be used to evaluate the device. For example, probe 108 of FIG. 2, which has a gas supply port 110, can be replaced by a light source 170 (FIG. 10). The light source 170 can irradiate into the tube and subsequent tests can be completed outside the tube, measuring transmission or other properties. Light source 170 may extend into the tube in the same way that probe 108 is pushed into disk or container holder 62, although a vacuum or seals are not necessarily required. Light source 170 can be a fiber optic source, a laser, a point source (such as an LED), or any other source of radiation. The source can radiate at one or more frequencies from deep UV (100nm) to far infrared
IMPI (100 microns)
INSTITUTO MEXICANO all intermediate frequenciesVw ™ Stó>
<img file="MX345403B_D0169.tif" />
limitation with respect to the source that can VI.A. As a specific example, refer to FIG. 10.
In FIG. 10, the tube or container 80 is placed on the disk or container holder 62 and a light source 17 0 is inserted at the end of the probe 108 in the tube. Light source 170 in this case may be a blue LED source of sufficient intensity to be received by detector 172 surrounding the exterior of container 80. The light source 17 0 can be, for example, a three-dimensional charge coupled device (CCD) comprising a set of pixels, such as 174, on its inner surface 176. The pixels, such as 174 , receive and sense the illumination radiated through the barrier or other coating 90 and the wall of the container 86. In this embodiment, detector 172 has a larger internal diameter relative to container 80 than the gap between electrode 164 and container 80 of FIG. 2 and has a cylindrical upper portion adjacent to the closed end 84 rather than a hemispherical upper portion. The outer detector 172 may have a smaller radial clearance from the container 80 and a more uniformly dimensioned clearance in its upper portion adjacent the closed end 84. This can be achieved, for example, by providing a common center of curvature for
IMPI ^ the closed end 84 and the top of the ΙφΖ when the container 80 is seated. This variation can provide a more uniform inspection of the curved closed end 84 of the container 80, although any variation is contemplated as suitable.
V IA Before turning on the light source, it is measured with the CCD and the resulting value is stored as a background (which can be subtracted from subsequent measurements). The light source 170 is then turned on and measurements are made with the CCD. The resulting measurements can then be used to compute the total light transmission (and compare it to an uncoated tube to determine the average coating thickness) and the defect density (by taking photon counts on each element of the CCD and comparing them to a threshold value. - if the photon count is lower, then this corresponds to not enough light being transmitted). Low light transmission is likely the result of missing or too thin a coating - a defect in the tube coating. By measuring the number of adjacent elements that have a low photon count, the size of the defects can be estimated. By adding the size and number of defects, the quality of the tube can be determined or other properties can be determined that may be specific to the
254
IMPI ^ Mexican institute f¡¿ Ot LA PROMWAD Q «frequency of light source radiation 170. industrial
V IA In the embodiment of FIG. 10, sa ·· «puode. Energy is added outward through the interior surface of the container, such as through liner 90 and container wall 86, and can be detected with a detector 172 located on the exterior of the container. Various types of detectors 172 can be used.
V IA Since incident radiation from source 170 transmitted through barrier or other cladding 90 and vessel wall 80 may be greater for a lower angle of incidence (compared to a normal reference line relative to the vessel wall). container 80 at a given point), pixels, such as 174, that lie in a normal line through the wall of container 86 will receive more radiation than nearby pixels, although more than one pixel can receive part of the light that passes through a given portion of the. barrier or other type of coating, and light that passes through more than a given portion of the barrier or other type of coating 90 and the wall of container 80 will be received by a particular pixel such as 174.
V IA The degree of resolution of pixels, such as 174, to detect radiation that passes through a particular portion of the barrier or other type of coating
255 iWrQfiéuade Ut LA MOPltDAil INDUSTRIAL and the vessel wall 86 can be increased
CCD so that its set of pixels, such as 174, is very close to and conforms to the contour of the container wall 86. The degree of resolution can also be increased by selecting an essentially point or smaller light source, as shown in the diagram of FIG. 6, to illuminate the interior of the container 80. Using smaller pixels will also improve the resolution of the set of pixels on the CCD.
V IA In Figure 6, a point light source 132 (laser or LED) is positioned at the end of a rod or probe. (Point source refers to the light emanating from a small volume source similar to a mathematical point, which can be generated by a small LED or the diffuser tip of an optical fiber that radiates light in all directions, or the light emanated as a small transverse beam, such as coherent light transmitted by a laser). The point light source 132 can remain stationary or can move, for example, in the axial direction, while the characteristics of the barrier or other coating 90 and the wall of the container 80 are being measured. If it moves, the source of Spot light 132 can be moved up and down within device (tube) 80. Analogously to that described above, the inner surface
IMPI 88 from canister 8 0 can be scanned and can be iS®WTolil®w®r <sup>ccr</sup> OF THE PROPERTY
INDUSTRIAL carried out subsequent measurements with an external detector apparatus 134 to determine the integrity of the coating. An advantage of this method is that a similar linearly polarized or coherent light source with specific directionality can be used.
V IA The position of the point light source 132 can be indexed with respect to pixels, such as 174, so that the illumination of the detectors can be determined at the moment when the detector is at a normal angle to an area particular of liner 90. In the embodiment of FIG. 10, a cylindrical sensor 172, optionally with a curved end that conforms to the curve (if any) of the closed end 84 of a container 80, can be used to detect the characteristics of a cylindrical container 80.
V IA It will be understood, referring to FIG. 10, that the inspection station or device 24 or 34 can be modified by reversing the positions of the light or other radiation source 170 and the detector 172 so that the light radiates through the wall of the container 86 from the outside to the interior of container 80. If this resource is selected, in one embodiment a uniform source of incident light or other radiation can be provided by inserting
<img file="MX345403B_D0170.tif" />
257
IMPI the container 80 into an opening 182 through the INDUSTRIAL of a light source for an integrating sphere 186. A light source for an integrating sphere will scatter light or radiation from the source 170 on the outside of the container 80 and into the integrating sphere, so that the light passing through the respective points of the wall 8 6 of the container 80 will be relatively uniform. This will tend to reduce artifact-caused deformations relative to portions of wall 86 having different shapes.
V IA In the embodiment of FIG. 11, it can be shown that the detector 172 closely matches the barrier or other coating 90 or the interior surface 88 of the container 80. Because the detector 172 may be on the same side of the container wall 8 6 as the barrier or other type of coating 80, this proximity will tend to increase the resolution of pixels, such as 174, although in this embodiment the detector 172 will preferably be positioned correctly, relative to the barrier or other type of coating 90, to prevent them from scraping against each other possibly damaging the coating or the CCD equipment. Placing the detector 172 right next to the liner 90 can also reduce the refractive effects of the vessel wall 86, which
<img file="MX345403B_D0171.tif" />
258
INSTITUTO MiXICANO happens in the realization of FIG. 10 after ^ i ^^ r ^ zu other radiation passes through the barrier or other type of ...... - cladding 90, so that the signal to be detected can be differentially refracted depending on the local shape of container 80 and the angle of incidence of light or other radiation.
V IA Other barrier or other types of coating inspection techniques and devices may also be used. For example, fluorescence measurements can be used to characterize the treatment / coating on the device. Using the same apparatus as described in FIG. 10 and 6, a light source 132 or 170 (or other radiation source) can be selected that can interact with the polymeric material of the wall 86 and / or an adulterant in the polymeric material of the wall86.
Coupled with a detection system, it can be used to characterize a range of properties including defects, thicknesses, and other performance factors.
V IA Another inspection example is the use of X-rays to characterize the treatment / coating and / or the polymer itself. In FIGS. 10 or 6, the light source can be replaced with an x-radiation source and the external detector can be of a type that allows measurement of the
259 X-ray intensity. Experimental barrier or other coating can be performed using this technique.
V IA After molding a device 80, as in station 22, a number of possible problems can arise that will render any subsequent treatment or coating imperfect and possibly ineffective. If devices are inspected prior to coating for these problems, the devices can be coated using a highly optimized controlled process, optionally up to 6 sigma, which will ensure a desired result (or results) is obtained.
V IA Some of the possible problems that can interfere with treatment and coating include (depending on the nature of the coated article to be produced):
V IA 1. High density of particulate contamination defects (eg, each greater than 10 microns in its greatest dimension) or a lower density of high particulate contamination (eg, each greater than 10 microns in its greatest dimension). larger dimension).
V IA 2. Chemical or other surface contamination (eg silicone or oil mold release).
V IA 3. High roughness of the surface, characterized
260
IMPI ^
INSTITUTO MEXICANO by a large / high number of peaks and / or valleys abrÚ ^ tf ^^ TRiAi KS <3 can also be characterized by quantifying Ί a_ aspelea mritiff (Ra) which should be less than 100 nm.
T IA 4. Any defect in the device such as a hole that does not allow a vacuum to be created.
V IA 5. Any defects in the surface of the device used to create a seal (for example, the open end of a sample collection tube).
T IA 6. Lack of uniformity in wall thickness that can prevent or modify power coupling through thickness during treatment or coating.
V IA 7. Other defects that will render the barrier or other type of coating ineffective.
V IA To ensure that the treatment / coating operation is successful using the parameters of the treatment / coating operation, the device can be pre-inspected for one or more of the above possible problems or other problems. Previously, an apparatus was described for holding a device (a disk or container holder such as 3868) and moving it through a production process, including various tests. and a treatment / coating operation. Several can be implemented
261
<img file="MX345403B_D0172.tif" />
appropriate surface for treatment / rc; veatimi nntn
These include:
V IA 1. Optical inspection, eg transmission of radiation through the device, reflection of radiation from inside the device or from the outside, absorption of radiation by the device, or interference with radiation exerted by the device.
V IA 2. Digital inspection - for example, using a digital camera that can measure specific lengths and geometries (for example, how round, or otherwise how uniform or correct the shape of the open end of a collection tube is of samples with respect to a referent).
V IA 3. Check for vacuum leaks or pressure tests.
V IA 4. Sonic (ultrasonic) testing of the device.
V IA 5. X-ray analysis.
V IA 6. The electrical conductivity of the device (the material of the plastic tube and SiOx have different electrical resistance - of the order of 1020 Ohm-cm for quartz as the majority material and of the order of 1014 Ohm-cm for polyethylene terephthalate, for example).
VI .A.
262
The thermal conductivity of the
IMPI iNsrrrvro Mexican,. OF THE DlSpOSMMBlinAO PMfUDAD
<img file="MX345403B_D0173.tif" />
For example, the thermal conductivity of quartz — gomo matear-ia ··! majority is approximately 1.3 W- ° K / m, while the thermal conductivity of polyethylene terephthalate is 0.24 W- ° K / m).
V IA 8. Vessel wall degassing, which can optionally be measured as described below by post-coating inspection to determine degassing baseline.
V IA The above tests can be carried out at a station 24 as shown in FIG. 6. In this figure the device (eg, a sample collection tube) can be held in place and a light source (or other source) 132 can be inserted into the device and a suitable detector 134 is placed in the outside of the device to measure the proper result.
V IA If vacuum leaks are detected, the device and container holder can be attached to a vacuum pump and a measuring device can be inserted into the tube. The tests can also be performed as indicated elsewhere in the description.
V IA Processing station or device 24 may be a visual inspection station and may be configured to inspect one or more of the following:
inner surface 88
263 from a container,
<img file="MX345403B_D0174.tif" />
exterior 118 or interior wall 86 of til! 1 ρ 1SΠΈ'5 between its surfaces 88 and 118 for defects. Inspection of the outer surface 118, the inner surface 88, or the wall of the container 86 can be carried out from the outside of the container 80, particularly if the container is transparent or translucent for the type of radiation and wavelengths used in the inspection. Inspection of interior surface 88 can be facilitated, if desired, by providing a fiber optic probe inserted into container 80 through container port 92 so that a view of the interior of container 80 can be obtained from outside the container. 80. For example, an endoscope or baroscope can be used in this environment.
V IA Another resource illustrated in FIG. 6 may be to insert a light source 132 into a container 80. Light transmitted through the wall of the container 86 and artifacts of the container 80 revealed by the light can be detected from outside the container 80, such as using a detector measurement apparatus 134. This station or device 24 can be used, for example, to detect and correct or remove misaligned vessels 80 that are not properly seated in the port.
264
<img file="MX345403B_D0175.tif" />
distortion, impurity or other visible defect on <sup>1</sup> ίο · —Wall flGT Visual inspection of container 80 can also be performed by a worker examining container 80, instead of or in addition to mechanical inspection.
V IA Processing station or device 26, shown in more detail in FIG. 7, may optionally be configured to inspect the interior surface 88 of the container 80 for defects and, for example, to measure the loss of gas pressure through the wall of the container 86, which can be done prior to providing a barrier or other type of coating. This test can be carried out by creating a pressure difference between the two sides of the barrier liner 90, such as by pressurizing or creating a vacuum within the container 80; insulating the interior 154 of the container 80 so that the pressure remains constant without leakage around the seal or gas permeation through the wall of the container; and measuring the pressure change per unit time that builds up from these problems. This measurement will not only reveal any gas leaking through the vessel wall 86, but will also detect a leaking seal between the mouth 82 of the vessel and the O-ring or other seal 100, which may indicate a <sup>265</sup> IMPIAS
MEXICAN INSTITUTE
M LA rtOjñgpAD. problem with canister alignment 8 0 or with IttMTWicimi. seal 100. In either case, the undue aseTTPddu Je £ uimi »tube can be corrected or removed from the processing line, which saves time when trying to achieve or maintain an adequate vacuum level during processing and avoids dilution of process gases due to air entering through a defective seal.
V IA The above systems can be integrated into a multi-stage manufacturing and inspection method.
V IA FIG. 1, as described above, shows a schematic structure of the steps of a possible method (although this invention is not limited to a single concept or method). First, container 80 is visually inspected at the station or with device 24, which may include the dimensional measurement of container 80. If defects are detected, the device or container 80 is rejected and the disk or container holder, such as 38, is inspected for defects, recycled, or removed.
V IA The leakage rate or other characteristics of the mounting of a container holder 38 and the seated container 80, for example, at station 26, are then evaluated and stored for comparison after coating. He
266 disc or container support 38 moves
<img file="MX345403B_D0176.tif" />
for example, up to the coating stage 28 EJ device or container 8 0 is coated with SiOx or other barrier or other type of coating with a frequency for the power supply of, for example, 13.56 MHz. Once coated, the container holder is re-examined for its leak rate or other characteristics (this may be carried out as a second test at test station 26 or a duplicate station or similar, such as 30 - use of a duplicate station can increase system production)
V IA Measurement after coating can be compared to measurement without coating. If the relationship between these values exceeds a preset necessary level, indicating acceptable overall coating performance, the container holder and device move. Next is an optical test station 32, for example, with a blue light source and an external integrating sphere detector to measure the total light transmitted through the tube. The value may be required to exceed a preset limit at which the device is rejected or recycled for additional coating. Then (for non-rejected devices), a second optical test station 34 can be used.
267 IMPI ^
INSTm / TO MUtCANO
DELA PROP1WAD 'C **
In this case, a light source can be inserted into the tube or container 80 and propelled into illtíld. ' slowly while taking measurements with an out-of-tube tubular CCD detector array. The data is subsequently analyzed on a computer to determine the density distribution of the defects. Based on the measurements, the device is approved for final packaging or rejected.
V IA Optionally, the above data can be recorded and graphically represented (eg electronically) using statistical process control techniques to ensure quality up to 6 sigma.
V IB inspection of container detecting outgassing of container wall through barrier layer
V IB Another embodiment is a method of inspecting a barrier or other type of layer on a material that degasses a vapor, which has several stages. A sample of material is provided that degasses a gas and has at least a partial barrier layer. Optionally, a differential pressure may be provided across the barrier layer, such that at least part of the material being degassed is on the high pressure side of the barrier layer. In another option, gas can be allowed <sup>268</sup> IMPIí
INSTITUTO MIXICANO degassed to diffuse without providing a difér ^^^ under pressure. The degassed gas is measured. If a differential pressure across the barrier layer, degassing can be measured on the higher pressure or lower pressure side of the barrier layer.
V IB In addition, the effectiveness of the inner coating (previously applied) can be measured by measuring the diffusion rate of a specific species or materials adsorbed on the device wall (before coating). Compared to uncoated (untreated) pipe, this type of measurement can provide a direct measure of the barrier or other properties of the coating or treatment, or the presence or absence of the coating or treatment. The coating or treatment detected, instead of or in addition to being a barrier layer, can be a lubricating layer, a hydrophobic layer, a decorative coating or other types of layers that modify the degassing of the substrate, either increasing it or decreasing it.
V IB As a specific example, using the container holder of FIG. 2 and referring again to FIG. 7, a device or container 80 can be inserted into the disk or container holder 44 (the test can also be carried out on a seated container 80 carried in
269 IMPI®
MEXICAN INSTITUTE V ^ *<sup>8 </sup>OF RILOFlITY L% s
INDUSTRIAL a disk or container holder, such as 44, that is moved from another operation such as coating / treatment). Once the vessel holder is moved into the barrier test area, the measurement tube or probe 108 can be inserted inside (similarly to the gas tube for lining, even though the measurement tube it does not need to spread as far into the tube). Both valves 136 and 148 can be opened and the inside of the tube can be emptied (a vacuum is created).
V IB Once the desired measurement pressure is reached, valves 13 6 and 14 8 can be closed and gauge 152 can begin to measure pressure. By measuring the time it takes to reach a particular pressure (greater than the initial pressure) or by measuring the pressure reached after a period of time, you can measure the rate of increase (or rate of leakage) of the tube, the container support , the pump channel and all other parts that are connected to the inner volume but isolated by valve 1 and valve 2. If this value is subsequently compared to a bare tube, the ratio of the two measurements (the value of the coated tube divided by the value of the bare tube) can provide a measure of the rate of leakage through the coated surface of the tube. . This measurement technique may require minimizing the interior volume of the container support, the
270 pump channel
<img file="MX345403B_D0177.tif" />
other parts connected to the inner volume but cyclable by · valves 1 and 2 (except the tube / device) to minimize the impact of gas permeation or degassing of these surfaces.
V IB In this invention distinctions are made between permeation, leakage and surface diffusion or outgassing.
Permeation, as used herein in reference to a container, is the advancement of a material through a wall 346 or other obstruction, such as from the outside of the container to the inside or vice versa along path 350 in the FIG. 29 or the inverse of that trajectory.
Degassing refers to the movement of an absorbed or adsorbed material, such as gaseous molecule 354 or 357 or 359, outward from wall 346 or cladding 348 in FIG. 29, for example, through liner 348 (if present) and into container 358 (right in FIG. 29). Degassing can also refer to the movement of a material, such as 354 or 357, out of wall 34 6, to the left as shown in FIG. 29, therefore, toward the outside of container 357 as illustrated.
271
Degassing can also refer to
<img file="MX345403B_D0178.tif" />
of material adsorbed from the surface of an example article, the gaseous molecule 355 from the exposed surface of the barrier coating 90.
Leakage refers to the movement of a material around the obstruction represented by wall 346 and liner 348 rather than through or out of the surface of the obstruction, such as passing between a closure and the wall of a container closed with a closure.
V IB Permeation is indicative of the rate of gas movement through a gap / defect free material and does not refer to leakage or outgassing. Referring to FIG. 29, showing a wall of a container or other substrate 346 having a barrier coating 348, the permeation consists of a gas completely passing through the substrate 346 and the coating 348 along the path 350 through both layers. Permeation is considered a thermodynamic process and therefore relatively slow.
V IB Permeation measurements are very slow, since the permeating gas must pass completely through an unfractured wall of the plastic article. In the case of vacuum blood collection tubes, a measure of the permeation of
272 gas through your wall as an indication
<img file="MX345403B_D0179.tif" />
propensity of the vessel to lose vacuum over time, but it is usually an extremely slow measure, usually requiring a test duration of six days, therefore not fast enough to allow in-line liner inspection. Such tests are typically used for offline testing of a sample of vessels.
VI.B. Permeation tests are also not a very sensitive measure of the barrier effectiveness of a thin coating on a thick substrate. Since all gas flow is through the coating and the substrate, variations in the flow through the thick substrate will introduce a variation that is not due to the effectiveness of the coating barrier per se.
VI.B. The inventors found a much faster and potentially more sensitive way to measure the barrier properties of a coating - by measuring the outgassing of rapidly separated air or other gaseous or volatile constituents from the vessel wall through the coating. The gaseous or volatile constituents can be any material that is actually degassed or they can be selected from one or more specific materials to be detected. The
273 constituents may include, but are not limited to,
<img file="MX345403B_D0180.tif" />
nitrogen, air, carbon dioxide water vapor, he.
Volatile organic materials such as alcohols, ketones, hydrocarbons, coating precursors, substrate components, by-products of coating preparation such as volatile organosilicon, by-products of coating substrate preparation, other constituents that are present or are introduced through the substrate, or mixtures or combinations of any of these.
Surface diffusion and degassing are synonymous. Each term refers to a fluid initially adsorbed or absorbed on the wall 34 6, such as the wall of a container, and that is introduced into the adjacent space by the action of a motive force, such as creating a vacuum (creating the movement of air indicated by arrow 352 in FIG. 29) within a container having a wall to propel fluid out of the wall into the container. Degassing or diffusion is considered a relatively fast, kinetic process. It is contemplated that, for a new wall 346 with considerable resistance to permeation along path 3 50, outgassing rapidly displaces molecules, such as 354, that are closer to interface 356 between wall 346 and the barrier layer 348. This differential degassing is
274 suggested by the large number
<img file="MX345403B_D0181.tif" />
such as 354, which are close to interface 356 which are shown as degassing and by the large number of molecules, such as 358, which are further away from interface 356 and not shown as degassing.
V IB Therefore, another method of inspecting a barrier layer on a material that degasses a vapor is contemplated, which includes several steps. A sample of material is provided that degasses a gas and has at least a partial barrier layer. A differential pressure is provided throughout the barrier layer such that at least some of the material to be degassed is initially on the high pressure side of the barrier layer. The degassed gas carried to the lower pressure side of the barrier layer is measured during a test to determine whether the barrier is present or its effectiveness as a barrier.
V IB In this method, the material that degasses a gas can include a polymeric compound, a thermoplastic compound, or one or more compounds that have both properties. The material that degasses a gas can include polyester, for example, polyethylene terephthalate. The material that degasses a gas can include a polyolefin, for two examples polypropylene, a copolymer
275 IΜ ΡIS
KXICANO INSTITUTE
OF THE PRONBTY O »cycloolefinic or a combination of these. The matef'í'ST '<sup>TO THE</sup>that degasses a gas can be composed of different abé írtácer'iáléé, at least one of which degasses a vapor. An example is a polypropylene and polyethylene terephthalate bilayer framework. Another example is a bilayer structure of cycloolefinic copolymer and polyethylene terephthalate. These materials and composites are examples; Any suitable material or combination of materials can be used.
V IB Optionally, the material that degasses a gas is provided in the form of a container having a wall with an external surface and an internal surface, the internal surface containing a cavity. In this embodiment, the barrier layer is optionally disposed on the wall of the container, optionally on the inner surface of the wall of the container. The barrier layer could also be arranged on the outer surface of the container wall. Optionally, the material that degasses a gas can be provided in the form of a film.
V IB The barrier layer can be a total or partial coating of any of the barrier layers described herein. The barrier layer may have a thickness less than 500 nm, or less than 300 nm, or less than 100
276 nm, or less than 80 nm, or less than 60 nm, or mend ^^ Mf<sub>?</sub>© ANnn ^ industrial less than 40 nm, or less than 30 nm, or less than 20 nm, or less than 10 nm, or less than 5 nm.
V IB In the case of a coated wall, the inventors have discovered that diffusion / degassing can be used to determine the integrity of the coating. Optionally, a differential pressure may be provided in the barrier layer creating the vacuum at least partially in the cavity or interior space of the container. This can be done, for example, by connecting the cavity via conduit to a vacuum source to create the vacuum in the cavity at least partially. For example, an uncoated PET wall 34 6 of a container that has been exposed to ambient air will outgas a number of oxygen and other gas molecules, such as 354, from its interior surface for some time after creating the vacuum. If the same PET wall is lined on the inside with a 34 8 barrier coating, the barrier coating will stop, retard or reduce this outgassing. This applies, for example, to a SiOx 348 barrier coating, which outgasses less than a plastic surface. By measuring this degassing differential between coated and uncoated PET walls, the barrier effect of the 348 coating for degassed material can
277 be determined quickly.
<img file="MX345403B_D0182.tif" />
V IB If the barrier coating 348 is imperfect, due to holes, cracks, gaps or areas of insufficient thickness, density or composition, known or theoretical, the PET wall will preferentially outgas through its imperfections, thus increasing the total amount of degassing. The main source of gas collected is from dissolved gas or vaporizable components on the (subs) surface of the plastic article next to the liner, not from outside the article. The amount of outgassing beyond the baseline level (for example, the amount that passes or is released by a standard coating without blemishes or the least achievable degree of blemish or a medium or acceptable degree of blemish) can be measured in various ways to determine the integrity of the coating.
V IB The measurement can be carried out, for example, by providing a degassing measurement cell that communicates with the cavity and the vacuum source.
V IB The measurement cell can implement any of several different measurement technologies. An example of a suitable measurement technology is microflow technology. For example, the mass flow rate of the degassed material can be measured. The measurement can be carried out in a molecular flow mode of operation.
The measurement is a determination of the volume of gas degassed through the barrier layer per time interval.
V IB Gas degassed on the lower pressure side of the barrier layer can be measured under effective conditions to distinguish the presence or absence of the barrier layer. Optionally, the effective conditions to distinguish the presence or absence of the barrier layer include a test duration of less than one minute or less than 50 seconds or less than 40 seconds or less than 30 seconds or less than 20 seconds or less than 15 seconds. seconds or less than 10 seconds or less than 8 seconds or less than 6 seconds or less than 4 seconds or less than 3 seconds or less than 2 seconds or less than 1 second. '
V IB Optionally, the measurement of the presence or absence of the barrier layer can be confirmed to at least a 6 sigma level of certainty within any previously identified time interval.
