[go: up one dir, main page]

WO1993023773A1 - Process for preparation of oxygen permeable polymer material - Google Patents

Process for preparation of oxygen permeable polymer material Download PDF

Info

Publication number
WO1993023773A1
WO1993023773A1 PCT/JP1993/000635 JP9300635W WO9323773A1 WO 1993023773 A1 WO1993023773 A1 WO 1993023773A1 JP 9300635 W JP9300635 W JP 9300635W WO 9323773 A1 WO9323773 A1 WO 9323773A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
methacrylate
acrylate
butyl
process according
Prior art date
Application number
PCT/JP1993/000635
Other languages
English (en)
French (fr)
Inventor
Kenji Yasuda
Tetsuo Ito
Osamu Kurita
Original Assignee
Ciba-Geigy Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ciba-Geigy Ag filed Critical Ciba-Geigy Ag
Publication of WO1993023773A1 publication Critical patent/WO1993023773A1/en

Links

Classifications

    • 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
    • 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

Definitions

  • This invention relates to a process for preparation of an oxygen permeable polymer material particularly useful as ophthalmic materials such as contact lenses and intraocular lenses .
  • plastic materials for example, polymethyl meth- acrylate
  • ophthalmic mate ⁇ rials such as contact lenses and intraocular lenses.
  • conventional ophthalmic materials have problems that sxygen permeabilities are low and contaminants in tear and intraocular fluid are easily attached thereto so that, for example, when said materials are processed into contact lenses, such contact lenses cannot be worn continuously for a long time.
  • this material has a drawback that its properties change greatly depending on the copolymerization ratio of siloxanyl monoacrylate or siloxanyl monomethacrylate and fluoroacrylate or fluoromethacrylate.
  • the copolymerization ratio of siloxanyl monoacrylate or siloxanyl monomethacrylate is made larger, oxygen perme ⁇ ability is improved, but there are problems that adsorption or attachment of contaminants are remarkable, and the material becomes too brittle and soft, whereby handlings are complicated in another sense.
  • the copolymerization ratio of fluoroacrylate or fluoro- methacrylate is made larger, contaminants are hardly adsorbed or attached, but there is a problem that oxygen permeability is lowered.
  • an object of this invention is to provide an improved process for preparation of an oxygen permeable polymer material having both excellent oxygen permeability and excellent mechanical processability.
  • the present inventors have studied intensively relations between pro- Determinations for preparations of ophthalmic polymer materials comprising siloxanyl monoacrylate and/or siloxanyl mono ⁇ methacrylate, and fluoroacrylate and/or fluoromethacrylate, and characteristics of said polymer materials, and conse ⁇ quently found that by removing a substantial portion of a volatile organic solvent having compatibility with a mono ⁇ mer component during polymerization of the monomer compo ⁇ nent in the presence of the volatile organic solvent, an oxygen permeable polymer material having both extremely excellent oxygen permeability and good processability can be obtained, to accomplish this invention.
  • this invention comprises a process for preparation of an oxygen permeable polymer material, which comprises mixing a monomer component comprising one or more polymer- izable monomer (s) represented by formula (1) shown below and/or one or more polymerizable monomer(s) represented by formula (2) shown below and one or more crosslinkable monomer(s) with a volatile organic solvent having compati ⁇ bility, and then polymerizing the mixture while removing a substantial portion of the above volatile organic solvent from a polymerization system,
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 may be the same or different from each other and each represent an alkyl group, a fluoroalkyl group, a phenyl group, a vinyl group, a hydrogen atom, provided that R 1 and R 2 , R 3 and R 4 or R 5 and R 6 cannot be hydrogen atoms at the same time,
  • Y 1 , Y 2 and Y 3 may be the same or different from each other and are each an alkyl group, a fluoroalkyl group, a phenyl group, a vinyl group or a hydrogen atom, provided that the case where no less than two of Y 1 , Y 2 and Y 3 are hydrogen atoms is excluded,
  • Z represents an alkyl group, a fluoroalkyl group, a tri— alkylsilylalkylene group or a hydrogen atom, and k is an integer from 0-100, preferably 0-20,
  • R 7 represents an alkyl group, a fluoroalkyl group, a fluorine atom or a hydrogen atom
  • R 8 represents a hydrogen atom or an alkyl group, preferably a Ci to C20 alkyl group; or a fluoroalkyl group; preferably a Ci to C20 fluoroalkyl group bonded through a divalent hydrocarbon group, preferably a C to C4 hydrocarbon group; or an aminoalkyl, hydroxyalkyl or epoxyalkyl group; prefer ⁇ ably a Ci to Cio aminoalkyl, a C to Cio hydroxyalkyl or a Ci to C o epoxyalkyl group; a C3 to CQ monocyclic or a C ⁇ to C16 bi- or tricyclic hydrocarbon group; an arylalkyl group; or an aryl group. (Best modes for practicing the invention)
