Polymeric materials and additives therefor.
Abstract
A polymer additive for improving the reheat characteristics of a polymer or polymeric composition comprises an inorganic material which is such that a 2.5mm thick polyethylene terephthalate plaque incorporating the inorganic material has, when tested, an absorption ratio of less than 0.9, wherein the absorption ratio is either the ratio of A1/A2 or the ratio A1/A3, wherein: A1 is the maximum absorption between 400nm and 550nm; A2 is the maximum absorption between 700 to 1100 nm; A3 is the maximum absorption between 700 to 1600 nm. Preferred inorganic materials are titanium nitride, indium tin oxide and lanthanum hexaboride.

Term
Term ended
Expired 30 March 2025, 1.5 years ago.
- Priority
- Filed
- Granted
- Expired
- Today
11 claims: 3 independent, 8 dependent
- 1REIVINDICACIONES Habiéndose descrito la invención como antecede, se reclama como propiedad lo contenido en las siguientes reivindicaciones:1. Una composición que comprende un material polimérico y nitruro de titanio para mejorar las características de recalentamiento de un material polimérico, caracterizada porque la composición incluye 25 ppm o menor de nitruro de titanio en base en el peso del material polimérico.
- 2Una composición de conformidad con la reivindicación 1, caracterizada porque el nitruro de titanio es materia coloidal o nanoparticulada.
- 3Una composición de conformidad con la reivindicación 1, caracterizada porque el material polimérico comprende un polímero termoplástico seleccionado del grupo de polímeros:poliésteres, policarbonatos, poliamidas, poliolefinas, poliestirenos, polímeros de vinilo, polímeros acrílicos y copolímeros y mezclas de los mismos.
- 4Una composición de conformidad con la reivindicación 1, caracterizada porque el material polimérico es poli(tereftalato de etileno) o un copolímero del mismo.
- 5Un método para mejorar las características de recalentamiento de un material polimérico, caracterizado porque comprende poner en contacto el material polimérico o IMPI INSTITUTO MEXICANO DE LA PROPIEDAD INDUSTRIAL poner en contacto uno o más monómeros distribuidos para ser polimerizados, para preparar el material polimérico con nitruro de titanio, en donde después de poner en contacto con nitruro de titanio el material polimérico incluye 25 ppm o menos de nitruro de titanio en base en el peso del material polimérico.
- 6Un método de conformidad con la reivindicación 5, caracterizado porque el nitruro de titanio es materia coloidal o nanoparticulada.
- 7Un método de conformidad con la reivindicación 5, caracterizado porque el tamaño de partícula promedio del nitruro de titanio es de 100 nm o menor.
- 8Un método de conformidad con la reivindicación 5, caracterizado porque el material polimérico comprende un polímero termoplástico seleccionado del grupo de polímeros:poliésteres, policarbonatos, poliamidas, poliolefinas, poliestirenos, polímeros de vinilo, polímeros acrílicos y copolímeros y mezclas de los mismos.
- 9Un método de conformidad con la reivindicación 5, caracterizado porque el material polimérico es poli(tereftalato de etileno) o un copolímero del mismo.
- 10Una composición de conformidad con la reivindicación 1, caracterizada porque el tamaño de partícula promedio del nitruro de titanio es de 100 nm o menor.
- 11Un método de conformidad con la reivindicación IMPI 5, caracterizado porque el nitruro de titanio es proporcionado en una formulación concentrada que comprende un portador y nitruro de titanio. IMPI WSTTTVTO MEXICANO DE LA PROPIEDAD INDUSTRIAL
Independent claims11
350 paragraphs in 65 sections, as filed
(54) Title: POLYMERIC MATERIALS AND ADDITIVES FOR THEMSELVES. (54) Title: POLYMERIC MATERIALS AND ADDITIVES THEREFOR.
(57) Summary
A polymer additive to improve the superheat characteristics of a polymer or polymer composition comprises an inorganic material that is such that a 2.5mm thick polyethylene terephthalate plate incorporating the inorganic material has, when tested, a ratio absorption less than 0.9, where the absorption ratio is the ratio of A1 / A2 or the ratio A1 / A3, where: A1 is the maximum absorption between 400 nm and 550 nm; A2 is the maximum absorption between 700 and 1100 nm; A3 is the maximum absorption between 700 and 1600 nm. Preferred inorganic materials are titanium nitride, indium tin oxide, and lanthanum hexaboride.
(57) Abstract
A polymer additive for improving the reheat characteristics of a polymer or polymeric composition comprises an inorganic material which is such that a 2.5mm thick polyethylene terephthalate plaque incorporating the inorganic material has, when tested, an absorption ratio of less than 0.9, where the absorption ratio is either the ratio of A1 / A2 or the ratio A1 / A3, wherein: A1 is the maximum absorption between 400nm and 550nm; A2 is the maximum absorption between 700 to 1100 nm; A3 is the maximum absorption between 700 to 1600 nm. Preferred inorganic materials are titanium nitride, indium tin oxide and lanthanum hexaboride.
Institute
Mexican Property
Industrial
PATENT TITLE NO. 337335
I KNOW
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Owner (s): COLORMATRIX EUROPE LIMITED
Address: Units 9-11, Unlty Grove, Knowsley, L34 9GT, ENGLAND
Name: POLYMERIC MATERIALS AND ADDITIVES FOR THEMSELVES
Classification:
Inventor (s):
lnt.CI.8: C08J3 / 20; C08K3 / 10
ANTHONY JARVIS; MARK FROST; MARK RULE
REQUEST
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0407114.8
Validity: Twenty f the Token of Maturity: 30
The reference patent is copyrighted with conformity with the article *. 23 of the s and coBada from the hos.
presentation of the
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garzo de 2025 l articles 1, 2 fraction V, 6 fragtíjíp.ifl, and 59 of the Industrial Property Law.
, the present patent has a validity of twenty articles that cannot be expended, at and will be subject to the payment of the fee to keep the articles 6 ° fraction IU and 7 ° oís 2 de laley de la on 08/02/1904. 25/10 / ljB6, 12/26/1997, 1 05/1999, 01/27/3012 and 06/04 / 3β 12), articles 1st, 3rd faction V '(DOF 12/14/1999, signed the ones lll and 30 of the Organic Statues
Industrial Option (DOR 12/27/1999, amended on 10/10 Z2OO2, 07/29/2004, 08/04/2004 and 09/13/2 (7); 1st, 3rd delega faMaaMBMaBBMBaaBBBBaaaMaBBBM | BMBaMaBaaBBaiHiaaaaBBaBlMaiBaalBaaMaK of
1/2004, 16/06/2005, 25/(1/2006, 0*5/2009,06/01/2010?
I and III of <Regulation of / 2004 and 7> 9/2007); articles 1, 3, 4,
Q Pl 2 hko a), 4 ° and 12 ° fracciom 01B7 / 2002, 15/07/2004, 28 / deBnstituto Mexicano de la sus el presente Industrial (Diario con fum Federación (D.
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, 04/08/2004 and 09/13/2007).