V IB Optionally, the degassed gas on the lower pressure side of the barrier layer is measured under effective conditions to determine the barrier enhancement factor (BIF) of the barrier layer, compared to the same material without a barrier layer. The BIF can be determined,<sup>279</sup> IMPI ^
INSTITUTO MEXICANO for example, providing two groups of packaging ^ SS ^^ R ^ iaq ^ applying a barrier layer to a g-mp <-> pnvaspñ:
evaluating a barrier property (such as degassing rate in micrograms per minute or other suitable measure) in packages that have a barrier; performing the same test with containers that lack a barrier; and establishing a relationship between the properties of materials that have a barrier and those that do not. For example, if the degassing rate through the barrier is one third of the degassing rate without a barrier, the barrier has a BIF of 3.
V IB Optionally, the degassing of a plurality of different gases can be measured, in cases where more than one type of gas is present, such as nitrogen and oxygen in the case of degassed air. Optionally, the degassing of all or virtually all degassed gases can be measured. Optionally, the degassing of virtually all degassed gases can be measured simultaneously, for example, using a physical measure such as the combined mass flow rate of all gases.
V IB Measurement of the numerical or partial pressure of individual gas species (such as oxygen or helium) degassed from the sample can be performed more rapidly. Baru »t i./vrnyriEizmj than barometric tests, but airspeed tests it is reduced to the point where only one traction * ef degassing is of the measured species. For example, if nitrogen and oxygen are degassed from the PET wall in a ratio of approximately 4: 1 from the atmosphere, but only oxygen degassing is measured, the duration of the test would need to be five times that of an equally sensitive test (in terms of the number of molecules detected to obtain results of sufficient statistical quality) that measures all the degassed species from the wall of the vessel.
V IB For a given level of sensitivity, it is contemplated that a method that takes into account the volume of all species degassed from the surface will provide the desired level of confidence more rapidly than a test that measures degassing of a specific species such as atoms. of oxygen. Therefore, degassing data can be generated which has practical utility for online measurements. Such in-line measurements can optionally be carried out in each manufactured container, in this way the number of idiosyncratic or isolated defects is reduced and these are potentially eliminated (at least at the time of measurement).
V IB In a practical measure, a factor that changes the <sup>281</sup> IMPIí
.. ,,. ,,. ,. . ,, - INSTITUTO MEXICANO 1 apparent amount of degassing is the leak that ppaBapu ^ gr an imperfect seal, such as the seal of the container seated in a vacuum receptacle as the vacuum is created in the degassing test. Leakage refers to a fluid that is diverted from a solid wall of the article, for example, a fluid that passes between a blood tube and its closure, between a syringe plunger and a syringe barrel, between a container and its cap, or between a mouth of a container and a seal on which the mouth of the container sits (due to an imperfect or improperly seated seal). The word leak generally indicates gas / gas movement through an opening in the plastic article.
V IB Leakage and (if necessary in a given situation) permeation can be included in the basic level of degassing, so that an acceptable test result ensures that the canister is properly seated in the vacuum receptacle (hence , its seated surfaces are intact and properly formed and positioned), the wall of the container does not support an acceptable level of permeation (therefore, the container wall is intact and properly formed) and the coating has sufficient barrier integrity.
V IB Degassing can be measured in several ways, by barometric measurement (measuring the change in pressure within the vessel over a period of time dadR5<sup>r</sup>^^ á ^ SSS ^ INDUSTRIAL the initial vacuum was created) or by measuring the partial pressure or flow rate of degassed gas from the sample. Equipment is available that measures the mass flow rate in a molecular flow mode of operation. An example of such equipment that is available from commercial suppliers and employs microflow technology is available from ATC, Inc., Indianapolis, IN. Please refer to US Patent Nos. 5861546, 6308556, 6584828, and EP1356260, which are incorporated herein by reference, for a more detailed description of this known equipment. Also refer to Example 8 of this description, which shows an example of a degassing measurement to differentiate coated polyethylene terephthalate (PET) tubes from uncoated tubes quickly and accurately.
V IB For a container made of polyethylene terephthalate (PET), the microflow rate is very different for the SiOx coated surface compared to the uncoated surface. For example, in Practical Example 8 of this description, the microflow rate for PET was greater than or equal to 8 micrograms after a test lasting 30 seconds, as shown in FIG. 31. This rate for uncoated PET was much higher than the measured rate for SiOx coated PET, which was less than
283
IMPIá 6 micrograms after a test with an ME ^ Df the HORIETY or
INDUSTRIAL seconds, again as shown in FIG. 31.
V IB One possible explanation for this difference in flow rate is that uncoated PET contains approximately 0.7 percent equilibrium moisture; This high moisture content is believed to be responsible for the observed high microflow rate. With a SiOx coated PET plastic, the SiOx coating can have a higher level of surface moisture than an uncoated PET surface. Under the test conditions, however, the barrier coating is believed to prevent further desorption of moisture from the majority PET plastic, resulting in a lower microflow rate. Also z the oxygen or nitrogen microflow rates of uncoated PET plastic versus SiOx coated PET are expected to be distinguishable.
V IB Modifications to the above test may be appropriate for a PET tube when other materials are used. For example, polyolefin plastics tend to have low moisture content. An example of a low moisture content polyolefin is TOPAS® cycloolefin copolymer (COC), with an equilibrium moisture content (0.01 percent) and a much lower moisture permeation rate than for PET. In the case of COC, the
284 Uncoated COC plastic can microflow similar to, or even less than, plastic.COG ^ “” ““ · 'coated with SiOx. This is most likely due to the higher surface moisture content of the SiOx coating and the lower equilibrium bulk moisture content and lower permeation rate of an uncoated COC plastic surface. This makes the differentiation of uncoated and coated COC articles more difficult.
The present invention shows that exposure of the surfaces to be tested of COC articles to moisture (coated and uncoated) results in improved and consistent microflow separation between SiOx coated and uncoated COC plastics. This is shown in Example 19 in this description and in FIG. 57. Exposure to humidity can simply be exposure to relative humidity between 35% and 100%, in a room with controlled relative humidity, or direct exposure to a source of hot (humidifier) or cold (vaporizer) humidity. ), preferring the latter.
V IB Although the validity and scope of the invention are not limited in accordance with the veracity of this theory, it appears that adulteration or addition of moisture to uncoated COC plastic increases its moisture and other content.
285
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Degasable with respect to the surface of di INDUSTRIAL noniPAO with saturated SiOx. This can also be achieved by exposing the coated and uncoated tubes to other gases including oxygen, nitrogen or their mixtures, eg air.
V IB Therefore, before measuring the degassed gas, the barrier layer can be contacted with water, eg water vapor. Water vapor can be provided, for example, by contacting the barrier layer with air having a relative humidity of 35% to 100%, alternatively 40% to 100%, alternatively 40% to 50%. Instead of or in addition to water, the barrier layer can be contacted with oxygen, nitrogen or a mixture of oxygen and nitrogen, for example, ambient air. The contact time can be from 10 seconds to an hour, alternatively from one minute to thirty minutes, alternatively from 5 minutes to 25 minutes, alternatively from 10 minutes to 20 minutes.
Alternatively, the wall 346 to be degassed can be adulterated or supplemented on the side opposite the barrier layer 348, for example, by exposing the left side of the wall 346 as shown in FIG. 11 to a material that will adsorb on wall 346 and subsequently degas to the right or left as shown in FIG. 29. Adulterate a wall or other material, such as
286 ΐΜΡ „η
346, on the left by adsorption, measuring posCSSISSíMfenSle 'the degassing of the adulterated material on the right (or vice versa), differs from the permeation measurement in that the adulterated material is part of the wall 346 at the time it is measured degassing, as opposed to a material that travels the full path 350 through the wall at the time gas passing through the cladding is measured. Adsorption can occur over an extended period of time, as one embodiment before coating 348 is applied and as another embodiment after coating 348 is applied and prior to examining it for outgassing.
V IB Another potential method to increase the separation of the microflow response between uncoated and SiOx-coated plastics is to modify the measurement pressure and / or temperature. Increasing the pressure or decreasing the temperature when measuring outgassing can result in a higher relative binding of water molecules in SiOx-coated COC than in uncoated COC. In this way, the degassed gas can be measured at a pressure of 0.1 Torr to 100 Torr, alternatively 0.2 Torr to 50 Torr, alternatively 0.5 Torr to 40 Torr, alternatively 1 Torr to 3 0 Torr, alternatively 5 Torr to 100 Torr, alternatively 10 Torr to 80 Torr, alternatively 15 Torr
<img file="MX345403B_D0184.tif" />
at 50 Torr. The gas temperature from 0 ° C to ° C, as an alternative to
V IB Another contemplated way to measure outgassing, in any embodiment of the present invention, is to employ a micrometer measurement technique. It is contemplated that such a technique allows smaller mass differences in degassing to be measured, potentially on the order of 10-12 g (picograms) to 10-15 g. (femtograms). This smaller mass detection enables the differentiation of coated versus uncoated surfaces as well as different coatings in less than a second, optionally less than 0.1 s, optionally in a matter of microseconds.
V IB Micro Corbel sensors (MCL) in some cases may respond to the presence of a degassed or otherwise provided material by bending or otherwise moving or changing shape due to absorption of molecules. Micro Corbel (MCL) sensors in some instances can respond by changing their resonance frequency. In some cases, the MCL sensors can change in these two ways or in another way. They can operate in different environments such as a gaseous, liquid or vacuum environment. In gases, the micro-bracket sensors can
288 operate as an artificial nose, with which
<img file="MX345403B_D0185.tif" />
. ---- INDUSTRIAL curvature of a microfabricated array of eight polymer-coated silicon brackets is characteristic of different solvent vapors, flavors and beverages. The use of any other type of electronic nose, operated by means of any technology, is also contemplated.
Various electronic MCL designs, including piezoresistive, piezoelectric, and capacitive methods, have been applied and are contemplated to measure movement, shape change, or frequency change of MCLs after exposure to chemicals.
V IB A specific example of a degassing measurement can be carried out as follows. At least one micro bracket is provided which has the property, when in the presence of a degassed material, of moving or changing shape. The micro bracket is exposed to the degassed material under conditions effective to cause the micro bracket to move or change shape. Then the movement or the different shape is detected.
V IB As an example, movement or the different shape can be detected by reflecting an incident energy beam from a portion of the micro-corbel that moves or changes shape, before and after exposing the micro-corbel to
<img file="MX345403B_D0186.tif" />
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degassing, and measuring the deflection reW $ ^ ggg> * cd INDUSTRIAL beam reflected at a point separate from the bracket. The shape is optionally measured at a point separate from the bracket because the amount of beam deflection under given conditions is proportional to the distance from the measurement point to the beam reflection point.
V IB Several suitable examples of an incident energy beam are a photon beam, an electron beam, or a combination of two or more of these. Alternatively, two or more different beams may be reflected from the MCL along different incident and / or reflected paths, to determine movement or change of shape from more than one perspective. One type of incident energy beam specifically contemplated is a coherent photon beam, such as a laser beam. Photons, as described in this description, are inclusive defined to include wave energy as well as photon or particle energy per se.
V IB An alternative example of measurement benefits from the property of certain MCLs of change in resonant frequency when an ambient material is encountered in an effective amount to achieve a change in resonant frequency. This type of measurement can be carried out in the following way. At least one micrometer is provided that resonates at a
290
MEXICAN INSTITUTE
OF THE PROPERTY different frequency when in the presence of a degassed iffá'f ^ ÍPiar '. The micro-corbel can be exposed to maternal degassing under conditions effective to cause the micro-corbel to resonate at a different frequency. The different resonant frequency is then detected by any suitable means.
V IB As an example, the different resonant frequency can be detected by inputting energy into the micrometer to induce it to resonate before and after exposing the micrometer to degassing. The differences between the resonant frequencies of the MCL are determined before and after exposure to degassing. Alternatively, instead of determining the resonant frequency difference, an MCL can be provided that is known to have a resonant frequency when in the presence of a sufficient concentration or amount of a degassed material. The different resonant frequency or the resonant frequency that signals the presence of a sufficient amount of the degassed material is detected using a harmonic vibration sensor.
As an example of the use of MCL technology to measure outgassing, an MCL device can be incorporated into a quartz vacuum tube connected to a container and a vacuum pump. A harmonic vibration sensor can be constructed that
291 uses a piezoresistive bracket
<img file="MX345403B_D0188.tif" />
acquire from commercial suppliers, bridge circuits of
Wheatstone, a positive feedback controller, an excitatory piezo actuator, and a phase locked loop (PLL) demodulator. See, for example,
Hayato Soné, Yoshinori Fujinuma and Sumió Hosaka Picogram Mass Sensor Using Resonance Frequency Shift of Cantilever, Jpn. J. Appl. Phys. 43 (2004) 3648;
Hayato Soné, Ayumi Ikeuchi, Takashi Izumil, Haruki Okano2 and Sumió Hosaka Femtogram Mass Biosensor Using SelfSensing Cantilever for Allergy Check, Jpn. J. Appl. Phys. 43 (2006) 2301).
To prepare the MCL for detection, one side of the micrometer can be coated with gelatin. See, for example, Hans Peter Lang, Christoph Gerber, STM and AFM Studies on (Bio) molecular Systems: Unraveling the Nanoworld, Topics in Current Chemistry, Volume 285/2008. The water vapor that is desorbed from the surface of the vacuum coated container binds with the gelatin, which causes the bracket to bend and its resonant frequency to change, as measured by a laser deflection of a surface of the bracket. It is contemplated that the change in mass of a coated versus an uncoated container should be resolved within fractions of a second and should be highly reproducible. The
292 iMPIt articles mentioned above in relatedM ^ tlfe ^^ n ^ corbel technology are incorporated herein by reference due to their specific MCL descriptions and equipment setups that can be used to detect and quantify degassed species.
Alternative coatings to MCL for moisture detection (phosphoric acid) or oxygen detection may be applied in place of or in addition to the gelatin coating described above.
SAW. B. It is also contemplated that any of the degassing test setups contemplated herein may be combined with a SiOx coating station. In such an arrangement, the measurement cell 362 could be as illustrated above, using the main vacuum channel for PECVD as the bypass 386. In one embodiment, the measurement cell, generally indicated 3 62, of FIG. 30, can be incorporated into a container support, such as 50, where the diverter channel 386 is configured as the main vacuum line 94 and the measurement cell 362 is a side channel.
VI.B. This combination of the measurement cell 362 with the vessel holder 50 would optionally allow the degassing measurement to be carried out without breaking the vacuum used for PECVD. Optionally, the vacuum pump
293 for PECVD, it would be operated for a period d preferably standardized to pump part or all of the residual reactive gases remaining after
<img file="MX345403B_D0189.tif" />
coating stage (an evacuation of less than one Torr, with an additional option of admitting a small amount of air, nitrogen, oxygen or other gas to purge or dilute process gases prior to evacuation). This would activate the combined processes of coating the container and testing the coating to detect the presence and level of the barrier.
SAW. B. Those skilled in the art will also appreciate, after reviewing this description, that the degassing measurements and all of the other barrier measurement techniques described can also be used for many different purposes or in addition to determining efficacy. of a barrier layer. In one example, the test can be used on coated or uncoated vessels to determine the degree of outgassing of the vessel walls. This test can also be used, for example, in cases where an uncoated polymer is required to outgas less than a specified amount.
SAW. B. For another example, these degassing measurements and all other gassing techniques can be used.
294 £ PI iwtttvto MEXICAN DE LA FtOHEDAD measure of the barrier described in films of <sup>IN</sup>BS? 'Rera coated or uncoated, as an esLd'Ll'ta test or as an online test to measure variations in the outgassing of a film as it passes through the measuring cell. The test can be used to determine the continuity or barrier effectiveness of other types of coatings, such as aluminum coatings, or EVOH barrier coatings or layers of packaging films.
SAW . B. These degassing measurements and all of the other barrier measurement techniques described can be used to determine the effectiveness of a barrier layer applied on the side of a container wall, film, or the like opposite the measurement cell, such as as a barrier layer applied to the exterior of a container wall and in which outgassing into the container wall is investigated. In this instance, the flow differential would be for permeation through the barrier coating, followed by permeation through the film or wall of the substrate. This measure would be particularly useful in cases where the substrate film or wall is quite permeable such as a very thin or porous film or wall.
SAW. B. These degassing measurements and all
295 other measurement techniques used to determine
<img file="MX345403B_D0190.tif" />
the effectiveness of a barrier layer that is an inner layer of a container wall, film or the like. In this case, the measuring cell would detect any outgassing through the layer adjacent to the measuring cell plus the outgassing, through the barrier layer, of the layer or layers more remote from the measuring cell than the layer of barrier.
VI.B. These outgas measurements and all other barrier measurement techniques described can be used to determine the percent coverage of a barrier material pattern on a material that is outgassed, for example by determining the degree of outgassing of the partially coated material. with the barrier as a proportion of the amount of degassing expected if there were no barrier present anywhere in the material.
VI.B. One test technique that can be used to increase the speed of degassing tests of a container, which can be used with any conduct of a degassing test in the description, is to reduce the empty volume of the container, for example, by inserting a plunger or closure on the container to reduce the empty volume of the portion of the container evaluated.
<img file="MX345403B_D0191.tif" />
empty given, of
296
Reducing the void volume allows the vessel to quickly build to a level thereby decreasing the test interval.
VI.B. Many other applications for the degassing measurements described herein and all other barrier measurement techniques described will become apparent to those skilled in the art after examining this disclosure.
VII. PECVD TREATED VESSELS
VII. The containers are contemplated to have a barrier coating 90 (shown, for example, in FIG. 2), which can be a SiOx coating applied with a thickness of at least 2 nm, or at least 4 nm, or at least 7 nm, or at least 10 nm, or at least 20 nm, or at least 30 nm, or at least 40 nm, or at least 50 nm, or at least 100 nm, or at least 150 nm, or at least 200 nm, or at least 30 0 nm, or at least 4 00 nm, or at least 500 nm, o at least 600 nm, or at least 700 nm, or at least 800 nm, or at least 900 nm The coating can have a thickness up to 1000 nm or at most 900 nm or at most 800 nm or at most 700 nm or at the most
600 nm or at most 500 nm or at most 400 nm or at most 300 nm or at most 200 nm or at most 100 nm or at most 90nm or at most 8 0 nm or at most 7 0 nm or at most 60 nm or at most 50 nm or at most 40 nm or at most 30 nm or at most 20 nm or at most 10 nm or at most 5 nm. Specific thickness ranges are expressly acknowledged as for any of the minimum thicknesses expressed above plus any thickness greater than or equal to the maximum thicknesses expressed above.
The thickness of the SiOx or other coating can be measured, for example, by transmission electron microscopy (TEM) and its composition can be measured by X-ray photoelectron spectroscopy (XPS).
VII. It is contemplated that the choice of the material whose permeation in the coating is to be avoided and the nature of the SiOx coating applied may affect its effectiveness as a barrier. For example, two examples of a material that permeation is commonly intended to avoid are oxygen and water / steam. Materials are usually a better barrier for one than the other. This is believed to be so, at least in part, because oxygen is transmitted through the coating by a different mechanism than water.
VII. Oxygen transmission is affected by physical characteristics of the coating, such as thickness, the presence of cracks, or other physical details of the coating. On the other hand, it is believed that water transmission is usually affected by chemical factors, that is
298 that is, by the material of which more than by physical factors.
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that at least one of these factors has a considerable concentration of OH residues in the coating, which leads to a higher rate of transmission of water through the barrier. A SiOx coating often contains OH moieties and therefore a physically solid coating containing a high proportion of OH moieties constitutes a better barrier for oxygen than for water. A physically solid carbon-based barrier, such as amorphous carbon or diamond-like carbon (DLC), commonly constitutes a better barrier to water than a SiOx coating since the carbon-based barrier generally has a higher concentration. low of OH residues.
VII. However, other factors make a SiOx coating preferred, such as its effectiveness as an oxygen barrier and its strong chemical similarity to glass and quartz. Glass and quartz (when used as the base material of a container) are two materials that have long been known to present a very high barrier against the transmission of oxygen and water, and are also substantially inert to many materials that they are usually placed in containers. Thus, it is often desirable to optimize barrier properties.
299
<img file="MX345403B_D0194.tif" />
against water, such as the water vapor transmission rate (WVTR) of a SiOx coating, rather than choosing a different or additional type of coating to act as a barrier against water transmission.
VII. Several contemplated ways to improve the WVTR of a SiOx coating are described below.
VII. The ratio between the concentration of organic residues (carbon and hydrogen compounds) and that of OH residues in the deposited coating can be increased. This can be achieved, for example, by increasing the proportion of oxygen in the feed gases (for example, by increasing the oxygen feed rate or by decreasing the feed rate of one or more of the other constituents). The reduced incidence of OH residues is believed to result from increasing the degree of reaction of the oxygen feed with the hydrogen in the silicone source to produce a more volatile water in the PECVD exhaust and a lower concentration of trapped OH residues. or incorporated into the cladding.
VII. More energy can be applied in the PECVD process, either by increasing the plasma generation energy level or by applying the energy for a longer period or both. An increase in applied energy should
300
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be done with care when using for isTnw ^ gjf ^ gr industrial tube or other plastic device, as it also tends to distort the treated container to the extent that the tube absorbs the plasma generating energy. This is why RF energy is preferred in the context of the present application. Distortion of medical devices can be reduced or eliminated by employing the energy in series of two or more pulses separated by a cooling time, cooling the containers while applying energy, applying the coating in less time (usually making it thinner), selecting a frequency of applied coating that is minimally absorbed by the base material selected to be coated and / or applying more than one coating, allowing time to elapse between the respective energy application stages. For example, high energy pulses can be used with a duty cycle of 1 millisecond on, 99 millisecond off, while continuing to feed the process gas. Subsequently, the process gas acts as a refrigerant, as it continues to flow between the pulses. Another alternative is to reconfigure the energy applicator, for example, adding magnets to confine the plasma and increase the effective energy application (the energy actually produced by the incremental coating, as opposed to the energy of
301 heating waste
<img file="MX345403B_D0198.tif" />
unwanted). This resource results in the application of coating-forming energy per total watt-hour of energy applied. See, for example, US Patent 5,904,952.
V II. An oxygen post-treatment can be applied to the coating to remove OH residues from the previously deposited coating. This treatment is also contemplated to remove volatile organosilicon compounds or silicones, or to oxidize the coating to form more SiOx.
V II. Tube with plastic as base material can be preheated.
V il. A different volatile source of silicon, such as hexamethyldisilazane (HMDZ), can be used as part or all of the silicone feed. It is contemplated that changing the feed gas to HMDZ will solve the problem since this compound, as supplied, does not contain oxygen residues. It is contemplated that a source of OH moieties in the coating with source of
HMDSO is the hydrogenation of at least part of the oxygen atoms present in unreacted HMDSO.
V II. A composite coating can be used, such as a coating based on carbon combined with SiOx. This can be carried out, for example, by changing the reaction conditions or by adding substituted or unsubstituted, such as an alkane, alchem alkyne, to the feed gas, as well as an organosilicon-based compound. Refer, for example, to US Patent 5,904,952, which states in a relevant part: For example, the inclusion of a lower hydrocarbon, such as propylene, provides carbon moieties and improves most of the properties of deposited films (except for light transmission) and bond analysis indicates that the nature of the film is silicon dioxide. However, the use of methane, methanol or acetylene produces films that are silicone in nature.
The inclusion of a small amount of nitrogen gas in the gas stream provides traces of nitrogen in the deposited films and increases the deposition rate, improves the optical transmission and reflection properties in glass and varies the refractive index in response to different amounts of N2. The addition of nitrous oxide to the gas stream increases the deposition rate and improves the optical properties, but tends to decrease the hardness of the film.
VII. A diamond-like carbon coating (DLC) can be formed as the main or only coating deposited. This can be done, for example, by changing the reaction conditions or by feeding methane, hydrogen and<sup>303</sup> IMPIAS,. ·, „. _ -. jNj ^ TVTC .MEXICAN helium to a PECVD process. These alimentary OMMwee 'reactions have no oxygen, so OH moieties cannot be formed. In one example a coating of
SiOx inside a syringe tube or barrel and an exterior DLC coating can be applied on the outside surface of a syringe tube or barrel. 0 SiOx and DLC coatings can both be applied as a single layer or multiple layers of a syringe barrel or tube inner liner.
VII. Referring to FIG. 2, the barrier or other type of coating 90 reduces the transmission of atmospheric gases into the container 80 through its interior surface 88. Or the barrier or other type of coating 90 reduces the contact between the contents of the container 80 and the surface. interior 88. The barrier or other type of coating may comprise, for example, SiOx, amorphous carbon (eg, diamond-like), or a combination of these.
VII. Any coating described herein can be used to coat a surface, for example a plastic surface. It can also be used as a barrier layer, eg, as a barrier against a gas or liquid, preferably against water vapor, oxygen and / or air. It can also be used to prevent or reduce
304
I ΜΤΙ mechanical and / or chemical effects that the surface would have on a compound or composition if the surface -— were not coated. For example, it can prevent or reduce precipitation of a compound or composition, for example insulin precipitation or blood clotting or platelet activation.
V II.A. Vacuum blood collection containers
V II.A.1. Tubes
V II.AI Referring to FIG. 2, more details of a container such as 80 are shown. The illustrated container 80 may be generally tubular with an opening 80 at one end of the container and a closed opening 84 opposite it. Container 80 also has a wall 86 that defines an interior surface 88. An example of the container 80 is a medical sample tube, such as a vacuum blood collection tube such as that commonly used by a phlebotomist to draw a sample of a patient's blood by venipuncture for use in a medical laboratory.
V II.AI Container 80 may be made, for example, of thermoplastic material. Some examples of suitable thermoplastic material are polyethylene terephthalate or a polyolefin such as polypropylene or a polycycloolefinic copolymer.
305 . , ¡Nstitvtomexicano
V II.A.1. Container 80 can be manufactured by any suitable method, such as by molding. ίηνρ.ηΗήη, blow molding, mechanical work, fabrication from casing materials or by other suitable means. PECVD can be used to form a SiOx coating on the inner surface.
