WO1998036006A1 - Compositions polymerisables comprenant un oligomere urethane comme agent de reticulation, polymeres et polymeres hydrates obtenus a partir de ces compositions, et articles finis et semi-finis formes a partir de ces polymeres - Google Patents
Compositions polymerisables comprenant un oligomere urethane comme agent de reticulation, polymeres et polymeres hydrates obtenus a partir de ces compositions, et articles finis et semi-finis formes a partir de ces polymeres Download PDFInfo
- Publication number
- WO1998036006A1 WO1998036006A1 PCT/FR1998/000205 FR9800205W WO9836006A1 WO 1998036006 A1 WO1998036006 A1 WO 1998036006A1 FR 9800205 W FR9800205 W FR 9800205W WO 9836006 A1 WO9836006 A1 WO 9836006A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- meth
- composition according
- acrylate
- monomers
- urethane
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/26—Esters of unsaturated alcohols
- C08F222/28—Diallyl maleate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/041—Lenses
- G02B1/043—Contact lenses
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S525/92—Polyurethane having terminal ethylenic unsaturation
Definitions
- Polymerizable compositions comprising a urethane oligomer as a crosslinking agent, polymers and hydrated polymers obtained from these compositions, and finished and semi-finished articles formed from these polymers.
- the present invention generally relates to polymerizable compositions comprising a hydrophilic monomer or a mixture of hydrophilic monomers and a crosslinking agent which, after polymerization, lead to crosslinked polymers which can be hydrated to form hydrogels having improved mechanical properties, particular elongation at break, while having a high hydrophilicity rate and often higher than that of known hydrogel polymers.
- the invention also relates to polymers obtained by polymerization of these polymerizable compositions as well as the corresponding hydrated polymers (hydrogels).
- the invention also relates to finished or semi-finished articles formed from these polymers and hydrated polymers.
- ophthalmic articles such as contact lenses and separation membranes, for example membranes for reverse osmosis.
- the polymers according to the invention are particularly useful, when they have the appropriate transparency, for the manufacture of ophthalmic articles such as contact lenses.
- Materials for hydrophilic contact lenses must simultaneously have a certain number of advantageous characteristics, namely: - a high hydrophilicity rate; and
- the lens can be inadvertently torn or deformed by user, and if the hydrophilic rate is too low, the oxygen permeability of the lens may become insufficient, resulting in a risk of clouding of the cornea of the user's eye. It is difficult to reconcile the two characteristics indicated above in the same hydrogel material. In fact, when the hydrophilicity rate increases, it is generally found that the mechanical properties of the hydrogel material drop.
- the Russian author's certificate USSR 82 5548 proposes crosslinked hydrophilic polymer compositions whose transparency and mechanical properties are improved.
- the specific crosslinking agents contemplated in this latter document are polyethylene glycol dimethacrylate having a molecular weight of 1,500 and an oligourethane dimethacrylate having a molecular weight 456, the crosslinking agent being used in an amount of 5 to 20% by weight.
- the subject of the invention is therefore a polymerizable composition
- a polymerizable composition comprising a hydrophilic monomer or mixture of monomers and a crosslinking agent which, after polymerization, provides a crosslinked hydrogel polymer having a high hydrophilicity rate and properties mechanical, in particular a much improved elongation at break.
- the subject of the invention is also the polymers and hydrated polymers obtained by polymerization of the polymerizable compositions according to the invention.
- Another subject of the invention is finished and semi-finished articles formed from the above polymers, and in particular ophthalmic articles such as contact lenses.
- the polymerizable composition comprises a hydrophilic monomer or a mixture of hydrophilic monomers and an effective amount of crosslinking agents, characterized in that the crosslinking agent comprises a urethane oligomer having a molar mass of between 500 and 5000 , terminals included, and the chain of which carries two to six (meth) acrylate functions or a mixture of these polyurethane oligomers.
- polyurethane olygomers useful as crosslinking agents in the polymerizable compositions of the invention are therefore polyurethane oligomers functionalized with two to six acrylate and / or methacrylate functions, preferably two or three functions, with preferably still two functions (meth). acrylates at the end of the chain.