<img file="MX337335B_D0003.tif" />
Arenal No. 550. Floor 1,
Col. Pueblo Santa María Tepepan. Xochimilco. CP 16020 Mexico City
Tel (55) 53 34 07 00 wsvw.impi.gob rix
Issue Date: February 26, 2016
THE DIVISIONAL DIRECTOR OF PATENTS
<img file="MX337335B_D0004.tif" />
NAHANNY CANAL REYES
Salt · '
<img file="MX337335B_D0005.tif" />
<img file="MX337335B_D0006.tif" />
MX / 2016/15440
POLYMERIC MATERIALS AND ADDITIVES FOR
<img file="MX337335B_D0007.tif" />
MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY
THE SAME
DESCRIPTION OF THE INVENTION
The present invention relates to polymeric materials and additives thereto, and in particular, although not exclusively, relates to polymer compositions having improved reheat properties, the use of such compositions, and a method of producing the same. . Also, the invention relates to a polymer reheating additive that can be used with polymers and that can be useful when applied to thermoplastic polymers, especially those used in the container manufacturing field.
Polymers are frequently used to produce preforms (parisons) which are heated with infrared heating lamps before being blow molded into articles, including liquid containers such as beverage bottles and the like. Heat lamps used to reheat polymer preforms (parisons) for the commercial manufacture of liquid containers such as beverage bottles, are typically quartz lamps having a broad light emission spectrum of 500nm to over 1500nm, that is, infrared heating lamps. Polyester, especially polyethylene terephthalate (PET), is poorly absorbed in the region between 500 and 1400 nm. Therefore, in order to speed up the overheating step
REF; 235560
<img file="MX337335B_D0008.tif" />
IMPI
MEXICAN INSTITUTE
OF THE PROPERTY
INDUSTRIAL in the production of bottles, or to reduce the amount of energy required for reheating, light-absorbing agents in the region between 700 and 1300 nm can be added to the polyester polymer as reheat additives.
A variety of black-body and gray-body absorbent compounds have previously been used as reheat additives to improve the heating rate characteristics of polyester under infrared heating lamps. These compounds are typically black iron oxide, elemental antimony, black carbon, and copper chromite. The term 'black carbon' includes graphite, any form of carbon black, charcoal, activated carbon, and the like. However, these materials are inefficient in the ways in which they have been used and generally high levels of overheating cannot be obtained by using the materials without severe darkening of the polymer. Therefore, the amount of absorbent materials that can be added to a polymer is limited by the impact of those materials on the visual properties of the polymer, such as transparency. This is particularly relevant if the preforms are to be used to manufacture liquid containers such as beverage bottles, especially for use to contain mineral water, where high transparency and an absence of color are considered essential. Transparency is usually represented as L * in the CIELAB system, where 100 is the
<img file="MX337335B_D0009.tif" />
highest and 0 is the darkest. In general, darker color overheating additives can be added only in very small amounts due to their negative impact on L *.
An object of the present invention is to address the problems described above.
In accordance with a first aspect of the invention, a composition is provided to improve the superheat characteristics of a polymeric material, the composition comprises an inorganic material.
In accordance with a second aspect of the invention, a composition is provided comprising:
a polymeric material;
an inorganic material to improve the superheat characteristics of the polymeric material, where the inorganic material is such that a 2.5mm thick polyethylene terephthalate plate incorporating the inorganic material has, when tested, an absorption ratio less than 0.9, where the absorption ratio is the A1 / A2 ratio or the ratio
Al / A3, where:
<td>To the</td><td>is</td><td>the</td><td>absorption</td><td>maximum</td><td>between</td><td> 400</td><td colspan="2">nm and 550 nm</td>
<td>A2</td><td>is</td><td>the</td><td>absorption</td><td>maximum</td><td>between</td><td> 700</td><td>and</td><td>1100 nm;</td>
<td>A3</td><td>is</td><td>the</td><td>absorption</td><td>maximum</td><td>between</td><td> 700</td><td>and</td><td>1600 nm.</td>
Preparing the 2.5mm thick plate for
<img file="MX337335B_D0010.tif" />
IMPI test inorganic materials and tests my Aden spt as described in (A) or (B) below:
(A) An inorganic material to be tested is thoroughly mixed with dry polymer pellets from a bottle grade PET having an IV of 0.8 +/- 0.02 and pure terephthalic acid and ethylene glycol main monomers. An example of such material is VORIDIAN 9921 which is referenced below. The mixture is then used to prepare 2.5mm thick plates with the use of an injection molding machine. More details on the procedure are provided in Examples 22 to 24 below.
(B) An inorganic material to be tested is added to monomers (eg, pure terephthalic acid and ethylene glycol major monomers arranged to produce the aforementioned PET) and the monomers are polymerized. A plate can be subsequently produced from the polymer prepared as described in (A).
The preferred test is as described in (A).
The ability of an inorganic material to meet the requirements of the second aspect invention may depend on the chemical identity of the inorganic material and may depend on the physical characteristics of the inorganic material such as particle sizes and shapes. In one case, a particular chemical type of inorganic material at a first particle size may not satisfy the test.
IMPIfé
MEXICAN INSTITUTE OF PROPERTY
INDUSTRIAL ^ “β».
exposed according to the second aspect; However, ....... the same chemical type can a second particle size (which can be smaller than the first particle size) satisfy the test described and, therefore, can be a Useful material to include in a polymeric material to improve the overheating characteristics of the polymeric material.
Suitably, the absorption ratio is less than 0.85. Preferably, the ratio is less than 0.80 and more preferably it is less than 0.75.
Suitably, for a selected inorganic material, at least one (preferably both) of the following situations applies: the absorption ratio A1 / A2 is less than 0.70; and / or the absorption ratio A1 / A3 is less than 0.90.
Preferably, for a selected inorganic material, at least one (preferably both) of the following situations applies: the absorption ratio A1 / A2 is less than 0.65; and / or the A1 / A3 absorption ratio is less than 0.85.
More preferably, for a selected inorganic material, at least one (preferably both) of the following situations applies: the absorption ratio A1 / A2 is less than 0.60; and / or the absorption ratio A1 / A3 is less than 0.80.
In an especially preferred embodiment, for a selected inorganic material, at least one (preferably both) of the following situations applies:
IMPI
<img file="MX337335B_D0011.tif" />
absorption ratio A1 / A2 is less than 0.50; y7<sup>t</sup>u the ifGlaoióo.! The absorption A1 / A3 is less than 0.80.
Suitably, a selected inorganic material has an A1 / A2 absorption ratio of less than
0.80, preferably less than 0.70, more preferably less than 0.60, especially less than 0.56.
Each of the absorption ratios A1 / A2 and A1 / A3 can be greater than 0.2.
In accordance with a third aspect of the invention, the use of an inorganic material as described in accordance with the first or second aspects is provided to improve the superheat characteristics of a polymeric material.
In accordance with a fourth aspect of the invention, a concentrated formulation is provided for addition to a polymeric material or to one or more monomers arranged to be polymerized to prepare a polymeric material, the formulation comprises a vehicle and an inorganic material as described according with the first or second aspects.
The formulation can include a vehicle that is a solid at standard temperature and pressure (STP) or can comprise a liquid vehicle. When the vehicle is a solid, the formulation is suitably a master batch. When the vehicle is a liquid, the inorganic material can be dissolved or, more preferably, dispersed in the liquid.