V il.A.1. If the container 80 is intended to be used as a vacuum blood collection tube, it can desirably be strong enough to withstand substantially a total internal vacuum without substantially deforming when exposed to external pressure of 760 Torr or atmospheric pressure and other conditions of pressure. coating processing. This property can be provided, in a thermoplastic container 80, by providing a container 80 made of suitable materials with suitable dimensions and a glass transition temperature higher than the processing temperature of the coating process, for example, a cylindrical wall 86 that has sufficient thickness for its diameter and material.
V II.A.1. Medical containers or containers, such as' sample collection tubes and syringes, are relatively small and are injection molded with relatively thick walls, which allows a vacuum to be created within without being crushed by atmospheric pressure.
306 environmental. Thus, they are stronger than the<sup>¿</sup> αχευιΓί
INSTITUTO MEXICANO PE LA FROTlíDAI 'INDUSTRIAL soft drinks or other plastic containers that appear thinner or larger. Since sample collection tubes designed for use as vacuum vessels are generally designed to withstand full vacuum during storage, they can be used as vacuum chambers.
V II.Al Such adaptation of the vessels to be their own vacuum chambers could eliminate the need to place the vessels in a vacuum chamber for PECVD treatment which is generally carried out at very low pressure. Using a container as its own vacuum chamber can speed up processing time (since loading and unloading of parts in a separate vacuum chamber is not necessary) and can lead to simpler equipment setups . Also, a vessel holder is contemplated, for certain embodiments, that will hold the device (for alignment with gas tubes and other appliances), seal the device (so that a vacuum can be created by attaching the vessel holder to a gas pump). vacuum) and will move the device between the molding and subsequent processing stages.
V II.Al A container 80 used as a
307 J 1VI PI «NSTHVTC M JUCANC ^« SffiGSÍjF nt the MümuAu vacuum blood collection should be able to give<sup>wn</sup>^ 0 ^ t> ru3b ^ - ^<sup>í</sup>* ^ the external atmospheric pressure, while éT'VcLUlU is created within it to a reduced pressure useful for the intended application, without leakage and without a considerable volume of air or other atmospheric gas penetrating the tube (as without pass through closure) through wall 86 during its useful life. If the newly molded container 80 cannot meet this requirement, it can be processed by coating the interior surface 88 with a barrier or other type of coating 90. It is desirable to treat and / or coat the interior surfaces of these devices (such as collection tubes of samples and syringe barrels) to impart various properties that will offer advantages over existing polymeric devices and / or to mimic existing glass products. It is also desirable to measure various properties of the devices before and / or after treatment or coating.
V II.A.1.a. A deposited coating of an organosilicon precursor made by polymerizing the organosilicon precursor in situ
V II.A.1.a. A process for applying a lubricating layer on a substrate, for example the inside of the barrel of a syringe, is contemplated, comprising applying one of the described precursors on or near a substrate with a
308 1 to 5000 nm thickness, optionally 10 to IrWtF ^ nm, optionally 10-200 nm, optionally 20. to 10U HUI Clc * thickness, and crosslink or polymerize (or both) the coating, optionally in a process with PECVD, to provide a lubricated surface. The coating applied by this process is contemplated to be new.
V II.A.1.a. A SiwOxCyHz coating, where w is 1, x in this formula is about 0.5 to 2.4, and is about 0.6 to about 3, and z is 2 to about 9, preferably where w is 1, x is about 0.5 to 1 , y is about 2 to about 3, and z is 6 to about 9, applied by PECVD, it is also useful as a hydrophobic coating. Coatings of this type are contemplated to be hydrophobic, regardless of whether they function as lubricating layers. A coating or treatment is defined as hydrophobic if it decreases the wettability of a surface, compared to the corresponding uncoated or untreated surface. Thus, hydrophobicity is a function of the green substrate and the treatment.
The degree of hydrophobicity of a coating can be modified by varying its composition, its properties or its method of deposition. For example, a SiOx coating with no or little hydrocarbon content is more hydrophilic
309 than a SiwOxCyHz coating with the
<img file="MX345403B_D0199.tif" />
substituents defined in this description. Generally speaking, the higher the content of the C-Hx moiety (for example, CH, CH2, or CH3) in the coating, either by weight, volume, or molarity, relative to its silicon content, the more hydrophobic is the coating.
A hydrophobic coating can be very thin, with a thickness of at least 4 nm or at least 7 nm or at least 10 nm or at least 20 nm or at least 30 nm or at least 40 nm or at least 50 nm or at least 100 nm or at least 150 nm or at least 200 nm or at least 300 nm or at least 400 nm or at least 500 nm or at least 600 nm or at least 700 nm or at least 8 00 nm or at least 900 nm . The coating may be up to 1000 nm or at most 900 nm or at most 800 nm or at most 700 nm or at most 600 nm or at most 500 nm or at most 400 nm or at most 300 nm or at most 200 nm thick. or at most 100 nm or at most 90 nm or at most 80 nm or at most 70 nm or at most 60 nm or at most 50 nm or at most 40 nm or at most 30 nm or at most 2 0 nm or at most 10 nm or at most 5 nm. Specific thickness ranges composed of any of the minimum thicknesses stated above plus any thickness greater than or equal to the maximum thicknesses stated above are expressly contemplated.
V il.A.1.a. A utility of this type of coating<sup>310</sup> IMPI 63
INSTITUTO MEXICANO Οί, Ι Λ ΗΟΜΕΟΑβ V? —X hydrophobic is to insulate the wall of a thermoplastic tube ^^ íVécncFr, for example, made of polyethylene terephthalate- (PET ·)<sup>1</sup>, say? · 'the blood collected inside the tube. The hydrophobic coating can be applied over a hydrophilic SiOx coating that is on the inner surface of the tube. The SiOx coating increases the barrier properties of the thermoplastic tube and the hydrophobic coating modifies the surface energy of the interface between the blood and the tube wall. The hydrophobic coating can be prepared by providing a precursor selected from those identified in this description. For example, the hydrophobic coating precursor may comprise hexamethyldisiloxane (HMDSO) or octamethylcyclotetrasiloxane (OMCTS).
VII.A.1.a. Another use of the hydrophobic coating is to prepare a glass cell preparation tube. The tube has a wall defining a cavity, a hydrophobic coating on the inner surface of the glass wall, and contains citrate as a reagent. The hydrophobic coating can be prepared by providing a precursor selected from those identified elsewhere in this disclosure. For example, the hydrophobic coating precursor may comprise hexamethyldisiloxane (HMDSO) or octamethylcyclotetrasiloxane (OMCTS). Other material that can be used as<sup>311</sup> IMPI source for INDUSTRIAL coatings
<img file="MX345403B_D0200.tif" />
is an alkyltrimethoxysilane of formula:
R-Si (OCH3) 3 in -which R is a hydrogen atom or an organic substituent, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, vinyl, alkyne, epoxide or others. Combinations of two or more of these are also contemplated.
V II.A.1.a. Combinations of acidic or basic catalysis and heating, using an alkyltrimethoxysilane precursor as described above, can condense the precursor (removing ROH by-products) to form cross-linked polymers, which can optionally be further cross-linked following an alternative method. A specific example is that of Shimojima et. to the. J. Mater. Chem., 2007, 17, 658-663.
V II.A.1.a. A SiwOxCyHz coating can be applied as a backcoat after applying a SiOx barrier coating to the interior surface 88 of the container 80 to provide a lubricating surface, particularly if the surface coating is a liquid Organosiloxane compound at the end of the coating process .
V II.A.1.a. Optionally, after applying the
312 SiwOxCyHz coating, can be cured
INDUSTRIAL after the PECVD process. Radiation curing methods can be used, including those initiated by UV (formation of free radicals or cations), electron beam (E-beam) and thermal as described in Development Of Novel Cycloaliphatic Siloxanes For Thermal And UV-Curable Applications (Ruby Chakraborty Dissertation, 2008).
V II.A.1.a. Another method of providing a lubricating coating is to use a silicone mold release agent when injection molding the thermoplastic container to be lubricated. For example, it is contemplated that any of the release agents and latent monomers that cause the formation of the thermal lubricant coating in situ during the molding process may be used. Or the monomers mentioned above can be adulterated to form traditional mold release agents to achieve the same result.
V II.A.1.a. A lubricating surface is particularly contemplated for the inner surface of a syringe barrel as described in more detail below. A lubricated internal surface of a syringe barrel can reduce the plunger sliding force required to advance a plunger in the barrel during syringe operation, or the breakout force for a plunger
313 begins to move after a preloaded plunger has pushed the interposed lubricant..n adhered ^ · to the cylinder, for example due to breakdown of the lubricant between the plunger and cylinder. As explained elsewhere in this description, a SiwOxCyHz coating can also be applied, where w is 1, x in this formula is from about 0.5 to about 2.4, and is from about 0.6 to about 3, and z is 2 to about 9, on the inside surface 88 of container 80 to improve adhesion of a SiOx backcoat.
V II. A. 1.a. Therefore, the coating 90 may comprise a SiOx layer and a SiwOxCyHz layer, where w is 1, x in this formula is about 0.5 to 2.4, and is about 0.6 to about 3, and z is about 2 to about 9, preferably where w is 1, x is about 0.5 to 1, and is about 2 to about 3, and z is about 6 to about 9. The SiwOxCyHz layer can be deposited between the SiOx layer and the inner surface of the container. Or the SiOx layer can be deposited between the SiwOxCyHz layer and the inner surface of the container. Or three or more alternating or graded layers can also be used between these two coating compositions. The<sup>314</sup> IMPI ^ SiOx layer can be deposited adjacent to '^ SB SiwOxCyHz or at a remote location, with. ^ profir a cnpn · interposed of another material. The SiOx layer can be deposited adjacent to the interior surface of the container. Or the SiwOxCyHz layer can be deposited adjacent to the inside surface of the container.
V II.A.1.a. Another resource contemplated herein, for adjacent layers of SiOx and SiwOxCyHz, is a graduated compound whose composition ranges from SiwOxCyHz, where w is 1, x in this formula is approximately 0.5 to 2.4, and is approximately 0.6 to approximately 3, yz is from 2 to about 9, preferably where w is 1, x is from about 0.5 to 1, and is from about 2 to about 3, and z is from 6 to about 9, at SiOx. A graded composite can be separate layers of SiwOxCyHz and SiOx with a transmission or interface of intermediate composition between them, or separate layers of SiwOxCyHz and SiOx with a different intermediate layer of intermediate composition between them or a single layer that changes continuously or in stages of a SiwOxCyHz composition to a more SiOx-like composition, traversing the coating in a normal direction.
V II.A.1.a. The grade in the graduated compound can go in any direction. For example, the composition of
IMPI
SiwOxCyHz can be applied directly to the industrial can be graduated to obtain a composition further from the SiOx surface. Or the SiOx composition can be applied directly to the substrate and graduated to a composition further away from the SiwOxCyHz surface. A graded coating is particularly contemplated if one coating of one composition adheres to the substrate better than the other, in which case the best adhesion composition can, for example, be applied directly to the substrate. It is contemplated that the more distant portions of the graded coating may be less compatible with the substrate than the adjacent portions of the graded coating, since at any point, the coating gradually changes its properties, such that adjacent portions with almost the same coating depth they have almost identical composition and more physically spaced portions with substantially different depths can have more diverse properties. It is also contemplated that a coating portion that forms a better barrier against material transfer from or to the substrate may be directly bonded to the substrate, to prevent the more remote coating portion that forms a poorer barrier from becoming contaminated with the material. whose contact is intended
<img file="MX345403B_D0201.tif" />
316 obstruct or impede with the barrier.
<img file="MX345403B_D0202.tif" />
MEXICAN INSTITUTE OF INDUSTRIAL TOCHEDAD
<img file="MX345403B_D0203.tif" />
V II.A. 1.a. The coating, instead of being graded, can optionally have abrupt transitions from one layer to the next, without there being a substantial compositional gradient. Such coatings can be prepared, for example, by providing the gases to produce a layer as a constant state flow in a non-plasma state, then activating the system with a brief discharge of plasma to form a coating on the substrate. If a subsequent coating is to be applied, the gases for the previous coating are cleared and the gases for the next coating are applied in a steady state mode before activating the plasma, thereby again forming a distinct layer on the substrate surface. or its outermost anterior lining, with little gradual transition, if any, at the interface.
V II.Alb Citrated blood tube having a wall lined with a deposited hydrophobic layer of an organosilicon precursor
V II.Alb Another embodiment is a cell preparation tube having a wall provided with a hydrophobic coating on its inner surface and containing an aqueous sodium citrate reagent. Hydrophobic coating can also be applied over a coating
317 hydrophilic SiOx on the inner surface
<img file="MX345403B_D0204.tif" />
<img file="MX345403B_D0205.tif" />
The SiOx coating increases the barrier properties of the thermoplastic tube and the hydrophobic coating modifies the surface energy of the contact surface between the blood and the tube wall.
V II.Alb The wall is made of thermoplastic material with an internal surface that defines a cavity.
V II.Alb A blood collection tube according to Embodiment VII.Alb may have a first layer of SiOx on the inner surface of the tube applied as explained in this description to function as an oxygen barrier and extend shelf life. of a vacuum blood collection tube made of thermoplastic material. A second coat of SiwOxCyHz can then be applied, where w is 1, x in this formula is about 0.5 to 2.4, and is about 0.6 to about 3, and z is 2 to about 9, preferably where w is 1 , x is from about 0.5 to 1, and is from about 2 to about 3, and z is from 6 to about 9, on the barrier layer on the inner surface of the tube to provide a hydrophobic surface. The coating effectively reduces platelet activation from blood plasma treated with a sodium citrate additive and <sup>318</sup> LMPW • NSTI ^ flM ^ djANO exposed to internal surface, compared to uncoated wall type. - ----- ~ - trf'JifíTririWr · ai r, τ,
V II.Alb PECVD is used to form a coating on the inner surface with the following structure: SiwOxCyHz. Unlike conventional citrate blood collection tubes, the blood collection tube with a hydrophobic coating of SiwOxCyHz does not require a baked-on silicone coating on the vessel wall, such as is conventionally applied to prepare the surface. of the hydrophobic tube.
V II.Alb Both layers can be applied using the same precursor, eg HMDSO or OMCTS, and different PECVD reaction conditions.
V II.Alb A sodium citrate anticoagulant reagent is then introduced into the tube, emptied and sealed with a closure to produce a tube for vacuum blood collection. Those skilled in the art will be familiar with the components and formulation of the reagent. An effective amount of the aqueous sodium citrate reagent is introduced into the cavity of the tube to inhibit clotting of the blood introduced into the tube.
V II.Alc Double-walled plastic container lined with a SiOx barrier - layers of COC, PET, SiOx <sup>319</sup> £ Μρτ
V II.Alc Another embodiment is a container with a wall at least partially containing i <h ¢). The wall has an inner polymeric layer contained in a
<img file="MX345403B_D0206.tif" />
outer polymeric layer. One of the polymeric layers is a layer at least 0.1 mm thick of a cycloolefinic copolymeric resin (COC) that defines a barrier against water vapor. Another of the polymeric layers is a layer at least 0.1 mm thick of a polyester resin.
V II.Alc The wall includes an oxygen barrier layer of SiOx having a thickness of about 10 to about 500 angstroms.
V II.Alc In one embodiment, illustrated in FIG. 36, the container 80 may be a double-walled container having an inner wall 408 and an outer wall 410, respectively, made of the same or different materials. A particular embodiment of this type can be prepared with one wall molded from a cycloolefinic copolymer (COC) and the other wall molded from a polyester, such as a polyethylene terephthalate (PET), with a SiOx coating as described above on the surface. interior 412. As needed, an adherent coating or layer may be inserted between the inner and outer walls to promote adhesion between them. An advantage of this construction of
<img file="MX345403B_D0207.tif" />
<img file="MX345403B_D0208.tif" />
wall is that walls that have different preparose ^ can combine to form a composite with the respective properties of each wall.
V II.Alc For example, inner wall 408 can be made of PET coated on inner surface 412 with a SiOx barrier layer, and outer wall 410 can be made of COC. SiOx coated PET, as shown elsewhere in this description, is an excellent oxygen barrier, while COC is an excellent water vapor barrier providing a low water vapor transition rate (WVTR ). The composite container can have superior oxygen and water vapor barrier properties. This construction is contemplated, for example, for a medical vacuum specimen collection tube that contains an aqueous reagent, as shipped, and has a substantial shelf life, so it should have a barrier that prevents vapor transfer. of water outward or the transfer of oxygen or other gases inward through its composite wall during its useful life.
V II.Alc For example, the inner wall 408 may be made of COC coated on the inner surface 412 with a barrier layer of SiOx, and the outer wall 410 may be made of PET. This construction is contemplated, for
321 example,
IMPI jKSTrWTO M1XJCANO for a pre-filled syringe containing
<img file="MX345403B_D0209.tif" />
sterile aqueous as shipped. The b¡ will prevent oxygen from entering the syringe through its wall. The inner wall of COC will prevent the ingress or egress of other materials, such as water, thereby preventing water in the sterile aqueous fluid from leaching materials from the wall material into the syringe. The inner wall of COC is also contemplated to prevent water derived from the aqueous sterile fluid from leaking out of the syringe (thereby undesirably concentrating the aqueous sterile fluid) and this will prevent the non-sterile water or other fluids from being out of the syringe will enter through the wall of the syringe and render the contents non-sterile. The inner wall of COC is also contemplated as useful in decreasing the breaking force or friction of the plunger against the inner wall of a syringe.
V II.Ald Method of manufacturing a double-walled plastic container - COC, PET, SiOx layers
V II.Ald Another embodiment is a method of manufacturing a container having a wall with an inner polymeric layer contained in an outer polymeric layer, one layer made of COC and the other of polyester. The container is manufactured by a process that includes introducing layers of COC and polyester resin into an injection mold through
322 of concentric injection nozzles.
IMPI
MEXICAN INSTITUTE
IX THE INDUSTRIAL NOPISOAD
<img file="MX345403B_D0210.tif" />
V II.Ald An optional additional step cenaiate — err applying an amorphous carbon coating to the container by PECVD, as an inner coating, an outer coating or as an intermediate coating located between the two layers.
V II.Ald An optional additional step is to apply a barrier layer of SiOx to the inside of the vessel wall, where SiOx is defined as above. Another optional additional step consists in the post-treatment of the SiOx layer with a process gas consisting essentially of oxygen and essentially free of a volatile silicon compound.
V II.Ald Optionally, the SiOx coating can be formed at least partially from a silazane feed gas.
V II.Ald The container 80 shown in FIG. 36 can be made from the inside out, for example, by injection molding the inner wall into a first mold cavity, subsequently removing the core and molded inner wall from the first mold cavity to a second larger mold cavity, subsequently injection molding the outer wall against the inner wall in the second mold cavity. Optionally,
323 an adherent layer can be provided over
<img file="MX345403B_D0211.tif" />
outside of the molded inner wall prior to overmolding the outer wall onto the adherent layer.
V II.Ald O container 80 shown in FIG. 36 can be done from the outside in, for example, by inserting a first core into the mold cavity, injection molding the outer wall into the mold cavity, subsequently removing the first core from the first molded wall, and inserting a second smaller core. , subsequently injection molding the inner wall against the outer wall still in the mold cavity. Optionally, an adherent layer may be provided on the inner surface of the molded outer wall prior to overmolding the inner wall onto the adherent layer.
V II.Ald O container 80 shown in FIG. 36 can be manufactured in a two-chamber mold. This can be done, for example, by injection molding the material for the inner wall introduced by an inner nozzle and the material for the outer wall introduced by a concentric outer nozzle. Optionally, an adherent layer can be provided through a third concentric nozzle arranged between the inner and outer nozzles. The nozzles can feed the materials of <sup>324</sup> ΙΜΡΙ «
INSTITUTO MEXICANO respective wall simultaneously. A resource<sup>1</sup>* ^^^ start feeding the wall material through the outer nozzle a little before feeding the inner wall material through the inner nozzle. If there is an intermediate concentric nozzle, the flow order can start with the outer nozzle and continue in sequence from the middle nozzle and then from the inner nozzle. 0 the feed start order can start from the inner nozzle and run out in reverse order compared to the preceding description.
V II.Ale Barrier coating made of glass
V II.Ale Another embodiment is a container that includes a container, a barrier liner, and a closure. The container is generally tubular and made of thermoplastic material. The container has a mouth and a cavity joined at least in part by a wall having an internal surface interconnected with the cavity. There is at least one essentially continuous barrier cladding made of glass on the inner surface of the wall. A closure covers the mouth and isolates the container cavity from ambient air.
V II.Ale Container 80 may also be made, for example, of glass of any type used in medical or laboratory applications, such as glass from
325 Calcium soda, borosilicate glass or other forms here <S8fiS industrial X glass. Other containers, of any shape or size, made of any material, are also contemplated for use in the system 20. One function of the coating on a glass container may be to reduce the ingress of ions into the glass, intentionally or as impurities, for example sodium, calcium or others, from the glass to the contents of the container, such as a reagent or blood in a vacuum blood collection tube. Another function of coating a glass container in whole or in part, such as selectively on surfaces that are in sliding contact with other parts, is to provide lubricity to the coating, for example, to facilitate insertion or removal of a plug or a passage of a sliding element such as a piston in a syringe. Another reason for lining a glass container is to prevent a reagent or a mixture intended to be introduced into the container, such as blood, from sticking to the container wall or causing an increase in the coagulation rate of the blood in contact with the container wall.
V II.Alei A related embodiment is a container as described in the previous paragraph, in which the barrier coating is made of soda glass
326 calcium, borosilicate glass or other type of vine
<img file="MX345403B_D0212.tif" />
V II.A.2. Plugs
V II.A.2. FIGS. 23-25 illustrate a container 268, which may be a vacuum blood collection tube, having a closure 270 to isolate cavity 274 from the environment. The closure 270 comprises an inwardly facing surface 272 exposed to the cavity 274 of the container 268 and a wall contacting surface 276 that is in contact with the inner surface 278 of the container wall 280. In the illustrated embodiment the closure 270 is an assembly of a plug 282 and a shield 284.
V II.A.2.a. Method of applying a lubricant coating on a plug in a vacuum chamber
V II.A.2.a. Another embodiment is a method of applying a coating over an elastomeric plug such as 282. The plug 282, separated from the container 268, is placed in a chamber that is substantially under vacuum. A reaction mixture is provided that includes plasma-forming gas, ie, a gaseous organosilicon compound, optionally an oxidizing gas, and optionally a gaseous hydrocarbon. Plasma forms in the reaction mixture, which is brought into contact with the plug. A coating of SiwOxCyHz is deposited, where w is 1, x in this formula is about 0.5 to 2.4, and is about 0.6 to about 3, and
327
My pi
MUUCANO INSTITUTE. -. . -. . . . DS LA raONCDAt »z is 2 to about 9, preferably where w neeruli ·, x is about 0.5 to 1, and is about 2 u · about 3, and z is 6 to about 9, over at least a portion of the plug.
V II.A.2.a. In the illustrated embodiment, the surface that contacts wall 276 of closure 270 is coated with a lubricating coating 286.
V II.A.2.a. In some embodiments, the SiwOxCyHz coating effectively reduces the transmission of one or more of the plug constituents, such as a metal ion that is a constituent of the plug, or container wall, into the container cavity. Certain elastomeric compositions of the type useful in making a stopper 2 82 contain trace amounts of one or more metal ions. These ions should sometimes not migrate into cavity 274 or contact the contents of the container in substantial amounts, particularly if sampling container 268 is to be used to collect a sample for trace metal analysis. Coatings having relatively low organic content, ie where y and z are low or equal to zero, are contemplated, for example, to be particularly useful as a metal ion barrier in this application. For silica as a metal ion barrier, please refer to
328 For example, Anupama Mallikarjunan,
Jasbir
<img file="MX345403B_D0213.tif" />
Yang, Shyam P. Murarka, and Toh-Ming Lu, The Effect of
Interfacial Chemistry on Metal Ion Penetration into Polymeric
Films, Mat. Res. Soc. Symp. Proc., Vol. 734, pp. B9.60.lB9.60.6 (Materials Research Society, 2003); Patents of
USA - 5578103 and 6200658, and European Application EP0697378
A2, all of which are incorporated herein by reference. It is contemplated, however, that some of the organic content may be useful in providing a more elastic coating and in adhering the coating to the elastomeric surface of plug 282.
V il.A.2.a. In some embodiments, the SiwOxCyHz liner may be a composite of a material with a first and a second layer, in which the first layer or inner layer 288 interconnects with the elastomeric plug 282 and effectively reduces the transmission of one or two. more constituents of plug 282 in the container cavity. The second layer 286 can interconnect with the inner wall 280 of the container and effectively reduces friction between the plug 282 and the inner wall 280 of the container when the plug 282 is seated on or in the container 268. These compounds are described in relation with syringe liners elsewhere in the description.
329 IMPI?
Mexican INSTTTVTO V CE LA PHOPISDAD \
V II.A.2.a. Or the first and second layer 288 '<sup>NE</sup>y ™ 286 are defined by a coating of graded properties, in which the y and z values are greater in the first layer than in the second layer.
V II.A.2.a. The SiwOxCyHz coating can be applied, for example, by PECVD substantially as previously described. The SiwOxCyHz coating can be, for example, 0.5 to 5000 nm (5 to 50,000 Angstroms) thick or 1 to 5000 nm thick or 5 to 5000 nm thick or 10 to 5000 nm thick or 20 to 5000 nm thick or 50 to 5000 nm thick or 100-5000 nm thick or 200-5000 nm thick or 500-5000 nm thick or 1000-5000 nm thick or 2000-5000 nm thick or 3000-5000 nm thick or between 4000 and 10,000 nm thick.
V II.A.2.a. Certain advantages are contemplated for plasma-coated lubricant layers, over much thicker conventional spray applied silicone lubricants (one micron or more). Plasma coatings have a much lower migratory potential to penetrate the blood than micron-coated or powdered silicones, because the amount of plasma-coated material is much less as it can be applied more closely to the coated surface and bind better. in
330
<img file="MX345403B_D0214.tif" />
position.
VII.A.2.a.
