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WO1982003397A1 - Hydrogels de methacrylate de silicone pour des verres de contact - Google Patents

Hydrogels de methacrylate de silicone pour des verres de contact Download PDF

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Publication number
WO1982003397A1
WO1982003397A1 PCT/US1982/000352 US8200352W WO8203397A1 WO 1982003397 A1 WO1982003397 A1 WO 1982003397A1 US 8200352 W US8200352 W US 8200352W WO 8203397 A1 WO8203397 A1 WO 8203397A1
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Prior art keywords
percent
methacrylate
trimethylsiloxy
group selected
bis
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PCT/US1982/000352
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English (en)
Inventor
John D Mccarry
William M Foley Jr
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Priority to AU83382/82A priority Critical patent/AU8338282A/en
Publication of WO1982003397A1 publication Critical patent/WO1982003397A1/fr
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    • 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
    • C08F30/00—Homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F30/04—Homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F30/08—Homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • 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

Definitions

  • This invention relates to optical contact lenses and, more particularly, to optical contact lenses, lens materials and optical quality copolymers having qualities rendering them suitable for use in optical contact lenses, e.g. clarity, machinability, strength and durability, arid which also possess unique and vastly improved oxygen permeability and wettability.
  • the lenses of this invention and the lens polymers are copolymers of silicone monomers and prepolymers, and acrylate and methacrylate monomers, and include substituents which vastly improve wettability and oxygen permeability such as pentafluorostyrene, and vinyl pyrrolidinone to improve wettability.
  • Polymethylmethacrylate is rigid and durable but relatively impermeable to oxygen.
  • the hydrogel materials based on hydrophilic polymers such as polyhydroxyethyl- methacrylate are soft and have poor durability. In addition, they provide an environment which is favorable for bacterial growth and are only moderately impermeable to oxygen.
  • Silicone rubber is soft and resilient and is highly permeable to oxygen.
  • a filler which increases the refractive index of the mixture, must be added to improve the durability.
  • the precision machining and polishing which is necessary in the fabrication of a corrective contact lens is extremely difficult with the elastomeric silicone rubbers.
  • the prior art also teaches copolymers prepared by copolymerizing a polysiloxanylalkyl ester of acrylic or methacrylic acid with an alkanol ester of acrylic or methacrylic acid.
  • the polysiloxanylalkyl ester monomer has the structural formula
  • X and Y are selected from the class consisting of C 1 -C 5 alkyl groups, phenyl groups and Z groups;
  • Z is a group of the structure
  • A is selected from the class consisting of C 1 -C 5 alkyl groups and pheny ⁇ -groups; R is selected from the class consisting of methyl groups and hydrogen; m is an integer from one to five; and n is an integer from one to three.
  • alkanol ester comonomers included: methyl acrylate and methacrylate ethyl acrylate and methacrylate propyl acrylate and methacrylate isopropyl acrylate and methacrylate butyl acrylate and methacrylate amyl acrylate and methacrylate hexyl acrylate and methacrylate heptyl acrylate and methacrylate octyl acrylate and methacrylate
  • copolymers of the prior art comprise about 10-60 parts by weight of one or more of the polysilo- xanylalkyl ester monomers copolymeriz ⁇ d with about 49-90 parts by weight of one or more of the alkanol ester comonomers.
  • the comonomer mixture containing between about 0.05-2% by weight of the free radical initiator is heated to a temperature between 30oC.-100oC, preferably below 70oC., to initiate and complete the polymerization.
  • the polymerization can be carried out directly in a contact lens mold to form a lens generally having the desired configuration.
  • the polymerization mixture can be heated in a suitable mold or container to form discs, rods or sheets which can then be machined to the desired shape using conventional equipment and procedures employed for fabricating lenses from polymethyl methacrylate.
  • the temperature is preferably maintained below 70oC. in order to minimize the formation of bubbles in the copolymer.