Preferably, the formulation includes less than 90%
MEXICAN INSTITUTE
DS THE PROPERTY
INDUSTRIAL by weight of inorganic materials that are cnron rp dpscribe according to the first or second aspects. Preferably, the sum of the% by weight of all inorganic materials in the formulation is less than 90% by weight, more preferably less than 75% by weight, especially less than 40% by weight. Preferably, the sum of the% by weight of all the particulate material (including inorganic materials) in the formulation is less than 90% by weight, more preferably less than 75% by weight, especially less than 40% in weigh. The preferred formulation includes at least 0.0005% by weight, preferably at least 0.001% by weight, of inorganic materials which are as described according to the first or second aspects.
When the concentrated formulation comprises a solid master batch, the sum of the weight% of inorganic materials which are as described according to the first or second aspects may be up to 90% by weight, up to 50% by weight or up to
40% by weight.
When the concentrated formulation comprises a liquid, for example a liquid dispersion comprising the inorganic material, the sum of the% by weight of inorganic materials that are as described in accordance with the first or second aspects may be up to 90% by weight, up to 50% by weight or up to 40% by weight.
A liquid vehicle can be a vegetable or mineral oil or a glycol. A particularly preferred glycol is
<img file="MX337335B_D0012.tif" />
MEXICAN INSTITUTE OF PROPERTY
INDUSTRIAL
<img file="MX337335B_D0013.tif" />
ethylene glycol, especially if the inorganic material particles are to be added to a PET polymerization reaction mixture. It can also be favorable if the inorganic material is ground in the liquid vehicle. Grinding serves to decompose any agglomerates present in primary particles.
Other components such as surfactants, thickening agents, and stabilizers can be added to improve dispersion in the liquid vehicle.
Other polymer additives can also be included in a liquid vehicle such as slip property modifiers, acetaldehyde removal agents, IV modifiers, barrier agents such as Amosorb®, flame retardant agents, finish modifiers. surface, conductivity modifiers and colors.
In accordance with a fifth aspect of the invention, a method is provided for improving the superheat characteristics of a polymeric material, the method comprises contacting the polymeric material or contacting one or more monomers arranged to be polymerized to prepare the material polymeric with an inorganic material as described according to the first or second aspects or otherwise, as described herein.
The polymeric material or monomers can be contacted with a powder comprising or consisting of
<img file="MX337335B_D0014.tif" />
IMPI
MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY essentially of inorganic material; or they can be contacted with a concentrated formulation as described according to the fourth aspect.
Whichever method is used to contact the polymeric material and the inorganic material, it is preferred that sufficient of the inorganic material is added so that at least 0.01 ppm, suitably at least 0.1 ppm, preferably at least 1 ppm, more preferably at least 2 ppm, even more preferably at least 3 ppm, especially at least 4 ppm, based on the weight of the polymeric material, they are present in the polymeric material in contact with the inorganic material or they are present in a polymeric material that can be prepared from monomers arranged to be polymerized to prepare the polymeric material. Suitably less than 1000 ppm, preferably less than 500 ppm of the inorganic material are present in the polymeric material.
The ratio of the weight of polymeric material (or the weight of monomers arranged to be polymerized to prepare the polymeric material) to the weight of the inorganic material that comes in contact with the polymeric material (or monomers) is appropriately in the range of 10<sup>3 </sup>to 10<sup>6</sup>, preferably in the range of 2 χ 10<sup>3</sup> to 2.5 χ 10<sup>5</sup>.
Contacting one or more monomers with an inorganic material as described may be a convenient way to
<img file="MX337335B_D0015.tif" />
IMPI
MEXICAN INSTITUTE · ϊΆ · Ι
OF THE PROPERTY '·
INDUSTRIAL incorporate the inorganic material as it can easily be mixed into the monomers and / or polymer in downstream steps to react / process the monomers and / or the polymer. Suitably, the inorganic material is incorporated into a monomer stream containing an alcohol group if the polymeric material is a PET.
The method of the fifth aspect may include making granules or pellets comprising the polymeric material and inorganic material.
In accordance with a sixth aspect of the invention, a polymer reheat additive is provided which comprises an inorganic material having a higher intrinsic absorbency in the infrared region of the spectrum (between 700 and 1400 nm) than in the visible region of the spectrum of light (between 400 and 700 nm).
In accordance with a seventh aspect of the invention there is provided a polymer reheating additive comprising an inorganic material having at least an absorption maximum in the infrared region of the spectrum (between 700 and 1400 nm) that is greater than any maximum of absorption in the visible region of the spectrum (between 400 and 700 nm).
Likewise, the invention provides a thermoplastic molding composition comprising a reheat additive as described herein. Also, in accordance with the invention, a molded article is provided.
<img file="MX337335B_D0016.tif" />
formed from such a composition of moldtíU. The<sup>1</sup> It can be carried out by thermoforming or injection molding.
In one embodiment, the inorganic material can be a different material from any form of black carbon, metal antimony, iron oxide, or copper chromite.
Certain inorganic materials have been found to be useful in reheat applications. Particular inorganic materials and some of their physical and / or chemical characteristics are described herein. Preferably, inorganic materials absorb light in the infrared region, are compatible with thermoplastic molding compositions, are non-toxic, and have an aesthetically neutral or positive impact on the color of a molded article formed from a composition to which they are added. .
In accordance with an eighth aspect of the invention, there is provided a thermoplastic molding composition comprising a polyester and at least one reheating additive comprising an inorganic material different from any form of black carbon, metal antimony, iron oxide or chromite copper, the reheating additive is present in the composition in an amount effective to absorb light in the infrared region and, therefore, reduce the energy requirement for reheating to a blow molding temperature
<img file="MX337335B_D0017.tif" />
<img file="MX337335B_D0018.tif" />
an article molded from the composition ......— ·· -.....
Selected additives and / or inorganic materials described herein can allow a polymer to have an improved reheat characteristic, where the polymer overheats and therefore reaches a temperature above its glass transition temperature faster and, therefore, reheat times can be reduced and productivity can be increased. Therefore, the described additives can allow more efficient handling of the polymer.
The polymer may comprise polymer particles, with the additive dispersed in all of the polymer particles. Alternatively, the polymer may be a solid or it may be fragmented with the additive disposed within the polymer. The additive may comprise colloids or particles, but will preferably comprise nanoparticles. The nanoparticles can comprise particles with a particle diameter
<td colspan="5">average less than 1 miera, preferably less than 100 nm.</td><td rowspan="2">make</td>
<td>The</td><td>materials</td><td>inorganic</td><td>to the</td><td>That</td>
<td>reference in</td><td colspan="2">the present may be</td><td colspan="2">stoichiometric</td><td>or not</td>
<td colspan="2">stoichiometric (when</td><td>such ways</td><td>they can</td><td>exist)</td><td>; I know</td>
non-stoichiometric forms may prefer.
A class of inorganic materials (referred to herein as type 1) that can be used to improve the superheat characteristics can comprise materials
<img file="MX337335B_D0019.tif" />
that intrinsically present a greater abs'oxlieneiá eñtte 700 and 1400 nm than between 400 and 700 nm. Absorbance can be calculated by measuring the absorbance of a polyester plate containing the material at 400, 700, and 1100 nm, and then determining the percentage change in absorption that occurs between 400 and 700 nm, and then 700 at 1100 nm. Plates incorporating preferred inorganic materials have a% absorbency in the 700 to 1100 nm region which is greater than a% absorbency in the 400 to 700 nm region and has a positive value. A particularly preferred example of such an inorganic material is reduced indium tin oxide. The intrinsic absorbance, as used herein, can be taken to be the absorbance presented by a particle of the material when the particle size is small enough that a significant amount of the incident light is transmitted at each wavelength.