. , <sup>Μ</sup> induitual
Nanocoatings, as applied by PECVD, are contemplated to offer lower resistance to adjacent surface slip or adjacent fluid flow than micron coatings, since plasma coating tends to provide a smoother surface.
V II.A.2.a. Yet another embodiment is a method of applying a coating of SiwOxCyHz on an elastomeric plug. The cap can be used, for example, to close the container described above. The method includes several parts. A plug is placed in a chamber that is substantially under vacuum. A reaction mixture is provided comprising plasma-forming gas, ie, a gaseous organosilicon compound, optionally an oxidizing gas, and optionally a gaseous hydrocarbon. Plasma forms in the reaction mixture. The plug is contacted with the reaction mixture and deposits the SiwOxCyHz coating on at least a portion of the plug.
V II.A.2.a. In applying this method, to obtain higher values of y and z, it is contemplated that the reaction mixture may comprise a gaseous hydrocarbon, as described in more detail above and below. Optionally,
<img file="MX345403B_D0215.tif" />
331
<img file="MX345403B_D0216.tif" />
INSTITUTO MEXICANO DE LA PROPERTY The reaction mixture may contain oxygen ',<sup>NWST</sup>^ t contemplate smaller values of y and z or larger 3e x. u particularly to reduce oxidation and increase y and z values, the reaction mixture may be essentially free of an oxidizing gas.
V II.A.2.a. In applying this method to coat certain embodiments of the plug, such as plug 282, it is contemplated that it is not necessary to project the reaction mixture into the concavities of the plug. For example, the wall-contacting and inward-facing surfaces 276 and 272 of plug 282 are essentially convex and are therefore easily treated by a batch process in which a multiplicity can be inserted and treated. of plugs, such as 282, in a single reaction chamber that is basically under vacuum. It is also contemplated that, in some embodiments, the coatings 286 and 288 need not present as strong a barrier against oxygen or water as the barrier coating on the interior surface 280 of the container 268, since the plug material 282 can perform this function to a great extent.
V II.A.2.a. Many variations of the plug and the plug coating process are contemplated. Plug 282 can be contacted with plasma. Or plasma can
332
IMPI
<img file="MX345403B_D0217.tif" />
formed after the plug 282, producing a plasma pofcMOTtoEu and the plasma product can be contacted with the plug 282. The plasma can be formed by exciting the reaction mixture with electromagnetic energy and / or microwave energy.
V il.A.2.a. Variations of the reaction mixture are contemplated. The plasma-forming gas can include an inert gas. The inert gas can be, for example, argon or helium or other gases described in the present invention. The gaseous organosilicon compound can be or include, HMDSO, OMCTS, any of the other organosilicon compounds mentioned in the present invention or a combination of two or more of these. The oxidizing gas can be oxygen or other gases mentioned in the present invention or a combination of two or more of these. The gaseous hydrocarbon can be, for example, methane, methanol, ethane, ethylene, ethanol, propane, propylene, propanol, acetylene, or a combination of two or more of these.
V II.A.2.b. PECVD application of a coating of a group III or IV element and carbon on a plug
V II.A.2.b. Another embodiment is a method of coating a composition including carbon and one or more Group III or IV elements on an elastomeric plug. To carry out the method, a
333
ΙΜΡΙ ^ ΐ
<img file="MX345403B_D0218.tif" />
plug in a deposition chamber.
MEXICAN INSTITUTE OF THE PROA AGE
V II.A.2.b. A reaction mixture is provided.<sup>1</sup> the deposition chamber, which includes a plasma-forming gas with a gaseous source of a group III element, a group IV element, or a combination of two or more of these. The reaction mixture optionally contains an oxidizing gas and optionally contains a gaseous compound with one or more CH bonds. Plasma forms in the reaction mixture and the stopper is contacted with the reaction mixture. A coating of a Group III element or compound, a Group IV element or compound, or a combination of two or more of these is deposited on at least a portion of the plug.
V II.A.3. Plastic container covered with a barrier coating effective to provide 95% vacuum retention for 24 months
V II.A.3. Another embodiment is a container that includes a container, a barrier liner, and a closure. The container is generally tubular and made of thermoplastic material. The container has a mouth and a cavity joined at least in part by a wall. The wall has an internal surface that interconnects with the cavity. An at least essentially continuous barrier coating is applied on the inner surface of the wall. He
334 Barrier coating provides substantial shelf life. A closure form is provided
<img file="MX345403B_D0219.tif" />
container mouth and isolates the container cavity from ambient air.
V II.A.3. Referring to FIGS. 23-25, a container 268 such as a vacuum blood collection tube or other container is shown.
V II. A. 3. The container is, in this embodiment, a generally tubular container having at least one essentially continuous barrier liner and a closure. The container is made of a thermoplastic material and has a mouth and a cavity joined at least in part by a wall having an internal surface interconnected with the cavity. The barrier coating is deposited on the inner surface of the wall and is effective in maintaining at least 95%, or at least 90% of the initial level of vacuum of the container for a useful life of at least 24 months, optionally at least 30 months , optionally at least 36 months. The closure covers the mouth of the container and isolates the container cavity from ambient air.
V il.A.3. The closure, for example the closure 270 illustrated in the Figures or another type of closure, is provided to maintain a partial vacuum and / or to contain a sample and limit or prevent its exposure to oxygen or
335 pollutants. FIGS. 23-25 found in US Pat.
<img file="MX345403B_D0220.tif" />
No. 6,602,206, but the present discovery is not limited to that or any other particular type of closure.
V II.A.3. The closure 270 comprises an inward facing surface 272 exposed to the cavity 274 of the container 268 and a wall contacting surface 276 that is in contact with the inner surface 278 of the container wall 280. In the illustrated embodiment the closure 27 0 is an assembly of a plug 282 and a shield 284.
V II.A.3. In the illustrated embodiment, the plug 282 defines the surface that is in contact with the wall 276 and the inner surface 278, while the shield is largely or totally outside the covered container 268, retains and provides a holding tool for cap 282 and protects a person removing closure 270 from being exposed to any expelled contents from container 268, such as due to a pressure difference within and
I out of container 268, when container 268 is opened and air enters and leaves to equalize the pressure difference.
V II.A.3. It is also contemplated that the coatings on the wall of the container 280 and the wall-contacting surface 276 of the cap may be coordinated. The plug
336 can be coated with a layer of silicone lubf ^ f ^ fSJtíSmíÜD INDUSTRIAL container wall 280, made for example of PET or glass, can be coated with a harder SiOx layer or with an underlying SiOx layer and a lubricating coating layer.
V II.B. Syringes
V II.B. The foregoing description pays particular attention to the application of a barrier coating to a tube with a permanently closed end, such as a blood collection tube or, more generally, a specimen receiving tube 80. The apparatus is not limited thereto. device.
vil B. Another example of a suitable container, shown in FIGS. 20-22, is a syringe barrel 250 for a medical syringe 252. Such syringes 252 are sometimes supplied pre-filled with saline, a pharmaceutical preparation or the like for use in medical techniques. Pre-filled syringes 252 are also contemplated to benefit from a SiOx barrier or other type of coating on the inner surface 254 so that the contents of the pre-filled syringe 252 do not come into contact with the plastic of the syringe, for example, the cylinder of 250 syringe during storage. The barrier or other type of coating can be used to prevent seepage of the plastic components into the cylinder contents through the inner surface 254.
337
VII.Β.
conventional
A 250 syringe barrel can be opened both at the
<img file="MX345403B_D0221.tif" />
256, to receive a plunger 258, as in anteme fa? E> nbal .......
260, to receive a hypodermic needle, nozzle, or tubing to dispense the contents of syringe 252 or to receive material into syringe 252. But front end 260 may be optionally capped and plunger 258 may optionally be placed in position prior to use pre-filled syringe 256, closing both ends of barrel 250. A cap 262 can be installed for purposes of processing the syringe barrel 250 or assembled syringe, or to remain in position during storage of the pre-filled syringe 252, until such time as cap 262 is removed and (optionally) a hypodermic needle or other administration conduit on front end 260 to prepare syringe 252 for use.
V II.Bl Assemblies
V II.Bl FIG. 42 also shows an alternative construction of a syringe barrel that can be used, for example, in the embodiments of FIGS. 21, 26, 28, 30 and 34, and which is adapted for use with the container support 450 of said Figure.
V II.Bl FIG. 50 is an exploded view and FIG.
It is a view of the assembly of a syringe. Cylinder
338
<img file="MX345403B_D0222.tif" />
Syringe can be processed with inspection of containers 37-39, 44 and 53-54.
V II.Bl The cylinder facility 250 is a closed-end container that can be provided with a SiOx barrier or other type of coating on its interior surface 254 in the previously illustrated apparatus, optionally also providing a coating on the interior 264 of the cap and bypassing the interface between the inner cap 264 and the front end of the cylinder 260. For example, in FIG. twenty-one a suitable apparatus adapted for this use is shown which is analogous to FIG. 2 except for the replacement of the capped syringe barrel 250 with the container 80 of FIG. 2. VII.B.
V II.Bl FIG. 52 is a view similar to FIG. 42 but showing a syringe barrel being treated that does not have clamps or hand stops 440. The syringe barrel can be used with the container inspection and treatment apparatus of FIGS. 1-19, 27, 33, 35, 44-51 and 53-54.
V II.Bla Syringe with barrel lined with a deposited lubricating coating of an organosilicon precursor
V II.B.1.a. Yet another embodiment is a container with
339 a lubricating coating of SiwOxCyHz, of the t by the following process.
VII.B.1.a.
A precursor defined above is provided.
VII.B.1.a.
The precursor is applied to a substrate under conditions effective to form a coating.
The coating is polymerized or lattice, or both, to form a lubricated surface with a lower sliding force or plunger pull-out force than the untreated substrate.
V II.B.1.a. With respect to any of the embodiments VII and subparts, optionally the application step is carried out by vaporizing the precursor and providing it close to the substrate.
V II.B.1.a. With respect to any of the embodiments VII.A.1.ai, optionally a plasma, optionally a plasma other than a hollow cathode plasma, is formed proximate to the substrate. Optionally, the precursor is provided in the considerable absence of oxygen. Optionally, the precursor is provided in the considerable absence of a carrier gas. Optionally, the precursor is provided in the considerable absence of nitrogen. Optionally, the precursor is provided at an absolute pressure of less than 1 Torr. Optionally, the precursor is
340 provides close to a plasma emission. OR;
The reaction product of the precursor is applied to it at a thickness of 5000 nm thick or 10 ^ nm thick or 10-200 nm thick or 20-100 nm thick.
Optionally, the substrate comprises glass. Optionally, the substrate comprises a polymer, optionally a polycarbonate polymer, optionally an olefinic polymer, optionally a cycloolefinic copolymer, optionally a polypropylene polymer, optionally a polyester polymer, optionally a polyethylene terephthalate polymer.
Optionally, the plasma is generated by activating the gaseous reagent containing the precursor with electrodes fed, for example, at an RF frequency as defined above, for example, a frequency of 10 kHz to less than 300 MHz, more preferably 1 to 50 MHz, even more preferably 10 to 15 MHz, even more preferably 13.56 MHz.
Optionally, the plasma is generated by activating the gaseous reagent containing the precursor with electrodes supplied with an electrical power of 0.1 to 25 W, preferably 1 to 22 W, more preferably 3 to 17 W, even more preferably 5 to 14 W , even more preferably 7 to 11 W, in particular 8 W. The ratio between the power of
IMPI ^ electrodes and plasma volume can be INDUSTRIAL
W / mL, preferably it is 5 W / mL to 0.1 W / mL, more preferably it is 4 W / mL to 0.1 W / mL, even more preferably 2 W / mL to 0.2 W / mL. These power levels are suitable for applying lubricant coatings to syringes, sample tubes, and containers of similar geometry with a void volume of 1 to 3 mL in which plasma is generated by PECVD. It is contemplated that for larger or smaller objects, the applied power should therefore be increased or decreased to suit the process to the size of the substrate.
V II.B.1.a Another embodiment is a lubricant coating on the inner wall of a syringe barrel. The coating is produced from a PECVD process using the following materials and conditions. A cyclic precursor selected from a monocyclic siloxane, a polycyclic siloxane or a combination of two or more of these, as defined elsewhere in this disclosure, is preferably employed for lubricating coatings. An example of a suitable cyclic precursor comprises octamethylcyclotetrasiloxane (OMCTS), optionally mixed with other precursor materials in any proportion. Optionally, the cyclic precursor consists essentially of octamethylcyclotetrasiloxane (OMCTS), which
342
<img file="MX345403B_D0223.tif" />
amounts that do not change the basic and novel properties of the resulting lubricating coating, ie, its reduction in the plunger sliding force or the pulling force of the coated surface.
V II.B.1.a At least essentially no oxygen is added to the process. There may be some residual atmospheric oxygen in the syringe barrel and there may be residual oxygen fed in a previous stage and not completely depleted in the syringe barrel, this is defined herein as essentially no oxygen present. If no oxygen is added to the process, this is also covered by the scope of essentially no oxygen.
V II.B.1.a Sufficient power input is provided for plasma generation, for example, any power level used successfully in one or more practical examples of this description or described in the description, to induce the formation of a coating.
V II.B.1.a Materials and conditions employed are effective in reducing the sliding force or breakout force of the syringe plunger moving through the syringe barrel by at least 25 percent, alternatively at least 4 5 percent, as an alternative to ιμρι £ minus 60 percent, as an alternative more than<sup>Hsi</sup>yñ '?<sub>F</sub>^ £ ¿5 © o &
'INDUSTRIAL' cent, relative to an uncoated syringe barrel.
Reduction ranges for the sliding force or plunger breakout force of 20 to 95 percent, alternatively 30 to 80 percent, alternatively 40 to 75 percent, such as 60 to 70 percent alternative.
V il.B.1.a. Another embodiment is a container with a hydrophobic coating on the inner wall having the structure: SiwOxCyHz, where w, x, y and z are as previously defined. The coating is prepared as explained for the lubricant coating of similar composition, but under conditions effective to form a hydrophobic surface with a greater contact angle than the untreated substrate.
V II.B.1.a. With respect to any of the embodiments VII.A.1.a.ii, the substrate optionally comprises glass or a polymer. The glass is optionally borosilicate glass. The polymer is optionally a polycarbonate polymer, optionally an olefinic polymer, optionally a cycloolefinic copolymer, optionally a polypropylene polymer, optionally a polyester polymer, optionally a polyethylene terephthalate polymer.
IMPL
V II.Bla Another embodiment is a syringe
INDUSTRIAL a plunger, a syringe barrel and a lubricating layer. The syringe barrel includes an interior surface on which the plunger slides. The lubricating layer is disposed on the inner surface of the syringe barrel and includes a coating of a lubricating layer of SiwOxCyHz. The lubricating layer is less than 1000 nm thick and is effective in reducing the breakout force or plunger sliding force necessary to move the plunger within the cylinder. The reduction in the sliding force of the plunger is alternatively expressed as the reduction of the coefficient of friction of sliding of the plunger within the cylinder or the reduction of the plunger force. These terms are considered to have the same meaning in the present description.
V II.Bla The syringe 544 of FIGS. 50-51 comprises a plunger 546 and a syringe barrel 548. The syringe barrel 548 has an inner surface 552 over which the plunger 546 slides. The inner surface 552 of the syringe barrel 548 further comprises a lubricant coating 554 of SiwOxCyHz . The lubricating layer has a thickness less than 1000 nm, optionally less than 500 nm, optionally less than 200 nm, optionally less than 100 nm, optionally less than 50 nm, and effectively reduces the
345
<img file="MX345403B_D0224.tif" />
breakout force required to exceed adhn®MMExic £ Íel di tootudad
INDUSTRIAL plunger after storage or the plunger sliding force required to move the plunger within the cylinder once it has moved. The lubricating layer is characterized by having a sliding force or a plunger breakout force lower than that of the uncoated surface.
V II.B.1.a. Any of the foregoing precursors of any type can be used alone or in combination with two or more of them to provide a lubricating coating.
V II.B.1.a. In addition to using vacuum processes, low temperature atmospheric (non-vacuum) plasma processes can also be used to induce molecular ionization and deposition through the administration of precursor monomeric vapor preferably in a non-oxidizing atmosphere such as helium or argon. Regardless, thermal CVD by flash thermolysis deposition can be considered.
V II.B.1.a. The above methods are similar to vacuum PECVD in that the coating and surface crosslinking mechanisms can occur simultaneously.
V II.B.1.a. Another resource more contemplated for any
346
IMPIíg ^ coating or coatings described in Presea® »coating that is not applied uniformly over the entire interior 88 of a container. For example, a different or additional coating may be selectively applied to a cylindrical portion of the interior of the container, compared to the hemispherical portion of the interior of the container at its closed end 84, or vice versa. This resource is particularly contemplated for a syringe barrel or sample collection tube as described below, in which a lubricating surface may be provided over part or all of the cylindrical portion of the barrel, where the plunger or piston or seal slides. , and nowhere else.
V II.B.1.a. Optionally, the precursor may be provided in the presence, considerable absence or absence of oxygen, in the presence, considerable absence or absence of nitrogen, or in the presence, considerable absence or absence of a carrier gas. In one contemplated embodiment, only the precursor is delivered to the substrate and subjected to PECVD to apply and cure the coating.
V il.B.1.a. Optionally, the precursor can be provided at less than 1 Torr absolute pressure.
V II.B.1.a. Optionally, the precursor can be provided close to a plasma emission.
Optionally, the precursor product can be applied to the substrate in a thickness of 1 to
5000 nm or 10 to 1000 nm or 10-200 nm or 20 to 100 nm.
vii.bia
In any of the above embodiments, the substrate can comprise glass or a polymer, for example one or more of the following: a polycarbonate polymer, an olefinic polymer (for example, a cycloolefinic copolymer or a polypropylene polymer), or a polymer polyester (for example, a polyethylene terephthalate polymer).
V II.Bla In any of the above embodiments, the plasma is generated by activating the gaseous reagent containing the precursor with electrodes fed at an RF frequency as defined in the description.
V il.B.1.a. In any of the above embodiments, the plasma is generated by activating the gaseous reagent containing the precursor with electrodes supplied with sufficient electrical power to generate a lubricating coating. Optionally, the plasma is generated by activating the gaseous reagent containing the precursor with electrodes supplied with an electrical power of 0.1 to 25 W, preferably 1 to 22 W, more preferably 3 to 17 W, even more preferably 5 to 14 W , even more preferably 7 to 11 W, in particular 8 W. The
348
IMPI
<img file="MX345403B_D0225.tif" />
relationship between the power of the electrodes and the vojSSwm ^ * · “INDUSTRIAL plasma can be less than 10 W / mL, preferably it is from 5 W / mL to 0.1 W / mL, more preferably it is from 4 W / mL to 0.1 W / mL, even more preferably 2 W / mL to 0.2 W / mL. These power levels are suitable for applying lubricant coatings to syringes, sample tubes, and containers of similar geometry with a void volume of 1 to 3 mL in which plasma is generated by PECVD. It is contemplated that for larger or smaller objects, the applied power should therefore be increased or decreased to suit the process to the size of the substrate.
V il.B.1.a. The coating can be cured, for example, by polymerizing or crosslinking the coating, or both, to form a lubricated surface with a lower sliding force or plunger pull-out force than the untreated substrate. Curing can occur during the application process, such as PECVD, or it can be carried out or at least completed by separate processing.
V II.B.1.a. Although plasma deposition has been used herein to demonstrate coating characteristics, alternative deposition methods can be used as long as the chemical composition of the starting material is preserved as far as possible by also depositing a solid film that it sticks
349 to the base substrate
INSTITUTO MEXICANO DE LA HQFIÍDAI INDUSTRIAL
V II.B.1.a. For example, the coating material can be applied to the syringe barrel (in liquid state) by spraying the coating or dipping the substrate into the coating, where the coating is a pure precursor or a solvent-diluted precursor (allowing mechanical deposition of a coating finest). The coating can be optionally crosslinked using thermal energy, UV energy, electron beam energy, plasma energy, or any combination of these.
v il.B.1.a. The application of a silicone precursor, as described above, to a surface with a separate post-cure step is also contemplated. Application and cure conditions can be analogous to those used for atmospheric plasma curing of precoated polyfluoroalkyl ethers, a process performed under the trademark TriboGlide®. More details of this process can be found at http://www.triboglide.com/process.htm.
V II.B. 1.a. In such a process, the area of the part to be coated can optionally be pretreated with an atmospheric plasma. This pretreatment cleans and activates the surface so that it is receptive to the lubricant that is sprayed in the next stage.
350
V II.B.1.a. The lubricating fluid, in this ^ case Ain® 'INSTITUTO MEXICANO
TI LA f * OHIDA £> INDUSTRIAL the above precursors or a polymerized precursor, is subsequently sprayed on the surface to be treated. For example, IVEK precision dispersion technology can be used to precisely atomize the fluid and create a uniform coating.
V II.B.1.a. The coating is subsequently adhered or cross-linked to the part, again using an atmospheric plasma field. This immobilizes the coating and improves the performance of the lubricant.
VII.B.1.a.
Optionally, atmospheric plasma can be generated from ambient air in the container, in which case, no gas supply or vacuum extraction equipment is necessary. However, preferably, the container is at least substantially closed while the plasma is being generated, to minimize the need for power and avoid contact of the plasma with surfaces or materials outside the container.
V II.B.1.ai Lubricating coating: SiOx barrier, lubricating layer, surface treatment
Surface treatment
V II.B.1.ai Another embodiment is a syringe that comprises a cylinder that defines a cavity and that has an inner surface through which the plunger slides, that is <sup>351</sup>
TMPIá say, you receive a plunger for a contact from dnsljSá> OUi®nw
INDUSTRIAL with the inner surface.
V il.B.1.ai The syringe barrel is made of thermoplastic base material.
V II.B.1.ai Optionally, the inner surface of the cylinder is coated with a SiOx barrier layer as described elsewhere in this description.
V II.B.1.ai A lubricant coating is applied to the inner surface of the cylinder, plunger or both, to the previously applied SiOx barrier layer. The lubricating layer may be provided, applied and cured as set forth in embodiment VII.B.1.a or elsewhere in this description.
V II.Blai For example, the lubricant coating can be applied, in any embodiment, by PECVD. A lubricating coating made of an organosilicon precursor is deposited and is less than 1000 nm thick.
V II.Blai A surface treatment is carried out on the lubricant coating in an amount effective to reduce seepage or removable content of the lubricant coating, thermoplastic base material, or both. The treated surface can thus act as a solute retention article. This surface treatment can produce a surface coating, for example,
352 a surface coating
<img file="MX345403B_D0226.tif" />
less than 1 nm and less than 100 nm or less than 50 nm or less than 40 nm or less than 30 nm or less than 20 nm or less than 10 nm or less than 5 nm or less than 3 nm or less than 2 nm or less than 1 nm or less than 0.5 nm.
As used herein, leakage refers to a material transferred out of a substrate, such as a container wall, into the contents of the container, for example, a syringe. Typically, leaks are measured by storing the container filled with the intended content and subsequently analyzing the contents to determine what material leaked from the container wall into the intended content. Extraction refers to material removed from a substrate by introducing a solvent or dispersion medium other than the intended contents of the container, to determine what material can be removed from the substrate into the extraction medium under the conditions of the test.
V II.B.1.ai The surface treatment that results in a solute retention element can optionally be a coating of SiOx or SiwOxCyHz, each as previously defined in this description. In one embodiment, the surface treatment can be applied by depositing SiOx or SiwOxCyHz via PECVD. Optionally, the surface treatment can be applied using a<sup>353</sup> IMPí ^
INSTnyrO MEXICANO superior potency or stronger conditions of οχιβί ^^^ which are used to create the lubricated layer ..____ or, _ both, thereby providing a harder, finer and more continuous solute retention element 539. The surface treatment 'may be less than 100 nm deep, optionally less than 50 nm deep, optionally less than 40 nm deep, optionally less than 30 nm deep, optionally less than 20 nm deep, optionally less 10 nm deep, optionally less than 5 nm deep, optionally less than 3 nm deep, optionally less than 1 nm deep, optionally less than 0.5 nm deep, optionally between 0.1 and 50 nm deep in the lubricating coating.
V II.B.1.ai The solute retainer is contemplated to provide low solute filtration performance to the underlying lubricant layer and to the other layers, including the substrate, as required. This retention element would only need to be a solute retention element for large molecules of solute and oligomers (for example, siloxane monomers such as HMDSO, OMCTS, their fragments and mobile oligomers derived from lubricants, for example, a retention element of leaks) and not a gas barrier layer (02 / N2 / C02 / water vapor). A solute retainer can, however, also be a
ΙΜΡΙ £
INSTTTVTO MEXICANO gas barrier (for example, the coating according to the present invention. A good leak retention element can be created without gas barrier performance, using vacuum or atmospheric based PECVD processes. It is desirable that the leakage barrier be thin enough that, with movement of the syringe plunger, the plunger easily penetrates the solute retainer, exposing the plunger connector to the lubricating layer just below to form a Lubricated surface with lower sliding force or plunger pullout force than untreated substrate.
V II.B.1.ai In another embodiment, the surface treatment can be performed by oxidizing the surface of a previously applied lubricant layer, exposing the surface to oxygen in a plasma environment. The plasma environment described in the present disclosure can be used to form SiOx coatings. Or atmospheric plasma conditions in an oxygen rich environment can be employed.
V II.B.1.ai The lubricant layer and the solute retainer, regardless of how they are formed, can optionally be cured at the same time. In another embodiment, the lubricating layer may be at least partially cured, optionally completely.<sup>t</sup>*'<sup>ST</sup>5tting, after which a surface treatment can be provided and the solute retainer can be cured.
V II.Blai The lubricant coating and the solute retainer are compounded and present in relative amounts so as to be effective to provide a pull-out force, a plunger slip force, or both, less than the corresponding force necessary in the absence of lubricating coating and surface treatment. In other words, the thickness and composition of the solute retainer are such that they reduce leakage of material from the lubricating layer into the contents of the syringe, while allowing the underlying lubricating coating to lubricate the plunger. It is contemplated that the solute retaining member breaks easily and is fine enough for the lubricating layer to continue to function to lubricate the plunger as it moves.
