MX343282B

Method for detecting leakage in digitally modulated systems.

Abstract

In a method for detecting leakage in a digital cable system, at least one first signal is inserted on the cable system. The at least one first signal has an amplitude multiple tens of dB below the digital channel power of the digital channels carried on the cable system. A second signal containing the first signal is received. The second signal is converted to an intermediate frequency (IF) signal. The IF signal is digitized and samples of the digitized IF signal are obtained. Digitized samples of a third signal at the nominal frequency of the first signal at maximum amplitude converted to the IF are provided. The digitized IF signal and the digitized samples of a third signal at the nominal frequency of the first signal at maximum amplitude converted to the IF are correlated. The presence of the inserted first signal is detected based upon the result of the correlation. In another method, a pair of first signals are inserted on the cable system.

MX343282B, drawing sheet 1 — Sheet 1 of 77

Term

No projected expiry on record.

15 claims: 14 independent, 1 dependent

1
CLAIMS REIVINDICACIONES Habiéndose descrito la invención como antecede, se reclama como propiedad lo contenido en las siguientes reivindicaciones:Having described the invention as above, the content of the following claims is claimed as property: 1. Un método de fabricación de una lente de hidrogel con bloqueo de UV sustancialmente completamente polimerizada caracterizado porque comprende: one. A method of manufacturing a substantially fully polymerized UV blocking hydrogel lens characterized in that it comprises: polimerizar una mezcla de reacción de monómeros de por lo menos NVP y otro comonómero y una Bis O-hidroxi benzofenona sustituida o no sustituida, polimerizable por radicales libres, para proporcionar un dispositivo oftálmico de hidrogel sustancialmente completamente polimerizado. polymerize a reaction mixture of monomers of at least NVP and another comonomer and a substituted or unsubstituted, free radical polymerizable Bis O-hydroxy benzophenone to provide a substantially fully polymerized hydrogel ophthalmic device.
2
El método de conformidad con la reivindicación two. The method according to claim 1, caracterizado porque el dispositivo oftálmico de hidrogel sustancialmente completamente polimerizado tiene una superficie humectable. 1, characterized in that the substantially fully polymerized hydrogel ophthalmic device has a wettable surface.
3
The method according to either of claims 1 or 2, characterized in that the hydrogel ophthalmic device demonstrates sufficient UV light blocking to meet at least FDA Class II specifications for UV blocking. 3. El método de conformidad con cualquiera de las reivindicaciones 1 ó 2, caracterizado porque el dispositivo oftálmico de hidrogel demuestra suficiente bloqueo de luz UV para satisfacer por lo menos especificaciones de Clase II de la FDA para bloqueo de UV.
4
El método de conformidad con la reivindicación Four. The method according to claim 1, caracterizado porque además el paso de polimerización 1, characterized in that in addition the polymerization step IMPI IMPI INSTITUTO MRXICANi) DÉ LA MTOÉIITAD INDUSTRIAL produces substantially complete co-cure of a monomer system component of the monomer reaction mixture to provide a substantially fully copolymerized ophthalmic device. INSTITUTO MRXICANi) DÉ LA MtoÉIÍtAD INDUSTRIAL produce co-curado sustancialmente completo de un componente del sistema de monómero de la mezcla de reacción de monómeros para proporcionar un dispositivo oftálmico sustancialmente completamente copolimerizado.
5
The method according to claim 5. El método de conformidad con la reivindicación 1, caracterizado porque la benzofenona sustituida Bis Ohidroxi, sustituida o no sustituida, polimerizable por radicales libres se selecciona entre el grupo que consiste de acrilato de 1,3-Bis(4-benzoil-3-hidroxifenoxi)-2-propilo y metacrilato de 1,3-Bis(4-benzoil-3-hidroxifenoxi)-2-propilo y mezclas de los mismos. 1, characterized in that substituted or unsubstituted, substituted or unsubstituted, Bis Ohydroxy benzophenone is selected from the group consisting of 1,3-Bis (4-benzoyl-3-hydroxyphenoxy) -2-propyl acrylate and 1,3-Bis (4-benzoyl-3-hydroxyphenoxy) -2-propyl and mixtures thereof.
6
The method according to either of claims 1 or 4, characterized in that the substantially fully copolymerized ophthalmic device has a water content of about 42.3% to about 59.1% when fully hydrated. 6. El método de conformidad con cualquiera de las reivindicaciones 1 ó 4, caracterizado porque el dispositivo oftálmico sustancialmente completamente copolimerizado tiene un contenido de agua de aproximadamente 42.3% hasta aproximadamente 59.1% cuando está completamente hidratado.
7
The method according to claim 7. El método de conformidad con la reivindicación 1, caracterizado porque la Bis 0-hidroxi benzofenona sustituida o no sustituida, polimerizable por radicales libres es funcionalizada con un grupo mono acrilato o mono metacrilato polimerizable por radicales libres. 1, characterized in that substituted or unsubstituted, free radical polymerizable Bis 0-hydroxy benzophenone is functionalized with a free radical polymerizable mono acrylate or mono methacrylate group.
8
The method according to claim 8. El método de conformidad con la reivindicación 1, caracterizado porque la mezcla de monómeros además comprende un monómero hidrofóbico que contiene organosilicio. 1, characterized in that the monomer mixture further comprises an organosilicon-containing hydrophobic monomer. IMPI IMPI INSTITUTO MEXICANO m la mosieodü INDUJTíUAI. MEXICAN INSTITUTE m la mosieodü INDUJTíUAI.
9
The method according to claim 9. El método de conformidad con la reivindicación 8, caracterizado porque el monómero que contiene organosilicio está presente entre 0.1 hasta 75.8 por ciento en peso. 8, characterized in that the organosilicon-containing monomer is present between 0.1 to 75.8 weight percent.
10
The method according to claim 10. El método de conformidad con la reivindicación 8, caracterizado porque la mezcla de monómeros además comprende reticuladores hidrofóbicos seleccionados del grupo que consiste de dimetacrilato de etilenglicol (EGDMA), metacrilato de alilo (AMA) y mezclas de los mismos. 8, characterized in that the monomer mixture further comprises hydrophobic crosslinkers selected from the group consisting of ethylene glycol dimethacrylate (EGDMA), allyl methacrylate (AMA), and mixtures thereof.
12
The method according to claim 12. El método de conformidad con la reivindicación 11, caracterizado porque el monómero hidrofílico de reacción rápida se selecciona del grupo que consiste de ácidos carboxílicos insaturados, alcoholes acrílicos sustituidos, acrilamidas y mezclas de los mismos. 11, characterized in that the fast reacting hydrophilic monomer is selected from the group consisting of unsaturated carboxylic acids, substituted acrylic alcohols, acrylamides, and mixtures thereof.
13
The method according to claim 13. El método de conformidad con la reivindicación 11, caracterizado porque el monómero hidrofílico de reacción rápida se selecciona del grupo que consiste de ácido metacrílico, ácido acrílico, metacrilato de 2-hidroxietilo, acrilato de 2-hidroxietilo, metacrilamida, N,Ndimetilacrilamida (DMA), N-isopropilacrilamida (NIPAM) y mezclas de los mismos. 11, characterized in that the fast reacting hydrophilic monomer is selected from the group consisting of methacrylic acid, acrylic acid, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, methacrylamide, N, N-dimethylacrylamide (DIP), N-isopropylacrylamide (NIPAM) and mixtures thereof. INSTITUTO MEXICANO DE LA PXOPIEDAri industrial MEXICAN INSTITUTE OF THE PXOPIEDAri industrial
14
The method according to claim 14. El método de conformidad con la reivindicación 1, caracterizado porque la mezcla monomérica comprende además por lo menos un monómero hidrofílico de reacción lenta, por lo menos un monómero hidrofóbico etilénicamente insaturado y 1, characterized in that the monomer mixture further comprises at least one slow reacting hydrophilic monomer, at least one ethylenically unsaturated hydrophobic monomer and 5 an organic diluent and comprises a combined shaping and polymerization step by a method step selected from the group consisting of static melt and centrifugal melt. 5 un diluyente orgánico y comprende un paso combinado de conformación y polimerización por un paso de método seleccionado del grupo que consiste de fundido estático y fundido por centrifugación.
15
El método de conformidad con la reivindicación fifteen. The method according to claim 10 14, characterized in that it further comprises a step of exposing the polymerized materials to a solvent selected from the group consisting of water, 2-propanol, etc. and mixtures thereof. 10 14, caracterizado porque comprende además un paso de exposición de los materiales polimerizados a un solvente seleccionado del grupo que consiste de agua, 2-propanol, etc. y mezclas de los mismos. IMPI IMPI INSTITUTO MEXICANO DE LA PROPIEDAD INDUSTRIAL MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

Independent claims14

529 paragraphs in 66 sections, as filed

(54) Title: METHOD FOR DETECTING LEAKS IN DIGITAL MODULATED SYSTEMS.