A second class of inorganic materials (referred to herein as type 2) that can be used to improve superheat characteristics can comprise materials that have a higher absorption maximum in the region between 700 and 1400 nm than the average absorption between 400 and 700 nm. Absorption can be that measurement directly by a spectrophotometer. A particularly preferred example of such an inorganic material is titanium nitride.
Preferably, the additive and / or inorganic material
IMPI
MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY
<img file="MX337335B_D0020.tif" />
Described herein may be able to increase the energy absorption of a polymeric material in the near infrared light range (700 to approximately at least 1400 nm). More preferably, the additive and / or a selected inorganic material may be able to increase the energy absorption of the polymer in the near infrared light range more than it does in the visible light range (400 and 700 nm). Preferably, the selected inorganic material has a higher absorbency in the region between 700 and 1400 nm than between 400 and 700 nm of at least 10%, more preferably at least 25%, and much more preferably at least 50% and still more preferably at least 100%.
It is preferred that the additive and / or a selected inorganic material have an average energy absorption maximum in the range of 700 to 1400 nm which is greater than the average energy absorption in the range of 400 to 700 nm. Suitably, the maximum average energy absorption in the region between 700 and 1400 nm that is greater than the average absorption in the region between 400 and 700 nm is at least 1% greater, preferably at least 5% greater and more preferably it is at least 10% higher. With superlative preference the average absorption maximum is at least 50% higher.
If the particles of a selected inorganic material as described herein are too large, they can absorb all incident light both in the
IMPI
<img file="MX337335B_D0021.tif" />
visible portion as in the infrared portion of the-Trepe.ctra, "$", therefore, may not provide preferential absorption of infrared radiation. As the particle size is reduced, the relative absorption difference between the visible and infrared portions of the spectrum may increase until the intrinsic absorbance is reached. Therefore, the selection of a preferred particle size for the inorganic material may depend on the specific absorbency of an inorganic material in the visible and infrared portions of the electromagnetic spectrum.
The average particle size (suitably number average) of selected additive and / or inorganic material that can be used to increase energy absorption between 700 and 1400 nm may be less than 10 microns, preferably less than 1 micron and more preferably less than 100 nm.
Suitably at least 90%, (preferably at least 95%, more preferably at least 99%, especially about 100%) of the particles of the additive and / or inorganic material has a maximum dimension that is less than 10 microns , preferably less than 1 miera, more preferably less than 500 nm, especially less than 100 nm.
In one embodiment, the inorganic material can be of a particle size such that, when incorporated into a polymeric material, it is substantially optically
<img file="MX337335B_D0022.tif" />
IMPI
OR MEXICAN INSTITUTE
OF THE PROPERTY
INDUSTRIAL invisible. For example, substantially all of the 'pcLYtl'CüTSS' of the inorganic material may have a particle size that is below the critical wavelength of visible light.
In one embodiment, the selected additive and / or inorganic material may have flat or uniform absorption characteristics in the visible region of the spectrum with negligible absorption minimums and maximums. This may be desirable if a neutral or colorless plastic material is required, for example, for mineral water bottles. In another embodiment, the selected additive and / or inorganic material may have irregular or skewed absorption characteristics in the visible region of the spectrum and have minima with significant absorption maxima. This may be desirable for the production of colored bottles. An additive that can impart a blue color to a polymeric material, for example a plate or preform, may be especially desirable since it can act not only to improve the overheating profile of the polymeric material, but also to color the resulting plastic material. Polymers, particularly polyesters such as polyethylene terephthalate, are known to turn yellow upon exposure to elevated temperatures. In reality, polyethylene terephthalate turns yellow as it is manufactured. In some cases, a tint can be added to the polyester to adjust its color from a yellow back to a neutral hue.
<img file="MX337335B_D0023.tif" />
IMPI 'MEXICAN INSTITUTE
SAY THE PROPERTY
INDUSTRIAL
These shades are thus usually colorants<sup>1</sup> that impart a blue hue, a typical example is cobalt acetate. Therefore, additives and / or organic materials that impart a blue hue to a polymeric material, for example plate or preform, may also be good tints and may be especially desirable. However, additives and / or inorganic materials that give rise to other visual colors can also be used since when used in conjunction with a complementary color shading agent, usually a traditional dye, a neutral shade can easily be obtained.
Preferred inorganic materials may have absorption / absorbency characteristics as described in any statement herein, and additionally may have an absorption at 475nm that is less than absorption at 700nm. Absorption at 475nm is preferably less than absorption at both 600nm and 700nm. The absorption at 475 nm is more preferably less than the absorption at each of 550 nm, 600 nm and 700 nm. Absorption at 475 nm is preferably superlative less than absorption at each 400 nm, 550 nm,
600 nm and 700 nm.
A particularly preferred inorganic material for use as described herein comprises titanium nitride. Favorably, it imparts a blue color that has an absorption minimum in the visible region of approximately 475 nm.
<img file="MX337335B_D0024.tif" />
A reheat additive as described herein can be produced from many inorganic materials. The reheat additive and / or inorganic material described herein can be selected from one or more of the following group of materials: elemental metals, metalloids, oxides, doped oxides, mixed oxides, nitrides, silicides, or boride compounds. Preferably, the reheat additive and / or inorganic material is selected from one or more of the following group of materials: titanium nitride, zirconium nitride, indium tin oxide, reduced indium tin oxide, antimony oxide. tin, gold, silver, molybdenum or tantalum.
A reheat composition and / or additive described herein may further comprise one or more additional materials to aid in the reheat characteristics of the polymeric materials. Additionally or alternately, a composition and / or additive may further comprise one or more additional materials to influence the characteristics of a polymeric material. For example, one or more blackbody or graybody infrared absorbing materials can be incorporated with the additive which can result in the absorption of more near infrared radiation greater than 700nm. Such a black body or gray body infrared absorbent material may comprise black carbon, iron oxides, copper chromite or formed metal antimony
ΙΜΡΙ
<img file="MX337335B_D0025.tif" />
by reducing antimony trioxide Hurant-g the polymerization reaction. Other materials may include dyes, etc. A reheat composition and / or additive can be used in conjunction with organic materials, such as near-infrared dyes, which have an absorption maximum in the 700 to 1400 nm region.
Although the test referred to in accordance with the second aspect is conveniently carried out on a polyethylene terephthalate plate, inorganic materials that pass the test can be incorporated into any type of polymeric material to improve its performance characteristics. overheating, for example, when using infrared lamps.
The polymeric material can be essentially any polymer that is used to produce a plastic material, but preferably, the polymer comprises a thermoplastic polymer (including natural or synthetic polymers). Preferred thermoplastic polymers are those that can be used / used for injection molding of articles such as container preforms and the like. Preferably, the thermoplastic polymer is selected from one or more of the following groups of polymers: polyesters, polycarbonates, polyamides, polyolefins, polystyrenes, vinyl polymers, acrylic polymers, and copolymers and mixtures thereof. Preferred polymers are
IMPI
<img file="MX337335B_D0026.tif" />
Polyesters, polypropylene, and oslanbasto polypropylene, which can be suitably used to produce containers. Especially preferred polymers are polyesters such as those used to make liquid containers and particularly beverage bottles such as polyethylene terephthalate or a copolymer thereof. A composition comprising a polymer with an additive and / or the inorganic material as described can be used to produce preforms such as container preforms before the preforms are heated inserted into a stretch blow molding machine.