V II.Blai In one contemplated embodiment, the lubricity and surface treatment can be applied to the inner surface of the cylinder. In another contemplated embodiment, the lubricity and surface treatment can be applied to the plunger. In other
<img file="MX345403B_D0227.tif" />
In the contemplated embodiment, the surface treatment can be applied on the inner surface of the cylinder and on the plunger. In any of these embodiments, the optional SiOx barrier layer on the inside of the syringe barrel may be present or absent.
V II.Blai One contemplated embodiment is a configuration of a plurality of layers, eg, 3 layers, applied to the inner surface of a syringe barrel. Layer 1 may be a SiOx gas barrier applied by PECVD of HMDSO, OMCTS, or both, in an oxidizing atmosphere. Such an atmosphere can be provided, for example, by feeding HMDSO and oxygen gas to a PECVD coating apparatus as described in the present description. Layer 2 can be a lubricating layer using OMCTS applied in a non-oxidizing atmosphere. Such a non-oxidizing atmosphere can be provided, for example, by feeding OMCTS to a PECVD coating apparatus as described in the description, optionally in the substantial or complete absence of oxygen. A posterior solute retention element can be formed by a thin surface layer forming treatment of SiOx or
SiwOxCyHz as a solute retention element using high potency and oxygen using OMCTS and / or HMDSO.
357
V II. B. 1.ai IgunqsA INDUSTRIAL coatings with a plurality of layers are contemplated to have one or more of the following optional advantages, at least to some degree. They can overcome the stated difficulty of handling the silicone, because the solute retainer can confine the inner silicone and prevent it from migrating into the contents of the syringe or elsewhere, resulting in fewer silicone particles in the contents dispensed from the syringe and less opportunity for interaction between the lubricant coating and the contents of the syringe. They can also overcome the issue of lubricant layer migration away from the lubrication point, which improves the lubricity of the interface between the syringe barrel and the plunger. For example, the breakout force can be reduced as can the drag on the moving plunger or optionally both.
V il.B.1.ai It is contemplated that when the solute retainer breaks, the solute retainer continues to adhere to the lubricant coating and syringe barrel, which can prevent any particles from being trapped in the contents. administered from the syringe.
V II.B.1.ai Certain of these coatings will also provide manufacturing advantages, particularly if the <sup>358</sup> IMPIAS barrier coating, lining coating and surface treatment are applied in the same apparatus, for example, the PECVD apparatus illustrated. Optionally, the SiOx barrier coating, lubricating coating and surface treatment can be applied in a PECVD apparatus, thereby greatly reducing the amount of handling required.
Other advantages can be obtained by forming the barrier coating, the lubricating coating, and the solute retainer using the same precursors and varying the processes. For example, a SiOx gas barrier layer can be applied using a OMCTS precursor under high power / high 02 conditions, with subsequent application of the lubricant layer using a OMCTS precursor under low power conditions and / or in the considerable or complete absence of oxygen, ending with a surface treatment using a OMCTS precursor under conditions of intermediate power and intermediate oxygen levels.
VII.Blb Syringe with a barrel whose interior has a SiOX coating and whose exterior has a barrier coating
VII.Blb Yet another embodiment, illustrated in FIG. 50, is a 544 syringe that includes a 546 plunger, a cylinder
359
IMPI ^. . ,,. . MEXICAN INSTITUTE
8 and an inner and outer barrier liner ^^^ o ^ S ^ J * ^ 602. Cylinder 548 may be made of thermoplastic base material that defines a cavity 604. Cylinder 548 may have an interior surface 552 through which it slides the plunger 546 and an outer surface 606. A barrier coating 554 of SiOx, in which x is from about 1.5 to about 2.9, can be provided on the inner surface 552 of the cylinder
548. A barrier coating 602 of a resin may be provided on the outer surface 606 of cylinder 548.
VII.Blb In any embodiment, the thermoplastic base material can optionally include a polyolefin, for example, a polypropylene or cycloolefinic copolymer (for example, the material sold under the trademark TOPAS®), a polyester, for example, polyethylene terephthalate, a polycarbonate, for example a thermoplastic bisphenol A polycarbonate, or other materials. Composite syringe barrels are contemplated to have any of these materials as an outer layer and one of these identical or different materials as an inner layer. Any combination of composite sample tube or syringe barrel materials described elsewhere in the present disclosure may also be used.
360 ΙΜΡΙ «Mexican
ΠΕ LA ERONEDAE
V II.Blb In any embodiment, the '^' ^ ffeBinst may optionally include polTu InilldLinu chloride <- »homopolymer or copolymer form. For example, the PvDC homopolymers (common name: Saran) or copolymers described in US Patent 6,155,566, incorporated herein by reference, can be employed. The resin can optionally be applied to the outer surface of the cylinder in the form of a latex or other dispersion.
V II.Blb In any embodiment, syringe barrel 548 optionally may include a lubricating coating disposed between the plunger and the SiOx barrier coating. Suitable lubricating coatings are described elsewhere in this description.
V II.Blb In any embodiment, the lubricant coating can optionally be applied by PECVD and can optionally include material with the SiwOxCyHz composition.
V II.Blb In any embodiment, syringe barrel 548 optionally may include a surface treatment that covers the lubricant coating in an amount effective to reduce leakage of the lubricant coating, thermoplastic base material constituents, or both in cavity 604.
V II.Blc Method of preparing a syringe whose
IMPI ^ cylinder has an industrial inner liner outer barrier liner
V II.Blc Still another embodiment is a method of preparing a syringe, as described in any of the embodiments of part VII.Blb, which includes a plunger, a barrel, and an inner and outer barrier liner. A cylinder is provided with an inner surface on which the plunger slides and an outer surface. A SiOx barrier coating is provided on the inner surface of the cylinder by PECVD. A barrier coating of a resin is provided on the outer surface of the cylinder. The plunger and barrel are assembled to provide a syringe.
V II.Blc To obtain an effective coating (uniform wetting) of the plastic article with the aqueous latex, it is contemplated as useful to adjust the surface tension of the latex to the plastic substrate. This can be achieved by applying various methods, separately or in combination, for example reducing the surface tension of the latex (with surfactant or solvents) and / or corona pretreatment of the plastic article and / or chemical priming of the plastic article.
V II.Blc The resin can optionally be applied by dip coating the latex on the
362 outer surface of cylinder, coatedMnignt <g,<sub>AC</sub>^ pi ^ <sup>IN</sup> MtAMKJjUDAP spraying the latex onto the outer surface of the cylinder or both to provide plastic-based articles that offer improved gas and vapor barrier performance. Polyvinylidene chloride plastic laminated articles can be prepared which provide considerably improved gas barrier performance over non-laminated plastic article.
V II.Blc In any embodiment, the resin can optionally be thermally cured. The resin can optionally be cured by removing the water. Water can be removed by thermally curing the resin, exposing the resin to a partial vacuum or low humidity environment, catalytically curing the resin, or by other means.
V II.Blc An effective thermal cure program is contemplated to provide a final dry that allows crystallization of PvDC, which offers barrier performance. Primary cure can be carried out at an elevated temperature, for example, between 180-310 ° F (82-154 ° C), obviously depending on the heat tolerance of the thermoplastic base material. The barrier performance after the first cure optionally can be approximately 85% of the last barrier performance achieved after the final cure.
- IMPIf
MEXICAN INSTITUTE V
- <sub>π</sub>, , <sub>Ί</sub> _ ·, -, _ _ __ OF THE «REMAINING ΐ
V II.Blc Final cure can be carried out at temperatures in the room temperature range ^ —ta-1 — such as approximately 65-75 ° F (18-24 ° C) for an extended period of time (such as 2 weeks ) at an elevated temperature, such as 122 ° F (50 ° C) for a short time, such as four hours.
V II.Blc PvDC plastic laminates, in addition to superior barrier performance, are contemplated to optionally provide one or more desirable properties, such as colorless transparency, good gloss, abrasion resistance, printability and resistance to mechanical stress.
V II.B.2. Plungers
V II.B.2.a. With the front face of the piston lined with a barrier
V II.B.2.a. Another embodiment is a plunger for a syringe, which includes a piston and a push rod. The piston has a front face, a generally cylindrical side face, and a rear portion, the side face being configured to movably seat within a syringe barrel. The front face has a barrier coating. The push rod is coupled to the rear portion and is configured to advance the piston in a syringe barrel.
VII.Β.2.b. With
364 coating
<img file="MX345403B_D0228.tif" />
interconnected with the side face ..........
V II. B. 2. b. Another embodiment is a plunger for a syringe, including a piston, a lubricant coating, and a push rod. The piston has a front face, a generally cylindrical side face, and a rear portion. The side face is configured to movably seat within a syringe barrel. The lubricant coating is interconnected with the side face. The push rod is coupled to the rear portion of the piston and is configured to advance the piston in a syringe barrel.
V II.B.3. Two-piece syringe and Luer connector
V II.B.3. Another embodiment is a syringe that includes a plunger, a syringe barrel, and a Luer-type connector. The syringe includes a barrel with an inner surface through which the plunger slides. The Luer-type connector includes a conical luer-type fitting with an internal passage defined by an internal surface. The Luer-type connector is formed as a separate piece from the syringe barrel and attached to the syringe barrel by coupling. The luer taper liner liner has a SiOx barrier coating.
V II.B.3. Referring to FIGS. 50-51, the
I<sup>M</sup>IJ
-syringe 544 can optionally include a connecTESIx
Luer 556 comprising a Luer 558 taper fitting to receive a cannula mounted on a complementary Luer taper fitting (not shown, conventional). The conical luer fitting 558 has an internal passage 560 defined by an internal surface 562. The luer fitting 556 is optionally formed as a separate piece from the syringe barrel 548 and attached to the syringe barrel 548 by a coupling 564. As illustrated in FIGS: 50 and 51, the coupling 564 in this case has a male portion 566 and a female portion 568 that engage to secure the Luer-type connector in at least a substantially leak-proof manner to cylinder 548. The inner surface 562 of the conical luer fitting may include a barrier coating 570 of SiOx. The barrier coating can be less than 100 nm thick and it effectively reduces oxygen ingress into the luer-type liner. The barrier coating can be applied before the Luer connector is attached to the syringe barrel. The syringe of FIGS. 50-51 also has an optional circlip 572 that is internally threaded so as to lock the complementary luer taper of a cannula in place over the taper fitting 558.
- IMPIAS
MMICANO INSTITUTE. ,,,. oe LA FJpriSDAO Om
V II. B. 4. Lubricating Compositions - ReveSTOEmence. deposited lubricant of an organosilicon precursor prepared by polymerizing the organosilicon precursor in situ
V il.B.4.a. Product obtained through the process and lubricity
V II.B.4.a. Yet another embodiment is a lubricating coating. This coating can be of the type prepared by the following process.
V II.B.4.a. Any of the precursors mentioned elsewhere in the present description can be used alone or in combination. The precursor is applied to a substrate under conditions effective to form a coating. The coating is polymerized or lattice, or both, to form a lubricated surface with a lower sliding force or plunger pull-out force than the untreated substrate.
V II.B.4.a. Another embodiment is a method of applying a lubricating coating. An organosilicon precursor is applied to a substrate under conditions effective to form a coating. The coating is polymerized or lattice, or both, to form a lubricated surface with a lower sliding force or plunger pull-out force than the untreated substrate.
V il.B.4.b. Product obtained through the process and
367 another aspect of the _invention is a deposit by PECVD of a gas with analytical properties
V II.B.4.b. Even lubricant coating
<img file="MX345403B_D0229.tif" />
feed comprising an organometallic precursor, preferably an organosilicon precursor, preferably a linear siloxane, a linear silazane, a monocyclic siloxane, a monocyclic silazane, a polycyclic siloxane, a polycyclic silazane, or a combination of two or more of these. The coating has a density between
1.25 and 1.65 g / cm3 optionally between 1.35 and 1.55 g / cm3, optionally between 1.4 and 1.5 g / cm3, optionally between 1.44 and 1.48 g / cm3 as determined by X-ray reflectivity (XRR).
V il.B.4.b. Yet another aspect of the invention is a lubricant coating deposited by PECVD of a feed gas comprising an organometallic precursor, preferably an organosilicon precursor, preferably a linear siloxane, a linear silazane, a monocyclic siloxane, a monocyclic silazane, a polycyclic siloxane, a polycyclic silazane or a combination of two or more of these. The coating has a degassing component, one or more oligomers containing repeating (Me) 2SiO- moieties, as determined by gas chromatography / mass spectrometry.
Optionally
<img file="MX345403B_D0230.tif" />
VII.B.4.a or any of the
Optionally, the degassed component of the coating, as determined by gas chromatography / mass spectrometry, is substantially free of trimethylsilanol.
V II.B.4.b. Optionally, the degassed component of the coating can be at least 10 ng / test oligomers containing repeating - (Me) 2SiO- residues, as determined by gas chromatography / mass spectrometry using the following test conditions:
CG column: 30m X 0.25mm DB-5MS (J&W
Scientific), 0.25 pm film thickness
Flow rate: 1.0 mL / min, constant flow mode
Detector: Mass Selective Detector (MSD)
Injection mode: Separate injection (10: 1 separation ratio)
Degassing conditions: 1W (37 mm) chamber, purge for three hours at 85 ° C, flow 60 mL / min <sup>369</sup> IMPI ^
INSTITUTO MEXICANO '' Oven temperature: from 40 ° C (5 min.) To<sup>OF</sup>3 ^ J ^ ® ^ ° C / min .; held for 5 min at —--------- _
300 ° C.
V II.B.4.b. Optionally, the degassed component may include at least 20 ng / test oligomers containing repeating - (Me) 2SiO- moieties.
V II.B.4.b. Optionally, the feed gas comprises a monocyclic siloxane, a monocyclic silazane, a polycyclic siloxane, a polycyclic silazane, or a combination of two or more of these, for example a monocyclic siloxane, a monocyclic silazane, or any combination of two or more of these, for example, octamethylcyclotetrasiloxane.
V II.B.4.b. The lubricating coating of any embodiment may have a transmission electron microscope (TEM) thickness of between 1 and 500 nm, optionally between 20 and 200 nm, optionally between 20 and 100 nm, optionally between 30 and 100 nm.
V II. B. 4. b. Another aspect of the invention is a PECVD-deposited lubricant coating of a feed gas comprising a monocyclic siloxane, a monocyclic silazane, a polycyclic siloxane, a polycyclic silazane, or a combination of two or more of these. The coating has an atomic concentration of carbon,<sup>370</sup> IMPI
MEXICAN INITTTVTO DE LA F1IOREDAD normalized to 100% carbon, oxygen and, as determined by X-ray photoelectric spectroscopy (XPS) greater than the atomic concentration of carbon in the atomic formula for the feed gas.
Optionally, the liner meets the limitations of Embodiments VII.B.4.a or VII.B.4.b.
V II.B.4.b. Optionally, the atomic concentration of carbon is increased from 1 to 80 atomic percent (as calculated and based on the XPS conditions of Example 15), alternatively 10 to 70 atomic percent, alternatively 2 0 to 60 atomic percent, alternatively 30 to 50 atomic percent, alternatively 35 to 45 atomic percent, alternatively 37 to 41 atomic percent.
V II. B. 4. b. Another aspect of the invention is a PECVD-deposited lubricant coating of a feed gas comprising a monocyclic siloxane, a monocyclic silazane, a polycyclic siloxane, a polycyclic silazane, or a combination of two or more of these. The coating has an atomic concentration of silicon, normalized to 100% carbon, oxygen, and silicon, as determined by X-ray photoelectron spectroscopy (XPS) less than the atomic concentration of silicon in the atomic formula for the feed gas.
<img file="MX345403B_D0231.tif" />
<sup>371</sup> IMPI ·
MEXICAN INSTITUTE
M LA PAOFIHMt)
Optionally, the cladding meets the limitations of Embodiments VII. B. 4th year VII. B. 4. b. '<sup>1,1</sup> —
V II.B.4.b. Optionally, the atomic concentration of silicon is decreased from 1 to 80 atomic percent (as calculated and based on the XPS conditions of Example 15), alternatively 10 to 70 atomic percent, alternatively 2 0 to 60 atomic percent, alternatively 3 0 to 55 atomic percent, alternatively 40 to 50 atomic percent, alternatively 42 to 46 atomic percent.
V il.B.4.b. Lubricating coatings that have combinations of two or more properties mentioned in Section VII.B.4 are also expressly contemplated.
V II.C. Containers in general
V II.C. A coated container or container, as described herein and / or prepared in accordance with a method described herein, can be used for the receipt and / or storage and / or administration of a compound or composition. The compound or composition can be sensitive, for example, sensitive to air, sensitive to oxygen, sensitive to humidity and / or sensitive to mechanical influences. It can be a biologically active compound or composition, for example a drug such as insulin or a composition comprising insulin. In other
372 Aspect, it may be a biological fluid, preferably a body fluid, for example blood or a fraction of blood. In certain aspects of the present invention, the compound or composition is a product to be administered to a subject in need, for example, a product to be injected, such as blood (as in the transfusion of blood from a donor to a recipient or the reintroduction of blood from a patient into the same patient) or insulin.
V il.c. A coated container or container, as described herein and / or prepared in accordance with a method described herein, may also be used to protect a compound or composition contained within it against the mechanical and / or chemical effects of the surface of the uncoated material. For example, it can be used to prevent or reduce precipitation and / or platelet coagulation or activation of the compound or a component of the composition, for example, insulin precipitation or blood clotting or platelet activation.
V II.C. It can also be used to protect a compound or composition contained within it against the exterior environment of the container, for example by preventing or reducing the entry of one or more compounds from the environment surrounding the container into the interior space of the container. Said environmental compound can be a gas or a liquid, for
373 example, an atmospheric gas or liquid that contains
INSTITUTO MILANO M LA PRaNSDAD INDUSTRIAL air and / or water vapor.
V II.C. A coated container, as described herein, can also be vacuum and stored in a vacuum state. For example, the liner allows for better vacuum maintenance, compared to a corresponding unlined container. In one aspect of this embodiment, the coated container is a blood collection tube. Said tube may also contain an agent to prevent blood clotting or platelet activation, for example EDTA or heparin.
V II.C. Any of the embodiments described above can be prepared, for example, by providing as a container a tube with a length of from about 1 cm to about 200 cm, optionally from about 1 cm to about 150 cm, optionally from about 1 cm to about 120 cm, optionally from about 1 cm to about 100 cm, optionally from about 1 cm to about 80 cm, optionally from about 1 cm to about 60 cm, optionally from about 1 cm to about 40 cm, optionally from about 1 cm to about 30 cm, and processing with a probe electrode as described below. Particularly for
374 <sub>η</sub> , , , <sub>=</sub> ίΜΡΙ ^^ the longer lengths in the above ranges, 'INDUSTRIAL that the relative movement between the probe and the vessel may be helpful during coating formation. This can be done, for example, by moving the container relative to the probe or by moving the probe relative to the container.
V II.C. In these embodiments, it is contemplated that the coating may be thinner or less complete than may be preferred for a barrier coating, since the container in some embodiments will not require the high barrier integrity of a blood collection tube when empty.
V il.C. As an optional feature of any of the above embodiments, the container has a central axis.
V II.C. As an optional feature of any of the above embodiments, the container wall is flexible enough to flex at least once at 20 ° C, without breaking the wall, in a range of at least substantially straight to a radius of curvature in the central axis not greater than 100 times the length of the external diameter of the container.
V II.C. As an optional feature of any of the above embodiments, the radius of curvature in the
<img file="MX345403B_D0232.tif" />
IMPI central axis is not greater than 90 times the INBUfflUAL greater than 80 times the length or is not greater than 70 times the length or is not greater than 60 times the length or is not greater than 50 times the length or is not greater than 4 0 times the length or not more than 30 times the length or not more than 20 times the length or not more than 10 times the length or not more than 9 times the length or not more than 8 times the length or is not more than 7 times the length or is not more than 6 times the length or not more than 5 times the length or not more than 4 times the length or not more than 3 times the length or not more than 2 times the length or not more than the external diameter of the container.
V II.C. As an optional feature of any of the above embodiments, the container wall can be a fluid contacting surface made of a flexible material.
V II.C. As an optional feature of any of the above embodiments, the cavity of the container may be the passage for fluid from a pump flow.
V II.C. As an optional feature of any of the above embodiments, the container may be a blood bag adapted to keep blood in good condition for medical use.
WICKED
V II.C., VII. D. As an INDUSTRIAL feature of any of the above embodiments, the polymeric material can be a silicone elastomer or a thermoplastic polyurethane, as two examples, or any material suitable for contact with blood or insulin.
V II.C.<sub>;</sub> VII.D. In an optional embodiment, the container has an internal diameter of at least 2mm or at least 4mm.
V II.C. As an optional feature of any of the above embodiments, the container is a tube.
V il.C. As an optional feature of any of the above embodiments, the cavity has at least two open ends.
V il.Cl Vessel containing viable blood with a deposited coating of an organosilicon precursor
V II.Cl Still another embodiment is a container containing blood. Several non-exhaustive examples of such a container are a blood transfusion bag, a blood sample collection container in which the sample has been collected, the tubes of a heart-lung machine, a wall-mounted blood collection bag. flexible tubes, or tubes used to collect blood from a patient during surgery and reintroduce the blood into the
<img file="MX345403B_D0233.tif" />
377 vasculature of the patient. If the to pump blood, a pump a centrifugal pump or a pump has a wall. The wall has a defined cavity. The inner surface of the wall has an at least partial coating of SiwOxCyHz, where preferably w is 1, x is from about 0.5 to 2.4, and is from about 0.6 to about 3, and z is from 2 to about 9, more preferably where w is 1, x is about 0.5 to 1, and is about 2 to about 3, and z is 6 to about 9. The coating can be thin with a monomolecular thickness or with a thickness of about 1000 nm. The container contains viable blood in its cavity that is in contact with the SiwOxCyHz coating, which can be returned to the vascular system of a patient.
V II.Cl One embodiment is a container that contains blood, includes a wall, and has an internal surface that defines a cavity. The inner surface has at least a partial coating of SiwOxCyHz. The coating may also comprise or consist essentially of SiOx, where x is as defined in the present description. The coating thickness is in the monomolecular thickness range
<img file="MX345403B_D0234.tif" />
378 I Μ Ρ I
MEXICAN INSTITUTE OF PROPERTY iNouyriUAi.
approximately 1000 nm thick on the inner surface. The container contains viable blood in its cavity that is in contact with the SiwOxCyHz coating, which can be returned to the vascular system of a patient.
V II.C.2. A deposited coating of an organosilicon precursor that reduces blood clotting or platelet activation in the container
V II.C.2. Another embodiment is a container that has a wall. The wall has an internal surface that defines a cavity and has at least one at least partial coating of SiwOxCyHz, where preferably w, x, y and z are as previously defined: w is 1, x is from about 0.5 to about 2.4, and is from about 0.6 to about 3, and z is from 2 to about 9, more preferably where w is 1, x is from about 0.5 to 1, and is from about 2 to about 3, and z is from 6 to about 9. The thickness of the coating is a monomolecular thickness at approximately 1000 nm thick on the inner surface. The coating effectively reduces coagulation or platelet activation of blood exposed to the inner surface, compared to the same type of wall without coating with SiwOxCyHz.
V II. C. 2. It is contemplated that the incorporation of a
IMPI
INDUSTRIAL
<img file="MX345403B_D0235.tif" />
Coating of
379
SiwOxCyHz will reduce the tendency to form blood clots, compared to its properties in contact with an unmodified SiOx or polymeric surface. This property is contemplated to potentially reduce or eliminate the need to treat blood with heparin, such as by reducing the necessary blood concentration of heparin in a patient undergoing surgery of a type that requires blood to be drawn and subsequently returned from the patient, such as when a heart-lung machine is used during heart surgery. It is contemplated that this will reduce the complications of surgery involving the passage of blood through said container, reducing complications due to bleeding resulting from the use of heparin.
vil.C.2. Another embodiment is a container that includes a wall and has an internal surface that defines a cavity. The internal surface has an at least partial coating of SiwOxCyHz, the thickness of said coating being monomolecular thickness at approximately 1000 nm thick on the internal surface, the coating being effective to reduce coagulation or platelet activation of blood exposed to the internal surface. .
V il.C.3. Container containing viable blood coated with a Group III or IV element<sup>380</sup> IMPIAS
V II. C. 3. Another embodiment is a container containing blood and having a wall with a surface-intexiia-qus.
defines a cavity. The inner surface has an at least partial coating of a composition comprising one or more group III elements, one or more group IV elements, or a combination of two or more of these. The thickness of the coating is between a monomolecular thickness and about 1000 nm thick, inclusive, on the inner surface. The container contains in its cavity viable blood that is in contact with the lining, which can be returned to the vascular system of a patient.
V II.C.4. Coating of a group III or IV element that reduces blood clotting or platelet activation in the container
V II.C.4. Optionally, in the container of the preceding paragraph, the coating of the group III or IV element effectively reduces coagulation or platelet activation of blood exposed to the inner surface of the container wall.
V II.D. Pharmaceutical administration containers
V II.D. A coated container or container, as described herein, can be used to prevent or reduce the leakage of a compound or composition contained in
381 said container towards the environment that
Other uses are also contemplated
<img file="MX345403B_D0236.tif" />
<img file="MX345403B_D0237.tif" />
surrounds the <sup>Μ</sup>, £? ° ΒβΑΐ :. 'NDUSTRIAI of the coating and
<img file="MX345403B_D0238.tif" />
container, as described herein, resulting in:
evident in view of any part of the description and claims.
V II.Dl Container containing insulin with a deposited coating of an organosilicon precursor
V II.Dl Another embodiment is a container that contains insulin and includes a wall with an internal surface defining a cavity. The inner surface has at least a partial coating of SiwOxCyHz, preferably where w, x, and z are as previously defined: w is 1, x is about 0.5 to 2.4, and is about 0.6 to about 3, and z is 2 at about 9, more preferably where w is 1, x is from about 0.5 to 1, and is from about 2 to about 3, and z is from about 6 to about 9. The coating can have a monomolecular thickness thickness at about 1000 nm thick on the inner surface. Insulin is disposed within the cavity in contact with the SiwOxCyHz coating.