(54) Title: METHOD FOR DETECTING LEAKAGE IN DIGITALLY MODULATED SYSTEMS.

(57) Summary

In a method of detecting leaks in a digital cable system, at least a first signal is inserted into the cable system. At least a first signal has an amplitude of multiple tens of dB below the channel power of the digital channels carried in the cable system. A second signal containing the first signal is received. The second signal is converted to an intermediate frequency (IF) signal. The IF signal is digitized and samples of the digitized IF signal are obtained. Digitized samples of a third signal at the nominal frequency of the first signal at the maximum amplitude converted to the IF are provided. The digitized IF signal and the digitized samples of a third signal of the nominal frequency of the first signal at the maximum amplitude converted to IF are correlated. The presence of the first inserted signal is detected based on the result of the correlation. In another method, a pair of first signals are inserted into the cable system.

(57) Abstract

In a method for detecting leakage in a digital cable system, at least one first signal is inserted on the cable system. The at least one first signal has an amplitude multiple tens of dB below the digital channel power of the digital channels carried on the cable system. A second signal containing the first signal is received. The second signal is converted to an intermedíate frequency (IF) signal. The IF signal is digitized and samples of the digitized IF signal are obtained. Digitized samples of a third signal at the nominal frequency of the first signal at maximum amplitude converted to the IF are provided. The digitized IF signal and the digitized samples of a third signal at the nominal frequency of the first signal at maximum amplitude converted to the IF are correlated. The presence of the inserted first signal is detected based upon the result of the correlation. In another method, a pair of first signáis are inserted on the cable system.

_SE_ «« MÍA et tCWOMtA

Mexican Institute of Industrial Property

PATENT TITLE NO. 343282

Owner (s): TRILITHIC, INC.

Address: 9710 Park Davis Drive, Indianapolis, Indiana, 46235, USA

Name: METHOD FOR DETECTING LEAKS IN DIGITAL MODULATED SYSTEMS.

Classification: IC.8: H04N17 / 00

Inventor (s): RALEIGH BENTON STELLE IV; DENNIS L. ORNDORFF

Number;

MX / a / 2016 / 0t6635

REQUEST

Jumo Filing Date 2012

Divisional Patent Number: 334827

PRIORITY

<td>Country:</td><td></td><td>Date:</td><td>Number:</td>

<td>US</td><td></td><td>November 29, 2011</td><td> 61/564,429</td>

<td>US</td><td></td><td>January 30, 2012</td><td> 61/592,195</td>

Validity: Twenty year?

Date of Venfeimieñto: June 26, 2032, the patent of reference was granted on articles 1, 2 fraction V, 6 fraction Ut, and tstfs IB Industrial Property Law.

In accordance with article 23 of the Industrial Property Law, this patent has a non-extendable twenty-year term, effective from the filing date of <at Wemeeional request and will be subject to-saasdetetanfi to keep the rights in force. ®

Whoever signs the Industrial Property pi (I $ 6/01/2004, 06/16/2004 subsection a), 4 'and 12th frai the title does so based on the extensive by articles & <tractions III and 7a bis 2 (faith the Federation Office of the River Law (DOF) 27 / OeZteet, amended fli OSM / i994, 10/25/1996, 12/26/19 * 7, 05/17/1999, 01/25/1QB6, 05/06 / 2009,06 / 01/2010, 18/06 / 2t> WíWSHBi ^ Woi / 2012 and 09/04/2012); articles i, 3rd fraction V ions I ¿III of the Regulation of the Mexican Institute of Industrial Property (DOF 14/12/199 ·, amended on 07/28/2004 and 7709 / 200ή; 1 and “ty” defESte Organic tuto 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 Clause a) of the Agreement that delegates powers to the Deputy Directors General, Coordinator, Divisional Directors, Holders of the 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).

Issue Date: October 31, 2016

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MEXICAN INSTITUTE Dt THE INDUSTRIAL PROPERTY

MANUFACTURE METHOD OF SILICONE HYDROGEL LENS WITH

FULLY POLYMERIZED ULTRAVIOLET (UV) LOCK

Field of the Invention

The present invention relates to ophthalmic devices, and more particularly to a method of manufacturing a substantially fully polymerized UV-blocking hydrogel lens which comprises polymerizing a mixture of monomers of at least NVP and another comonomer and a Bis or -substituted or unsubstituted hydroxy benzophenone, free radical polymerizable, to provide a hydrogel ophthalmic device that has a wettable surface and enough UV light blocking to meet at least Class II specifications for UV blocking.

15 Background of the Invention

The development of a market-successful ophthalmic device formed from traditional silicone hydrogel materials often requires post-cure generation of a wettable surface. Traditional silicone hydrogel contact lenses can demonstrate silicone chain coating, in this case silicone rich domains residing on the surface of a lens. Silicone chain coating can create hydrophobic areas on the lens surface. These hydrophobic surface areas can adversely affect the

Ref .: 252199

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,,,,,,,, _. , OF THE MCFIFUAD lens wettability. The treatment of poartpusr ^ rtaab'-Qe — Ta surface of the lens to improve the humiliation frijÍbiil i dad ea- ^ ef-i'ca'Z but expensive; the additional step adds cost and time to the manufacturing process. An alternative to post surface cure treatment is the incorporation of relatively high molecular weight polyvinylpyrrolidone (PVP) (eg 300kDa) into the device by adding monomers to the mixture prior to curing. The resulting material has non-covalently bonded incorporated PVP, due to its high molecular weight, it will not easily leach out of a hydrated lens. Still other methods are needed to provide hydrophilic polymers in the device of a polymerized device.

Incorporation of substantial amounts of relatively slow reacting hydrophilic monomers such as Nvinylpyrrolidone (NVP), along with faster reacting comonomers in the monomer mixture can create a successful ophthalmic device by forming chains of mainly homo-polyvinylpyrrolidone (PVP) in situ while the device heals. However, monomers typically found in ophthalmic devices that form monomer mixtures can include relatively slow reacting monomers such as NVP, 0-vinyl carbonates, 0-vinyl esters (eg, vinyl acetate), O esters -allyl, O-allyl carbonates and N-vinyl carbamates as well

as monomers that react relatively as acrylates, methacrylates, acrylamide,r tné ta cYl laillas y1 styrenics. In systems that form devices that contain fast and slow reaction monomer mixtures (as can be found in monomer mixtures to form silicone hydrogels) a difference in the reaction kinetics of the system that forms the device (for example, in addition to C = C vs. transfer of hydrogen atoms) makes these systems particularly susceptible to incomplete cure. Therefore, the relatively sensitive kinetics of the curing reaction in these device forming systems makes it difficult to create a successful ophthalmic device.

US 5,135,965 describes certain mixtures of monomers containing N-vinylpyrrolidone (NVP) and UV absorbers capable of binding to the device after reaction and extraction for infraocular lens applications. The formulations described in US 5,135,965 are not silicone hydrogels.

Summary of the Invention

Here we describe a method of manufacturing a substantially fully polymerized UV blocking hydrogel lens which comprises polymerizing a mixture of monomers of at least NVP, and at least one other comonomer and a bis or hydroxybenzophenone substituted or not substituted free radical polymerizable, to provide a hydrogel ophthalmic device having a surface

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INSTITUTO MSXICANO OI LA FÍOFlít'AD wettable and sufficient UV light blocking to üfüfflglir less Class II specifications passes the ,b'l'üqueiü'de · W. '* FDA Class II Blocker-Classified Contact Lenses are recommended by the American Optometric Association for general-purpose uses. These lenses must block more than 70% of UVA and 95% UVB rays to be considered as FDA Class II UV blockers. More preferably a substantially fully polymerized UV-blocking silicone hydrogel having large chains of polyvinylpyrrolidone (PVP) formed in situ during cure.

In yet another aspect, the invention includes articles prepared by the method described herein. The method of the invention herein is applicable to prepare a wide variety of polymeric materials, either rigid or soft. Especially preferred polymeric materials are lenses including contact lenses, phakic and aphakic infraocular lenses, and corneal implants, although all polymeric materials including biomaterials are contemplated to be within the scope of this invention. Preferred articles prepared by the method described herein are optically clear and useful as a contact lens.