  • solution, emulsion or suspension polymerization to prepare the novel copolymers, using techniques conventionally used in the preparation of polymers from ethylenically unsaturated monomers.
  • the copolymer thus produced may be extruded, pressed or molded into rods, sheets or other convenient shapes which are then mach-ined to produce the contact lenses.
  • Improved wettability was imparted to the copolymer by the addition of from about 0.1% to about 10% by weight of one or more hydrophilic monomers to the copolymerization mixture.
  • hydrophilic monomers include hydroxyalkyl acrylates and methacrylates wherein the alkyl group contains 1 to 4 carbon atoms, acrylic and methacrylic acid, acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylami glycidyl acrylate and methacrylate and N-vinylpyrrolidone.
  • the wettability of the surface of contact lenses made from these copolymers was improved by the application of a wetting agent such as, for example, a dilute aqueous solution of alkyldimethylbenzylammonium chloride, by exposure of the surface to a corona discharge or by chemical treatment of the surface with a strong oxidizing agent such as nitric acid.
  • a wetting agent such as, for example, a dilute aqueous solution of alkyldimethylbenzylammonium chloride
  • a strong oxidizing agent such as nitric acid.
  • the rigidity of the contact lenses prepared from such copolymers could be' varied by changing the ratio of comonomers and/or their chemical composition.
  • Contact lenses prepared from acrylate monomers are more flexible than those prepared from methacrylate monomers.
  • a copolymer of a polysiloxanylalkyl methacrylate and an alkyl methacrylate fabricated into a contact lens is more rigid than a lens prepared from the copolymer of the corresponding acrylates.
  • the rigidity of a contact lens prepared from the aforesaid materials could be increased by the incorporation into the copolymer composition of 0.01% to about 2% by weight of a crosslinking monomer such as a polyol dimethacrylate or diacrylate or a polyol acrylic ester of higher functionality, for example, ethylene glycol dimethacrylate, butylene glycol dimethacrylate, neopentyl glycol diacrylate and pentacrythritol triacrylate or tetra-acrylate.
  • a crosslinking monomer such as a polyol dimethacrylate or diacrylate or a polyol acrylic ester of higher functionality, for example, ethylene glycol dimethacrylate, butylene glycol dimethacrylate, neopentyl glycol diacrylate and pentacrythritol triacrylate or tetra-acrylate.
  • the refractive index of polymethylmethacrylate is 1.49.
  • the refractive indices of the copolymers referred to above could be varied between 1.35 and 1.50 by varying the ratio and nature of the comonomers. In general, increasing the polysiloxanyl monomer content of the copolymer will decrease its. refractive index.
  • the nature of the substituents on the silicon atoms of the polysiloxanyl monomer also importantly affects the refractive index of the copolymer. Lower straight chain alkyl substituents produce copolymers of lower refractive index while polysiloxanyl monomers having phenyl substituents on.
  • the present invention is an improvement over the prior art lenses and comprises lenses, lens polymers and methods of preparing contact lenses and contact lens polymers of specific and unique copolymeric composition having unique and surprising advantages.
  • the invention features particular copolymers of monoacrylic siloxane, as described in the aforesaid prior art patent, and diacrylie siloxane, such copolymers possessing very much improved and unexpected advantages over the prior art and also possessing properties not predictable from known characteristics of prior art polymer- and copolymer systems.
  • the invention features particular copolymers which include a pentfluorostyrene moiety which vastly improves oxygen permeability and yet possess highly advantageous characteristics as a lens polymer.
  • Still another and very important facet of the invention is a particular set of copolymers of wettable poly(hydroxyalkyl methacrylate-siloxane-methacrylate-n-vinyl pyrrolidinone) which have extremely high wettability and yet are clear and otherwise suitable as lens polymers. Lenses made of the aforementioned copolymer systems and methods of forming the same are also facets of this invention.
  • lens polymer is commonly and widely used in the contact lens industry and is used herein to mean a polymer or copolymer material which possesses physical and optical characteristics which render the material suitable for being formed into and used as a lens, and in this particular application, as a contact lens.