Polyethylene terephthalate used for injection molding purposes is typically post-condensed and has a molecular weight in the region of approximately 25,000 to 30,000. However, it has also been proposed to use a fiber grade polyethylene terephthalate that is more economical but is not post-condensed, with a lower molecular weight in the region of about 20,000. Furthermore, it has been suggested to use polyethylene terephthalate copolyesters containing repeating units of at least 85 mol% terephthalic acid and at least 85 mol% ethylene glycol. Dicarboxylic acids that can be included, along with terephthalic acid, are exemplified by italic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, cyclohexanedicarboxylic acid, cyclohexanediacetic acid, acid
<img file="MX337335B_D0027.tif" />
diphenyl-4,4'-dicarboxylic acid, succinic acid, .. glutaic acid? iep; · 'adipic acid, azelaic acid and sebaic acid. Other diols that can be incorporated into copolyesters, in addition to ethylene glycol, include diethylene glycol, triethylene glycol, 1,4-cyclohexanedimethanol, propane-1,3-diol, butane-1,4-diol, pentane-1,5-diol, hexane-1 , 6-diol, 3-methylpentane-2,4-diol, 2-methyl pentane-1,4-diol, 2,2,4-trimethylpentane-l, 3-diol, 2-ethylhexane-1,3-diol, 2,2- diethylpropane-l, 3-diol, hexane-1,3diol, 1,4-di (hydroxyethoxy) -benzene, 2,2-bis- (4-hydroxycyclohexyl) -propane, 2,4-dihydroxy-l, 1, 3,3-tetramethyl-cyclobutane, 2,2-bis- (3-hydroxyethoxyphenyl) -propane, and 2,2-bis- (4-hydroxy propoxyphenyl) -propane. In this specification the term polyethylene terephthalate includes not only polyethylene terephthalate but also such copolyesters.
Injection molding of polyethylene terephthalate and other polyester molding compositions is typically carried out with the use of an injection molding machine and a maximum barrel temperature in the range of about 260 ° C to about 285 ° C or plus, for example, up to about 310 ° C. Drying time at this maximum temperature is typically in the range of from about 15 seconds to about 5 minutes or more, preferably from about 30 seconds to about 2 minutes.
In a preferred embodiment of the present invention, the additive and / or organic material is capable of increasing the
<img file="MX337335B_D0028.tif" />
,, IMPI ¿INSTITUTO MEXICANO
SAY THE PROPERTY
INDUSTRIAL reheating percentage ratio - pur unit of<sup></sup>clarity lost compared to an equivalent preform made of a polymer containing a traditional black-body or gray-body absorbent such as any form of black carbon or metal antimony formed by reduction of antimony trioxide.
In a method as described in accordance with the fifth aspect, the inorganic material is preferably different from black carbon, metal antimony, iron oxide or copper chromite.
The fifth aspect method may use an additive and / or organic material as described herein. Polymers containing the additive will be particularly suitable for use in injection molding of a rticles. Furthermore, the additive can be dispersed in a liquid. If the additive is dispersed in a liquid then the liquid can be applied to the polymer in the polymerization stage or the injection molding stage. Such an article could potentially be any article that can be injection molded. Preferably, the article is a preform that can then be stretch blow molded into a liquid container such as beverage bottles with the use of infrared heating lamps.
The invention extends to a product comprising a polymeric material and an inorganic material as
<img file="MX337335B_D0029.tif" />
described herein, for example, according eoii · el - 'ppi<sup>i</sup>mey or second aspects.
Such a product may include at least 0.01 ppm, suitably at least 0.1 ppm, preferably at least 1 ppm, more preferably at least 2 ppm, even more preferably at least 3 ppm, especially at least 4 ppm, based in the weight of the polymeric material in the product. Suitably, the product includes less than 10 00 ppm, preferably less than 500 ppm of the inorganic material based on the weight of the polymeric material.
In the product, the ratio of the weight of the polymeric material to the weight of the inorganic material is suitably in the range of 10<sup>3</sup> to 10<sup>6</sup>, preferably in the range of 2 x 10<sup>3</sup> a 2.5 x 10<sup>5</sup>.
The product may be in the form of pellets or granules.
The product may be a molded article. In this case, it can be a preform, for example for a container and / or a container per se. A preferred container is a bottle.
The invention extends to a method of making a product, the method comprising heating a composition comprising a polymeric material and an inorganic material as described herein, for example, according to the first or second aspects, and forming the composition. in a configuration to define the product.
The method may include a molding process
I JM. Ρ ϊ
MEXICAN INSTITUTE
PROPERTY 0 * omi¡E¡
INDUSTRIAL injection, for example, to make preforins dg rrmtpnpflnr ........—
In the method of making the product, the composition is preferably heated with the use of an infrared source, for example, one or more infrared heating lamps.
In accordance with another aspect of the present invention, there is provided an article made from a polymer containing an inorganic material additive that has intrinsically higher absorbency between 700 and 1400 nm than between 400 and 700 nm. In another aspect of the present invention, there is provided an article made of a polymer containing the inorganic material additive having a higher absorption maximum in the region between 700 and 1400 nm than the average absorption between 400 and 700 nm. A particularly preferred item may be a container preform. An especially preferred container preform is one that can be heated with infrared heating lamps before being stretch blow molded into a liquid container such as a beverage bottle. The types of beverage such a bottle may contain include, but are not limited to, beer, fruit juice, carbonated and still mineral water, and other carbonated soft drinks.
In accordance with another aspect of the present invention, there is provided a method for increasing the superheat characteristics of a polymer, which comprises incorporation into the polymer particles of at least one inorganic material,
IMPI
<img file="MX337335B_D0030.tif" />
so that the polymer has a relation pnrcontaVereca! unit per unit loss of clarity greater than an equivalent polymer containing a traditional black-body or gray-body absorbent such as black carbon or metal antimony formed by reduction of antimony trioxide or iron oxide or copper chromite.
A further aspect of the present invention envisages the use of an inorganic material (not black carbon, metal antimony, iron oxide, or copper chromite) to improve the reheating properties of a polymer or polymer composition.
In another aspect of the present invention, there is provided a molded article formed from a polymer or polymer composition mixed with an inorganic additive (not black carbon, metal antimony, iron oxide, or copper chromite).
In various aspects of the invention, the inorganic / additive material can be selected from one or more of the following group of materials: titanium nitride, zirconium nitride, indium tin oxide, reduced indium tin oxide, antimony oxide. tin, gold, silver, molybdenum or tantalum. The inorganic / additive material is preferably a nanoparticle having an average particle size of less than 1 micron. Preferably, the average particle size of the inorganic / additive material is 100nm or less. The polymer or polymer composition is preferably selected from one or
<img file="MX337335B_D0031.tif" />
MEXICAN INSTITUTE OF PROPERTY
INDUSTRIAL plus the following group of polymers -; - polyethers, polycarbonates, polyamides, polyolefins, polystyrenes, vinyl polymers, acrylic polymers and copolymers and mixtures thereof. The article produced from a polymer comprising the polymer and inorganic / additive material is preferably injection molded. Where the article is a container preform, the preform is preferably used in a stretch blow molding process that requires a heating step with infrared heating lamps, to produce bottles suitable for use to contain liquids such as beverages.