  • X in formula (1) includes a divalent hydrocarbon group or a divalent oxahydrocarbon group which is unsubstituted or substituted by hydroxy group, preferably a Ci to C o alkyl- ene group or a C 4 to Cio oxaalkylene group unsubstituted or substituted by hydroxy group, for example, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group and an octylene group, and the divalent hydrocarbon group of R 8 in formula (2) includes a Ci to C 4 alkylene group such as a methylene group, an ethylene group, a propylene group and a butylene group; a glycerol group and a propylglycerol group.
  • the alkyl group includes, for exam ⁇ ple, linear or branched alkyl groups, preferably Ci - C20 linear or branched alkyl, more preferably Ci - Cio linear or branched alkyl, further preferably Ci - C5 linear or branched alkyl, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, an n- pentyl group, an isopentyl group, a neo-pentyl, a hexyl group, a heptyl group, an oct l group, a 2-ethylhexyl group, a nonyl group, a de
  • R 1 to R 6 or Y 1 to Y 3 in for- mula (1) and R 7 and R 8 in formula (2) may be the same or different from each other, respectively and when k in for ⁇ mula (1) is 2-100, plural -Si(R 3 ) (R 4 )-0- groups may be the same or different from each other.
  • polymerizable monomer represented by formula (1) examples include siloxanyl monomethacrylates or siloxanyl monoacrylates such as pentamethyldisiloxanyl- methyl methacr late, pentamethyldisiloxanylmethyl acrylate, pentamethyldisiloxanylpropy1 methacrylate, pentamethyldi- siloxanylpropyl acrylate, methylbis(trimethylsiloxy) silyl- propyl methacrylate, methylbis (trimethylsiloxy) silylpropyl acrylate, tris (trimethylsiloxy)silylpropyl methacrylate, tris (trimethylsiloxy) silylpropyl acrylate, methylbis (tri ⁇ methylsiloxy) silylpropylgl cerol methacrylate, methylbis- (trimethylsiloxy) silylpropylglycerol acrylate, tris (tri ⁇ methylsiloxy) silylpropylpropy
  • specific examples of the polymerizable monomer repre ⁇ sented by formula (2) include fluoromethacrylates or fluoroacrylates such as 2,2,2-trifluoroethyl methacrylate, 2,2,2-trifluoroethyl acrylate, 2,2,2-trifluoroethyl- ⁇ - fluoroacrylate, 2,2, 2-trifluoroethyl- ⁇ -trifluoromethyl acrylate, 2,2,3, 3-tetrafluoropropyl methacrylate, 2,2,3,3- tetrafluoropropyl acrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 2,2,2, 2*,2',2'-hexafluoroisopropyl methacrylate, 2 ,2,2,2', 2', 2'- hexafluoroisopropyl acrylate, 2,2,3,4, 4, 4-hexafluorobut
  • preferred monomers are siloxanyl monomethacrylates or siloxanyl monoacrylates such as pentamethyldisiloxanyl- methyl methacrylate, pentamethyldisiloxanylmethyl acrylate, pentamethyldisiloxanylpropyl methacrylate, pentamethyl- disiloxanylpropyl acrylate, methylbis (trimethylsiloxy) - silylpropyl methacrylate, methylbis (trimethylsiloxy) silyl ⁇ propyl acrylate, tris (trimethylsiloxy) silylpropyl meth- acrylate and tris (trimethylsiloxy) silylpropyl acrylate; fluorosiloxanyl methacrylates or fluorosiloxanyl acrylates such as (3,3,3-trifluoropropyldimethylsiloxy)bis (trimethyl ⁇ siloxy) silylmethyl methacrylate, (3,3,3-trifluoropropyldimethylsil
  • the crosslinkable monomer in this invention is a poly- functional compound having two or more polymerizable unsaturated groups which can be copolymerized with the polymerizable monomer represented by formula (1) or formula (2) .
  • this crosslinkable monomer does not include a compound having a vinyl group bonded to an Si atom among the polymerizable monomers represented by formula (1) .
  • crosslinkable monomer examples include polyfunctional methacrylates or polyfunctional acrylates each having or not having a fluorine atom, such as ethylene glycol dimethacrylate, ethylene glycol diacryl- ate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, propylene glycol dimeth ⁇ acrylate, propylene glycol diacrylate, 1, 4-butanediol di- methacrylate, 1,4-butanediol diacrylate, neopentyl glycol dimethacryalte, neopentyl glycol diacrylate, trimethylol- propane trimethacrylate, trimethylolpropane triacrylate, bisphenol A dimethacrylate, bisphenol A diacrylate, bistri- fluoromethyl bisphenol A dimethacrylate
  • preferred monomers are polyfunctional methacrylates such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1, 4-butanediol dimethacrylate, neo ⁇ pentyl glycol dimethacrylate, trimethylolpropane trimeth- acrylate and bisphenol A dimethacrylate; and siloxanyl dimethacrylates of
  • the copolymerization ratio of the polymerizable monomer(s) represented by formula(e) (1) and/or (2) and the crosslink- able monomer in this invention is generally 99.5/0.5 to 5/95, preferably 99/1 to 10/90 in terms of weight ratio.
  • this vinyl group can be also polymerized so that it is desired that the copolymerization ratio of the above crosslinkable monomer is controlled depending on the desired crosslinking degree of a polymer material to be obtained.
  • a polymerizable monomer other than the above-mentioned may be used in combination, if desired.