Brief Description of the Figures

Figure 1A is a teflon-covered tear sample representation as a section of a spherical contact lens; Figure IB is a representation of the sample

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

Shown at 1A with the slot cut and ready to be placed on the calipers of an Instron 4502 appliance.

Figure 2A is a representation of the die for cutting dog bone-shaped tensile specimens from the contact lens; Figure 2B is a mounting representation of the tear sample in the clamps of an Instron 4502 apparatus.

Detailed description of the invention

Unless clearly stated otherwise, all materials used in the formation of a monomer mixture according to the invention herein are listed as a percentage by weight. Furthermore, unless clearly stated otherwise, it will be understood that all amounts of materials used to make the monomers and monomer mixtures described herein represent the statistical mean of a normal distribution of weight values as commonly found in laboratory or commercial manufacturing of monomers and monomer mixtures described in this document. Therefore, unless clearly stated otherwise, all numerical values should be understood as being modified by the term approximately.

The term "substantially fully polymerized" as used herein means the inclusion ratio of the relative monomer of the cured device reflects the ratio of the relative monomer of the monomer mixture before curing.

That is, if a monomer present in the monomer mixture

IMPI before curing is not fully incorporated into *

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polymerized, one can see this variation.<img file="MX343282B_D0011.tif" /> removable. More importantly, the properties of the polymerized device that depend on the presence of a particular monomer present in the monomer mixture before curing, for example surface wettability and water content, may reflect the absence of the particular monomer. of the polymerized device. In the case of the comparative examples containing methacrylamide compounds, the addition of a benzotriazole blocker causes both increased variability in wetting of the lens surface and a rather pronounced drop in water content. This indicates that the NVP present in the methacrylamide-containing monomer mixtures of the comparative examples prior to curing was not substantially incorporated into the cured polymerized matrix. Therefore, the methacrylamide and benzotriazole blocker contains comparative examples that are not substantially fully polymerized.

Differential scanning photo calorimetry (DSC) is another example of an analytical technique that can be used to demonstrate whether a monomer system is substantially fully polymerized. There may be other analytical techniques that can be used to demonstrate the monomer system is substantially fully polymerized or to be developed in the future.

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MEXICAN INSTITUTE „a„ zDt THE PROPERTY

The term monomer, as used herein, is variation of molecular weight compounds. m (an ooteo oaeo, '' typically have average molecular weight numbers from about 700 to about 100,000) that can be polymerized. Furthermore, the term monomer, as used herein, refers to medium to high molecular weight compounds, sometimes referred to as macromonomers, (in this case, monomers that typically have average molecular weight numbers greater than 700) that contain capable functional groups. additional polymerization. Prepolymers are partially polymerized monomers that are capable of further polymerization. Therefore, the terms organosilicon-containing monomers, silicone-containing monomers, and hydrophilic monomers are understood to include monomers, macromonomers, and prepolymers.

An organosilicon-containing monomer contains at least one [--YES - O-] or at least one repeating unit [-Yes-- (C2-C7 alkyl) * Si - 0-], in a monomer, macromonomer or prepolymer. Preferably, total Si and bound O are present in the organosilicon-containing monomer in an amount greater than 5 percent by weight, and more preferably greater than 30 percent of the total molecular weight of the organosilicon-containing monomer. A silicone-containing monomer is one that contains at least one repeating unit [--YES - O-], in a monomer, macromonomer, or prepolymer.

fast such

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The monomers typically found in INOphthalmic agents that form monomer mixtures include slow-reacting "children" such as N-vinylpyrrolidone (NVP), 0-vinyl carbonates, 0-vinyl esters (eg, vinyl acetate), 0- esters allyl, O-allyl carbonates and N-vinyl carbamates, as well as more reactive monomers such as acrylates, methacrylates, acrylamides, methacrylamides and styrenics. In systems that form devices that contain fast and slow reaction monomer mixtures (such as can be found in monomer mixtures to form silicone hydrogels) a difference in reaction behavior (eg, free radical cure vs. transfer of hydrogen atoms) makes these systems particularly susceptible to incomplete cure. The relative sensitivity of the curing process of these device forming systems makes it difficult to create a successful ophthalmic device. Incorporation of substantial amounts of relatively slow reacting hydrophilic monomer such as NVP together with faster reacting comonomers into the monomer mixture according to the invention here can create a successful ophthalmic device by forming chains of homo polyvinylpyrrolidone (PVP) mainly in situ while the device cures.

The use of UV blockers in ophthalmic devices is known. UV light in the 210 to 315 nm range can cause damage to the cornea. Therefore, eye devices

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MEXICAN INSTITUTE containing UV absorbers are desirable ^^^ S ^ Sr for those patients who spend time with HpraH at ... a-go-ja free. Functionalized benzotriazole type UV absorbers (eg those of Structural Formulas I-IV) have been commonly used as UV blockers for fine articles such as contact lenses due to their relatively high extinction coefficient in the UV region.

Formula i

Formula ii

Formula III

Formula IV or

Formula v

1,3-bis (4-benzoill-3-hydroxyphenoxy) -2-propyl acrylate

Formula VI (BPM-2)

1,3-bis (4-benzoyl) -3-hydroxyphenoxy-2-propyl methacrylate

Formula VII (BPA-1)

2- (4-Benzoyl-3-hydroxyphenoxy) ethyl acrylate

For monomer systems forming ophthalmic devices containing both slow-reacting monomers such

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MEXICAN INSTITUTE OF LA FROPIEL'AP

1Λ a rnvní-.vnv as NVP and rapid reaction monomers, the use of 'iSTSSftte of benzotriazole UV typically results ! J”Eir · '' Ulf-cruradcr incomplete NVP and a subsequent loss of unreacted or partially oligomerized NVP during extraction. If one is looking to make silicone hydrogel lenses that contain benzotriazole UV blockers as well as PVP formed in situ, incomplete curing of the NVP can result in lower water content and compromised surface properties (in this case, poorly wettable lenses). Therefore, it was surprising and unexpected to discover that in a method of manufacturing a substantially fully polymerized UV-blocking hydrogel lens comprising the polymerization of a mixture of monomers of at least NVP and another comonomer and a Bis O-hydroxy free radical polymerizable or substituted unsubstituted benzophenone, Provides a hydrogel ophthalmic device that has a wettable surface and enough UV light blocking to meet at least Class II specifications for UV blocking. Contact lenses classified with the FDA Class II Blocker are recommended by the American Optometric Association for general-purpose uses. These lenses must block more than 70% UVA and 95% UVB to be considered as FDA Class II UV Blockers. Preferred compositions for use in the method of the invention herein preferably have both hydrophilic monomers

MEXICAN INSTITUTE / J

SAY PROPERTY and hydrophobic. Depending on the specific application, useful articles that were made according to the method of the invention herein may require hydrophobic monomers containing organosilicon. These organosilicon-containing hydrophobic monomers can be present between 0.1 to 75.8 percent by weight, more preferably between 2 to 20 percent by weight, even more preferably between 5 to 13 percent by weight. The amounts of hydrophobic monomers that do not contain organosilicon will be 0 to 60 percent by weight. Examples of hydrophobic materials that do not contain organosilicon include alkyl acrylates and methacrylates.

Depending on the application, useful articles made in accordance with the invention herein may also require bulky monomers such as those described in US Patent No. 6921,802, including methacryloxypropyl tris (trimethylsiloxy) silane (TRIS), pentamethyldisiloxanyl methylmethacrylate, tris (trimethylsiloxy) methacryloxy prcpylsilane, acrylate phenyltrytramethyl-disyloxanylethyl, methyl silyl] propyl vinyl, 3- [tris (trimethylsiloxy) silyl] prppil allyl carbamate, and 3- [tris (trimethylsiloxy) silyl] propyl vinyl carbonate. These bulky monomers, when present, can be present in more than 0 to 41.2 weight percent, 34 to 41 weight percent, or even 25 to 41 weight percent.

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OF THE PROPERTY

In general, hydrogels containing orgaií6Jtori'lLicitr¿They are prepared by polymerization of a qatí CHATItílifcí 'pui lu' mixture minus a silicone-containing monomer and at least one hydrophilic monomer. The organosilicon-containing monomer can function as a crosslinking agent (a crosslinker that is defined as a monomer having multiple polymerizable functionalities) or a separate crosslinker can be employed. Hydrophobic crosslinkers would include methacrylates such as ethylene glycol dimethacrylate (EGDMA) and allyl methacrylate (AMA). The amounts of crosslinkers used in the method of the invention herein can be between 0 to 76 weight percent, 2 to 20 weight percent, or 5 to 13 weight percent.