- the functionalized polyurethane oligomers which are particularly recommended are the difunctional oligomers, and more particularly with the two (meth) acrylate functions at the end of the chain.
- the polyurethane oligomers useful in the polymerizable compositions according to the invention have a molar mass of between 500 and 5000, limits included, better ranging from 500 to 3000, and better still from 1000 to 3000.
- Urethane oligomers useful as crosslinking agents, according to the invention can be aliphatic or aromatic oligomers, aliphatic oligomers being preferred.
- urethane oligomers useful in the present invention polyurethane diacrylate oligomers are particularly recommended.
- the amount of urethane oligomer used in the compositions according to the invention must be an effective amount, that is to say sufficient to ensure appropriate crosslinking of the composition.
- the urethane oligomers useful as crosslinking agents in the polymerizable compositions according to the invention are used in an amount of 0.05 to 4 parts by weight, preferably 0.1 to 1 part by weight, and better still 0, 1 to 0.5 parts by weight per 100 parts by weight of the mixture of monomers present in the initial polymerizable composition.
- the di- or tri (meth) acrylic urethane oligomers according to the invention can be obtained by reacting a polyol (diol or triol), in the presence of a hydroxylated (meth) acrylate monomer with a poly functional polyisocyanate.
- the diol can be chosen from:
- linear aliphatic diols such as alkane-diol, polycaprolactone-diol, polyether-diol, polyester-diol and polycarbonate-diol and aromatic diols.
- the preferred diol is a propylene glycol of formula:
- the polyisocyanate used can be of aliphatic or aromatic type. Examples of aliphatic isocyanates which can be used are also described in US Pat. No. 5,246,630.
- Aliphatic urethane oligomers are obtained by reacting an aliphatic polyol and an aliphatic polyisocyanate. To obtain an aromatic urethane oligomer, it is sufficient that at least one of the precursors, either the polyol or the polyisocyanate, comprises an aromatic group.
- urethane oligomers according to the invention can also be obtained commercially.
- examples of urethane oligomers usable in the context of the present invention commercially available, mention may be made of the following products supplied by the company CRAY VALLEY:
- the polymerizable compositions according to the invention contain a hydrophilic monomer or a mixture of hydrophilic monomers.
- hydroxyalkyl (meth) acrylates are those in which the alkyl group generally contains from 1 to 4 carbon atoms.
- hydroxyalkyl (meth) acrylate examples include 2-hydroxyethylmethacrylate (HEMA), hydroxypropylacrylate, hydroxypropyl (meth) acrylate and 2,3-dihydroxypropylmethacrylate (glycerylmethacrylate).
- HEMA 2-hydroxyethylmethacrylate
- hydroxypropylacrylate hydroxypropyl (meth) acrylate
- 2,3-dihydroxypropylmethacrylate 2,3-dihydroxypropylmethacrylate
- alkoxy derivatives of the hydroxyalkyl (meth) acrylate are mono-di- or triethoxylated compounds, having an alkyl group generally containing from 1 to 4 carbon atoms.
- N-vinyl-2-pyrrolidone N-vinyl-2-piperidone
- N-vinyl-caprolactam N-vinyl-2-caprolactam
- amido derivatives of the (meth) acrylic compounds useful as hydrophilic monomers in the compositions of the present invention mention may be made of (meth) acrylamide, N-methyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-diacetone (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, and N-methylaminoisopropyl (meth) acrylamide.
- aminoalkyl (meth) acrylates useful as hydrophilic monomers in the compositions of the present invention, mention may be made of raminoethyl (meth) acrylate, dimethylaminoethylmethacrylate, methylaminoethylmethacrylate, and diethylaminoethylmethacrylate.
- hydrophilic ionic monomers useful in the present invention, mention may be made of (meth) acrylic acid, as well as cationic monomers such as quaternary ammonium derivatives of (meth) acrylic acid.