  • a hydrophilic monomer such as acrylic acid, methacrylic acid,* vinyl pyri- dine, N-vinyl-2-pyrrolidone and 2-hydroxyethyl methac- X. - ate, hydrophilicity can be imparted on the surface of a polymer material to be obtained.
  • the volatile organic solvent in this invention is an or ⁇ ganic solvent which does not substantially inhibit polymer- ization reaction nor participate the reaction and has com ⁇ patibility.
  • the compatibility means compatibility with both the monomer component and the resulting copoly ⁇ mer.
  • preferred are those hav ⁇ ing a boiling point of 150"C or lower.
  • volatile organic solvent examples include saturated hydrocarbons such as n-pentane, n-hexane, n-heptane r 2-methylhexane . , 2,4-dimethylpentane, cyclopen- tane and methylcyclopentane; unsaturated hydrocarbons such as 1-hexene, 1-heptene, cyclohexene, benzene and toluene; halogenated hydrocarbons such as dichloromethane, chloro ⁇ form, carbon tetrachloride, fluorobenzene and hexafluo- robenzene; ethers such as diethyl ether, diisopropyl ether, ethyl vinyl ether and tetrahydrofuran; and acetates such as ethyl acetate, n-propyl acetate and n-butyl acetate.
  • saturated hydrocarbons such as n-pentane,
  • the volatile organic solvents in this invention may be used singly or in combination of two or more kinds.
  • the amount of the volatile organic solvent to be used in this invention is generally 5—200 parts by weight, prefer ⁇ ably 5-100 parts by weight based on 100 parts by weight of all monomer component. If the amount of the volatile organic solvent to be used is less than 5 parts by weight, oxygen permeability of a polymer material obtained may not be improved sufficiently, while if it exceeds 200 parts by weight, a polymer material obtained by polymerization may be easily deformed by shrinkage to lower processability.
  • the polymerization in this invention is carried out gener- ally by radical polymerization, and there may be used meth ⁇ ods such as
  • ® a method in which polymerization is carried out by using a thermal polymerization initiator such as benzoyl peroxide and azobisisobutyronitrile, for example, in an amount of 0.01—5 parts by weight based on 100 parts by weight of all monomer component and, if necessary, raising a polymerization temperature stepwise,
  • a thermal polymerization initiator such as benzoyl peroxide and azobisisobutyronitrile
  • ⁇ a method in which polymerization is carried out by using a photopolymerization initiator such as benzoin, benzophenone and ichler's ketone, for example, in an amount of 0.01-5 parts by weight based on 100 parts by weight of all monomer component, irradiating UV rays and, if necessary, raising a polymerization temperature step- wise,
  • a photopolymerization initiator such as benzoin, benzophenone and ichler's ketone
  • ® a method in which polymerization is carried out by using a thermal polymerization initiator and a photopoly- erization initiator in combination under irradiation of UV rays and, if necessary, raising a polymerization tempera ⁇ ture stepwise, ⁇ a method in which polymerization is carried out under irradiation of, e.g. UV rays.
  • thermal polymerization initiator When polymerization is carried out in the presence of a thermal polymerization initiator by raising a polymeriza ⁇ tion temperature stepwise, two or more kinds of thermal polymerization initiators having different decomposition temperatures may be used in combination.
  • polymerization is carried out by using a thermal polymerization initiator and a photopolymerization initiator in combination, irradiating UV rays under atmosphere of an inactive gas such as nitro ⁇ gen, and raising a polymerization temperature stepwise.
  • Polymerization is preferably carried out at a temperature ranging from 0 to 150 ° C and, in the initial polymerization stage, preferably at a temperature ranging from 0 to 30 'C. It is also preferred to raise the temperature gradually from the intermediate stage to the final stage of the poly ⁇ merization. Polymerization is preferably carried out at atmospheric pressure. Polymerization time depends on the rate-determining step. An inert gas, e.g. nitrogen gas may be passed through to remove volatile organic solvents, even after termination of polymerization. In total, 4 to 48 hours are usually preferred.
  • An inert gas e.g. nitrogen gas may be passed through to remove volatile organic solvents, even after termination of polymerization. In total, 4 to 48 hours are usually preferred.
  • the velocity of gas flow is preferably 0.1 to 1 liter/min in the initial polymerization stage, and the gas flow may be gradually increased towards the final polymerization stage, e.g. to about 5 liter/min.
  • the polymerization while removing a sub- stantial portion of the volatile organic solvent from a polymerization system means that at least 70 % by weight or more, preferably 80 % by weight or more of the solvent mixed with the monomer component before initiation of poly ⁇ merization is removed during polymerization.
  • the solvent still remaining after the polymerization can be removed almost completely by a suitable method such as a method of volatilization under reduced pressure and a method of evap ⁇ oration by heating.