A wide variety of hydrophilic monomers can be used in the method of the present invention. Appropriate hydrophilic monomers include slow reacting monomers such as vinyl lactams such as NVP and l-vinylazonan-2-one. Depending on the application, useful articles may also require, in addition to slow-reacting hydrophilic monomers, fast-reactive hydrophilic monomers such as unsaturated carboxylic acids, methacrylic and acrylic acids; substituted acrylic alcohols, such as 2-hydroxyethyl methacrylate and 2-hydroxyethyl acrylate; and acrylamides, such as methacrylamide, N, N-dimethylacrylamide (DMA), and N-isopropylacrylamide (NIPAM).

MEXICAN INSTITUTE _,. . _ „OF THE PROPERTYv

Hydrophilic monomers will be present by multiply or by combined weight in amounts of ent: »O '· ί> 5 hao ^» percent by weight, between 30 to 50 percent by weight, between 35 to 45 percent by weight.

The use of large amounts of slow reacting silicone monomers in the method of the invention herein is advised. Slow reacting silicone monomers could include, for example, vinyl carbonate and vinyl carbamate manomers as described in the Patents.

Americans Nos. 5,070,215 and 5,610,252 (Bambury et al).

An organic diluent can be included in the initial monomer mix. As used herein, the term organic diluent encompasses organic compounds that minimize the incompatibility of the components in the initial monomer mixture and are substantially non-reactive with the components in the initial mixture. Additionally, the organic diluent serves to minimize phase separation of polymerized products produced by polymerization of the monomer mixture. Also, the organic diluent will generally be relatively non-flammable.

Contemplated organic diluents include alcohols such as tert-butyl alcohol (TBA), tert-amyl alcohol, hexanol and nonanol; diols, such as ethylene glycol; and polyols, such as glycerol. Preferably, the organic diluent is sufficiently soluble in the extraction solvent to facilitate its

MEXICAN INSTITUTE-OF PROPERTY, SMjpSjy removal of a cured article during the passage of "appropriate organic diluents will be o ^ idenfece 1 for · a ·· person experienced in the art.

The organic diluent is included in an amount effective to provide the desired effect (eg, minimal phase separation of polymerized products). Generally, the diluent is included at 0 to 6 0% by weight of the monomer mixture, with 1 to 40% by weight, which is more preferred, 2 to 30% by weight being even more preferred and 3 to 25% by weight, being especially preferred.

In accordance with the present process, the monomer mixture, which comprises at least one slow-reacting hydrophilic monomer, at least one ethylenically unsaturated hydrophobic monomer, and optionally the organic diluent, is formed and cured by conventional methods such as static or molten melt by spinning.

The reaction mechanism of lens formation can be free radical polymerization using initiators such as azábisisobutironitrilo (AIBN) and peroxide catalysts under conditions such as those established in the patent

No. 3,808,179, incorporated herein by reference.

Photoinitiation of the polymerization of the monomer mixture as is well known in the prior art can also be used in the article formation process as described herein.

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INSTITUTE D? THE

Dyes and the like can be added to TcE ^ Wézc

MEXICANO DI LA FKOPltRAO monomers before polymerization.

Following polymerization, the organic diluent and extractables are removed from the cured article to improve the biocompatibility of the article. Releasing unpolymerized monomers and oligomerized monomers into the eye during lens installation can cause irritation and other problems. Therefore, once the biomaterials formed according to the method described herein have undergone the polymerization step, they are subsequently subjected to an extraction step to prepare them for packaging and eventual use. The extraction step is carried out by exposing the polymerized materials to various solvents such as water, 2-propanol, etc., and mixtures thereof for variable periods of time. For example, an extraction process involves immersing the polymerized materials in isopropyl alcohol for approximately one hour, removing the alcohol, and then immersing the polymerized materials in an aliquot of water for approximately thirty minutes, removing the aliquot of water and then autoclaving the material polymerized in water or buffer solution.

After extraction of the unreacted monomers and any organic diluents, the shaped article, for example an RGP lens, is optionally machined by various

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processes known in the prior art. The paáy ^ JWrRilíiec1 It includes the lathe that cuts a supprfirip of lpnt-p_ tn-rnn qiiA cuts an edge of the lens, polishing an edge of the lens or polishing an edge of the lens or surface. The present process is particularly advantageous for processes in which a lens surface is turned, since machining of a lens surface is especially difficult when the surface is tacky or rubbery.

Generally, such machining processes are carried out before the article is released from a mold part. After the machining operation, the lens can be released from the mold part and hydrated. Alternatively, the article can be machined after removal of the mold part and then hydrated.

The following examples are provided to enable a person skilled in the art to practice the invention and are merely illustrative of the invention. The examples are not to be construed as limiting the scope of the invention as defined in the claims.

Ex emplos

All solvents and reagents were obtained from commercially available sources as identified below and are used as received.

IMPIfy

MEXICAN INSTITUTE K Dí LA FWOHEOAL »<

<td>Material</td><td>Seller</td>

<td>TRIS</td><td>Silar LaboratOTTyy 1 ‘ </td>

<td>Ma2D37</td><td>Gelest</td>

<td>NVP-distilled</td><td>Aldrich</td>

<td>CIX-4</td><td>Novasep</td>

<td>DMA-Distilled</td><td>Aldrich</td>

<td>Irg 819</td><td>Aldrich</td>

<td>Hexanol</td><td>Sigma Aldrich</td>

<td>Nonanol</td><td>Aldrich</td>

<td>Monomer SA</td><td>Aldrich</td>

<td>Mountain bike</td><td>Aldrich</td>

<td>BPA-2</td><td>Polysciences Inc</td>

<td>BPM-2</td><td>Monomer-Polymer Dajac Labs</td>

<td>BPA-1</td><td>Aldrich</td>

<td>Reactive blue ink = IMVT</td><td>Arran</td>

<td>ML-EDS-6</td><td>Gelest</td>

<td>HEMA</td><td>Cyro Industries</td>

* rRurijpr.L »'* ¿33tv2j4.

INDUSTRIAL ^ aa

Methacryloxypropyltris (trimethylsiloxy) silane TRIS

Ma2D37

N-vinylpyrrolidone

NVP

diethylene glycol bis (N-vinyl carbamate)

Ν, Ν-dimethylacrylamide

IRG 819 (photoinitiator)

HO

Monomer SA (UV Blocker)

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MBXICANQ INSTITUTE OF INDUSTRIAL PROPERTY

2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetrabutyl) phenol

1,3-bis (4-benzoyl-3-hydroxyphenoxy) -2-propyl acrylate

BPA-2

1,3-bis (4-benzoyl-3-hydroxyphenoxy) -2-propyl methacrylate

BPM-2

ΒΡΑ-1

3- (2H-Benzo [d] [1,2,3] triazol-2-yl) -4hydroxyphenethyl methacrylate

Formula i

Bis (2-methacrylate) de (((9,10-dioxo-4a, 9,9a, 10-tetrahydroanthracene-l, 420 diyl) bis (azanodiyl) bis (4, l-phenylene) bis (ethane-2,1 -diilo)

M1-EDS6 (EDS = ethylenedisiloxane)

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MEXICAN INSTITUTE OF RROFIRDAD

INDUSTRIAL

OR

2-hydroxyethyl methacrylate

HEMA or

MalD20

Analytical measurements

Mechanical properties

Modulus and elongation tests were carried out according to ASTM D-1708a, using an Instron instrument (Model 4502) where the hydrogel film sample is immersed in BBS (isotonic physiological borate buffered saline, pH 6.87.2 , Osmolality 270-320); An appropriate size for the film sample is the reference length of 22 mm and the width of 4.75 mm, where the sample also has ends that form a dog bone shape as shown in Figure 2A to accommodate the grip of the sample with clamps of the Instron instrument, and a thickness of 200 ± 50 microns.

Method for determining resistance to

IMPIAS

INSTITUTO Me-XICANO Dt LA ΝΙΟΝΕΟαΡ, IHpU tear of

U3TR spherical hydrogel contact

Sample preparation

one. Remove the first lens from its packaging and place it from the front side down the cutting block.

two. Gently wipe off any excess fluid from the surface at one edge.

3. Cover the front and back sides of that edge with Teflon tape as shown in Figure 1A and cut the tape to a rectangle.

Four. Once covered, place the sample in a Petri dish filled with BBS to rehydrate.

Test procedure

one. Lower the saline tank into the Instron 4502 equipped with it.

two. Take the sample from the saline solution and cut through the approximately 1mm tape on the lens beyond the tape to start the tear as shown in Figure IB.

3. Mount one side on the upper clamp and the other side on the lower clamp as shown in Figure 2B so that the initiated tear is kept in tension.