The invention will now be illustrated by way of example only with reference to the figures and the following examples, in which:
Figure 1 illustrates the effect an additive has on a polymer through the transmission spectrum. The figure shows 60nm particles of titanium nitride (TiN) in PET, and for comparison the transmission spectrum for the commercially available reheat polymer CBlle (Voridian) containing a prior art infrared absorbent additive. Also shown is the transmission spectrum of a PET polymer (9921W) that does not contain an infrared absorbent reheat additive.
Figure 2 shows the transmission spectrum for an additive comprising 40 nm indium oxide particles27
<img file="MX337335B_D0032.tif" />
tin reduced. Such material has a higher absorbance in the infrared compared to the visible spectrum.
Figure 3 illustrates the spectral energy distribution of Philips IRK halogen infrared heating lamps.
EXAMPLES
Preforms were made using a 160 ton HUSKY injection molding machine that made two preforms by injection. Each preform weighed approximately 34 grams and was cylindrical, approximately 13 0 mm in length with a threaded cap base. These preforms could be blown into one liter bottles with a petaloid base.
Polyester injection molding took place at 270 ° C. The general-purpose polystyrene injection molding took place at 200 ° C.
The polymers used were:
B60 (DuPontSA) - a commercial, grade, non-reheat, bottle-grade resin PET resin.
B60 without shade (DuPontSA) - the same as B60 but without any shade, therefore it shows the natural yellow color of the resin.
9921W (Voridian) - a commercial, grade, non-reheat, bottle-grade resin PET resin.
Laser + (DuPontSA) - a commercial bottle-grade reheat resin.
<img file="MX337335B_D0033.tif" />
CBlle (Voridian) - a commercial bottle grade -reca-í'giifcaniiento resin.
General-purpose polystyrene (GPS).
Both CBlle and Laser + are reheat resins that contain metal antimony as the reheat aid. CBlle is approximately twice as hot but has approximately twice the reduction in clarity as Laser-t-.
Where the inorganic particle compound was ground, the milling took place as follows: the inorganic particle compound (5 g) was stirred in an oil that those skilled in the art know is compatible with the polymer in which the inorganic particles leave to incorporate (total mass of oil and particle mixture = 50 g). The oil and particle mixture was then transferred to an approximately 55% 100 ml glass jar filled with small glass beads (diameter 1.2 mm). The glass bottle was shaken at 600 shakes per minute on a Red-Devil paint shaker. The ground dispersion was used immediately.
The following inorganic particle compounds were used as reheat aids.
one. Titanium nitride, 60nm and 30nm average primary particle size, provided by Neomat of Riga, Latvia.
2. Reduced indium-tin oxide, average primary particle size less than 40 nm, was provided by
MEXICAN INSTITUTE
OF THE PROPERTY
INDUSTRIAL
Nano Products Corp. Longmont, Co., USA.
3. Antimony-tin oxide, 30nm average primary particle size was provided by NanoPhase
Technologies, Romeoville, ll, USA.
Four. Lanthanum hexaboride nanopowder, average primary particle size less than 40 nm, was provided by NanoProducts Corp. Longmont, Co., USA.
5. Cobalt Siliconide Powder (CoSi<sub>2</sub>) 1000 nm average particle size was provided by Alfa-Aesar.
The near infrared dye used was provided by ADS Dyes, Toronto, Canada. Lamp Black 101 (carbon black) was supplied by Degussa. Sigma-Aldrich provided all other materials.
The inorganic material particles were mixed into the previously made polymer pellets by placing the powder or liquid dispersion of inorganic material particles in a cuvette provided with a lid containing the hot, dry polymer pellets and then shaking the cuvette by hand to mix the two together. The mixture of polymer pellets and inorganic material particles was then immediately used to make preforms by means of an injection molding process.
one. Urine preferences
EXAMPLE 1
TiN ground 60 nm at 25 ppm in B60 resin.
IMPI $ 5 ^ INSTITUTO MEXICANO τΧΧ DS LA PROPIEDAD
INDUSTRIAL
EXAMPLE the
TiN ground 60 nm at 25 ppm in 9921W resin.
EXAMPLE Ib
TiN ground 30 nm at 25 ppm in 9921W resin.
EXAMPLE 2
TiN ground at 5 ppm in B60 resin without shade.
EXAMPLE 3
TiN ground at 10 pm in B60 resin without shade.
EXAMPLE 4
Lab Powder<sub>6</sub> at 100 ppm in B60 resin.
EXAMPLE 5
LaB<sub>6</sub> ground at 100 ppm in B60 resin.
EXAMPLE 6
100 ppm ITO powder in B60 resin.
EXAMPLE 6a
ITO powder at 100 ppm in 9921W resin.
EXAMPLE 7
ITO resin ground at 100 ppm in B60 resin.
EXAMPLE 8
ATO powder at 463 ppm in B60 resin.
EXAMPLE 9
ATO ground at 100 ppm in B60 resin.
EXAMPLE 10
TiN ground at 10 ppm and ITO ground at 10 ppm in resin
B60 without nuance.
<img file="MX337335B_D0034.tif" />
IMPI
EXAMPLE 11 ____TiN ground at 10 ppm and near infrared inorganic dye at 50 ppm in B60 resin without shade.
EXAMPLE 12
TiN ground at 10 ppm and tantalum nanopowder at 100 ppm in B60 without nuance.
EXAMPLE 13
TiN ground at 5 ppm and ITO ground at 75 ppm in resin
B60 without nuance.
EXAMPLE 14
TiN ground at 10 ppm and ITO ground at 50 ppm in resin
B60 without nuance.
EXAMPLE 15
Mo nano-sized powder at 250 ppm in B60 resin.
EXAMPLE 16
Cobalt silicide at 100 ppm in B60 resin.
EXAMPLE 17
ITO ground at 100 ppm in GPS.
EXAMPLE 18
TiN ground at 25 ppm in GPS.
The colors of the preforms were measured with the use of a Minolta cm-3700d spectrophotometer (D<sub>6</sub>s lighting,
10th observer, specular included, UV included) linked to an IBM compatible PC.
Preform overheating tests are
<img file="MX337335B_D0035.tif" />
performed by measuring the ambient temperature of a preform using a Raytek MiniTemp laser digital infrared thermometer and then placing it in a stretch blow molding bottle machine with a single preform setting, using the nine infrared heating lamps Philips IRK halogen lamps set to 75% power. The preforms were heated for 35 seconds after which time the temperature of the preform was recorded. The spectral energy distribution of the lamps placed in this machine is shown in figure 3. The temperature difference (temperature after 35 seconds of heating minus the ambient temperature of the preform) was then used to calculate the% change in the overheating in relation to the control without overheating (B60 or B60 without nuance).
EXAMPLE 19
Formulation of inorganic particles in ethylene glycol suitable for direct addition to a polyester polymerization reaction
Reduced indium-tin oxide (5g) or titanium nitride (5g) was stirred in ethylene glycol (up to 50g) and added to a 50% glass jar filled with small glass grinding beads (~ 1.2mm of diameter). The sample in the bottle was ground by shaking it on the Red-Devil paint shaker at 600 spm for 10 minutes. The mixture was then ready
<img file="MX337335B_D0036.tif" />
to add directly to a polyester polymerization reaction mixture.