  • the removing rate of the solvent may be constant, or the removing rate of the solvent may be increased or decreased gradually.
  • the removing rate of the solvent may be the same at the respec ⁇ tive stages, it may be increased successively or decreased successively at the respective stages, or further the removing rate may be the highest or the lowest at the middle stage of polymerization among the respective stages.
  • a polymerization vessel or polymeriza- tion device which can remove the volatile organic solvent during polymerization should be used.
  • a polymeriza— tion vessel or polymerization device includes, for example, those having gaps through which the above organic solvent can be volatilized during polymerization, or those which are tightly sealed, but can be opened at a suitable stage during polymerization.
  • a method of carrying out polymerization while removing a volatile organic solvent has conventionally been used as a method of controlling a polymerization temperature in gen- eral solution polymerization and precipitation polymeriza ⁇ tion, using an organic solvent.
  • said method is a technique which has not yet been attempted in the prepara ⁇ tion of an oxygen permeable polymer material such as oph ⁇ thalmic materials, which require precision processing.
  • the polymerization in this invention can be carried out by, for example, a process for the preparation of a copolymer with a lump shape in which a mixture of a monomer component and a volatile organic solvent is polymerized while remov- ing a substantial portion of the volatile organic solvent.
  • the copolymer with a lump shape obtained is cut and polished into a predetermined shape such as contact lenses and intraocular lenses.
  • the polymer material obtained according to this invention exhibits machinability and polishability similar to those of conventional hard lenses comprising polymethyl meth ⁇ acrylate. Thus, the polymer material can be easily pro- Stepd into a molded product with a predetermined shape
  • hydrophilicity is imparted to the sur ⁇ face by alkaline treatment, plasma treatment using, e.g. oxygen and nitrogen, plasma polymerization treatment using a hydrophilic group-containing compound, vapor deposition, sputtering or ion plating treatment using, e.g. an inor ⁇ ganic oxide, or the like.
  • Oxygen permeability The polymer material is processed into contact lenses and measured at 35°C in a 0.9 % by weight physiological saline solution by using a scientific research type film oxygen permeation meter manufactured by Rika Seiki Kogyo.
  • Discs comprising the polymer material are measured at a wavelength of 500-600 nm by using a double beam spectrophotometer Model 200-20 manu ⁇ factured by Hitachi, Ltd.
  • ⁇ - Cut surface has luster, but is slightly opaque
  • 20 parts by weight of 2,2, 2-trifluoroethyl methacrylate, 30 parts by weight of methyl methacrylate, 50 parts by weight of n-hexane, and 0.1 part by weight of benzoin methyl ether and 0.1 part by weight of azobisisobutyronitrile as poly ⁇ merization initiators are mixed sufficiently at room tem- perature, and the mixture is poured into a polymerization vessel made of polyethylene (radius: 2 cm, height: 4 cm) of which the upper side is opened. This polymerization vessel is placed in another polymerization vessel (inner volume: 500 cm 3 ) to which nitrogen can be introduced.
  • a reaction mixture having the same composition as that of Example 1 is poured into a glass tube and replacement with nitrogen is carried out.
  • polymerization is carried out to obtain a copolymer block.
  • the copolymer block is dried under vacuum at 120 * C for 48 hours to remove n-hexane.
  • the copolymer block after removing n-hexane is deformed greatly and cannot maintain its columnar shape, whereby it is impossible to mount it on a lathe for cutting.
  • the oxygen permeable polymer material obtained according to the method of this invention has extremely high oxygen permeability and also excellent machinability and polisha- bility. Further, in this invention, a substantial portion of a volatile organic solvent is removed during polymeriza ⁇ tion so that a step of removing a solvent after polymeriza ⁇ tion is not required or a step of removing a solvent can be simplified. Thus, the oxygen permeable polymer material obtained according to this invention is extremely useful as ophthalmic materials which require precision processing such as contact lenses and intraocular lenses, and accord ⁇ ing to this invention, such ophthalmic materials can be prepared extremely rationally.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Optics & Photonics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Physics & Mathematics (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Eyeglasses (AREA)
  • Materials For Medical Uses (AREA)
  • Prostheses (AREA)
PCT/JP1993/000635 1992-05-14 1993-05-14 Process for preparation of oxygen permeable polymer material WO1993023773A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP4/146771 1992-05-14
JP4146771A JPH05310837A (ja) 1992-05-14 1992-05-14 酸素透過性高分子材料の製造方法