Four. Raise the saline tank around the sample.

5. Allow the sample to hydrate for at least 30 seconds before beginning the test.

NOTE: Once the sample is assembled make sure that the

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MEXICAN INSTITUTE OF THE ΡΧΟ ^ ΕΟΑΓ, INDUSTRIAL

load has not read more than 0.1 g. If it is greater than 0.1 g, remove the sample and rebalance the load until 0. OÓOg ± 0.002 'is reached. Then replace the sample in the lugs and raise the tank.

6. Using the software control, enter the thickness of the sample and start the test.

7. Once the first test has completed the tear, review the graph and load displacement data to determine if the data should be maintained (archived) or rejected. Any huge flaws, such as discontinuities in the graph, must be rejected. If the first displacement marker is to the left of the first peak in the load, then move it to the first peak in the load. Repeat for the remaining samples for the sample lot.

8. Once all samples in a batch are tested print a copy of the results.

Data register

Report the average tear strength and standard deviation. Note in the application and raw data sheet that the data has been calculated using the average thickness at a diameter of 6 mm (or at the center thickness if the anterior and posterior radius could not be obtained).

Materials and equipment needed

Description- This test procedure describes the materials and procedure used to determine the modulus of spherical hydrogel contact lenses.

IMPIOUS

MEXICAN INSTITUTE OF PROPERTY,. . - _ INDUSTRIAL 1. An Instron Model 4502 mechanical tester along with a 250g load cell installed in the stationary crosshead.

two. A saline tank attached to the Instron to keep the sample hydrated during the test.

3. Test job data acquisition package and data station (computer and printer).

Four. A set of 10 lenses (minimum) for testing.

5. A pair of Teflon forceps for handling contact lenses.

6. A wood cutting block.

7. A hammer.

8. A die to cut the tensile samples from the contact lens. Samples should be cut to the dimensions shown in Figure 2A.

9. Teflon tape.

10. A pair of scissors.

eleven. A Petri dish filled with BBS.

Instrument setup

one. Using the anterior and posterior radii given for the lot tested, convert the center thickness subjected to the average thickness to a diameter of 6 mm. Use the average thickness of the lens dimensions.

two. Adjust the Instron handles to separate to accommodate a 6mm reference length sample.

3. Raise the saline tank around the

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MEXICAN INSTITUTE DB LA FROCTEDAP INDUSTRIAL

handles so the handles can be balanced for 10 to 15 minutes before use.

Four. Calibrate the instrument so that the loading screen reads 0.000 ± 0.002 g. NOTE: Use a feed rate of 6.35 mm / min.

5. Select method number 10 so that the modulus is calculated between 0.25 g and 2 g loads.

Sample preparation

one. Remove the first lens from the package and place it from the front side down on the cutting block.

two. Cut a tensile sample by centering a die designed to prepare a shape as shown in Figure 2A on the back surface of the lens and hammering the die back side once.

. Remove the tensile sample from the die and tape from the front and back of each edge as shown in Figure 2B.

Four. Cut the ribbon into a rectangle.

5. Once covered, place the sample in a Petri dish filled with BBS to rehydrate.

Test procedure

one. Lower the saline tank into the Instron 4502.

two. Take the sample out of the saline solution and mount one edge on the upper clamp and the other on the lower clamp as shown in Figure 2B so that the sample is taut and straight.

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MIXICAN INSTITUTE Say LA FSOMBDAD

3. Raise the saline tank aT2®3 £ dor * -Se - = ^ a sample. ......... -

Four. Allow the sample to hydrate for at least 30 seconds before beginning the test. NOTE: Once the sample is assembled make sure that the load has not read more than 0.100 g. If it is greater than 0.100 g, withdraw the sample and rebalance the load until 0.000 g ± 0.002 is reached. Then replace the sample on the lugs and raise the tank.

5. Using the software control, enter the thickness of the sample and start the test.

6. Once the first sample has been broken, review the graph and load displacement data to determine if the data should be kept (archived) or rejected. Any huge flaws, such as discontinuities in the graph, must be rejected. Enlarge the slant region of the module to determine if the tangent was drawn correctly. Repeat for the remaining samples for the sample lot.

7. Once all samples in a batch are tested print a copy of the results.

Data register

Report the mean modulus and standard deviation. Observe in the application and on the raw data sheet that the data has been calculated using the average thickness in a diameter of 6 mm (or the central thickness if the anterior and posterior radius cannot be obtained).

IMPI O0

Captive contact angle measurements

Captive bubble testing was performed using the First Ten Angstroms instrument (Model FTA Series 1000); Equipped with a 50mm high speed USB camera with image capturing capabilities. Make sure the interfacial tension of the water test has been performed and has met the acceptable criteria before performing the captive bubble test.

BBS Packaging Solution Protocol Lenses

Prepare lenses in a batch of three each, which are transferred with the tweezers of the individual containers in Petri dishes filled to the mark with 18 Meg of water. Latex gloves are worn for the duration of sample preparation and captive bubble testing. Note: BBS samples are soaked for a minimum of 15 minutes prior to testing. Analysis of the first lens sample

After pretreatment of the lens samples use tweezers to mount a lens sample to the nickel lens mounting tool, then place the tool on the tool holding element.

Place the element in a glass tray filled to the mark with 18 Meg of water. Place the element on the TLC 1000 platform. In MENU select Stage Z +, move the polarity to +21.00 (move the lower platform / lens / element in the

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MEXICAN INSTITUTE OF LA MOREDA »INDUSTRIAL

correct position). In Menu select Z-Tip ±, move the polarity to -18.00 (move the needle tip in the correct position). Menu: select SUPPLY. If the bubble is not observed at this time, manually pump until the first bubble appears. Press START. The bubble will begin to increase in size until it is a short distance from the surface of the lens, then stop automatically (Observe if it seems that the bubble is going to touch the surface of the lens immediately press STOP. Enter .03 in the polarity value, then press scroll - until the bubble almost contacts the lens surface. Select Y stage Z +, shift +, 0.250 to set the white reflection lines to the bubble junction point. Enter 0.03 in the polarity value box again, then press scroll - until the bubble first contacts the surface of the lens. Wait a second or two to see if the point of contact seems to extend horizontally. If not, scroll once more. Press RUN (start movie event), wait for an audible beep sound, press PUMP, wait 1 to 2 seconds, then press PUMP.

The moment the bubble separates from the lens surface press ABORT (pressing ABORT ends the film event). Save the movie as a file in a folder in E \: FTA in the captive bubble folder, in this case,

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MEXICAN INSTITUTE OF THE PHOPIEDAD

New folder: 11-XXX. Create a movie file *1· For each lens in the same lot. Presioxiaf BUMEEAR 'ΈΝ to reduce the size of the bubble to its original dispensing size. Menu: Z + tip, move +.03 3-5 times then enter +18.00 to raise the needle tip to the appropriate height for the next sample. Menu: Stage Z +, move -21.00 to lower the platform / lens / lower element in the appropriate position for the next sample. Remove the lens element / sample / cuvette from the stage. Remove the element from the tray. Remove the lens holder from the element and discard. Using tweezers, obtain the next lens sample to be tested. Use fresh 18 Meg water to rinse and up to the bucket between each batch. At the end of the day: deselect VIDEO to turn off. Rinse the tray, lens holders, allow to air dry and store under aluminum foil. Use the Y Stage + shift - or + 0.250 to adjust th e white stage lines used to align with the bubble in contact with the lens surface. Use Stage X + offset - or + 0.10 or another value to adjust both sides of the stage to approximately the same height.

Wilhelmy Plate wettability measurement - Determination of hysteresis cycle area

Wilhelmy plate hysteresis cycle measurements were performed on a Kruss Model K100MK2 processor sphygmomanometer.

Process

Sample lenses to be analyzed s er 'errrj'ua'cj ai un ·' in DDO1 overnight to remove any remaining components from the packaging solution. Once rinsed, the samples were removed from the solution and placed in fresh BBS for at least 15 minutes. The Pt anchor (used to load the sample) was flamed with a propane torch to remove all surface contamination. All lenses will be cut into strips using a sharp blade to the following dimension: 10mm long x 3.3mm wide. Attach the Pt anchor to the sample strip within 1mm of the bottom. A tt ac h the top half of the lens strip to the sample clip on the instrument, and place it on the electro-balance bracket. Fill the dip tank with fresh BBS. Lower the cut lens specimen and clamp in the fresh BBS such that the bottom of the lens is approximately 1mm above the BBS solution. Set the immersion speed for running and 6 mm / min and the total distance traveled to 9.5 mm. Discard the results of the first immersion cycle while the lens is rehydrated after sample preparation. Perform three additional dive cycles.