  • Such material must be clear, have an adequately high refractive index, i.e., above about 1.25 and generally up to about 1.5, the higher the refractive index the more correction availability, and must also be firm and rigid enough to be machined and polished, and tough enough to be handled and worn as a contact lens.
  • the present invention includes lenses formed from a lens polymer consisting essentially of the solid polymerization product of comonomers consisting essentially of:
  • R 1 is a group selected from -O-;
  • R 2 is a group selected from -C n H 2n+1 ; -C 6 H 5 ;
  • R 3 is a group selected from
  • R 4 through R 13 inclusive, each is a group selected from C n H 2n+1 ; -C 6 H 5 ; or [-O-Si-(CH 2 )] n -R 14 ;' R 14 is a group selected from -C n H 2n+1 ; -C 6 H 5 or
  • n -R 15 R.- is a group selected from -C n H 2n+1 ; C 6 H 5 ;
  • n is a positive integer from 1 to 5; and (b) from about 1 weight percent to about 95 weight percent silicone diacrylate or dimethacrylate having the formula
  • R 1 is a group selected from -O-; R 3 and R 3 , each is a group selected from
  • R 4 through R 13 inclusive, each is a group selected from C n H 2 n+1; -C 6 H 5 ; or [-0-Si-(CH 2 )] n -R 14 ; R 14 is a group selected from -C n H 2n+1 ; -C 6 H 5 or
  • R 15 is a group selected from -C n H 2+1 ; -C 6 H 5 ;
  • the present invention includes lens polymers which have physical and optical properties suitable for being formed into contact lenses consisting essentially of the polymerization product of the following comonomers:
  • R 1 is a group selected from -O-;
  • R 2 is a group selected from -C n H 2n+1 or -C 6 H 5 .
  • R 3 is a group selected from
  • R 4 through R 13 inclusive, each is a group selected from
  • R 14 is a group selected from -CH 3 ; -C 6 H 5 or
  • R 15 is a group selected from -CH 3 ; -C 6 H 5 ;
  • R 1 is a group selected from -O-; R 3 and R 3 , each is a group selected from
  • R 4 through R 13 inclusive, each is a group selected from
  • R 14 is a group selected from -C n H 2n+1 ; -C 6 H 5 or [-O-Si-(CH 2 ) 2 ] n -R 15
  • R 15 is a group selected from -C n H 2n+1 ; -C 6 H 5 ;
  • n is a positive integer from 1 to 3.
  • Representative silicone monomethacrylates include:
  • Exemplary silicone diacrylates and dimethacrylates include:
  • Embodiments Silicone dimethacrylate (diacrylate) esters which are new to the art, have been copolymerized with specific hydrophilic monomers to give hydrogels with excellent optical properties in the hydrated state.
  • hydrogels may be adjusted over a wide range, by incorporating silicone methacrylate esters in the hydrogel formulation.
  • silicone methacrylate esters A wide variety of lens types and prescriptions may be fabricated, which has not been possible with previous hydrogel formulations.
  • a further advantage of these formulations lies in the fact that they combine high oxygen permeability with good wetting.
  • the oxygen permeability of the silicone dimethacrylate esters shows a wide variation within the group.
  • the silicone dimethacrylate ester monomer has the structure
  • X and Y are selected from the class consisting of C 1 - C 3 alkyl groups, phenyl groups, pentafluorophenyl groups, pyrrolidinonylethyl groups, pyrrolidinonylpropyl groups and 2 groups;
  • Z is a group of the structure
  • a and B are selected from the class consisting of C 1 - C 3 alkyl groups, phenyl groups, pentafluorophenyl groups, pyrrolidinonyl ethyl groups, pyrrolidinonyl propyl groups.
  • R is selected from the class consisting of methyl groups and hydrogen, m is an integer from zero to five; m' is an integer from one to five; n is an integer from one to three.