Results
one. Preform colors
<td></td><td>L</td><td>to</td><td>b</td><td>C</td><td>h °</td>
<td>B60</td><td> 78.96</td><td> -0.69</td><td> 1.61</td><td> 1.75</td><td> 113.3</td>
<td>B60 without nuance</td><td> 80.82</td><td> -0.47</td><td> 3.25</td><td> 3.28</td><td> 98.2</td>
<td>9921W</td><td> 77.19</td><td> -0.89</td><td> 4.52</td><td> 4.6</td><td> 101.2</td>
<td>Laser +</td><td> 70.25</td><td> -0.27</td><td> 0.84</td><td> 0.88</td><td> 107.6</td>
<td>CB11e</td><td> 60.54</td><td> -0.96</td><td> 2.66</td><td> 2.83</td><td> 109.9</td>
<td>Example 1</td><td> 64.03</td><td> -3.33</td><td> -4.10</td><td> 5.29</td><td> 230.9</td>
<td>Example 1a</td><td> 63.12</td><td> -2.89</td><td> -3.87</td><td> 5.01</td><td> 215.3</td>
<td>Example 1b</td><td> 54.47</td><td> -4.51</td><td> -7.20</td><td> 8.50</td><td> 237.9</td>
<td>Example 2</td><td> 77.40</td><td> -1.15</td><td> 0.96</td><td> 1.50</td><td> 140.2</td>
<td>Example 3</td><td> 73.62</td><td> -1.89</td><td> -0.37</td><td> 1.93</td><td> 191.0</td>
<td>Example 4</td><td> 70.64</td><td> -0.46</td><td> 7.33</td><td> 7.34</td><td> 93.6</td>
<td>Example 5</td><td> 67.88</td><td> -1.67</td><td> 6.69</td><td> 6.89</td><td> 104.1</td>
<td>Example 6</td><td> 76.63</td><td> -0.60</td><td> 6.56</td><td> 6.59</td><td> 95.2</td>
<td>Example 6a</td><td> 74.89</td><td> -0.59</td><td> 8.35</td><td> 8.37</td><td> 94.0</td>
<td>Example 7</td><td> 76.46</td><td> -0.67</td><td> 8.82</td><td> 8.84</td><td> 94.4</td>
<td>Example 8</td><td> 63.83</td><td> 0.95</td><td> 14.3</td><td> 14.3</td><td> 86.2</td>
<td>Example 9</td><td> 75.85</td><td> -0.78</td><td> 6.76</td><td> 6.80</td><td> 96.55</td>
<td>Example 10</td><td> 73.66</td><td> -1.86</td><td> 0.07</td><td> 1.86</td><td> 117.9</td>
<td>Example 11</td><td> 69.78</td><td> -5.02</td><td> 13.51</td><td> 14.4</td><td> 110.4</td>
<td>Example 12</td><td> 66.48</td><td> -1.34</td><td> 0.50</td><td> 1.43</td><td> 159.4</td>
<td>Example 13</td><td> 74.32</td><td> -1.22</td><td> 5.57</td><td> 5.70</td><td> 102.3</td>
<td>Example 14</td><td> 72.44</td><td> -1.84</td><td> 1.74</td><td> 2.54</td><td> 136.7</td>
<td>Example 15</td><td> 66.22</td><td> -0.57</td><td> 1.10</td><td> 1.24</td><td> 117.3</td>
<td>Example 16</td><td> 76.08</td><td> -1.08</td><td> 3.20</td><td> 3.38</td><td> 108.7</td>
<td>Gps</td><td> 85.50</td><td> -0.08</td><td> 0.68</td><td> 0.68</td><td> 96.92</td>
<td>Example 17</td><td> 83.43</td><td> -0.20</td><td> 4.31</td><td> 4.31</td><td> 92.7</td>
<td>Example 18</td><td> 71.62</td><td> -2.03</td><td> -5.22</td><td> 5.60</td><td> 248.7</td>
IMPI
<img file="MX337335B_D0037.tif" />
2. Overheating vs. clarity
<td></td><td>% of overheating</td><td>% Overheat / Unit Clarity Lost</td>
<td>B60</td><td> 0</td><td> 0</td>
<td>B60 without nuance</td><td> 0</td><td> 0</td>
<td>9921W</td><td> 0</td><td> 0</td>
<td>Gps</td><td> 0</td><td> 0</td>
<td>Laser +</td><td> 7.5</td><td> 0.80</td>
<td>CB11e</td><td> 17.0</td><td> 0.92</td>
<td>Example 1</td><td> 16.8</td><td> 1.05</td>
<td>Example 1a</td><td> 16.9</td><td> 1.20</td>
<td>Example 1b</td><td> 22.3</td><td> 0.91</td>
<td>Example 2</td><td> 18.0</td><td> 0.99</td>
<td>Example 3</td><td> 5.4</td><td> 0.74</td>
<td>Example 4</td><td> 14.0</td><td> 0.61</td>
<td>Example 5</td><td> 15</td><td> 1.35</td>
<td>Example 6</td><td> 16.9</td><td> 6.76</td>
<td>Example 6a</td><td> 17.0</td><td> 7.39</td>
<td>Example 7</td><td> 18.1</td><td> 7.24</td>
<td>Example 8</td><td> 17.9</td><td> 1.18</td>
<td>Example 9</td><td> 2.0</td><td> 0.64</td>
<td>Example 10</td><td> 9.6</td><td> 1.32</td>
<td>Example 11</td><td> 10.3</td><td> 0.92</td>
<td>Example 12</td><td> 11.2</td><td> 0.78</td>
<td>Example 13</td><td> 17.1</td><td> 2.71</td>
<td>Example 14</td><td> 16.9</td><td> 2.13</td>
<td>Example 15</td><td> 16.5</td><td> 1.30</td>
<td>Example 16</td><td> 5.7</td><td> 1.11</td>
<td>Example 17</td><td> 18.2</td><td> 8.79</td>
<td>Example 18</td><td> 12.7</td><td> 0.91</td>
In each case, the inorganic material reheating aid system has been able to increase the% superheat of the control resin into which it was incorporated, and since the heating was for a fixed time of 35 seconds, the superheat rate was thus increased. . In fact, in several cases there was not only an increase in overheating with respect to the control, but the ratio of% of overheating per unit of clarity
<img file="MX337335B_D0038.tif" />
Lost IMPI was superior to preforms made from · do-lao two · commercial reheat resins. This gave rise to preforms with the same superheat as the two commercial superheat standards, but a higher clarity value which makes them desirable for use by the mineral water bottle industry.
EXAMPLE 20
Type one inorganic materials - Determination of absorbency
Absorbance was determined by measuring the absorbance of plates containing the inorganic material particles as follows.
The plates were prepared using a BOY 22 ton injection molding machine that produces plates measuring 75 x 50 mm, two thicknesses, 2 and 2.5 mm.
Plates comprising 9921W were prepared containing reduced indium tin oxide (powder) at 100 ppm. Control plates, CBlle and Laser + were also prepared.
The spectrum of the plates in the 300 to 1100 nm region was measured with the use of a Perkin-Elmer Lambda 35 uv-vis spectrophotometer linked to an IBM compatible PC.