Plot the force exerted on the sample as a function of the distance traveled by the three cycles and average the results. Integrate the area joined by the curve of the average force graph and report this value as the area of the hysteresis cycle.

Table 1. Comparative examples [* Material not included in the comparative example / Example]

OR

OJ

THE

Csl

Table 2. Examples [* Material not included in Comparative Examples / Examples]

LD O LO O tn rH Γ4 C \ |

Table

ΓΟ

<td rowspan="3">| Contact angle |</td><td>His</td><td> 13 (3.3)</td><td>fO rd rd * "</td><td> 40 (28.4)</td><td> 87 (4.9)</td><td>IN rd rd rd</td><td> 12 (4.6)</td><td> 12 (0.4)</td><td> 11 (1.3)</td><td>9 (2.1)</td>

<td colspan="2">Cycle of one area !WP</td><td> 1.44</td><td> 2.11</td><td> 1.56</td><td> 2.01</td><td> 1.83</td><td> 1.43</td><td> 0.67</td><td> 0.91</td><td> 96'0</td>

<td colspan="2">% of cured</td><td> 100</td><td> 100</td><td> 100</td><td>Γ0 in</td><td> 001</td><td> 100</td><td></td><td></td><td></td>

<td colspan="2">Class UV</td><td>None</td><td>II</td><td>H H</td><td>H H</td><td>H H</td><td>H 1—1</td><td>| None</td><td>II</td><td>H H</td>

<td colspan="2">% elongation</td><td> 150(76)</td><td> 111(75)</td><td> 97(68)</td><td> 170 (100) 1</td><td>1 205 (43)</td><td> 169 (56)</td><td> 155(34)</td><td> 191(55)</td><td> 198(32)</td>

<td colspan="2">Traction</td><td> 65(33)</td><td> 57(33)</td><td> 38(25)</td><td> 38(23)</td><td> 89(21)</td><td> 77(29)</td><td> 57(12)</td><td> 75(22)</td><td> 93(13)</td>

<td colspan="2">Module</td><td> 74(3) _</td><td> 90(7)</td><td> 64 (5)</td><td> 37(6)</td><td>two THE</td><td> 76(5)</td><td> 63(5)</td><td> 70(3)</td><td> 86(5)</td>

<td colspan="2">Blocker parts% in weight</td><td>or</td><td> 0.7</td><td>rd</td><td>ΓΊ</td><td>rd</td><td></td><td>OR</td><td>it is</td><td>rd</td>

<td colspan="2">Block- dor L</td><td>none</td><td>S 165</td><td>BPA-l</td><td>BPA-l</td><td>BPA-2</td><td>BPA-2</td><td>None</td><td>BPA-2</td><td>CN to</td>

<td colspan="2">Sample ID</td><td>Example comparative 9</td><td>4 -ΓΊ OO ω oh</td><td>0 $ rd Μ η O (Ί W ü rd</td><td>% 4-1 0 rt • r ~> 6 m WO i — 1</td><td>Γ * 0 rd i 'Γ) W</td><td>faith1</td><td>00 0 rd & iS *</td><td>σ » £ F IS1</td><td>Example 10</td>

LO ** »3

OR

OI

Table

<td>Example 14</td><td> 33.64</td><td> 3.65</td><td> 3.70</td><td> 35.84</td><td> 0.25</td><td> 4.94</td><td> 0.33</td><td>it is THE rd</td><td> 0.02</td><td></td><td> ^1.23</td><td></td><td> 72(5)</td><td colspan="2"> 66(16)</td><td> 141(35)</td><td> 8(0.2)</td><td> 59.1(0.1)</td><td> 37(0.4)</td><td>XI</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td rowspan="2">neither</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>fri</td><td>P</td><td></td>

<td> 0</td><td>Cn</td><td>neither</td><td>ftí</td><td></td><td> 0</td><td>sj</td><td> &</td><td>neither</td><td> -3</td><td></td><td>Hl</td><td> £¡</td><td>Ό</td><td>ΠΙ</td><td>tn</td><td></td><td>α></td><td>Q</td><td>c</td><td>rd</td>

<td>faith</td><td></td><td> *·</td><td> 2</td><td>faith</td><td>or</td><td>H</td><td>H</td><td>to</td><td>Hey</td><td>to</td><td>to</td><td>to</td><td>faith</td><td>to</td><td></td><td>oV</td><td>to</td><td>or</td><td>to</td><td>or</td>

THE

OR

ΓΜ tn

CS

'.wwras »

Table ιη

<td rowspan="3">Contact angle</td><td>Hist</td><td> 9(0.4) 1</td><td> 9(1.0)</td><td> 10(1.5)</td><td> 60(1.7)</td><td> 63(2.1)</td>

<td colspan="2">Sample ID</td><td>Comparative Example 1</td><td>Comparative example 2</td><td>Comparative example 3</td><td>Comparative Example 4</td><td>Comparative example 5</td>

<0 rd i — I XI rd H

<td rowspan="3">Contact angle</td><td>Hist.</td><td> 13 (3.3)</td><td> 13 (1-4)</td><td> 12 (4.6)</td>

<td colspan="2">Class UV</td><td>none</td><td>H H</td><td>H H</td>

<td colspan="2">Cycle Area WP !</td><td>pL.44</td><td> 2.11</td><td> 1.43</td>

<td colspan="2">toilet (%)</td><td> 45.1</td><td>( 43.1 L__</td><td> 45.1</td>

<td colspan="2">Blocker (%)</td><td>OR</td><td> 0.7</td><td> 2.0</td>

<td colspan="2">Block- dor</td><td>none</td><td> 8</td><td>BPA-2</td>

<td colspan="2"></td><td>σ » you Ή 8</td><td>í¡ § Ϊ 8 S</td><td>Example 4</td>

OR

C \ l

LD

THE

ΓΜ

Results

As shown by the water content data in Tables 3 and 5, the use of benzotriazole blockers (SA monomer) in monomer systems results in incomplete cure of NVP with subsequent loss of unreacted or partially oligomerized NVP during extractions. Furthermore, in the presence of SA monomer many lenses in a given batch will exhibit very large lead contact angles and increased contact angle variability. This variability is not observed when the SA monomer UV blocker is removed from the formulation.

Preferred modalities

one. A method of manufacturing a substantially fully polymerized UV blocking hydrogel lens comprises:

polymerization of a mixture of at least NVP monomers and another comonomer and a free radical polymerizable Bis o-hydroxy benzophenone to provide a hydrogel ophthalmic device having a wettable surface, and sufficient UV light blocking to satisfy at least the class II specifications for UV blocking.

two. The method of modality 1 also includes:

reacting the monomer mixture under appropriate conditions to cause substantially completely co-cure of the monomer system component of the reaction mixture to provide a substantially completely copolymerized ophthalmic device containing UV blocker.

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

3. The method of embodiment 1, wherein the substituted bis o-hydroxy benzophenone is selected from the group consisting of 1,3-bis acrylate (4-benzoyl-3-hydroxyphenoxy-2-propyl and 1,3-bis methacrylate (4-benzoyl-3-hydroxyphenoxy) -2-propyl and mixtures thereof.

Four. The method of embodiment 2, wherein the substantially completely copolymerized UV blocker containing ophthalmic device has an equilibrium water content of from about 42.3% to about 59.1% when fully hydrated.

5. The method of embodiment 2, wherein the substantially completely copolymerized UV blocker containing ophthalmic device has a recoil contact angle of approximately 21.

6. The method of embodiment 2, wherein the substantially completely copolymerized UV blocker containing ophthalmic device has a lead contact angle of between about 29 and about 33.

7. A UV-blocking contact lens that contains inserted PVP and that has a water content of about 42.3% to about 59.1% when fully hydrated.

8. Mode 7 UV-blocking contact lens has a reverse contact angle of approximately

21.

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INDUSTRIAL

9. The Mode 7 UV-blocking contact lens has a forward contact angle of between about 29 and about 33.

10. A UV-blocking silicone hydrogel contact lens that contains introduced PVP and has a water content of about 42.3% to about 59.1% when fully hydrated.

eleven. The Mode 10 UV-blocking silicone hydrogel contact lens has a recoil contact angle of approximately 21.

12. The Mode 10 UV-blocking silicone hydrogel contact lens has a forward contact angle of between about 29 and about 33.

13. The method of embodiment 1, wherein the free radical polymerizable substituted or unsubstituted Bis ohydroxy benzophenone is functionalized with a free radical polymerizable mono acrylate or mono methacrylate group.