  • One embodiment of the invention provides an optical contact lens having clarity, wettability and machinability and having superior oxygen permeability consisting essentially of the polymerization product of the following with suitable polymerization initiators:
  • Another embodiment of the invention provides an optical contact lens having clarity, wettability and machinability and having superior oxygen permeability consisting essentially of the polymerization product of the following with suitable polymerization initiators:
  • a further optical contact lens according to this invention has clarity, wettability and machinability and superior oxygen permeability and consists essentially of the polymerization product of the following with suitable polymerization initiators:
  • the invention also provides an optical contact lens having clarity, wettability and machinability and having superior oxygen permeability consisting essentially of the polymerization product of the following with suitable polymerization initiators:
  • an optical contact lens having clarity, wettability and machinability and having superior oxygen permeability consisting essentially of the polymerization product of the following with suitable polymerization initiators: (a) from 15 percent to 85 percent of tris (trimethylsiloxy) silylpropyl methacrylate or 1, 3-bis-methacryloxypropyl 1-1, 1, 3, 3-tetrakis (trimethylsiloxy)-disiloxane, or mixtures thereof, in a ratio of from 1:100 to 100:1; (b) optionally up to 10 percent of alkoxy methacrylate;
  • Neozapon FLE (BASF)* (as a colorant) 0.01g
  • the above were thoroughly mixed, placed in molds and cured at 79°C for five hours.
  • the lens blanks were hard and clear with an equilibrium hydration level of 13.7%.
  • N-vinyl pyrrolidinone 25 .00g Methacrylic Acid 0 .30g
  • Neozapon FLE (BASF) 0 .01g
  • the above were thoroughly mixed and then cured at 86oC for sixteen hours.
  • the lens blanks were hard and clear, machined and polished very well.
  • the equilibrium hydration level was 23.5%.
  • Methacrylate 1 5 - Bis (methacryloxypropyl) 5.00g
  • Methacrylate 1 5 - Bis (methacryloxypropyl) - 1.00g
  • the above were thoroughly mixed and cured at 84-86.5°C for thirteen hours.
  • the lens blanks were hard and clear, machined and polished well.
  • the equilibrium hydration level was 30.0%, the oxygen permeability was very high.
  • Lenses made from these lens blanks had exceptional oxygen permeability and excellent wetting.
  • Lenses produced from these lens blanks had exceptional oxygen permeability and excellent wetting.
  • Example 12 1, 3 - Bis-methacryloxypropyl 10.00g 1,1,3, 3-tetrakis (trimethylsiloxy) disiloxane Tris (trimethylsiloxy) silyl- 5.00g propyl Methacrylate Pentafluorostyrene 5.05g VAZO 52 (2, 2' Azobis 0.04g
  • VAZO 52 0.09g The above were thoroughly mixed and cured at 72-74°C for four hours, to give lens blanks with good hardness and machinability. Lenses made from these lens blanks had exceptional oxygen permeability and excellent wetting.
  • Example 15 1, 3 Bis-methacryloxypropyl - 11.00g
  • VAZO 52 0.06g The above were thoroughly mixed, dried over MgSO 4 , filtered and cured at 60-90°C for three hours to give lens blanks with good wetting and superior oxygen transmissibility.
  • Example 17 The above were mixed thoroughly, dried over MgSO 4 , filtered and cured at 60-90oC for two and one half hours, to give lens blanks with good wett.ing and superior oxygen transmissibility.
  • Example 17 The above were mixed thoroughly, dried over MgSO 4 , filtered and cured at 60-90oC for two and one half hours, to give lens blanks with good wett.ing and superior oxygen transmissibility.
  • Example 20 The above were thoroughly mixed, dried over MgSO 4 , filtered and cured at 70-75°C, under N 2 for 4 to 6 hours.
  • the lens blanks had a hardness of 74-75D and gave lenses with superior wetting and oxygen permeability.