- the polymerizable composition according to the invention can comprise one of the above monomers, alone, or else any mixtures of these monomers.
- compositions according to the invention comprise, as hydrophilic monomer, 2-hydroxyethylmethacrylate.
- mixtures of hydrophilic monomers which are particularly recommended for the compositions of the present invention, mention may be made of mixtures of 2-hydroxyethylmethacrylate / acrylamide and / or
- N, N-dimethylacrylamide optionally combined with glyceryl methacrylate (GMA).
- GMA glyceryl methacrylate
- the hydrophilic monomer or the mixture of hydrophilic monomers in the polymerizable compositions according to the invention represents at least 35% by weight relative to the total weight of the monomers present in the initial polymerizable composition.
- the hydrophilic monomer or the mixture of hydrophilic monomers represents 50% or more by weight relative to the total weight of the monomers present in the initial polymerizable composition.
- the polymerizable composition according to the invention may also comprise one or more hydrophobic monomers whose function is, most often, to reinforce the mechanical properties of the final polymer matrix and / or to adjust its water content.
- hydrophobic monomers mention may be made of alkyl (meth) acrylate, and in particular methyl methacrylate (MMA).
- MMA methyl methacrylate
- the latter hydrophobic monomer can advantageously be used as a mixture with an N-vinyl lactam (meth) acrylate derivative such as N-vinylpyrrolidone.
- hydrophobic monomers it is also possible to use, as hydrophobic monomers in the compositions of the invention, an oligomer of the above-mentioned hydrophobic monomers.
- the hydrophobic monomers When they are present, the hydrophobic monomers generally represent from 5 to 40%, preferably 10 to 30% by weight relative to the total weight of the monomers present in the initial composition.
- the polymerizable compositions of the invention may also contain one or more conventional crosslinking agents.
- Examples of such conventional crosslinking agents are ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate such as diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate; long chain di (mefh) acrylates such as hexamethylene di (mefh) acrylate; vinyl (meth) acrylate; allyl (meth) acrylate; divinylbenzene, diallylphthalate, and trimeth icrylolpropane trimethacrylate.
- polyethylene glycol di (meth) acrylate such as diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate
- long chain di (mefh) acrylates such as hexamethylene di (mefh) acrylate
- vinyl (meth) acrylate vinyl (meth) acrylate
- allyl (meth) acrylate divinylbenzene, diallylphthalate,
- these conventional crosslinking agents are used in conventional amounts generally between 0.1 and 2 parts by weight per 100 parts by weight of the mixture of monomers present in the initial polymerizable composition.
- the polymerizable compositions according to the invention may also contain various conventional additives such as dyes, photochromic pigments, and UV absorbers.
- compositions according to the invention are compositions which can be polymerized by thermal and / or photochemical routes.
- the polymerizable compositions according to the invention also comprise conventional amounts of thermal initiators and / or photochemical initiators.
- thermal initiators which can be incorporated into the polymerizable compositions according to the invention, mention may be made of azo initiators such as azo bis isobutyronitrile (AIBN) or azo bis dimethylvaleronitrile or also peroxides such as benzoyl peroxide or isopropyl percarbonate.
- AIBN azo bis isobutyronitrile
- azo bis dimethylvaleronitrile or also peroxides such as benzoyl peroxide or isopropyl percarbonate.
- the photoinitiators which can be used in the polymerizable compositions according to the invention can be any compound producing free radicals under irradiation, either by itself or by cooperation with another proton-donating compound. That is to say that the photoinitiators used can be either of the photocleavable type or of the photoactivatable type.
- a photocleavable photoinitiator comprises one or more compounds which function by directly generating one or more free radicals which initiate polymerization, while a photoactivable photoinitiator is formed from a system producing such radicals by a photo-assisted redox reaction between a light absorbing compound and a hydrogen or electron donor, both present in the system. It is, of course, possible to use mixtures of these two types of photoinitiator.
- photocleavable compounds known per se are, for example, alkoxyacetophenone derivatives, benzoin ethers, phosphine-oxides, benzoyloxime derivatives.