V II.Dl Another embodiment is an insulin-containing container that includes a wall and has an internal surface that defines a cavity. The inner surface has
382
<img file="MX345403B_D0239.tif" />
an at least partial coating of Siw0xCyHawnfi®áSJ4 (X os u wWmp thickness of the coating of monomolecular thickness at approximately 1000 nm thick on the inner surface. Insulin, for example, pharmaceutical insulin authorized by the FDA for human use, is disposed within of the cavity in contact with the SiwOxCyHz coating.
V II.Dl It is contemplated that the incorporation of a SiwOxCyHz coating will reduce adhesion or the tendency to form precipitates of insulin in an insulin pump delivery tube, compared to its properties in contact with an unmodified polymeric surface. . This property is contemplated to potentially reduce or eliminate the need to filter the insulin passing through the administration tube to remove a solid precipitate.
V II.D.2. Deposited coating of an organosilicon precursor that reduces precipitation of insulin in the container
V II.D.2. Optionally, in the container from the previous paragraph, the SiwOxCyHz coating effectively reduces the formation of a precipitate with the insulin that is in contact with the inner surface, compared to the same surface without the SiwOxCyHz coating.
V II.D.2. Another embodiment is a container that
II »
383 again comprises an internal wall and that defines a cavity, includes at least one lining that
<img file="MX345403B_D0240.tif" />
The partial inner surface of SiwOxCyHz. The thickness of the coating is in the range of monomolecular thickness to about 1000 nm thick on the inner surface. The coating effectively reduces the formation of a precipitate with the insulin that is in contact with the inner surface.
V II.D.3. Container containing insulin with a coating of a Group III or IV element
V il.D.3. Another embodiment is a container that contains insulin and includes a wall with an internal surface defining a cavity. The inner surface is at least partially coated with a composition comprising carbon, one or more group III elements, one or more group IV elements, or a combination of two or more of these. The coating can have a thickness in the range of monomolecular thickness to about 1000 nm thick on the inner surface. Insulin is arranged within the cavity in contact with the coating.
V II.D.4. Coating of a group III or IV element that reduces the precipitation of insulin in the container
<img file="MX345403B_D0241.tif" />
384
V II.D.4. Optionally, in the above container, coating a composition, comprising carbon, one or more Group III elements, one or more Group IV elements, or a combination of two or more of these, effectively reduces the formation of a precipitate with the insulin that is in contact with the inner surface, compared to the same surface without the coating.
PRACTICAL EXAMPLES
Example 0: Basic protocols for forming and coating syringe tubes and cylinders
The vessels evaluated in the working examples below were formed and coated according to the following protocol examples, unless otherwise indicated in individual examples. The particular parameter values stated in the following basic protocols, for example electrical power and process gas flow, are typical values. Whenever parameter values are changed compared to these typical values, this will be noted in subsequent practical examples. The same applies to the type and composition of the process gas.
Protocol for forming a COC tube (used, for example, in Examples 1, 19)
385
PREVENTS
Cycloolefin tubes (COC) in the shape and size commonly used as vacuum blood collection tubes (COC tubes) were injection molded from Topas® 8007-04 cycloolefin copolymer (COC) resin, available from Hoechst AG, Frankfurt am Main, Germany, which has these dimensions: 75 mm in length, 13 mm in external diameter and 0.85 mm in wall thickness, each having a volume of approximately 7.25 cm3 and a rounded, closed end.
Protocol for forming a PET tube (used, for example, in Examples 2, 4, 8, 9, 10)
Polyethylene terephthalate (PET) tubes of the type commonly used as cast blood collection tubes (PET tubes) were injection molded into the same mold used for the COC Tube Forming Protocol, which has these dimensions: 75mm of length,. 13 mm external diameter and 0.85 mm wall thickness, each having a volume of approximately 7.25 cm3 and a rounded, closed end.
Protocol for coating the interior of tubes with SiOx (used, e.g., in Examples 1, 2, 4, 8, 9, 10, 18, 19)
The apparatus shown in FIG. 2 with the sealing mechanism of FIG. 45 which is an embodiment with Delrin® acetal resin, marketed by EI du Pont de Nemours and Co., Wilmington Delaware, United States, with an external diameter of 1.75 inches (44 mm) and a height of 1.75 inches (44 mm) . Container holder 50 was stored in a Delrin® frame that allowed the device to move in and out of electrode (160).
Electrode 160 was made of copper with a Delrin® shield. The Delrin® shield was formed around the outside of the copper electrode 160. The electrode 160 was approximately 3 inches (76 mm) high on the inside and approximately 0.75 inches (19 mm) wide.
Tube used as container 80 was inserted into container holder 50 by sealing the base with Viton® 490, 504 O-rings (Viton® is a registered trademark of Dupont Performance Elastomers LLC, Wilmington Delaware, USA) around the outside of the tube ( FIG. 45). Tube 80 was carefully moved into the sealing position over the extended (fixed) 1/8 inch (3 mm) diameter bronze probe or counter electrode 108 and was driven against a copper plasma screen.
The 610 copper plasma screen was a perforated copper foil material (K&S Engineering, Chicago Illinois, USA, copper mesh Part No.LXMUW5) cut to
387
<img file="MX345403B_D0242.tif" />
fit the tube OD position by abutment surface 494 <sup>M</sup> radially extending industrial locking device that acted as a lock for tube insertion (refer to FIG. 45). Two pieces of copper mesh were tightly fitted around the bronze probe or counter electrode 108, ensuring good electrical contact.
The bronze probe or counter electrode 108 extended approximately 70 mm into the tube and had a No. 80 wire arrangement (diameter = 0.0135 inches or 0.343 mm). The bronze probe or counter electrode 108 extended through a Swagelok® connector (available from Swagelok Co., Solon Ohio, USA) located at the bottom of the vessel holder 50, extending through the base frame of the vessel holder. fifty. The bronze probe or counter electrode 108 was grounded in the RF matching network cover.
The gas supply port 110 consisted of 12 holes in the probe or counter electrode 108 along the length of the tube (three on each of the four sides oriented at 90 degrees to each other) and two holes in the cap of the gas. aluminum covering the end of the gas supply port 110. The gas supply port 110 was connected to a stainless steel assembly comprising Swagelok® connectors incorporating a ball valve
388 manual for venting, a thermopan pressure gaugeNsWrutBjWkicXíalVs & ft
THE FROrUDAP
INDUSTRIAL diversion connected to the vacuum pumping line. Additionally, the gas system was connected to gas supply port 110 allowing process gases, oxygen and hexamethyldisiloxane (HMDSO) to flow through gas supply port 110 (at process pressures) into the tube.
The gas system comprised an Aalborg® GFC17 mass flow meter (Part No. EW-32661-34, Cole-Parmer Instrument Co., Barrington Illinois, USA) to allow oxygen to flow in a controlled manner at 90 sccm (or at flow specific indicated for a particular example) in the process and a 49.5 inch (1.26 inch) polyether ether ketone (PEEK) capillary (OD 1/16 inch (1.5mm), ID ID 0.004 inch (0.1mm)) m) in length. The PEEK capillary end was inserted into liquid hexamethyldisiloxane (HMDSO, Alfa Aesar® Part number L16970, Grade NMR, available from Johnson Matthey PLC, London). Liquid HMDSO was drawn through the capillary due to the lower pressure in the tube during processing. The HMDSO was subsequently vaporized into a vapor at the outlet of the capillary as it entered the low pressure region.
To ensure that the condensation of the liquid HMDSO does not exceed this point, the gas stream (including the
389 oxygen) was diverted to the pump line cua;
flowing into the tube for processing through a Swagelok® 3-way valve. Once the tube was installed, the valve of the vacuum pump was opened to the container holder 50 and into the tube.
The vacuum pump system comprised a rotary vane vacuum pump and an Alcatel bellows. The pumping system allowed to reduce the pressure inside the tube to pressure (s) less than 200 mTorr while the process gases flowed at the indicated rates.
Once the base vacuum level was reached, the vessel holder assembly 50 was shifted to the electrode assembly 160. The gas stream (oxygen and HMDSO vapor) was flowed into the copper gas supply port 110 ( adjusting the 3-way valve on the pump line to gas supply port 110). The pressure inside the tube was approximately 300 mTorr, as measured by a capacitance manometer (MKS) installed in the pumping line near the valve that controlled the vacuum. In addition to the tube pressure, the pressure within the gas supply port 110 and gas system was also measured with the thermocouple vacuum gauge connected to the gas system. The pressure used to be less than 8 Torr.
Once the gas flowed into the tube, it was
390
ΪΜΡΙ ^ turned on the RF power supply 'Se!
INDUSTRIAL -fixed power. A source of al-i τη Anta ojon RF of. 600 watts ENI ACG-6 (at 13.56 MHz) at a fixed power level of approximately 50 watts. The output power was calibrated in this and all the following protocols and examples using an RF Watt Meter, Bird Corporation Model 43, connected to the RF output of the power supply during operation of the coating apparatus. The following relationship was found between the power supply dial setting and the output power: RF output power = 55 x
Dial settings. In the applications prior to the present application, a factor of 100 was used, which was incorrect. The RF power supply was connected to a COMDEL CPMX1000 autotuning that matched the complex impedance of the plasma (which was to be created in the tube) to the 50 ohm output impedance of the power supply
ENI ACG-6 RF. The transmitted power was 50 watts (or the specific amount indicated for a particular example) and the reflected power was 0 watts so that the applied power was supplied into the tube. The RF power supply was controlled by a laboratory timer and the power versus time was set at 5 seconds (or the specific period of time indicated for a
ΙΜΡΙ @ particular example). After starting the industrial power, it established a uniform plasma inside the tube.
| The plasma was held for the full 5 seconds until the RF power was cut off by the timer. The plasma produced a coating of silicon oxide approximately 20 nm thick (or the specific thickness indicated in a particular example) on the inside of the tube surface.
After coating, the gas flow was diverted back to the vacuum line and the vacuum valve was closed. The vent valve was then opened causing the pressure inside the tube to return to atmospheric pressure (approximately 760 Torr). The tube was carefully removed from the vessel holder assembly 50 (after moving the vessel holder assembly 50 out of the electrode assembly 160).
Protocol for coating the inside of the tube with a hydrophobic coating (used, eg, in Example 9)
The apparatus shown in FIG. 2 with the sealing mechanism of FIG. 4 5 which is a specific contemplated embodiment. Container holder 50 was made from Delrin® acetal resin, sold by EI du Pont de Nemours and Co., Wilmington Delaware, USA, with
392 an outside diameter of 1.75 inches (44 mm). «MDUSTRIAl
1.75 inches (44 mm). Container holder 50 was stored in a Delrin® frame that allowed the device to move in and out of electrode (160).
Electrode 160 was made of copper with a shield
Delrin®. The Delrin® shield was formed around the outside of the copper electrode 160. The electrode 160 was approximately 3 inches (76 mm) high on the inside and approximately 0.75 inches (19 mm) wide.
Tube used as container 80 was inserted into container holder 50 by sealing the base with Viton® 490, 504 O-rings (Viton® is a registered trademark of Dupont Performance Elastomers LLC, Wilmington Delaware, USA) around the outside of the tube ( FIG. 45). The tube
80 it was carefully moved into the sealing position over the extended (fixed) 1/8-inch (3mm) diameter bronze probe or counter electrode 108 and propelled against a copper plasma screen.
The 610 copper plasma screen was a perforated copper foil material (K&S Engineering, Chicago Illinois, United States, copper mesh Part No LXMUW5) cut to fit the outer diameter of the tube and held in place by a stop surface 494 that extended radially and acted as a lock for tube insertion (refer to FIG. 45). They were adjusted bísenrrod ^ -. D<sup>J</sup> from u 'NT - :; vti<sub>Ua</sub> of copper mesh around the bronze probe or counter electrode 108, guaranteeing good electrical contact.
The bronze probe or counter electrode 108 extended approximately 70 mm into the tube and had a No. 80 wire arrangement (diameter = 0.0135 inches or 0.343 mm). The bronze probe or counter electrode 108 extended through a Swagelok® connector (available from Swagelok Co., Solon Ohio, USA) located at the bottom of the vessel holder 50, extending through the base frame of the vessel holder. fifty. The bronze probe or counter electrode 108 was grounded in the RF matching network cover.
The gas supply port 110 consisted of 12 holes in the probe or counter electrode 10 8 along the length of the tube (three on each of the four sides oriented at 90 degrees to each other) and two holes in the cap aluminum that covered the end of the gas supply port 110. Gas supply port 110 was connected to a stainless steel assembly comprising Swagelok® connectors incorporating a manual ball valve for venting, a thermocouple gauge, and a diverter valve connected to the vacuum pump line. Also, the gas system was connected to the gas supply port
394
IMPI
110 allowing process gases to flow through gas supply port 110 (at process pressures) into the tube.
The gas system comprised a mass flow meter
Aalborg® GFC17 (Part No EW-32661-34, Cole-Parmer Instrument Co., Barrington Illinois, United States) so that oxygen would flow in a controlled manner at 60 sccm (or at the specific flow indicated for a particular example) in the process and a polyether ether ketone (PEEK) capillary (outer diameter, OD 1/16 inches (1.5 mm), ID ID 0.004 inches (0.1 mm)) 49.5 inches (1.26 m) long. The PEEK capillary end was inserted into liquid hexamethyldisiloxane (HMDSO, Alfa Aesar® Part number L16970, Grade NMR, available from Johnson Matthey PLC, London). Liquid HMDSO was drawn through the capillary due to the lower pressure in the tube during processing. The HMDSO was subsequently vaporized into a vapor at the outlet of the capillary as it entered the low pressure region.
To ensure that the condensation of the liquid HMDSO did not go beyond this point, the gas stream (including oxygen) was diverted into the pump line when it was not flowing into the tube for processing by means of a 3-way valve. Swagelok®. Once I know
395
<img file="MX345403B_D0243.tif" />
<img file="MX345403B_D0244.tif" />
<img file="MX345403B_D0245.tif" />
Installed support tube, 50 vessels vac pump valve
INSTITUTO MEXICANO • E LA PROPERTY and inside the tube. industrial
The vacuum pump system comprised a rotary vane vacuum pump and an Alcatel bellows. The pumping system allowed to reduce the pressure inside the tube to pressure (s) less than 200 mTorr while the process gases flowed at the indicated rates.
Once the base vacuum level was reached, the vessel holder assembly 50 was shifted to the electrode assembly 160. The gas stream (oxygen and HMDSO vapor) was flushed into the copper gas supply port 110 (by adjusting the 3-way valve on the pump line to gas supply port 110). The pressure inside the tube was approximately 270 mTorr, as measured by a capacitance manometer (MKS) installed in the pumping line near the valve that controlled the vacuum. In addition to the tube pressure, the pressure within the gas supply port 110 and gas system was also measured with the thermocouple vacuum gauge connected to the gas system. The pressure used to be less than 8 Torr.
Once the gas flowed into the tube, the RF power supply was turned on at its fixed power level. A 600 watt ENI ACG-6 RF power supply (at 13.56 MHz) was used at a power level
IMPI
MUICANO INSTITUTE
The source of aliWSSmó
<img file="MX345403B_D0246.tif" />
396 fixed approximately 39 watts.
RF signal was connected to an automatic adjustment COMDET ,,, GPMX.1 Ω.0, Q ... which adjusted the complex impedance of the plasma (which was to be created in the tube) to the output impedance of 50 ohm of the source ENI ACG-6 RF power supply. The transmitted power was 39 watts (or the specific amount indicated for a particular example) and the reflected power was 0 watts so that the applied power was delivered into the tube. The RF power supply was controlled by a laboratory timer and the power versus time was set at 7 seconds (or the specific time period indicated for a particular example). After starting the RF power, a uniform plasma was established inside the tube. The plasma was held for the full 7 seconds until the RF power was interrupted by the timer. The plasma produced a coating of silicon oxide approximately 20 nm thick (or the specific thickness indicated in a particular example) on the inside of the tube surface.
After coating, the gas flow was diverted back to the vacuum line and the vacuum valve was closed. The vent valve was then opened causing the pressure inside the tube to return to atmospheric pressure (approximately 760 Torr). The tube
<img file="MX345403B_D0247.tif" />
it was carefully removed from the 50 'pot holder assembly (after moving the pot holder assembly 50 out of the electrode assembly 160).
Protocol for forming a COC 5 syringe barrel (used, for example, in Examples 3, 5, 11-18, 20)
Syringe barrels (COC syringe barrels), CV Holdings Part 11447 were injection molded, each with a total volume of 2.8 mL (excluding the Luer-type connector) and a nominal delivery volume of 10 mL or 1 mL displacement. plunger, Luer adapter type, made from Topas® 8007-04 cycloolefin copolymer (COC) resin, sold by Hoechst AG, Frankfurt am Main, Germany, having these dimensions: approximately 51mm in total length, 8.6mm inner diameter of the syringe barrel, and 1.27mm wall thickness in the cylindrical portion, with an integral 9.5mm length capillary Luer needle adapter molded into one of the ends and two molded holding clamps near the other end.
Protocol for coating the inside of a COC syringe barrel with SiOx (used, e.g., in Examples 3, 5, 18)
An injection molded COC syringe barrel was coated on the inside with SiOx. The apparatus shown
398
ΡΙ in FIG. 2 with the '£' * sealing mechanism industmai modified to support a COC syringe barrel with a butt seal at the base of the COC syringe barrel.
Additionally, a cap was fabricated from a stainless steel Luer connector and a polypropylene cap that sealed the end of the COC syringe barrel (illustrated in FIG. 26), allowing a vacuum to be created in the cylinder of COC syringe.
Container holder 50 was made from Delrin® with an outer diameter of 1.75 inches (44 mm) and a height of 1.75 inches (44 mm). Container holder 50 was housed in a Delrin® frame that allowed the device to move out and into electrode 160.
Electrode 160 was made of copper with a shield
Delrin®. The Delrin® shield was formed around the outside of the copper electrode 160. The electrode 160 was approximately 3 inches (76 mm) high on the inside and approximately 0.75 inches (19 mm) wide. The COC syringe barrel was inserted into container holder 50, sealing the base with Viton® O-rings.
The COC syringe barrel was carefully moved to the sealing position on the extended 1/8 inch diameter (3mm) bronze probe (fixed) or counter electrode 108 and pushed against a plasma screen
399 coppermade.
The copper plasma screen e 'NSTITUTO M1XICANO £> e la raorieoAo INDUSTRIAL perforated copper foil (K&S Engineering, copper mesh _
Part No.LXMUW5) cut to fit the outside diameter of the COC syringe barrel and held in position 5 by a stop surface 4 94 that acted as a lock for the insertion of the COC syringe barrel. Two pieces of copper mesh were tightly fitted around the bronze probe or counter electrode 108, ensuring good electrical contact.
The probe or counter electrode 108 extended approximately 20 mm into the COC syringe barrel and was open at its end. The bronze probe or counter electrode 108 extended through a Swagelok® connector located in the bottom of the vessel holder 50, extending through the base frame of the vessel holder 50. The bronze probe or counter electrode 108 was connected to ground on the cover of the RF matching network.
Gas supply port 110 was connected to a stainless steel assembly comprising Swagelok® connectors incorporating a manual ball valve for venting, a thermocouple gauge, and a diverter valve connected to the vacuum pump line. Additionally, the gas system was connected to process gas supply port 110 <r ^ # SÉtífé ™ allowing gases to
INDUSTRIAL hexamethyldisiloxane (HMDSO) will flow through gas supply port 110 (at process pressures) into the COC syringe barrel.
The gas system comprised a mass flow meter
Aalborg® GFC17 (Cole Parmer Part No EW-32661-34) for oxygen to flow in a controlled manner at 90 sccm (or at the specific flow indicated for a particular example) in the process and a PEEK capillary (OD 1/16 inches (3mm), ID
0.004 inches (0.1 mm)) of 49.5 inches (1.26 m) in length. The PEEK capillary end was inserted into liquid hexamethyldisiloxane (Alfa Aesar® Part Number L16970, Grade NMR). Liquid HMDSO was drawn through the capillary due to the lower pressure in the COC syringe barrel during processing. The HMDSO was subsequently vaporized into a vapor at the outlet of the capillary as it entered the low pressure region.
To ensure that condensation does not occur
Liquid HMDSO past this point, the gas stream (including oxygen) was diverted to the pump line when it was not flowing into the COC syringe barrel for processing via a Swagelok® 3-way valve.
After the COC syringe barrel is installed, the <sup>521</sup> IMPI ^
MEXICAN INSTITUTE
203. The invention of any of Re 182-202, wherein a processing device is configured to measure air pressure loss through a wall of a container.
204. The invention of any of claims 182-203, wherein a processing device comprises a bearing surface for supporting the container holder in a predetermined position while the interior surface of the seated container is processed with the processing device.
205. The invention of claim 204, wherein, after seating the container opening over the container port, the container holder is transported coupled to the bearing surface.
206. The invention of any of claims 182-205, wherein another processing device comprises a second bearing surface for supporting the container holder in a predetermined position while processing the interior surface of the seated container with the other processing device.
207. The invention of claim 206, wherein, after seating the container opening over the container port, the container holder is transported coupled to the second bearing surface.
<img file="MX345403B_D0248.tif" />
. «2 IMPI 'NSTHV«> MEXICAN _ -. ...,. ,,. ^^ 3025 ^ 9.
208. The invention of any of the reivin'Cft ^ TBWSi
182-207, wherein another device d3 "" p LOt ΰ & aiit'i be comprises a third bearing surface to support the container support in a predetermined position while processing the interior surface of the container seated through the port of containers with the other processing device.
209. The invention of claim 208, wherein, after seating the container opening over the container port, the container holder is transported coupled to the third bearing surface.
210. The invention of any of claims 182-209, further comprising:
providing a third processing device separate from the first and second processing devices for processing containers;
transporting the container holder and the seated container from the second processing device to the third processing device; and processing the interior surface of the container seated through the container port with the third processing device;
211. The invention of any of claims 182-210, further comprising seating the opening of the
523
<img file="MX345403B_D0249.tif" />
IMPI container on the container port in a ^ ía ^ e ^^ processing. _______
212. The invention of any of claims 182-211, further comprising forming a coating on the interior of a container through the container port in a processing device.
213. The invention of any of claims 182-212, wherein processing in a processing device comprises inspecting the interior surface of a container for defects.
214. The invention of claim 213, wherein the inspection is carried out by inserting a detection probe into the container through the container port and detecting the condition of the interior surface of the container using the probe.
215. The invention of claim 214, further comprising radiating energy inward through the wall of the container and the interior surface of the container, and sensing the energy with the probe.
216. The invention of claim 214 or 215, further comprising sensing the condition of the interior surface of the container at numerous closely spaced positions on the interior surface of the container.
217. The invention of any of the claims
<img file="MX345403B_D0250.tif" />
524 IMPI
INSTITUTO MÍXlCANO OELATOOHEDAD
213-216, in which the inspection of a radiation source in the container is carried out through 5 dtíl poéft'o of containers and detecting the condition of the interior surface of the container by detecting radiation from the radiation source using a detector.
218. The invention of any of claims 213-217, further comprising radiating energy outward through the interior surface of the container and sensing the energy with a detector located outside the container.
219. The invention of any of claims 215-216, further comprising reflecting radiation from the interior surface of the container and detecting the energy with a detector located within the container.
220. The invention of any of claims 213-219, further comprising sensing the condition of the interior surface of the container at numerous closely spaced positions on the interior surface of the container.
221. The invention of any of claims 182-220, wherein processing in a processing device comprises applying a coating to the interior surface of a container.
222. The invention of any of claims 182-221, wherein the processing on a processing device comprises applying a coating as a
IMPI
<img file="MX345403B_D0251.tif" />
525
INSTITUTO MEXICANO „OE LA HROFtEDAD liquid on the inside surface of a container! 'S<sup>l</sup>?<sup>T</sup>"'Ai·
223. The invention of any of the "TeTU IIIÜIluuíuikw
182-222, wherein processing in a processing device comprises inspecting a coating on the interior surface of a container for defects.
224. The invention of any of claims 221-223, comprising inserting a detection probe into the container through the container port and detecting the condition of the coating using the probe.
225. The invention of any of claims 221-224, further comprising radiating energy inward through the wall of the container and sensing the energy with the probe.
226. The invention of any of claims 221-225, further comprising sensing the condition of the coating at numerous closely spaced positions on the interior surface of the container.
227. The invention of any of claims 223-131, further comprising carrying out the inspection step at a sufficient number of locations across the entire interior surface of the container to determine whether the container will effectively prevent pressure within the container, when initially emptied and its wall exposed to ambient atmosphere, increase to more than 20%
526 atmospheric pressure for a year.
<img file="MX345403B_D0252.tif" />
228. The invention of any of the claims
223-227, in which the inspection stage is carried out in a period of less than or equal to 30 seconds per container.
229. The invention of any of the claims
223-227, in which the inspection stage is carried out in less than or equal to 25 seconds per container.
230. The invention of any of claims 223-227, wherein the inspection step is carried out in less than or equal to 20 seconds per container.
231. The invention of any of claims 223-227, wherein the inspection step is carried out in less than or equal to 15 seconds per container.
232. The invention of any of claims 223-227, wherein the inspection step is carried out in less than or equal to 10 seconds per container.
233. The invention of any of claims 223-227, wherein the coating and inspection steps are carried out in less than or equal to 30 seconds per container.
2. 3. 4. The invention of any of claims 223-227, wherein the coating and inspection steps are carried out in less than or equal to 25 seconds per container
235. The invention of any of claims 223-227, wherein the coating and inspection steps are carried out in less than or equal to 20 seconds per container.
236. The invention of any of claims 223-227, wherein the coating and inspection steps are carried out in less than or equal to 15 seconds per container.
237. The invention of any of claims 223-227, wherein the coating and inspection steps are carried out in less than or equal to 10 seconds per container.