14. The mode 1 method, wherein the substantially completely copolymerized UV blocker containing ophthalmic device has a Wilhelmy plate area cycle of between 0.91 and 1.83.

fifteen. The method of embodiment 1, wherein the monomer mixture further comprises an organosilicon-containing hydrophobic monomer.

16. The method of embodiment 15, wherein the organosilicon-containing monomer is present in between 0.1 to

I Αί Ρ i SBB msTrruTO méxigano

DiLA RROPISDAI1 INDUSTRIAL

75.8 percent by weight.

17. The method of embodiment 15 wherein the organosilicon-containing monomer is present in from 2 to 20 weight percent.

18. The method of embodiment 15, wherein the organosilicon-containing monomer is present in from 5 to 13 weight percent.

19. The method of embodiment 15 wherein the monomer mixture further comprises hydrophobic monomers that do not contain organosilicon.

twenty. The method of embodiment 19 wherein the hydrophobic monomers that do not contain organosilicon are present in about 0 to 60 percent by weight.

twenty-one. The method of embodiment 19 wherein the hydrophobic monomers which do not contain organosilicon are selected from the group consisting of alkyl acrylates and alkyl methacrylates.

. The method of embodiment 15 wherein the monomer mixture further comprises a bulky monomer selected from the group consisting of methacryloxypropyl tris (trimethylsiloxy) silane (TRIS), pentamethyldisiloxanyl methylmethacrylate, methylaryl-phenylathylaryl-methylaryl-methylaryl-phenylaryl-methylaryl-methylaryl-methylaryl-phenylathylaryl-methylaryl-methylaryl-methylaryl. di (trimethylsiloxy) methacryloxymethyl silane, 3- [tris (trimethylsiloxy) silyl] propyl vinyl carbamate, 3- [tris (trimethylsiloxy) silyl] propyl carbamate

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MEXICAN INSTITUTE OF INDUSTRIAL ΡΒΟΡίΕΠΑΟ

allyl, and 3- [tris (trimethylsiloxy) silyl] propyl carbonate r ——— r —'-- 1 !! II vinyl, and mixtures thereof.

2. 3. The method of embodiment 22 wherein the bulky monomer is present in more than 0 to 41.2 percent by weight.

24. The method of embodiment 22 wherein the bulky monomer is present in more than 34 to 41 weight percent.

25. The method of embodiment 22 wherein the bulky monomer is present in more than 25 to 41 percent by weight.

26. The method of embodiment 15 wherein the monomer mixture further comprises a hydrophobic crosslinker selected from the group consisting of ethylene glycol dimethacrylate (EGLMA), allyl methacrylate (AMA), and mixtures thereof.

27. The method of embodiment 26 wherein the hydrophobic crosslinker is present in from 0 to 76 weight percent.

28. The method of embodiment 26 wherein the hydrophobic crosslinker is present in from 2 to 20 weight percent.

29. The method of embodiment 26 wherein the hydrophobic crosslinker is present at between 5 to 13 weight percent.

30. The method of embodiment 15 wherein the monomer mixture further comprises a slow reacting hydrophilic monomer in addition to NVP.

31. The method of embodiment 30 wherein the slow reacting hydrophilic monomer is l-vinylazonan-2-one.

32. The method of embodiment 15 wherein the monomer mixture further comprises a fast reacting hydrophilic monomer.

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33. The method of embodiment 32 wherein the fast reacting hydrophilic monomer is selected from the group consisting of unsaturated carboxylic acids, substituted acrylic alcohols, acrylamides, and mixtures thereof.

3. 4. The method of embodiment 32 wherein the fast reacting hydrophilic monomer is selected from the group consisting of methacrylic acid, acrylic acid, methacrylate of

2-hydroxyethyl, 2-hydroxyethyl acrylate, methacrylamide, N, N-dimethylacrylamide (DMA), N-isopropylacrylamide (NIPAM), and mixtures thereof.

35. The method of embodiment 32 wherein the fast reacting hydrophilic monomer is present in from 25 to weight percent.

36. The method of embodiment 32 wherein the fast reacting hydrophilic monomer is present in from 30 to 50 weight percent.

37. The method of embodiment 32 wherein the fast reacting hydrophilic monomer is present at between 35 to 45 weight percent.

38. The method of embodiment 30 wherein the slow reacting hydrophilic monomer is present in from 25 to weight percent.

39. The method of embodiment 30 wherein the slow reacting hydrophilic monomer is present in from 30 to 55 weight percent.

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M PROPERTY V> INDUSTRIAL

40. The method of modality 30 where the monomer

slow-reacting hydrophilic is present in 35 to 45 percent by weight.

41. The method of embodiment 1, wherein the monomer mixture further comprises at least one slow reacting hydrophilic monomer, at least one ethylenically unsaturated hydrophobic monomer, and an organic diluent comprising the combined step of shaping and polymerizing by a method selected from the group consisting of static melt and centrifugal melt.

42. The method of embodiment 41 further comprises the step of exposing the polymerized materials to a solvent selected from the group consisting of water, 2-propanol, etc., and mixtures thereof.

43. The method of modality 42 further comprises the step of autoclaving the polymerized material in water or buffer.

44. The modality 7 UV blocking contact lens has a Wilhelmy plate area cycle of between 0.91 and 1.83.

Four. Five. The Mode 10 UV blocking contact hydrogel lens has a Wilhelmy plate area cycle of between 0.91 and 1.83.

46. The modality 1 method as modified by either modality 2-6 or 13-43.

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47. The modality 1 method as modified by any combination of modalities 2-6 or 13-43.

48. The modality 7 contact lens as modified by the combination of modalities 8, 9 and 44.

49. The mode 10 contact lens, as modified by the combination of modes 11, 12, and 45.

fifty. A method of manufacturing a substantially fully polymerized UV-blocking hydrogel lens comprises:

polymerization of a reaction mixture of monomers of at least NVP and another comonomer and a free radical polymerizable Bis 0-hydroxy benzophenone to provide a substantially fully polymerized hydrogel ophthalmic device.

51. The method of embodiment 50 wherein the substantially fully polymerized hydrogel ophthalmic device has a wettable surface.

52. The 50 or 51 mode method wherein the hydrogel ophthalmic device demonstrates sufficient UV light blocking to meet at least the PDA Class II specifications for UV blocking.

53. The method of embodiment 50 wherein further the polymerization step produces substantially complete co-cure of a component of the monomer system of the monomer reaction mixture to provide a substantially fully copolymerized ophthalmic device.

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INDUSTRIAL

54. The method of embodiment 50, wherein the free radical polymerizable substituted bis-hydroxybenzophenone is selected from the group consisting of 1,3-bis (4-benzoyl-3-hydroxyphenoxy) -2-propyl acrylate and 1,3-methacrylate Bis (4-benzoyl3-hydraxyphenoxy) -2-propyl and mixtures thereof.

55. The method of modalities 50 or 53, wherein the substantially fully copolymerized ophthalmic device has a water content of about 42.3% to about 59.1% when fully hydrated.

56. The method of modalities 50 or 53, wherein the substantially fully copolymerized ophthalmic device has a recoil contact angle of approximately 21.

57. The method of modalities 50 or 53, wherein the substantially fully copolymerized ophthalmic device has a forward contact angle of between about 29 and about 33.

58. A UV-blocking contact lens that demonstrates sufficient blocking of UV light to meet at least FDA Class II specifications for UV blocking that contains introduced PVP and has a water content of approximately 42.3% to approximately 59.1 % when fully hydrated.

59. The Mode 58 UV blocking contact lens has a recoil contact angle of approximately 21.

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60. The 58 _____J 3MM UV blocking contact lens-——— MWM ^ rWTtlTr · - ** ^ · - has a lead contact angle of between approximately 29 and approximately 33.

61. A UV blocking silicone hydrogel contact lens demonstrates enough UV light blocking to meet at least FDA Class II specifications for UV blocking that contains introduced PVP and has a water content of about 42.3% to about 59.1 % when fully hydrated.

62. The Mode 61 UV-blocking silicone hydrogel contact lens has a recoil contact angle of approximately 21.

63. The Mode 61 UV-blocking silicone hydrogel contact lens has a forward contact angle of between about 2 and about 33.

64. The method of embodiment 50 wherein the free radical polymerizable Bis 0-hydroxy benzophenone is functionalized with a free radical polymerizable group.

65. The mode 50 method, wherein the substantially completely copolymerized UV blocker containing ophthalmic device has a Wilhelmy plate area cycle of between 0.91 and 1.83.

66. The method of embodiment 50, wherein the monomer mixture further comprises an organosilicon-containing hydrophobic monomer.