Publications (1)

Publication Number Publication Date
WO1993023773A1 true WO1993023773A1 (en) 1993-11-25

Family

ID=15415179

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1993/000635 WO1993023773A1 (en) 1992-05-14 1993-05-14 Process for preparation of oxygen permeable polymer material

Country Status (3)

Country Link
JP (1) JPH05310837A (ja)
AU (1) AU4087993A (ja)
WO (1) WO1993023773A1 (ja)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001071392A1 (en) * 2000-03-24 2001-09-27 Novartis Ag Crosslinkable or polymerizable prepolymers
WO2011045299A1 (en) 2009-10-12 2011-04-21 Sauflon Cl Limited Method of making a contact lens
US8044111B2 (en) 2007-11-30 2011-10-25 Novartis Ag Actinically-crosslinkable silicone-containing block copolymers
US8071658B2 (en) 2007-03-22 2011-12-06 Novartis Ag Prepolymers with dangling polysiloxane-containing polymer chains
US8071703B2 (en) 2007-03-22 2011-12-06 Novartis Ag Silicone-containing prepolymers with dangling hydrophilic polymer chains
US8506856B2 (en) 2007-12-10 2013-08-13 Novartis Ag Method for making silicone hydrogel contact lenses
US8524800B2 (en) 2006-12-13 2013-09-03 Novartis Ag Actinically curable silicone hydrogel copolymers and uses thereof
US8557940B2 (en) 2010-07-30 2013-10-15 Novartis Ag Amphiphilic polysiloxane prepolymers and uses thereof
US8993651B2 (en) 2010-10-06 2015-03-31 Novartis Ag Polymerizable chain-extended polysiloxanes with pendant hydrophilic groups