  • Example 22 1, 3 Bis-methacryloxypropyl 0.30g 1, 1', 3, 3'-tetrakis (trimethylsiloxy)-disiloxane Tris (trimethylsiloxy) silyl-propyl 6.00g
  • Example 23 3-Bis-methacryloxypropyl- 0.20g
  • the above were mixed thoroughly, dried over MgSO 4 , filtered, and cured for six hours at 70-77°C.
  • the lens blanks had a hardness of 80D and hydrated to 10%, with superior oxygen permeability.
  • the above were thoroughly mixed, then degassed under vacuum and repressured to atmospheric pressure with nitrogen.
  • the formulation was cured at 75oC for seventeen hours, to give lens blanks with good hardness, exceptional oxygen permeability, good wettability, and good optical properties.
  • siloxane methacrylates which are known to be hydrophobic, may be copolymerized with specific hydrophilic monomers tb give hydrogels with excellent optical properties in the hydrated state.
  • hydrogels may be adjusted over a wide range, giving hydrogels which are soft and flexible, to semi-soft and even ridged and hard. Thus, it is possible to fabricate a wide variety of lens types and prescriptions which is not possible, with other hydrogels.
  • hydrogels are their extremely high oxygen permeability coupled with excellent wettability. It has also been found, that while siloxane methacrylates are oxygen permeable, there is a wide variation in the oxygen permeability within this group of compounds, a fact which has not previously been reported.
  • siloxane methacrylates have been prepared which include hydriphilic groups, such as pyrrolidinone, within the molecule, thus enhancing wetting, while also maintaining high oxygen permeability.
  • silicone methacrylate (acrylate monomers are best described by the following generalized formulae:
  • X & Y are selected from the class consisting of
  • a and B are selected from the class consisting of C 1 - C 3 alkyl groups, phenyl groups, pentafluorophenyl groups; R is selected from the class consisting of methyl groups and hydrogen; m is a positive integer from one to five and n is a positive integer from one to three.
  • X, Y, and A may also be pyrrolidinonyl ethyl, pyrrolidinonyl propyl, hydroxyethyl or hydroxy-propyl, or dihydroxy propyl.
  • comonomers may also be included in the formulation to improve hardness and machinability, of the lens blank in the dry, unhydrated state, such as pentafluorostyrene, styrene, toluene, alkyl methacrylates, such as methyl methacrylate, ether methacrylates, such as methoxyethyl methacrylate and methacrylic acid.
  • Crosslinking comonomers in very small amounts, are also included in the formulation, such as ethyleneglycol dimethacrylate and triethylene glycol dimethacrylate. Others, known in the art, may also be used.
  • the above were thoroughly mixed and cured at 52-85 °C for one-half hour and at 85-93 °C for fourteen hours.
  • the lens blanks were clear and colorless, they machined and polished very well.
  • the equilibrium hydration level was 23%, the oxygen permeability was very high.
  • the aboye were thoroughly mixed, placed in molds, and cured at 99-100°C for seventeen hours.
  • the lens blanks were hard, clear, and colorless.
  • Any monomer which is reactive to form capped siloxanes may be considered for use in this invention, such as the acrylates which are analogous to the above methacrylates and the hydrophylic monomers referred to in the discussion of the prior art hereinbefore.
  • the oxygen permeability of the lens polymer of Example 7 has a DK value of 28.5 ⁇ 10 -11 , using the procedure and nomenclature of Fatt and St. Helen, "Oxygen Tension Under an Oxygen-Permeable Contact Lens", American Journal of Optometry, 1971, No. 7, pp. 545-555, whereas lens polymers described in the prior art Gaylord.
  • U.S. Patent No. 3, 808,178 have a DK value of only 4 ⁇ 10 -11 , obtained by converting values in said patent to DK values).
  • the aforementioned lens polymers of this invention pass substantial amounts of oxygen through lenses formed thereof within as little as 30 seconds whereas the best prior art lenses, now known to applicant, require 3 to 4 minutes before any significant amount of oxygen reached the other side of lenses.