- DAROCURE® 4265 mixture of aromatic ketones containing DAROCURE® 1173.
- photoactivatable photoinitiators examples include a free radical-producing absorber chosen from benzophenones, benzyles, xanthones, anthrones, thioxanthones, fluorenones, suberones, acridones, in association with, as proton donors, a compound of the type of ethers, alcohols, amines, amino acids, or organometallic compounds.
- a free radical-producing absorber chosen from benzophenones, benzyles, xanthones, anthrones, thioxanthones, fluorenones, suberones, acridones, in association with, as proton donors, a compound of the type of ethers, alcohols, amines, amino acids, or organometallic compounds.
- polymerization techniques of the polymerizable compositions according to the invention are conventional and known to those skilled in the art. It is possible, in particular, to polymerize by pure thermal route, by photochemical route or by combining one and the other of these processes.
- the polymerization can be carried out in bulk or in a solvent medium as is conventional.
- the articles obtained by polymerization of the polymerizable compositions according to the invention can be produced by directly molding the polymerizable composition in a mold having the desired shape, then by carrying out the polymerization of the polymerizable composition in the mold.
- the mold surfaces have the desired geometry and finish for the surfaces of the molded article.
- the polymers and articles obtained directly after molding and polymerization of the polymerizable compositions, according to the invention, are products in the dry state.
- Polymers and hydrated articles can be obtained by subjecting them to hydration in an aqueous saline solution, for example physiological saline, optionally buffered. This hydration is continued, generally at room temperature, for a sufficient time to obtain saturation hydration of the polymer or of the article.
- aqueous saline solution for example physiological saline, optionally buffered. This hydration is continued, generally at room temperature, for a sufficient time to obtain saturation hydration of the polymer or of the article.
- the polymers and hydrated articles (hydrogels) obtained have good mechanical performance with an elongation at break varying from 40 to more than 300% and a higher breaking strength or equal to 0.1 MPa and generally from 0.1 to 1.2 MPa.
- the improvement in mechanical properties, which manifests itself whatever the hydrophilicity level of the article, is particularly marked for polymers and articles having high hydrophilicity rates, greater than or equal to 40%, and in particular in the range of 40 to
- the average molar mass of the polymer thus obtained is lower than for the corresponding polymers, obtained thermally. It is therefore necessary to use an effective cross-linking agent when using the photochemical route, otherwise the mechanical properties will drop.
- the specific crosslinking agents of the present invention make it possible, in this case, to obtain hydrogels with good mechanical properties.
- the polymerizable compositions are prepared by mixing the hydrophilic monomers and the crosslinking agents indicated in the tables below and in the proportions indicated in these tables.
- All polymerizable compositions additionally contain, as polymerization initiators, 0.2 part by weight of azobis isobutyronitrile (AIBN) and 0.2 part by weight of DAROCURE® 4265, per 100 parts by weight of monomers present in the composition polymerizable.
- AIBN azobis isobutyronitrile
- DAROCURE® 4265 DAROCURE® 4265
- the mixtures are homogenized using a magnetic stirrer and protected from light.
- Polypropylene molds are filled with these mixes (150 ⁇ l per mold).
- the concave face of the mold makes it possible to obtain the convex face of the lens at its final geometry.
- the polymerization is then completed for 45 minutes at 100 ° C. in a thermostated oven.
- the lenses are then machined on the inner side (concave side of the lens), then hydrated overnight in physiological saline, at room temperature.
- the contact lenses obtained in the hydrated state have a thickness in the center varying from 0.15 to 0.20 mm.
- the percentage of elongation at break of each contact lens in the hydrated state is measured relative to the initial dimension of the lens as well as the stress (in MPa) exerted at break.
- FIG. 1 shows schematically the principle of such a measurement.
- This measure consists in exerting a force on the central part of the contact lens 1 on the concave face side by a movable element 2 along the geometric axis of the lens, the latter being moreover immobilized over its entire periphery by means blocking 3, 4.