Absorbance was then calculated by determining the% change in absorbance as it occurs in the visible region 400 to 700 nm, and then in the infrared region 700 to 1100 nm. This was done as follows:
IMPI
<img file="MX337335B_D0039.tif" />
((Absx2-Absxi) / Absxi) * 100 -Where Abs 1 and 2 are the absorption at 400, 700 or 1100 nm where λ2 is always greater than λΐ, that is, when λΐ = 400 nm then λ2 - 700 nm and when λΐ = 700 nm, then λ2 = 1100 nm.
<td></td><td>Absorbance% 400 to 700 nm</td><td>Absorbance% 700 to 1100 nm</td>
<td>9921W</td><td> -67</td><td> -13</td>
<td>Laser +</td><td> -33</td><td> 0.00</td>
<td>CBlle</td><td> -35</td><td> -1</td>
<td>ITO</td><td> -72</td><td> +45</td>
EXAMPLE 21
Type two inorganic materials - Absorbance measurement
A 9921W plate containing TiN (30nm to 15ppm) was prepared as above.
The plates were used to generate data from the spectrophotometer. The average absorbance over the 400 to 700 nm range and the maximum absorbance in the 700 to 1100 nm range were determined. The% difference between the two was calculated.
<td></td><td>700-1100 max</td><td>400-700 avg</td><td>diff.</td><td>% of diff</td>
<td>9921W</td><td> 0.0661</td><td> 0.103031</td><td> -0.03693</td><td> -35</td>
<td>Laser +</td><td> 0.1202</td><td> 0.137931</td><td> -0.01773</td><td> -13</td>
<td>CBlle</td><td> 0.1877</td><td> 0.212215</td><td> -0.02452</td><td> -12</td>
<td>TiN</td><td> 0.2463</td><td> 0.228938</td><td> 0.17362</td><td> + 8</td>
<img file="MX337335B_D0040.tif" />
EXAMPLES 22 AL · 24 --- 2.5 mm thick plates were made from a composition comprising an inorganic material selected as an additive incorporated in a polymer and compared with plates of the same dimensions made from the same polymer without the selected inorganic material and without other material differences apart from the lack of the additive. If the additive is incorporated during the polymerization, the comparison is made with a polymer made by the same procedure and polymerized under the same conditions but without the additive.
The plates were then evaluated with the use of a Varian Cary 500 UV-VIS-NIR spectrophotometer and the% transmission at wavelengths between 400nm and 550nm; 700nm and 1100nm; and 700 to 1600 nm was recorded. These figures were then converted into absorbance using the equation Absorbance = -LoglO (% transmission / 100).
The absorbance of the additive (at each wavelength) was obtained by subtracting the absorbance of the polymer containing the additive from the absorbance of the polymer without the additive.
The values for the maximum absorption between 400 nm and 550 nm (later called ABS-1), for the maximum absorption between 700 to 1100 nm (later called ABS-2) and for the maximum absorption between 700 and 1600 nm (called later ABS3) were determined by taking the maximum of each range. Then (NSTITUTO MEXICANO De LA FaOPJEDAO
INDUSTRIAL ABS-l / ABS-2 ratios were determined; and 'ABS-i / ABS-37 LOS' details on the evaluated materials and results are provided in the table below.
<td>Example No.</td><td>Additive details</td><td>Resin</td><td>ABSl / ABS-2 ratio</td><td>ABS1 / ABS-3 ratio</td>
<td> 22</td><td>10 ppm T¡N (ground)</td><td>B60 without nuance</td><td> 0.42</td><td> 0.42</td>
<td> 23</td><td>100 ppm ITO</td><td>9921W</td><td> 1.00</td><td> 0.74</td>
<td> 24</td><td>25 ppm LaB<sub>6</sub></td><td>B60 without nuance</td><td> 0.54</td><td> 0.54</td>
Additionally, plates prepared as described in Example 19 were tested as described for Examples 22 through 24 and were found to have similar performance.
<td>It is noted that</td><td>in relation to this date,</td><td>the</td>
<td>best method known for the</td><td>applicant to carry</td><td>the</td>
<td>practice the said invention,</td><td>is the one that is clear from</td><td>the</td>
present description of the invention.
<img file="MX337335B_D0041.tif" />
Contents65
41 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
34 members in 17 offices
Priority claims9
| Document | Office | Kind | Date |
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| 0407114 | United Kingdom | A | |
| 0407114 | United Kingdom | A | |
| 04071148 | United Kingdom | – | |
| 2005001231 | United Kingdom | W | |
| 2005001231 | United Kingdom | W | |
| 04071148 | – | – | – |
| GB0501231 | – | – | – |
| GB20040007114 | – | – | – |
| WO2005GB01231 | – | – | – |
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| GB0407114D0 | United Kingdom | D0 | |
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| WO2005095516A1 | World Intellectual Property Organization (WIPO) | A1 | |
| EP1756221A1 | European Patent Office (EPO) | A1 | |
| MXPA06011193A | Mexico | A | |
| CN1965028A | China | A | |
| US2007203279A1 | United States of America | A1 | |
| IN6317DE2006A | India | A | |
| BRPI0509279A | Brazil | A | |
| JP2007530762A | Japan | A | |
| ZA200608129B | South Africa | B | |
| RU2006135348A | Russian Federation | A | |
| RU2397999C2 | Russian Federation | C2 | |
| AU2005227732B2 | Australia | B2 | |
| CN1965028B | China | B | |
| US7820781B2 | United States of America | B2 | |
| CN101880445A | China | A | |
| EP2270094A1 | European Patent Office (EPO) | A1 | |
| US2011015325A1 | United States of America | A1 | |
| US8211983B2 | United States of America | B2 | |
| JP5009783B2 | Japan | B2 | |
| US2012225986A1 | United States of America | A1 | |
| CN101880445B | China | B | |
| US8552099B2 | United States of America | B2 | |
| CA2560567C | Canada | C | |
| MX337335BThis record | Mexico | B | |
| EP1756221B1 | European Patent Office (EPO) | B1 | |
| MX342126B | Mexico | B | |
| PT1756221T | Portugal | T | |
| BRPI0509279B1 | Brazil | B1 | |
| LT1756221T | Lithuania | T | |
| ES2592291T3 | Spain | T3 | |
| PL1756221T3 | Poland | T3 |
Numbers
- Publication
- 337335
- Publication, DOCDB
- 337335
- Publication, EPODOC
- MX337335
- Application
- 2012010673
- Application, DOCDB
- 2012010673
- Application, EPODOC
- MX20120010673
Titles2
- Spanish
- MATERIALES POLIMERICOS Y ADITIVOS PARA LOS MISMOS.
- English
- POLYMERIC MATERIALS AND ADDITIVES THEREFOR.
Classification
- CPC, 21
- C08L67/02
- B29C49/0005
- B29C49/06
- B29C51/002
- B29C2035/0822
- B29K2025/00
- B29K2033/08
- B29K2067/00
- B29K2069/00
- B29K2077/00
- B29K2105/16
- C08K3/01
- Y10T428/1321
- B29C2949/3024
- B29C2949/26
- B29C2949/28
- B29C2949/24
- B29C2949/22
- B29C2949/3032
- B29C49/0006
- B29C2949/0715
- IPC, 9
- C08J3 20
- C08K3 10
- B29C35 08
- B29C49 00
- B29C49 06
- B29C51 00
- C08K3 00
- C08K3 08
- C08L67 02