  • the ratio may be just slightly greater than 1:1 but significantly higher ratios must be avoided.
  • dimethacrylate siloxane based lens polymers were more oxygen permeable, by a very substantial factor, than monomethacrylate lens polymers, and that the inclusion of even small amounts, e.g. greater than about one weight percent, of the dimethacrylate siloxane greatly improved oxygen permeability.
  • harder lenses are formed with higher amounts of siloxane dimethacrylate or siloxane diacrylate, as compared with monomethacrylates or monoacrylates.
  • Vinyl pyrrolidinone and hydroxyalkyl methacrylates when copolymerized into the lens polymers increase wettability and level of hydration, and increase dry hardness of the lens, improving machinability and general physical characteristics for forming lenses; however, too much of either monomer in the system results in a polymer which is opaque and not -suitable for forming lenses.
  • vinyl pyrrolidinone may be copolymerized with siloxane dimethyl methacrylate (or equivalent di-acrylate capped siloxane) or with mixtures of mono- and di- methyl methacrylates (or equivalent mono- and di- acrylate capped siloxanes), the latter in a ratio of from about 1:20 to 99:1 di- to mono-, acrylate siloxane.
  • siloxane dimethyl methacrylate or equivalent di-acrylate capped siloxane
  • mixtures of mono- and di- methyl methacrylates or equivalent mono- and di- acrylate capped siloxanes
  • Hydroxyalkyl methacrylates and acrylates can be tolerated, and improve wetting and hydration, in amounts of from about ten percent, to significantly improve wetting, to about forty percent. Lesser amounts can be included, of course, but with diminishing effect upon the wettability and hydratability of the lens polymer which results from polymerization of the siloxane system with hydroxyalkyl acrylates and methacryleates.
  • Fluorinated vinyl-group containing monomers may be included in amounts of from trace levels to about thirty percent, ten to thirty being the preferred effective range, to increase the wettability and oxygen permeability of the resulting lens polymer, following polymerization of a mixture of mono- and di- methacrylate or acrylate siloxanes, as described before, with the fluorinated vinyl compound, with or without a "wetting" monomer such as vinyl pyrrolidinone or a hydroxyalkyl methacrylate or acrylate.
  • a "wetting" monomer such as vinyl pyrrolidinone or a hydroxyalkyl methacrylate or acrylate.
  • the ratio of monoacrylate (or methacrylates) siloxane to diacrylates (or methacrylate) siloxane should be from about 1:1 to about 2:1; whereas for soft lenses the ratio of these monomers should be 10:1 or greater.
  • Methacrylic acid and methylmethacrylate may also be included in the monomeric mixture before polymerization, in amounts of up to about two percent methacrylic acid and up to about thirty percent methyl methacrylate with destroying the advantages lens polymer characteristics of the subject invention.
  • These monomers when copolymerized into the polymers of this invention, tend to decrease oxygen permeability slightly but can be tolerated to the degree indicated and tend to improve the machinability of the resulting lens polymers.
  • This invention is useful in the manufacture of optical contact lenses and may be used in the manufacture of other optical devices.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

Polymeres pour des verres de contact, c'est-a-dire des polymeres possedant des proprietes optiques et mecaniques indiquees pour une utilisation dans des verres de contact, ce composant essentiellement de copolymeres de monomethacrylate et dimethacrylate de siloxane, et de copolymeres de ces materiaux avec de la vinyl pyrrolidinone et du pentafluorostyrene et aussi avec du methacrylate de methyle et de l'acide methacrylique, constituant un exemple des classes de monomeres pouvant etre comprises dans le systeme de polymeres des verres de contact.