- the movable element 2 is in this case a punch and the lens is maintained in an aqueous medium (isotonic solution). The lens then undergoes a deformation along the axis of application of the stress until the rupture of the material is observed (perforated lens).
- a traction / compression device equipped with a cage or single column and an ION load cell (brand ADAMEL-LHOMARGY, reference DY31) is used.
- the punch is made of stainless steel, diameter 2.50 mm.
- the measurement system includes a compression cell containing a 0.9% saline solution buffered to a pH of about 7.2 with a borate buffer.
- the contact lens is immersed in this saline solution for the duration of the measurement.
- a 0.9% saline solution or equivalent in osmolarity (of the order of 310 mOSm) and with a pH between 7.2 and 7.6 limits inclusive can be used for the measurement.
- the hydrophilicity rate is measured on final lenses hydrated to saturation with 0.9% NaCl saline.
- the measuring device is an ATAGO hand refractometer, graduated in% of water.
- the transparency of the material is evaluated with the naked eye in visible light.
- urethane oligomer crosslinking agents used are the products marketed by CRAY VALLEY under the names:
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Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/171,218 US6177507B1 (en) | 1997-02-14 | 1998-02-05 | Polymerizable compositions comprising a urethane oligomer as crosslinking agent, polymers and hydrated polymers obtained from these compositions, and finished and semi-finished articles formed using these polymers |
AU62980/98A AU6298098A (en) | 1997-02-14 | 1998-02-05 | Polymerizable compositions comprising a urethane oligomer as a crosslinking agent, polymers and hydrated polymers obtained using these compositions, and finished and semi-finished products manufactured using these polymers |
EP98906973A EP0894099A1 (fr) | 1997-02-14 | 1998-02-05 | Compositions polymerisables comprenant un oligomere urethane comme agent de reticulation, polymeres et polymeres hydrates obtenus a partir de ces compositions, et articles finis et semi-finis formes a partir de ces polymeres |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9701749A FR2759702B1 (fr) | 1997-02-14 | 1997-02-14 | Compositions polymerisables comprenant un oligomere urethane comme agent de reticulation, polymeres et polymeres hydrates obtenus a partir de ces compositions, et articles finis et semi-finis formes a partir de ces polymeres |
FR97/01749 | 1997-02-14 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1998036006A1 true WO1998036006A1 (fr) | 1998-08-20 |
Family
ID=9503728
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR1998/000205 WO1998036006A1 (fr) | 1997-02-14 | 1998-02-05 | Compositions polymerisables comprenant un oligomere urethane comme agent de reticulation, polymeres et polymeres hydrates obtenus a partir de ces compositions, et articles finis et semi-finis formes a partir de ces polymeres |
Country Status (5)
Country | Link |
---|---|
US (1) | US6177507B1 (fr) |
EP (1) | EP0894099A1 (fr) |
AU (1) | AU6298098A (fr) |
FR (1) | FR2759702B1 (fr) |
WO (1) | WO1998036006A1 (fr) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2832717A1 (fr) * | 2001-11-26 | 2003-05-30 | Essilor Int | Composition polymerisable par voie radicalaire conduisant a des verres organiques resistants au choc |
EP1785747A1 (fr) * | 2005-11-14 | 2007-05-16 | Essilor International (Compagnie Generale D'optique) | Lentille ophtalmique comportant un revêtement de protection contre la photodégradation et procédé pour preparer une telle lentille ophtalmique |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7977430B2 (en) * | 2003-11-25 | 2011-07-12 | Novartis Ag | Crosslinkable polyurea prepolymers |