238. The invention of any of claims 223-227, further comprising carrying out the sensing step at a sufficient number of locations throughout the interior surface of the container to determine whether the container will effectively prevent pressure within the container, When initially drained and its wall exposed to ambient atmosphere, increase to more than 20% ambient atmospheric pressure for a service life of at least 18 months.
239. The invention of any of claims 223-227, further comprising carrying out the step of <sup>528</sup> IMPI £
INSTITUTO MEXICANO g? detection at a sufficient number of positions on fwaiiAL 1 ^ inner surface of the container to de terrorn ^ rr— -if —- the barrier coating will effectively prevent pressure within the container, when initially emptied and its wall is exposed to the ambient atmosphere, increase to more than 20% ambient atmospheric pressure for a service life of at least two years.
240. The invention of any of claims 223-227, further comprising carrying out the sensing step at a sufficient number of locations across the entire interior surface of the container to determine whether the barrier coating will effectively prevent pressure within the The vessel, when initially emptied and its wall exposed to the ambient atmosphere, rises to more than 15% ambient atmospheric pressure over a one-year service life.
241. The invention of any of claims 223-227, further comprising carrying out the sensing step at a sufficient number of locations across the entire interior surface of the container to determine whether the barrier coating will effectively prevent pressure within the The container, when initially emptied and its wall exposed to the ambient atmosphere, rises to more than 10% ambient atmospheric pressure during a
529 shelf life of one year
MEXICAN INSTITUTE OF INSIISTAIAL PROPERTY
242. The invention of any of claims 223-241, wherein the inspection is carried out by inserting a radiation source into the container through the container port and detecting the condition of the coating by detecting radiation from the radiation source using a detector.
243. The invention of any of claims 223-242, further comprising radiating energy outward through the liner and wall of the container, and sensing the energy with a detector located outside the container.
244. The invention of any of claims 223-243, further comprising reflecting radiation from the liner and wall of the container, and detecting the energy with a detector located within the container.
245. The invention of any of claims 223-244, further comprising sensing the condition of the coating at numerous closely spaced positions on the interior surface of the container.
246. The invention of any of claims 223-245, wherein inspection for defects of a coating on the inside surface of the container is carried out by measuring the effectiveness of the barrier against
<img file="MX345403B_D0253.tif" />
530
IΜXi air pressure of container wall reveá'fTSÍa / w ^^^
247. The invention of any of claims 212-246, wherein the coating reduces the transmission of atmospheric gases into the container through its interior surface.
248. The invention of any of claims 212-247, wherein the coating reduces contact of the contents of the container with the interior surface.
249. The invention of any of claims 212-248, wherein the coating comprises SiOx, where x in this formula is from about 1.5 to about 2.9, alternatively from about 1.5 to about 2.6, alternatively about 2, elemental carbon, a fluorine-based material, SiwOxCyHz, where w is 1, x is about 0.5 to 2.4, and is about 0.6 to about 3, and z is 2 to about 9, or a combination of these.
250. The invention of any of claims 182-249, further comprising removing the container from the container holder after processing the interior surface of the seated container with the second processing device.
251. The invention of claim 250, further comprising:
after the container stage having an inner surface; and
531 removal
<img file="MX345403B_D0254.tif" />
opening and a wall defining a seating the opening of the second container over the container port.
252. The invention of any of claims 250-251, further comprising processing the inner surface of the second container seated through the container port with the first processing device.
253. The invention of any of claims 250-252, further comprising transporting the container support and the second seated container from the first processing device to the second processing device.
254. The invention of any of claims 250-253, further comprising processing the second container seated through the container port with the second processing device.
255. The invention of any of claims 182-254, further comprising forming the container in a mold, removing the container from the mold and, within 60 seconds after removing the container from the mold, seating the container opening over the port of containers.
256. The invention of any of the claims
<img file="MX345403B_D0255.tif" />
MEXICAN INSTITUTE
182-255, which further comprises forming the reci ^ íi ^ J ^^ Suveri ^ *; ® mold, removing the container from the mold and, in nn -pi = 3 ^ seconds after removing the container from the mold, seating the opening of the container over the container port.
257. The invention of any of claims 182-256, further comprising forming the container in a mold, removing the container from the mold and, within 25 seconds after removing the container from the mold, seating the container opening over the port of containers.
258. The invention of any of claims 182-257, further comprising forming the container in a mold, removing the container from the mold and, within 20 seconds after removing the container from the mold, seating the container opening over the port of containers.
259. The invention of any of claims 182-258, further comprising forming the container in a mold, removing the container from the mold and, within 15 seconds after removing the container from the mold, seating the container opening over the port of containers.
260. The invention of any of claims 182-259, further comprising forming the container in a mold, removing the container from the mold and, within 10 seconds after removing the container from the mold, seating the container opening over the port of containers.
533
IMPI ^ mlíójano Institute of the rtbwrpi d
261. The invention of any of the reiviriqTc & ™ ion% i? 182-260, which further comprises forming the container · ”βη<sup>1</sup>WT mold, remove the container from the mold, and within 5 seconds after removing the container from the mold, seat the container opening over the container port.
262. The invention of any one of claims 182-261, further comprising forming the container in a mold, removing the container from the mold and, within 3 seconds after removing the container from the mold, seating the container opening over the port of containers.
263. The invention of any of claims 182-262, further comprising forming the container in a mold, removing the container from the mold, and within 1 second after removing the container from the mold, seating the container opening over the port of containers.
III. C. Using a clamping tool to transport pipe to and from a coating station
64. A method of PECVD treatment of a first container, comprising:
providing a first container having an open end, a closed end, and an interior surface;
providing at least a first holding tool that is configured to selectively hold and release the closed end of the first container;
<sup>534</sup> IMPI ^. , INSTITUTO MEXICANO hold the closed end of the first recior »Sw first clamping tool; Using the first clamping tool, transporting the first container into position near a container holder configured to position the open end of the first container;
using the first clamping tool, advancing the first container axially and seating its open end in the container holder to establish sealed communication between the container holder and the interior of the first container;
introducing at least one gaseous reagent into the first container through the container holder;
forming plasma within the first container under conditions effective to form a reaction product of the reagent on the interior surface of the first container;
releasing the first container from the container holder; and using the first clamping tool or other clamping tool, axially transporting the first container away from the container holder; and releasing the first container from the holding tool used to transport it axially away from the container holder.
65. The invention of claim ΣδΤΤ ™<sup>1</sup>*<sup>1</sup> further comprising:
providing a reaction vessel different from the first vessel, the reaction vessel having an open end and an interior space;
seating the open end of the reaction vessel in the vessel holder, thereby establishing a sealed communication between the vessel holder and the interior space of the reaction vessel;
providing a PECVD reagent conduit within the interior space;
forming the plasma within the interior space of the reaction vessel under conditions effective to remove at least a portion of a reservoir of a PECVD reaction product from the reagent conduit;
releasing the reaction vessel from the vessel holder; and transporting the reaction vessel away from the vessel holder.
266. The invention of claim 264 or 265, further comprising:
providing at least a second holding tool;
functionally connect at least the first and second <sup>536</sup> ΪΜΡΙ ^
INSTITUTO MEXICANO DELAFKCFUIMD clamping tool to a serial conveyor; 'NoumtAL provide a second container that tWI'lt! Lili yALLSTO open, a closed end and an inner surface;
providing a holding tool configured to selectively hold and release the closed end of the second container;
clamping the closed end of the second container with the clamping tool;
using the holding tool, transporting the second container into position near a container support configured to seat the open end of the second container;
using the clamping tool, advancing the second container axially and seating its open end in the container support to establish sealed communication between the container support and the interior of the second container;
introducing at least one gaseous reagent into the second container through the container holder;
forming plasma within the second container 'under conditions effective to form a reaction product of the reagent on the interior surface of the second container;
releasing the second container from the container holder; and
537
Using the second holding tool or other holding tool, KSE axially transport the second container away from the container holder; and releasing the second container from the holding tool used to transport it axially away from the container holder.
IV. PECVD APPARATUS TO MAKE CONTAINERS
IV. A. PECVD apparatus including a vessel holder, an internal electrode, and a vessel as a reaction chamber
267. A PECVD device comprising:
a container holder having a port for receiving a container in a seated position for processing;
an internal electrode positioned to be inserted into a container seated in a container holder;
an outer electrode having an inner portion positioned to receive a container seated on the container holder; and a power source supplying alternating current to at least the inner or outer electrode to form plasma within a container seated on the container holder, the container defining a plasma reaction chamber.
<img file="MX345403B_D0256.tif" />
268. The invention of claim 267, wherein the inner electrode is a probe having a distal portion positioned to extend generally concentrically in a container seated in the container holder.
268a. The invention of claim 267 or 268, further comprising a source of reactive gas and a gas feed for feeding a reactive gas from the source of reactive gas into a container seated on the container holder.
269. The invention of claim 268a, wherein the gas feed is at the distal portion of the inner electrode.
270. The invention of claim 268a or 269, further comprising a passageway within the inner electrode for transporting the reactive gas from the source of the reactive gas to the distal portion of the inner electrode.
271. The invention of any of claims 267-270, further comprising a carrier gas source and a passage within the inner electrode for transporting a carrier gas from the carrier gas source to the distant portion! of the inner electrode.
272. The invention of any one of claims 267-271, wherein the outer electrode is generally cylindrical and is positioned to extend generally concentrically around a container asAV ^ JS ^ Rásiri container support. -
273. The invention of any of claims 267-272, wherein the outer electrode comprises an end cap.
274. The invention of claim 273, wherein a space defined between the end cap and the distal end of a container seated on the container holder is essentially uniform.
275. The invention of any of claims 267-274, wherein a defined gap between the outer electrode and a container seated on the container holder is essentially uniform.
276. The invention of any of claims 117-167 or 212-168, wherein the coating comprises a SiOx layer and a SiwOxCyHz layer, where w is 1, x in this formula is from about 0.5 to about 2.4, and is from about 0.6 to about 3, and z is from 2 to about 9.
278. The invention of claim 276 or 277, wherein the SiwOxCyHz layer is deposited on a SiOx layer that is deposited on the inner surface of the container.
279. The invention of claim 276 or 277, wherein
<img file="MX345403B_D0257.tif" />
540
ΙΝίΤΓΗΛΟ MEXICAN that the SiOx layer is deposited between
SiwOxCyHz and the inner surface of the vessel ^ g,
280. The invention of any of claims 276-279, wherein the SiOx layer is deposited adjacent to the SiwOxCyHz layer.
281. The invention of any of claims 276-280, wherein the SiOx layer is deposited adjacent the interior surface of the container.
282. The invention of any of claims 276-280, wherein the SiwOxCyHz layer is deposited adjacent to the interior surface of the container.
283. The invention of any of claims 280-282, wherein the SiOx and SiwOxCyHz layers are a compound graduated from SiwOxCyHz to SiOx.
284. The invention of any of claims 267-283, wherein the container further comprises a closure.
285. The invention of claim 284, wherein the closure comprises an inwardly facing surface exposed to the cavity of the container.
286. The invention of claim 284 or 285, wherein the closure comprises a wall contacting surface that is in contact with the inner surface of the container wall.
287. The invention of any one of claims .Λ.
<sup>541</sup> 'iMPie INSTITUTO MEXICANO 284-286, in which the closure further comprises a ta ^' AwMSrtiAi
288. The invention of claim 287 -. on-¿¡a that ··· closure comprises a protection in which the cap is retained.
289. The invention of claim 287 or 288, wherein the cap comprises a wall-contacting surface that is in contact with the internal surface of the container wall.
290. The invention of any of claims 284-289, wherein the stopper comprises an inwardly facing surface exposed to the cavity of the container.
290a. The invention of any of claims 267-290, further comprising a vacuum source for removing gas from a container seated in a container holder, the seated container defining a vacuum chamber.
291. The invention of any of claims 284-290a, wherein a portion of the container wall that is in contact with the surface in contact with the closure wall is coated with a SiwOxCyHz lubricating coating.
301. The invention of any of claims 284-300, wherein the coating of
542 . . IMPI 6
SiwOxCyHz is applied by PECVD. Mexican institute%<sup>JC</sup> DE IA PEOFIBDAD C
INDUSTRIAL
302. The invention of any of claims 291-301, wherein the SiwOxCyHz coating has a thickness of 0.5 to 5000 nm.
303. The invention of any of claims 291-301, wherein the SiwOxCyHz coating has a thickness of 100 to 5000 nm.
304. The invention of any one of claims 291-301, wherein the SiwOxCyHz coating has a thickness of 200 to 5000 nm.
305. The invention of any of claims 291-301, wherein the SiwOxCyHz coating has a thickness of 500 to 5000 nm.
306. The invention of any of claims 291-301, wherein the SiwOxCyHz coating has a thickness of 1000 to 5000 nm.
307. The invention of any of claims 291-301, wherein the SiwOxCyHz coating has a thickness of 2000 to 5000 nm.
308. The invention of any of claims 291-301, wherein the SiwOxCyHz coating has a thickness of 3000 to 5000 nm.
309. The invention of any of claims 291-301, wherein the SiwOxCyHz coating has a
543 thickness from 4000 to 10 000 nm.
IMPI
Mexican INSTITUTE Oí LZ MOflWAD INDUSTRIAL
310. A PECVD device comprising:
a container holder having a port for receiving a container in a seated position for processing;
an internal electrode positioned to be inserted into a container seated in a container holder;
an external electrode having an interior portion positioned to receive a container seated in a container holder;
a power source supplying alternating current to the inner and outer electrode to form a plasma in a container seated on the container holder;
a gas drain for transferring gas from or into a container seated in the port to define a closed chamber;
a source of reactive gas; and a gas source for feeding a reactive gas from the reactive gas source to a container seated on the container holder.
IV. B. PECVD apparatus that uses a clamping tool to transport tubes to and from a coating station
311. Device for PECVD treatment of a primer <sup>544</sup> • M Pifes' NSTn-UTO MEXICANO container having an open end, an outer space, an interior space, comprising: - a container support configured to seat the open end of a container;
a first holding tool configured to selectively hold and release the closed end of a container and, while holding the closed end of the container, transporting the container into proximity to the container holder;
a seat in the container support, the seat configured to establish sealed communication between the container support and the interior space of the first container;
an operatively connected reagent supply for introducing at least one gaseous reagent into the first container through the container holder;
a plasma generator configured to form plasma within the first container under conditions effective to form a reaction product of the reagent on the inner surface of the first container;
a container release mechanism for releasing the first container from the container holder; and a holding tool that is the first holding tool or another holding tool and is
545 configured to axially transport the primá ^ u-®® ^ $ 4'em away from the container support and subsequently release the first container.
312. The invention of claim 311, further comprising:
a reaction vessel other than the first vessel, the reaction vessel having an open end and an interior space and being configured to seat its open end on the container support and establish sealed communication between the container support and the interior space of the container reaction; and a PECVD reagent conduit positioned to enter the interior space of the reaction vessel when the reaction vessel is seated in the vessel holder;
wherein the plasma generator can be configured to form plasma within the interior space of the reaction vessel under conditions effective to remove at least a portion of a reservoir of a PECVD reaction product from the reagent conduit.
313. The invention of claim 311 or 312, further comprising:
a serial conveyor configured to transport
546 holding tools; and
<img file="MX345403B_D0258.tif" />
configured for a second holding tool to selectively hold and release the closed end of a container and, while holding the closed end of the container, transporting the container into proximity to the container holder;
the first and second clamping tools being operatively connected to a serial conveyor and configured to successively transport a series of at least two containers near the container support, seat the open ends of the containers on the container support, and establish communication sealed between the container support and the interior of the second container, axially transporting the containers away from the container support and releasing the containers from the clamping tools.
VB PECVD coating of the limited opening of a container (syringe capillary)
316. A method of coating an internal surface of a limited opening of a generally tubular container to be processed by PECVD, the method comprising:
provide a generally tubular container to be processed and which includes an outer surface, a <sup>547</sup> IMPI ^ '' OTííssas internal surface that defines a cavity, an abefffiPá<sup>1</sup>· Large nm with an internal diameter and a limited abef'LLlfá defined by an internal surface and having an internal diameter smaller than the internal diameter of the largest aperture;
providing a processing vessel with a cavity and an opening in the processing vessel.
connecting the opening of the processing container with the limited opening of the container to be processed to establish communication between the cavity of the container to be processed and the cavity of the processing container through the limited opening;
creating at least a partial vacuum in the cavity of the container to be processed and the cavity of the processing container;
introducing a PECVD reagent through the first opening, through the cavity of the container to be processed and then through the limited opening to the cavity of the processing container; and generating plasma adjacent to the limited aperture under conditions effective to deposit a coating of a PECVD reaction product on the inner surface of the limited aperture.
317. The method of claim 316, wherein the
548 container to be processed is a cylinder
<img file="MX345403B_D0259.tif" />
318. The method of claim 316 or 317, wherein the limited opening has a first connector and the processing container opening has a second connector adapted to fit the first connector in order to establish communication between the cavity of the processing container. and the cavity of the container to be processed.
319. The method of claim 318, wherein the first and second connectors are Luer-type safety connectors.
320. The method of claim 319, wherein at least the first or second connector is made of electrically conductive material.
321. The method of claim 299, 319 or 320, wherein at least the first or second connector is made of electrically conductive material.
322. The method of claim 299, 319, 320 or 299a, wherein at least the first or second connector is made of stainless steel.
323. The method of claim 319, wherein the respective first and second safety Luer connectors are male and female.
324. The method of claim 299, 319 or 323, which
549
<img file="MX345403B_D0260.tif" />
_. . .... IMPI also includes a seal positioned between θΙβτπχιταΗκι ^ Νο ftt LA ÜOFltDAD
INDUSTEH The second connector.
325. The method of claim 324, wherein the seal comprises an O-ring.
326. The method of claim 319, 323, 324 or 325, wherein one of the connectors comprises a locking ring with a thread and defining a first generally annular axially oriented stop and the other connector comprises a second generally annular axially oriented stop opposite the first stop when the connectors are engaged.
327. The method of claim 326, further comprising an annular seal engaged between the first and second abutments.
328. The method of any of claims 316-318, wherein the communication established between the cavity of the container to be processed and the cavity of the process container through the limited opening is at least substantially leak-proof.
329. The method of any of claims 316-328, wherein the introduction of a PECVD reagent through the larger opening of the container to be processed is carried out as follows:
providing a generally tubular inner electrode having an inner passage, a proximal end, a proximal end
550 PREVENT distant! and a distal opening adjacent the distal end and communicating with the interior passage;
inserting the distal end of the electrode adjacent to or into the larger opening of the container to be processed; and feeding a reactive gas through the distal opening of the electrode into the cavity of the container to be processed.
330. The method of claim 329, wherein the distal end of the electrode is positioned less than half the distance from the limited opening to the largest opening of the container to be processed, while feeding the reagent gas.
331. The method of claim 329, wherein the distal end of the electrode is positioned less than 40% of the distance from the limited opening to the largest opening of the container to be processed, while feeding the reagent gas.
332. The method of claim 329, wherein the distal end of the electrode is positioned less than 30% of the distance from the limited opening to the largest opening of the container to be processed, while feeding the reagent gas.
333. The method of claim 329, wherein the distal end of the electrode is positioned less than 20% <sub>551</sub> IMPI ^
MEXICAN INSTITUTE
OF THE V «a— INDUSTRIAL DEPTH of the distance from the opening limited to the largest opening of the container to be processed, while feeding the reactive gas.
334. The method of claim 329, wherein the distal end of the electrode is positioned less than 15% of the distance from the limited opening to the largest opening of the container to be processed, while feeding the reagent gas.
335. The method of claim 329, wherein the distal end of the electrode is positioned less than 10% of the distance from the limited opening to the largest opening of the container to be processed, while feeding the reagent gas.
336. The method of claim 329, wherein the distal end of the electrode is positioned less than 8% of the distance from the limited opening to the largest opening of the container to be processed, while feeding the reagent gas.
337. The method of claim 329, wherein the far end! of the electrode is positioned less than 6% of the distance from the limited opening to the largest opening of the container to be processed, while feeding the reagent gas.
338. The method of claim 329, wherein the
552
<img file="MX345403B_D0261.tif" />
the opening distance limited to the aberbuid ll [<Tyor of the vessel to be processed, while feeding the reagent gas.
339. The method of claim 329, wherein the far end! of the electrode is positioned less than 2% of the distance from the limited opening to the largest opening of the container to be processed, while feeding the reagent gas.
340. The method of claim 329, wherein the distal end of the electrode is positioned less than 1% of the distance from the limited opening to the largest opening of the container to be processed, while feeding the reagent gas.
341. The method of claim 329, wherein the distal end of the electrode is positioned within the larger opening of the container to be processed, while feeding the reagent gas.
342. The method of claim 329, wherein the distal end of the electrode is positioned outside the larger opening of the container to be processed, while feeding the reagent gas.
343. The method of any of claims 329-342, wherein the distal end of the electrode is
553 positioned distal to the limited opening. industrial
344. The method of any of the -relVl'nUTdaüTunes' 329-343, in which the electrode is moved axially during deposition of a PECVD reaction product.
3. 4. 5. The method of any of claims 316-344, wherein the plasma extends substantially throughout the syringe cavity and the limited opening.
346. The method of any of claims 316-345, wherein the plasma extends substantially throughout the syringe cavity, the limited opening, and the cavity of the processing container.
347. The method of any of claims 316-346, wherein the plasma has a substantially uniform color throughout the syringe cavity and the limited opening.
348. The method of any of claims 316-347, wherein the plasma has a substantially uniform color substantially throughout the syringe cavity, the limited opening, and the cavity of the processing container.
349<sub>TO</sub> The method of any of claims 316-348, wherein the plasma is substantially stable throughout the syringe cavity and the limited opening.
350. The method of any of the claims
554 'IMPIAS
IRSTrtVTO MEXICAN
FROM C * AGE TO INDUSTRIAL 316-349, where the plasma is substantially stable throughout the syringe cavity, limited opening and cavity of the processing vessel.
351. The method of any of claims 316-350, wherein the container opening of the processing container is the only opening.
352. The method of any of claims 316-351, wherein the volume of the cavity of the processing container is less than three times the volume of the cavity 300 of the container 250 to be processed.
353. The method of any one of claims 316-352, wherein the volume of the cavity of the processing container is less than twice the volume of the cavity of the container to be processed.
354. The method of any of claims 316-353, wherein the cavity volume of the processing container is less than the volume of the container cavity to be processed.
355. The method of any of claims 316-354, wherein the volume of the cavity of the processing container is less than 50% of the volume of the cavity 300 of the container 250 to be processed.
356. The method of any of claims 316-355, wherein the volume of the cavity of the container <sup>555</sup> IMPIAS fNSTnvroMAufiAh »t» wkr »oMi» AO processing is less than 25% of the volume of fT '<sup>s</sup>cavida3 300 of the container 250 to be processed. · ''
357. The method of any of claims 316-356, further comprising seating the larger opening of the generally tubular container to be processed in a container holder prior to creating at least a partial vacuum within the cavity 300 of the container 250 to be has to process.
358. The method of claim 357, further comprising seating the larger opening of the container to be processed in a port of the container holder.
359. The method of claim 357 or 358, further comprising inserting an internal electrode into the container to be processed and which is seated in the container holder.
360. The method of claim 357, 358 or 359, further comprising positioning the container to be processed relative to an external electrode having an interior portion positioned to receive the container to be processed while seated in the holder. containers.
361. The method of claim 357, 358, 359 or 330, further comprising activating a power source that supplies alternating current to the outer electrode to form <sup>556</sup> PREVENTS
INSTITUTO MEXICANO,,,, ... ______ j_ ____ DE LA PROPERTY plasma inside the container to be processedipywqwe eS ^ tee · seated on the container support. - ..<sup>1</sup> ·
362. The method of claim 361, further comprising connecting the internal electrode to ground.
363. The method of claim 357, 358, 359, 360, or 361, further comprising providing a source of vacuum to evacuate the interior of the container to be processed, the container to be processed defining a vacuum chamber.
364. The method of claim 363, further comprising providing a second vacuum chamber surrounding the container to be processed.
365. The method of claim 364, wherein the interior of the container is maintained at a lower vacuum level than the second vacuum chamber.
366. The method of claim 363, wherein the processing vessel is a conduit that communicates with a vacuum port in the vessel holder.
367. The method of any of claims 357-366, further comprising a source of reactive gas and a gas feed for feeding a reactive gas from the source of reactive gas into the container to be processed and which is seated in the container support.
. <sub>τ</sub>—<sup>557</sup> IMPI
MEXICAN INIMWRO _ _______, ___________ BE LA «OWEDAD
SAW. INSPECTION OF THE industrial VESSEL
VIA. Processing of the qtio MiLluyÍ TJ vessel pre-coating and post-coating inspection
399. A container processing method for processing a molded plastic container having an opening and a wall defining an interior surface, the method comprising:
inspect the inside surface of the newly molded container for defects;
applying a coating on the inside surface of the container after inspecting the newly molded container; and inspecting the coating for defects.
400. A container processing method for processing a molded plastic container having an opening and a wall defining an interior surface, the method comprising:
inspect the inside surface of the newly molded container for defects;
applying a barrier coating over the container after inspecting the newly molded container; and inspecting the interior surface of the container for defects after applying the barrier coating.
<img file="MX345403B_D0262.tif" />
<sup>558</sup>. IΜΡΙ
401. The invention of claim 400, §h<sup>THE</sup>iN ^ r ^ ue ^! § Inside surface of freshly molded container or inspects in numerous closely spaced positions on inside surface of container.
402. The invention of claim 400 or 401, wherein the interior surface of the container after applying the barrier coating is inspected at numerous closely spaced positions on the interior surface of the container.
403. The invention of claim 400, 401 or 402, wherein numerous closely spaced positions are located on the inside surface of the container and inspected on the newly molded container, lined with the barrier coating, and re-inspected after application the barrier coating.
VI.B. Container inspection detecting outgassing of the container wall through the barrier layer
404. A method of inspecting a barrier layer on a material that degasses a vapor, comprising:
providing a sample of material that degasses a gas and has at least a partial barrier layer; and measure the degassed gas.