PCT/US1982/000352 1981-03-24 1982-03-23 Hydrogels de methacrylate de silicone pour des verres de contact Ceased WO1982003397A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU83382/82A AU8338282A (en) 1981-03-24 1982-03-23 Silicone methacrylate hydrogels for contact lenses

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US24695681A 1981-03-24 1981-03-24
US246956810324 1981-03-24

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WO1982003397A1 true WO1982003397A1 (fr) 1982-10-14

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3304089A1 (de) * 1982-05-08 1983-11-10 Shin-Etsu Chemical Co., Ltd., Tokyo Sauerstoff-permeable harte kontaktlinse
GB2152522A (en) * 1981-12-04 1985-08-07 Polymer Technology Corp Contact lens materials
GB2163173A (en) * 1982-05-08 1986-02-19 Toyo Contact Lens Co Ltd Oxygen permeable hard contact lens of silicon copolymer
US4810764A (en) * 1988-02-09 1989-03-07 Bausch & Lomb Incorporated Polymeric materials with high oxygen permeability and low protein substantivity
US4826936A (en) * 1981-12-04 1989-05-02 Polymer Technology Corp. Silicone-containing contact lens material and contact lenses made thereof
US4900764A (en) * 1985-11-25 1990-02-13 Highgate Donald J Hydrophilic materials
EP0361929A3 (fr) * 1988-09-28 1991-02-27 Amo Puerto Rico Inc. Lentilles de contact
GB2249551A (en) * 1990-09-28 1992-05-13 Kansai Paint Co Ltd Cationically electrodepositable finely divided gelled polymers
US5194542A (en) * 1989-09-30 1993-03-16 Hoya Corporation Contact lens
WO1993023774A1 (fr) * 1992-05-15 1993-11-25 Bausch & Lomb Incorporated Hydrogels silicones a surface mouillable
WO1994018253A1 (fr) * 1993-02-12 1994-08-18 Bausch & Lomb Incorporated Hydrogels au silicone fluore
EP0799832A3 (fr) * 1996-04-04 1999-11-24 Fraunhofer-Gesellschaft Zur Förderung Der Angewandten Forschung E.V. Silanes fluorées hydrolysables, procédé pour la préparer et leur utilisation pour la production de polycondensats de l'acide siliciques et d'hétéropolycondensats de l'acide silicique
WO2003040157A1 (fr) * 2001-11-02 2003-05-15 Bausch & Lomb Incorporated Compositions de siloxysilane polymere a indice refractif eleve
WO2017147292A1 (fr) * 2016-02-23 2017-08-31 Lotus Leaf Coatings, Inc. Revêtements sol-gel pour lentilles de contact
WO2019026652A1 (fr) * 2017-08-01 2019-02-07 信越化学工業株式会社 Composé siloxane, et procédé de fabrication de celui-ci

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4182822A (en) * 1976-11-08 1980-01-08 Chang Sing Hsiung Hydrophilic, soft and oxygen permeable copolymer composition
US4242483A (en) * 1979-08-13 1980-12-30 Novicky Nick N Oxygen permeable hard and semi-hard contact lens compositions, methods and articles of manufacture
US4246389A (en) * 1979-06-25 1981-01-20 American Optical Corporation Contact lens composition having increased oxygen permeability
US4306042A (en) * 1980-09-02 1981-12-15 Neefe Russell A Method of making a contact lens material with increased oxygen permeability

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4182822A (en) * 1976-11-08 1980-01-08 Chang Sing Hsiung Hydrophilic, soft and oxygen permeable copolymer composition
US4246389A (en) * 1979-06-25 1981-01-20 American Optical Corporation Contact lens composition having increased oxygen permeability
US4242483A (en) * 1979-08-13 1980-12-30 Novicky Nick N Oxygen permeable hard and semi-hard contact lens compositions, methods and articles of manufacture