EP1751546A2 (fr) * | 2004-05-20 | 2007-02-14 | Albatros Technologies GmbH & Co. KG | Hydrogel imprimable pour biocapteurs |
US8899547B2 (en) | 2004-11-18 | 2014-12-02 | Qspex Technologies, Inc. | Molds and method of using the same for optical lenses |
US9042019B2 (en) | 2011-04-15 | 2015-05-26 | Qspex Technologies, Inc. | Anti-reflective lenses and methods for manufacturing the same |
US9335443B2 (en) | 2011-04-15 | 2016-05-10 | Qspex Technologies, Inc. | Anti-reflective lenses and methods for manufacturing the same |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0000507A1 (fr) * | 1977-07-20 | 1979-02-07 | Ciba-Geigy Ag | Procédé de préparation d'hydrogels sous forme de perles sphériques de plus grand diamètre |
SU825548A1 (ru) * | 1978-04-03 | 1981-04-30 | Lvovskij Polt Inst | Способ получения гидрогельного полимерного материала 1 |
US4376800A (en) * | 1981-04-13 | 1983-03-15 | Lu Chen I | Optical lenses prepared from crosslinkable acrylic compositions |
EP0453149A2 (fr) * | 1990-04-20 | 1991-10-23 | Sola International Holdings Limited | Composition de moulage |
-
1997
- 1997-02-14 FR FR9701749A patent/FR2759702B1/fr not_active Expired - Fee Related
-
1998
- 1998-02-05 WO PCT/FR1998/000205 patent/WO1998036006A1/fr not_active Application Discontinuation
- 1998-02-05 EP EP98906973A patent/EP0894099A1/fr not_active Withdrawn
- 1998-02-05 AU AU62980/98A patent/AU6298098A/en not_active Abandoned
- 1998-02-05 US US09/171,218 patent/US6177507B1/en not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0000507A1 (fr) * | 1977-07-20 | 1979-02-07 | Ciba-Geigy Ag | Procédé de préparation d'hydrogels sous forme de perles sphériques de plus grand diamètre |
SU825548A1 (ru) * | 1978-04-03 | 1981-04-30 | Lvovskij Polt Inst | Способ получения гидрогельного полимерного материала 1 |
US4376800A (en) * | 1981-04-13 | 1983-03-15 | Lu Chen I | Optical lenses prepared from crosslinkable acrylic compositions |
EP0453149A2 (fr) * | 1990-04-20 | 1991-10-23 | Sola International Holdings Limited | Composition de moulage |
Non-Patent Citations (1)
Title |
---|
DATABASE WPI Week 8206, Derwent World Patents Index; AN 82-11569E, XP002041381, "POLYMERIC HYDROGEL FOR SOFT CONTACT LENS MFR. - PREPD. FROM POLYVINYL PYRROLIDONE, HYDROXYALKYL METHACRYLATE AND CROSSLINKING AGENT" * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2832717A1 (fr) * | 2001-11-26 | 2003-05-30 | Essilor Int | Composition polymerisable par voie radicalaire conduisant a des verres organiques resistants au choc |
WO2003046028A1 (fr) * | 2001-11-26 | 2003-06-05 | Essilor International Compagnie Generale D'optique | Composition polymerisable par voie radicalaire conduisant a des verres organiques resistants au choc |
US7393880B2 (en) | 2001-11-26 | 2008-07-01 | Essilor International Compagnie Generale D'optique | Radically polymerizable composition resulting in shock resistant organic lenses |
EP1785747A1 (fr) * | 2005-11-14 | 2007-05-16 | Essilor International (Compagnie Generale D'optique) | Lentille ophtalmique comportant un revêtement de protection contre la photodégradation et procédé pour preparer une telle lentille ophtalmique |
FR2893422A1 (fr) * | 2005-11-14 | 2007-05-18 | Essilor Int | Lentille ophtalmique comportant un revetement de protection contre la photodegradation et procede pour preparer une telle lentille ophtalmique. |
US7815308B2 (en) | 2005-11-14 | 2010-10-19 | Essilor International (Compagnie Generale d'Opitique) | Ophthalmic lenses comprising a photodegradation protection coating and a process for producing such lenses |
Also Published As
Publication number | Publication date |
---|---|
EP0894099A1 (fr) | 1999-02-03 |
AU6298098A (en) | 1998-09-08 |
US6177507B1 (en) | 2001-01-23 |
FR2759702B1 (fr) | 1999-04-02 |
FR2759702A1 (fr) | 1998-08-21 |
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