405. The method of claim 404, wherein the
IMPI ^ material that degasses a gas comprising polymeric. ______
406. The method of claim 404 or 405, wherein the material that degasses a gas comprises a thermoplastic compound.
<td> 407.</td><td>He</td><td>anyone's method</td><td>from</td><td>The claims</td>
<td> 404-406,</td><td>in</td><td>the one that the material</td><td>what</td><td>outgas a gas</td>
<td>understands</td><td>a</td><td>polyester.</td><td></td><td></td>
<td> 408.</td><td>He</td><td>anyone's method</td><td>from</td><td>The claims</td>
<td> 404-407,</td><td>in</td><td>the one that the material</td><td>what</td><td>outgas a gas</td>
<td>understands</td><td colspan="2">polyethylene terephthalate.</td><td> •</td><td></td>
<td> 409.</td><td>He</td><td>anyone's method</td><td>from</td><td>The claims</td>
<td> 404-408,</td><td>in</td><td>the one that the material</td><td>what</td><td>outgas a gas</td>
<td>understands</td><td colspan="2">a polyolefin.</td><td></td><td></td>
<td> 410.</td><td>He</td><td>anyone's method</td><td>from</td><td>The claims</td>
<td> 404-409,</td><td>in</td><td>the one that the material</td><td>what</td><td>outgas a gas</td>
<td>understands</td><td colspan="2">Polypropylene.</td><td></td><td> •</td>
<td> 411.</td><td>He</td><td>anyone's method</td><td>from</td><td>The claims</td>
<td> 404-410,</td><td>in</td><td>the one that the material</td><td>what</td><td>outgas a gas</td>
<td>understands</td><td>a</td><td colspan="2">cycloolefinic copolymer.</td><td></td>
<td>411a</td><td></td><td>Anyone's method</td><td>from</td><td>The claims</td>
<td> 404-411,</td><td>what</td><td>also include putting</td><td>in</td><td>contact the layer of</td>
barrier with water before measuring degassed gas.
411b. The method of any of the claims
560 IMPIg
MEXICAN INSTITUTE
OF PROPERTY C industrial 404-411, further comprising contacting the barrier layer with water vapor before measuring the degassed gas.
411c. The method of any of claims 404-411, further comprising contacting the barrier layer with air at 35% -100% relative humidity prior to measuring the degassed gas.
411d. The method of any of claims 404-411, further comprising contacting the barrier layer with air at 40% -100% relative humidity prior to metering the degassed gas.
411e. The method of any of claims 404-411, further comprising contacting the barrier layer with air at 40% -50% relative humidity prior to metering the degassed gas.
411f. The method of any of claims 404-411, further comprising contacting the barrier layer with oxygen prior to metering the degassed gas.
411g. The method of any of claims 404-411, further comprising contacting the barrier layer with nitrogen prior to metering the degassed gas.
411h. The method of any of claims 411a-411g, wherein the contact time is 10 seconds to one hour.
561
<img file="MX345403B_D0263.tif" />
<sup>Dt</sup> ^ ÑDÜSTM * ·<sup>1</sup>411i. The method of any of the claims
411a-411g, where the contact time is
<img file="MX345403B_D0264.tif" />
e one minute to thirty minutes.
411j. The method of any of claims 411a-411g, wherein the contact time is 5 minutes to 25 minutes.
411k. The method of any of claims 411a-411g, wherein the contact time is 10 minutes to 20 minutes.
4111. The method of any of claims 404-411k, wherein the degassed gas is measured at a pressure of 0.1 Torr to 100 Torr.
411m. The method of any of claims 404-411k, wherein the degassed gas is measured at a pressure of 0.2 Torr to 50 Torr.
411n. The method of any of claims 404-411k, wherein the degassed gas is measured at a pressure of 0.5 Torr to 40 Torr.
411o. The method of any of claims 404-411k, wherein the degassed gas is measured at a pressure of 1 Torr to 30 Torr.
411p. The method of any of claims 404-411k, wherein the degassed gas is measured at a pressure of 5 Torr to 100 Torr.
<sup>562</sup> IMPI ^
411q. The method of any of the 404-411k, in which the degassed gas is_jmid ^. = »\ In» pressure from 10 Torr to 80 Torr.
411r. The method of any of claims 404-411k, wherein the degassed gas is measured at a pressure of 15 Torr to 50 Torr.
411s. The method of any of claims 404-411r, wherein the degassed gas is measured at a temperature of 0 ° C to 50 ° C.
411t. The method of any of the claims
404-411r, in which the degassed gas is measured at a temperature of 0 ° C to 21 ° C.
411u. The method of any of claims 404-411r, wherein the degassed gas is measured at a temperature of 5 ° C to 20 ° C.
412. The method of any one of claims 404-411u, wherein the material that degasses a gas is provided in the form of a container having a wall with an outer surface and an inner surface, the inner surface containing a cavity.
413. The method of claim 412, wherein the barrier layer is disposed on the inner surface of the container wall.
414. The method of claim 412 or 413, wherein
IMPIDE a differential pressure is provided across the barrier creating the vacuum at least partially 'in the validity;
415. The method of any of claims 412-414, further comprising connecting the cavity via conduit to a vacuum source to create the vacuum at least partially in the cavity.
416. The method of claim 415, further comprising providing a degassing measurement cell that communicates the cavity with the vacuum source.
417. The method of any of claims 404-416, wherein the measurement is carried out by determining the volume of material degassed through the barrier layer per time interval.
418. The method of any of claims 404-417, wherein the measurement is carried out using microflow technology.
419. The method of any of claims 404-418, wherein the measurement is carried out by measuring the mass flow rate of the degassed material.
420. The method of any of claims 404-419, wherein the measurement is carried out in a molecular flow mode of operation.
420a. The method of any of claims 404-420, wherein the measurement is carried out
IMPI
INDUSTUIAL
<img file="MX345403B_D0265.tif" />
564 cape:
providing at least one micro-bracket having the ability, when in the presence of a degassed material, to move or change shape;
exposing the micro-bracket to the degassed material under conditions effective to cause the micro-bracket to move or change shape; and detecting movement or different shape.
420b The method of claim 420a, wherein the different shape is detected by reflecting an incident energy beam from a shape-changing portion of the micro-bracket, before and after exposing the micro-bracket to degassing, and measuring the resulting deflection of the beam. reflected at a point separate from the bracket.
420c. The method of claim 420b, wherein the incident energy beam is selected from a photon beam, an electron beam, and a combination of two or more of these.
420d. The method of claim 420b, wherein the incident energy beam is a photon beam.
420e. The method of claim 420b, wherein the incident energy beam is a laser beam.
420f. The method of any of claims 404-420, wherein the measurement is carried out<sup>565</sup> IMPI ^^, INSTITUTO MEXICANO cabo: DE LA PROPIEDAD
INDUSTRIAL by providing at least one micrometer that resonates at a different frequency when in the presence of a degassed material;
exposing the micro-bracket to the degassed material under conditions effective to cause the micro-bracket to resonate at a different frequency; and detecting the different resonant frequency.
420g. The method of claim 420f, wherein the different resonant frequency is detected by feeding energy to the micrometer to induce it to resonate before and after exposing the micrometer to degassing, and determining the difference between the resonant frequencies before and after exposing the micrometer to degassing.
420h. The method of claim 420g, wherein the different resonant frequency is detected using a harmonic vibration sensor.
421. The method of claim 404, wherein the material that degasses a gas is provided in the form of a film.
422. The method of any of claims 404-421, wherein the barrier layer is a total or partial coating on a surface of the material that
566
<img file="MX345403B_D0266.tif" />
degasses.
IMPI
MEXICAN INSTITUTE
OF INDUSTRIAL PBOEIBILITY
425. The method of any of the claims
404-424, wherein the barrier layer comprises SiOx, where x is from about 1.5 to about 2.9.
426. The method of any of claims 404-425, wherein the barrier layer consists essentially of SiOx, where x is from about 1.5 to about 2.9.
427. The method of any of claims 404-426, wherein the barrier layer is less than 500 nm thick.
428. The method of any of claims 404-427, wherein the barrier layer is less than 300 nm thick.
429. The method of any of claims 404-428, wherein the barrier layer is less than 100 nm thick.
430. The method of any of claims 404-429, wherein the barrier layer is less than 80 nm thick.
431. The method of any of claims 404-430, wherein the barrier layer is less than 60 nm thick.
432. The method of any of the claims
567
<img file="MX345403B_D0267.tif" />
404-431, wherein the barrier layer is less than 50 nm thick.
433. The method of any of claims 404-432, wherein the barrier layer is less than 40 nm thick.
434. The method of any of claims 404-433, wherein the barrier layer is less than 30 nm thick.
435. The method of any of claims 404-434, wherein the barrier layer is less than 20 nm thick.
436. The method of any of claims 404-435, wherein the barrier layer is less than 10 nm thick.
437. The method of any of claims 404-436, wherein the barrier layer is less than 5 nm thick.
438. The method of any of claims 404-437, wherein the measurement of the degassed gas is carried out under conditions effective to distinguish the presence or absence of the barrier layer.
439. The method of claim 438, wherein the effective conditions for distinguishing the presence or absence of the barrier layer include a shorter test duration
<img file="MX345403B_D0268.tif" />
<img file="MX345403B_D0269.tif" />
568 one minute.
MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY
440. The method of claim 438; STi e ± 'that the effective conditions to distinguish the presence or absence of the barrier layer include a test duration of less than 50 seconds.
441. The method of claim 438, wherein the effective conditions for distinguishing the presence or absence of the barrier layer include a test duration of less than 40 seconds.
442. The method of claim 438, wherein the effective conditions for distinguishing the presence or absence of the barrier layer include a test duration of less than 30 seconds.
443. The method of claim 438, wherein the effective conditions for distinguishing the presence or absence of the barrier layer include a test duration of less than 20 seconds.
444. The method of claim 438, wherein the effective conditions for distinguishing the presence or absence of the barrier layer include a test duration of less than 15 seconds.
445. The method of claim 438, wherein the effective conditions for distinguishing the presence or absence of the barrier layer include a shorter test duration
<img file="MX345403B_D0270.tif" />
569 10 seconds.
IMPI »
INSTITUTO MEXICANO Ot LA PHOMWAD INDUSTRIAL
446. The method of claim 438, wherein the effective conditions for distinguishing the presence or absence of the barrier layer include a test duration of less than 8 seconds.
447. The method of claim 438, wherein the effective conditions for distinguishing the presence or absence of the barrier layer include a test duration of less than 6 seconds.
448. The method of claim 438, wherein the effective conditions for distinguishing the presence or absence of the barrier layer include a test duration of less than 4 seconds.
449. The method of claim 438, wherein the effective conditions for distinguishing the presence or absence of the barrier layer include a test duration of less than 3 seconds.
450. The method of claim 438, wherein the effective conditions for distinguishing the presence or absence of the barrier layer include a test duration of less than 2 seconds.
451. The method of claim 438, wherein effective conditions for distinguishing the presence or absence of the barrier layer include a shorter test duration.
<img file="MX345403B_D0271.tif" />
570 of 1 second.
IMPI
MEXICAN INSTITUTE OF THE moriSDAD hdusteiai
452. The method of any of the claims
438-451, wherein the measure of the presence or absence of the barrier layer is confirmed to at least a six sigma level of certainty.
453. The method of any of claims 438-452, wherein the measurement has at least a six sigma level of certainty.
454. The method of any of claims 404-453, wherein the measurement of the degassed gas on the lower pressure side of the barrier layer is carried out under conditions effective to determine the barrier enhancement factor of the layer barrier compared to the same material without a barrier layer.
455. The method of any of claims 404-454, wherein the degassing of a plurality of different gases is measured.
456. The method of any of claims 404-455, wherein the degassing of substantially all degassed gases is measured.
457. The method of any of claims 404-456, wherein the degassing of substantially all degassed gases is simultaneously measured.
458. The method of any of the claims
<img file="MX345403B_D0272.tif" />
<img file="MX345403B_D0273.tif" />
MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY
404-457, wherein the degassing of substantially all degassed gases is simultaneously measured.
572
Contents104
310 sheets
Sheet 1 Sheet 2 Sheet 3 Sheet 4 Sheet 5 Sheet 6 Sheet 7 Sheet 8 Sheet 9 Sheet 10 Sheet 11 Sheet 12 Sheet 13 Sheet 14 Sheet 15 Sheet 16 Sheet 17 Sheet 18 Sheet 19 Sheet 20 Sheet 21 Sheet 22 Sheet 23 Sheet 24 Sheet 25 Sheet 26 Sheet 27 Sheet 28 Sheet 29 Sheet 30 Sheet 31 Sheet 32 Sheet 33 Sheet 34 Sheet 35 Sheet 36 Sheet 37 Sheet 38 Sheet 39 Sheet 40 Sheet 41 Sheet 42 Sheet 43 Sheet 44 Sheet 45 Sheet 46 Sheet 47 Sheet 48 Sheet 49 Sheet 50 Sheet 51 Sheet 52 Sheet 53 Sheet 54 Sheet 55 Sheet 56 Sheet 57 Sheet 58 Sheet 59 Sheet 60 Sheet 61 Sheet 62 Sheet 63 Sheet 64 Sheet 65 Sheet 66 Sheet 67 Sheet 68 Sheet 69 Sheet 70 Sheet 71 Sheet 72 Sheet 73 Sheet 74 Sheet 75 Sheet 76 Sheet 77 Sheet 78 Sheet 79 Sheet 80 Sheet 81 Sheet 82 Sheet 83 Sheet 84 Sheet 85 Sheet 86 Sheet 87 Sheet 88 Sheet 89 Sheet 90 Sheet 91 Sheet 92 Sheet 93 Sheet 94 Sheet 95 Sheet 96 Sheet 97 Sheet 98 Sheet 99 Sheet 100 Sheet 101 Sheet 102 Sheet 103 Sheet 104 Sheet 105 Sheet 106 Sheet 107 Sheet 108 Sheet 109 Sheet 110 Sheet 111 Sheet 112 Sheet 113 Sheet 114 Sheet 115 Sheet 116 Sheet 117 Sheet 118 Sheet 119 Sheet 120 Sheet 121 Sheet 122 Sheet 123 Sheet 124 Sheet 125 Sheet 126 Sheet 127 Sheet 128 Sheet 129 Sheet 130 Sheet 131 Sheet 132 Sheet 133 Sheet 134 Sheet 135 Sheet 136 Sheet 137 Sheet 138 Sheet 139 Sheet 140 Sheet 141 Sheet 142 Sheet 143 Sheet 144 Sheet 145 Sheet 146 Sheet 147 Sheet 148 Sheet 149 Sheet 150 Sheet 151 Sheet 152 Sheet 153 Sheet 154 Sheet 155 Sheet 156 Sheet 157 Sheet 158 Sheet 159 Sheet 160 Sheet 161 Sheet 162 Sheet 163 Sheet 164 Sheet 165 Sheet 166 Sheet 167 Sheet 168 Sheet 169 Sheet 170 Sheet 171 Sheet 172 Sheet 173 Sheet 174 Sheet 175 Sheet 176 Sheet 177 Sheet 178 Sheet 179 Sheet 180 Sheet 181 Sheet 182 Sheet 183 Sheet 184 Sheet 185 Sheet 186 Sheet 187 Sheet 188 Sheet 189 Sheet 190 Sheet 191 Sheet 192 Sheet 193 Sheet 194 Sheet 195 Sheet 196 Sheet 197 Sheet 198 Sheet 199 Sheet 200 Sheet 201 Sheet 202 Sheet 203 Sheet 204 Sheet 205 Sheet 206 Sheet 207 Sheet 208 Sheet 209 Sheet 210 Sheet 211 Sheet 212 Sheet 213 Sheet 214 Sheet 215 Sheet 216 Sheet 217 Sheet 218 Sheet 219 Sheet 220 Sheet 221 Sheet 222 Sheet 223 Sheet 224 Sheet 225 Sheet 226 Sheet 227 Sheet 228 Sheet 229 Sheet 230 Sheet 231 Sheet 232 Sheet 233 Sheet 234 Sheet 235 Sheet 236 Sheet 237 Sheet 238 Sheet 239 Sheet 240 Sheet 241 Sheet 242 Sheet 243 Sheet 244 Sheet 245 Sheet 246 Sheet 247 Sheet 248 Sheet 249 Sheet 250 Sheet 251 Sheet 252 Sheet 253 Sheet 254 Sheet 255 Sheet 256 Sheet 257 Sheet 258 Sheet 259 Sheet 260 Sheet 261 Sheet 262 Sheet 263 Sheet 264 Sheet 265 Sheet 266 Sheet 267 Sheet 268 Sheet 269 Sheet 270 Sheet 271 Sheet 272 Sheet 273 Sheet 274 Sheet 275 Sheet 276 Sheet 277 Sheet 278 Sheet 279 Sheet 280 Sheet 281 Sheet 282 Sheet 283 Sheet 284 Sheet 285 Sheet 286 Sheet 287 Sheet 288 Sheet 289 Sheet 290 Sheet 291 Sheet 292 Sheet 293 Sheet 294 Sheet 295 Sheet 296 Sheet 297 Sheet 298 Sheet 299 Sheet 300 Sheet 301 Sheet 302 Sheet 303 Sheet 304 Sheet 305 Sheet 306 Sheet 307 Sheet 308 Sheet 309 Sheet 310
300 members in 22 offices
Priority claims35
| Document | Office | Kind | Date |
|---|---|---|---|
| 61177984 | United States of America | – | |
| 17798409 | United States of America | P | |
| 61222727 | United States of America | – | |
| 22272709 | United States of America | P | |
| 61213904 | United States of America | – | |
| 21390409 | United States of America | P | |
| 61234505 | United States of America | – | |
| 23450509 | United States of America | P | |
| 61261321 | United States of America | – | |
| 26132109 | United States of America | P | |
| 61263289 | United States of America | – | |
| 26328909 | United States of America | P | |
| 61285813 | United States of America | – | |
| 28581309 | United States of America | P | |
| 61298159 | United States of America | – | |
| 29815910 | United States of America | P | |
| 61299888 | United States of America | – | |
| 29988810 | United States of America | P | |
| 61318197 | United States of America | – | |
| 31819710 | United States of America | P | |
| 61333625 | United States of America | – | |
| 33362510 | United States of America | P | |
| 101627552 | European Patent Office (EPO) | – | |
| 101627560 | European Patent Office (EPO) | – | |
| 101627578 | European Patent Office (EPO) | – | |
| 101627586 | European Patent Office (EPO) | – | |
| 101627602 | European Patent Office (EPO) | – | |
| 101627610 | European Patent Office (EPO) | – | |
| 10162760 | European Patent Office (EPO) | A | |
| 10162758 | European Patent Office (EPO) | A | |
| 10162757 | European Patent Office (EPO) | A | |
| 10162756 | European Patent Office (EPO) | A | |
| 10162755 | European Patent Office (EPO) | A | |
| 10162761 | European Patent Office (EPO) | A | |
| 2010034586 | United States of America | W |
Members300
| Document | Office | Kind | |
|---|---|---|---|
| EP2251452A2 | European Patent Office (EPO) | A2 | |
| EP2251453A2 | European Patent Office (EPO) | A2 | |
| EP2251454A2 | European Patent Office (EPO) | A2 | |
| EP2251455A2 | European Patent Office (EPO) | A2 | |
| EP2251671A2 | European Patent Office (EPO) | A2 | |
| CA2761872A1 | Canada | A1 | |
| CA2761905A1 | Canada | A1 | |
| WO2010132579A2 | World Intellectual Property Organization (WIPO) | A2 | |
| WO2010132581A2 | World Intellectual Property Organization (WIPO) | A2 | |
| WO2010132584A2 | World Intellectual Property Organization (WIPO) | A2 | |
| WO2010132585A2 | World Intellectual Property Organization (WIPO) | A2 | |
| WO2010132589A2 | World Intellectual Property Organization (WIPO) | A2 | |
| WO2010132591A2 | World Intellectual Property Organization (WIPO) | A2 | |
| EP2253735A2 | European Patent Office (EPO) | A2 | |
| US2010298738A1 | United States of America | A1 | |
| EP2251453A3 | European Patent Office (EPO) | A3 | |
| EP2253735A3 | European Patent Office (EPO) | A3 | |
| EP2251452A3 | European Patent Office (EPO) | A3 | |
| EP2251454A3 | European Patent Office (EPO) | A3 | |
| EP2251671A3 | European Patent Office (EPO) | A3 | |
| EP2251455A3 | European Patent Office (EPO) | A3 | |
| WO2010132581A9 | World Intellectual Property Organization (WIPO) | A9 | |
| WO2010132579A3 | World Intellectual Property Organization (WIPO) | A3 | |
| WO2010132584A3 | World Intellectual Property Organization (WIPO) | A3 | |
| WO2010132585A3 | World Intellectual Property Organization (WIPO) | A3 | |
| WO2010132589A3 | World Intellectual Property Organization (WIPO) | A3 | |
| WO2010132591A3 | World Intellectual Property Organization (WIPO) | A3 | |
| US7985188B2 | United States of America | B2 | |
| US2011252899A1 | United States of America | A1 | |
| CA2799213A1 | Canada | A1 | |
| CA2799220A1 | Canada | A1 | |
| WO2011143329A2 | World Intellectual Property Organization (WIPO) | A2 | |
| WO2011143509A1 | World Intellectual Property Organization (WIPO) | A1 | |
| AU2010249033A1 | Australia | A1 | |
| AU2010249031A1 | Australia | A1 | |
| SG176008A1 | Singapore | A1 | |
| SG176011A1 | Singapore | A1 | |
| CA2803613A1 | Canada | A1 | |
| WO2012003221A1 | World Intellectual Property Organization (WIPO) | A1 | |
| MX2011012038A | Mexico | A | |
| MX2011012042A | Mexico | A | |
| IL215913D0 | Israel | D0 | |
| IL215914D0 | Israel | D0 | |
| WO2011143329A3 | World Intellectual Property Organization (WIPO) | A3 | |
| KR20120042748A | Republic of Korea | A | |
| CN102459693A | China | A | |
| CN102460131A | China | A | |
| US2012123345A1 | United States of America | A1 | |
| KR20120060781A | Republic of Korea | A | |
| TW201231710A | Taiwan Province of China | A | |
| JP2012526921A | Japan | A | |
| JP2012526922A | Japan | A | |
| AU2011252925A1 | Australia | A1 | |
| AR082615A1 | Argentina | A1 | |
| SG185520A1 | Singapore | A1 | |
| IL222932D0 | Israel | D0 | |
| CN102884412A | China | A | |
| CN102917805A | China | A | |
| HK1169840A1 | Hong Kong, China | A1 | |
| US2013041241A1 | United States of America | A1 | |
| EP2569611A1 | European Patent Office (EPO) | A1 | |
| CN103037982A | China | A | |
| EP2579996A2 | European Patent Office (EPO) | A2 | |
| AU2013202591A1 | Australia | A1 | |
| AU2013202893A1 | Australia | A1 | |
| CA2855353A1 | Canada | A1 | |
| WO2013071138A1 | World Intellectual Property Organization (WIPO) | A1 | |
| MX2012013129A | Mexico | A | |
| ZA201107835B | South Africa | B | |
| ZA201107871B | South Africa | B | |
| AU2012318242A1 | Australia | A1 | |
| RU2011150499A | Russian Federation | A | |
| RU2011150519A | Russian Federation | A | |
| JP2013526710A | Japan | A | |
| EP2605862A1 | European Patent Office (EPO) | A1 | |
| ZA201207881B | South Africa | B | |
| JP2013528117A | Japan | A | |
| JP2013531540A | Japan | A | |
| US2013200549A1 | United States of America | A1 | |
| US2013209766A1 | United States of America | A1 | |
| US8512796B2 | United States of America | B2 | |
| KR20130117648A | Republic of Korea | A | |
| US2013291632A1 | United States of America | A1 | |
| CA2887352A1 | Canada | A1 | |
| WO2013170052A1 | World Intellectual Property Organization (WIPO) | A1 | |
| EP2251453B1 | European Patent Office (EPO) | B1 | |
| EP2674513A2 | European Patent Office (EPO) | A2 | |
| US2014004022A1 | United States of America | A1 | |
| CA2878638A1 | Canada | A1 | |
| WO2014008138A2 | World Intellectual Property Organization (WIPO) | A2 | |
| EP2674513A3 | European Patent Office (EPO) | A3 | |
| PT2251453E | Portugal | E | |
| NZ596997A | New Zealand | A | |
| ES2452519T3 | Spain | T3 | |
| WO2014059012A1 | World Intellectual Property Organization (WIPO) | A1 | |
| ZA201208501B | South Africa | B | |
| PL2251453T3 | Poland | T3 | |
| CA2892294A1 | Canada | A1 | |
| US2014154399A1 | United States of America | A1 | |
| WO2014085346A1 | World Intellectual Property Organization (WIPO) | A1 |
3 legal events, as the office reported them to INPADOC
Over the term
Point at a mark for the eventEvents
| Event | Code | |
|---|---|---|
| Grant or registrationFG | FG | |
| Transfer or rightsGB | GB | |
| Transfer or rightsGB | GB |
Numbers
- Publication
- 345403
- Application
- 12038
Titles2
- Spanish
- REVESTIMIENTO POR PECVD UTILIZANDO UN PRECURSOR ORGANOSILÍCICO.
- English
- COATING BY PECVD USING AN ORGANOSILITICAL PRECURSOR.
Classification
- CPC, 32
- C23C16/045
- C23C16/54
- G01N15/082
- A61B5/150206
- C23C16/401
- C23C16/505
- C23C16/52
- C23C16/458
- Y10T428/13
- Y10T428/1383
- G01N33/0096
- A61M5/3129
- A61M2005/3131
- C23C16/503
- G01M3/26
- G01N21/9072
- G01N21/9081
- A61B5/154
- G01N23/2273
- B23Q7/04
- B05C13/025
- B05C13/00
- B23Q7/1494
- G01N33/00
- A61L31/088
- A61L31/10
- A61L31/14
- A61L2400/10
- A61L2420/02
- A61L2420/08
- C23C16/50
- G01N30/7206
- IPC, 6
- C23C16 30
- C23C14 40
- C23C16 24
- C23C16 50
- H01L21 205
- H10P14 24