US4306042A (en) * 1980-09-02 1981-12-15 Neefe Russell A Method of making a contact lens material with increased oxygen permeability

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2152522A (en) * 1981-12-04 1985-08-07 Polymer Technology Corp Contact lens materials
US4826936A (en) * 1981-12-04 1989-05-02 Polymer Technology Corp. Silicone-containing contact lens material and contact lenses made thereof
DE3304089C3 (de) * 1982-05-08 1994-08-11 Menicon Co Ltd Sauerstoffdurchlässige harte Kontaktlinse
GB2163173A (en) * 1982-05-08 1986-02-19 Toyo Contact Lens Co Ltd Oxygen permeable hard contact lens of silicon copolymer
DE3304089A1 (de) * 1982-05-08 1983-11-10 Shin-Etsu Chemical Co., Ltd., Tokyo Sauerstoff-permeable harte kontaktlinse
US4900764A (en) * 1985-11-25 1990-02-13 Highgate Donald J Hydrophilic materials
US4810764A (en) * 1988-02-09 1989-03-07 Bausch & Lomb Incorporated Polymeric materials with high oxygen permeability and low protein substantivity
EP0361929A3 (fr) * 1988-09-28 1991-02-27 Amo Puerto Rico Inc. Lentilles de contact
US5106930A (en) * 1988-09-28 1992-04-21 Ioptex Research Inc. Contact lenses
AU623436B2 (en) * 1988-09-28 1992-05-14 Amo Puerto Rico, Inc. Contact lens and materials therefore
US5194542A (en) * 1989-09-30 1993-03-16 Hoya Corporation Contact lens
GB2249551B (en) * 1990-09-28 1995-03-08 Kansai Paint Co Ltd Cationically electrodepositable finely divided gelled polymers and processes for producing the same
GB2249551A (en) * 1990-09-28 1992-05-13 Kansai Paint Co Ltd Cationically electrodepositable finely divided gelled polymers
US5254631A (en) * 1990-09-28 1993-10-19 Kansai Paint Co., Ltd. Cationically electrodepositable finely divided gelled polymers having a core-sheath structure obtained by emulsion polymerization
US5358995A (en) * 1992-05-15 1994-10-25 Bausch & Lomb Incorporated Surface wettable silicone hydrogels
WO1993023774A1 (fr) * 1992-05-15 1993-11-25 Bausch & Lomb Incorporated Hydrogels silicones a surface mouillable
US5387632A (en) * 1992-05-15 1995-02-07 Bausch & Lomb Incorporated Surface wettable silicone hydrogels
JP3422996B2 (ja) 1992-05-15 2003-07-07 ボシュ・アンド・ロム・インコーポレイテッド 表面ぬれ性シリコーンヒドロゲル
US5387662A (en) * 1993-02-12 1995-02-07 Bausch & Lomb Incorporated Fluorosilicone hydrogels
WO1994018253A1 (fr) * 1993-02-12 1994-08-18 Bausch & Lomb Incorporated Hydrogels au silicone fluore
US5539016A (en) * 1993-02-12 1996-07-23 Bausch & Lomb Incorporated Fluorosilicone hydrogels
EP0799832A3 (fr) * 1996-04-04 1999-11-24 Fraunhofer-Gesellschaft Zur Förderung Der Angewandten Forschung E.V. Silanes fluorées hydrolysables, procédé pour la préparer et leur utilisation pour la production de polycondensats de l'acide siliciques et d'hétéropolycondensats de l'acide silicique
WO2003040157A1 (fr) * 2001-11-02 2003-05-15 Bausch & Lomb Incorporated Compositions de siloxysilane polymere a indice refractif eleve
US7169874B2 (en) 2001-11-02 2007-01-30 Bausch & Lomb Incorporated High refractive index polymeric siloxysilane compositions
WO2017147292A1 (fr) * 2016-02-23 2017-08-31 Lotus Leaf Coatings, Inc. Revêtements sol-gel pour lentilles de contact
WO2019026652A1 (fr) * 2017-08-01 2019-02-07 信越化学工業株式会社 Composé siloxane, et procédé de fabrication de celui-ci
JP2019026607A (ja) * 2017-08-01 2019-02-21 信越化学工業株式会社 シロキサン化合物及びその製造方法

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