MEXICAN INSTITUTE OF INDUSTRIAL EROFIEDAD

67. The mode 64 method where the organosilicon-containing monomer is present between 0.1 to 75.8 weight percent.

68. The method of embodiment 64 wherein the organosilicon-containing monomer is present between 2 to 20 weight percent.

69. The method of embodiment 64 wherein the organosilicon-containing monomer is present between 5 to 13 weight percent.

70. The method of embodiment 65 wherein the monomer mixture further comprises hydrophobic monomers that do not contain organosilicon.

71. The method of embodiment 70 wherein the hydrophobic monomers that do not contain organosilicon are present in about 0 to 60 percent by weight.

72. The method of embodiment 70 wherein the hydrophobic monomer that does not contain organosilicon is selected from the group consisting of alkyl acrylates and alkyl methacrylates.

73. The method of embodiment 64 wherein the monomer mixture further comprises a bulky monomer selected from the group consisting of methacryloxypropyl tris (trimethylsiloxy) silane (TRIS), pentamethyldisiloxanyl methylmethacrylate, tris (trimethylsiloxy) methacryloxypropyl silane, acrylatyl-phenylathylaryl-phenylatyl-phenylatyl-methylaryl-phenylaryl-phenylaryl-methylaryl-phenylaryl-phenylaryl-methylaryl)

IMPI

MEXICAN INSTITUTE K LA INDUSTRIAL FROFIbDAD

methyl-di (trimethylsiloxy) methacryloxymethyl silane, 3 [tris (trimethylsiloxy) silylpropyl vinyl carbamate, 3 [tris (trimethylsiloxy) silylpropyl allyl carbamate, and 3 [tris (trimethylsiloxy) silylpropyl vinyl carbonate and mixtures thereof.

74. The method of embodiment 73 wherein the bulky monomer is present in more than 0 to 41.2 weight percent.

75. The method of modality 73 where the bulky monomer is present in more than 34 to 41 weight percent.

76. The method of modality 73 wherein the bulky monomer is present in more than 25 to 41 weight percent.

77. The method of embodiment 64 wherein the monomer mixture further comprises a hydrophobic crosslinker selected from the group consisting of ethylene glycol dimethacrylate (EGDMA), allyl methacrylate (AMA), and mixtures thereof.

<td>80. The</td><td>method</td><td>of</td><td>the</td><td>modality 77</td><td>in</td><td>where</td><td>the</td>

<td>crosslinkers</td><td colspan="2">hydrophobic</td><td colspan="3">are present between</td><td>0 to</td><td> 76</td>

<td>percent in</td><td>weight.</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>81. The</td><td>method</td><td>of</td><td>the</td><td>modality 77</td><td>in</td><td>where</td><td>the</td>

<td>crosslinkers</td><td colspan="2">hydrophobic</td><td colspan="3">are present between</td><td>2 up</td><td> 20</td>

<td>percent in</td><td>weight.</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>82. The</td><td>method</td><td>of</td><td>the</td><td>modality 77</td><td>in</td><td>where</td><td>the</td>

Hydrophobic crosslinkers are present between 5 to 13 weight percent.

83. The method of embodiment 64 wherein the monomer mixture further comprises a hydrophilic reaction monomer

INSTITUTO MEXICANO Dt LA pnOPIIDAD slow ikwstuial in addition to NVP.

84. The method of embodiment 32 wherein the slow reacting hydrophilic monomer is l-vinylazonan-2-one.

85. The method of embodiment 15 wherein the monomer mixture further comprises a fast reacting hydrophilic monomer.

86. The method of embodiment 85 wherein the fast reacting hydrophilic monomer is selected from the group consisting of unsaturated carboxylic acids, substituted acrylic alcohols, acrylamides, and mixtures thereof.

87. The method of embodiment 85 wherein the rapid reacting hydrophilic monomer is selected from the group consisting of methacrylic acid, acrylic acid, methacrylate of

2-hydroxyethyl, 2-hydroxyethyl acrylate, methacrylamide, Ν, Ν-dimethylacrylamide (DMA), N-isopropylacrylamide (NIPAM), and mixtures thereof.

88. The method of embodiment 85 wherein the fast reacting hydrophilic monomer is present between 25 to 60 weight percent.

89. The method of embodiment 85 wherein the fast reacting hydrophilic monomer is present between 30 to 50 weight percent.

90. The method of embodiment 85 wherein the fast reacting hydrophilic monomer is present between 35 to 45 weight percent.

INSTITUTO MEXICANO ¡X LA rKOPlEDAO industrial

91. The method of embodiment 83 wherein the slow reacting hydrophilic monomer is present between 25 to 65 percent by weight.

92. The method of embodiment 83 wherein the slow reacting hydrophilic monomer is present between 30 to 55 weight percent.

93. The method of embodiment 83 wherein the slow reacting hydrophilic monomer is present between 35 to 45 weight percent.

94. The method of embodiment 50 wherein the monomeric mixture further comprises at least one slow reacting hydrophilic monomer, at least one ethylenically unsaturated hydrophobic monomer and an organic diluent and comprises a combined step of shaping and polymerization by a selected method step from the group consisting of static melt and centrifugal melt.

95. The method of embodiment 94 further comprising a step of exposing the polymerized materials to a solvent selected from the group consisting of water, 2-propanol, etc., and mixtures thereof.

96. The method of embodiment 94 further comprises a step of autoclaving the polymerized material in water or buffer.

97. The Mode 58 UV blocking contact lens has a Wilhelmy plate area cycle of between 0.91 and 1.83.

IMPI

MEXICAN INSTITUTE m THE PROPERTY

INDUSTRIAL

98. The Mode 62 UV-blocking silicone hydrogel contact lens has a Wilhelmy plate area cycle of between 0.91 and 1.83.

Having thus described the inventive concepts and a number 5 of exemplary embodiments, it will be apparent to those skilled in the art that the invention can be implemented in various ways, and that modifications and improvements will readily occur to such persons. Therefore, the modalities are not intended to be limiting and are presented by way of example only. The invention is limited only as required by the following claims and equivalents thereof.

It is noted that in relation to this date, the best method known by the applicant to put the aforementioned invention into practice, is the one that is clear from the present description of the invention.

MEXICAN INSTITUTE M LA PROPI LOAD

INDUSTRIAL

Contents66

18 members in 6 offices

This recordMember, by publication datePriority claim

Priority claims19

Priority claims
Document	Office	Kind	Date
201161501423	United States of America	P	2011-06-27
201161501423	United States of America	P	2011-06-27
61501423	United States of America	–	2011-06-27
201161564429	United States of America	P	2011-11-29
201161564429	United States of America	P	2011-11-29
61564429	United States of America	–	2011-11-29
201261592195	United States of America	P	2012-01-30
201261592195	United States of America	P	2012-01-30
61592195	United States of America	–	2012-01-30
2012044123	United States of America	W	2012-06-26
2012044123	United States of America	W	2012-06-26
61501423	–	–	–
61564429	–	–	–
61592195	–	–	–
PCTUS2012044123	–	–	–
US201161501423P	–	–	–
US201161564429P	–	–	–
US201261592195P	–	–	–
WO2012US44123	–	–	–

Members18

Family members, oldest first
Document	Office	Kind
CA2838236A1	Canada	A1	2013-01-03
WO2013003301A1	World Intellectual Property Organization (WIPO)	A1	2013-01-03
MX2013014835A	Mexico	A	2014-03-27
EP2724545A1	European Patent Office (EPO)	A1	2014-04-30
US2014146864A1	United States of America	A1	2014-05-29
EP2724545A4	European Patent Office (EPO)	A4	2014-12-31
US9160407B2	United States of America	B2	2015-10-13
US2016037188A1	United States of America	A1	2016-02-04
MX343282BThis record	Mexico	B	2016-10-31
BR112013033527A2	Brazil	A2	2017-02-07
US9877050B2	United States of America	B2	2018-01-23
US2018152738A1	United States of America	A1	2018-05-31
BR112013033527A8	Brazil	A8	2018-07-17
EP2724545B1	European Patent Office (EPO)	B1	2019-03-06
CA2838236C	Canada	C	2019-06-18
US10334291B2	United States of America	B2	2019-06-25
BR112013033527B1	Brazil	B1	2022-10-25
BR112013033527B8	Brazil	B8	2023-01-10

Abstract

Term

PATENT TITLE NO. 343282

REQUEST

PRIORITY

MANUFACTURE METHOD OF SILICONE HYDROGEL LENS WITH

FULLY POLYMERIZED ULTRAVIOLET (UV) LOCK

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Priority claims19

Members18

Numbers

Titles2

Classification