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6271281B1 (en) * 1999-08-26 2001-08-07 Medennium, Inc. Homopolymers containing stable elasticity inducing crosslinkers and ocular implants made therefrom
SE0001352D0 (sv) * 2000-04-12 2000-04-12 Pharmacia & Upjohn Bv Injectable intraocular accommodating lens
JP5433999B2 (ja) * 2008-07-16 2014-03-05 Ｊｓｒ株式会社 フォトレジスト用樹脂の製造方法
JP6305323B2 (ja) * 2014-11-28 2018-04-04 信越化学工業株式会社 共重合体および眼科デバイス
CN113943933B (zh) * 2020-07-16 2023-09-29 江苏菲沃泰纳米科技股份有限公司 多层结构的复合膜及其制备方法和产品

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3350216A (en) * 1964-05-11 1967-10-31 Dow Corning Hydrophilic contact lens and method of making same
US4110264A (en) * 1976-10-29 1978-08-29 Neefe Charles W Permeable polymethylmethacrylate contact lens
US4604440A (en) * 1984-04-06 1986-08-05 Ceskoslovenska Akademie Ved Hydrophilic three dimensional polymer and a method for production thereof
US4613657A (en) * 1985-02-20 1986-09-23 Central Glass Company, Limited Method for anionic homopolymerization of α-trifluoromethylacrylate

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3350216A (en) * 1964-05-11 1967-10-31 Dow Corning Hydrophilic contact lens and method of making same
US4110264A (en) * 1976-10-29 1978-08-29 Neefe Charles W Permeable polymethylmethacrylate contact lens
US4604440A (en) * 1984-04-06 1986-08-05 Ceskoslovenska Akademie Ved Hydrophilic three dimensional polymer and a method for production thereof
US4613657A (en) * 1985-02-20 1986-09-23 Central Glass Company, Limited Method for anionic homopolymerization of α-trifluoromethylacrylate

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001071392A1 (en) * 2000-03-24 2001-09-27 Novartis Ag Crosslinkable or polymerizable prepolymers
US7091283B2 (en) 2000-03-24 2006-08-15 Novartis Ag Crosslinkable prepolymers from a hydrophilic monomer and a hydrophobic crosslinker
US7268189B2 (en) 2000-03-24 2007-09-11 Novartis Ag Polymers
US7566754B2 (en) 2000-03-24 2009-07-28 Novartis Ag Process for making contact lenses from prepolymers
US8721945B2 (en) 2006-12-13 2014-05-13 Novartis Ag Actinically curable silicone hydrogel copolymers and uses thereof
US8524800B2 (en) 2006-12-13 2013-09-03 Novartis Ag Actinically curable silicone hydrogel copolymers and uses thereof
US20120046382A1 (en) * 2007-03-22 2012-02-23 Zhou Jian S Prepolymers with dangling polysiloxane-containing polymer chains
US8071703B2 (en) 2007-03-22 2011-12-06 Novartis Ag Silicone-containing prepolymers with dangling hydrophilic polymer chains
US8071658B2 (en) 2007-03-22 2011-12-06 Novartis Ag Prepolymers with dangling polysiloxane-containing polymer chains
US8263679B2 (en) * 2007-03-22 2012-09-11 Novartis Ag Prepolymers with dangling polysiloxane-containing polymer chains
US8211955B2 (en) 2007-11-30 2012-07-03 Novartis Ag Actinically-crosslinkable silicone-containing block copolymers
US8044111B2 (en) 2007-11-30 2011-10-25 Novartis Ag Actinically-crosslinkable silicone-containing block copolymers
US8506856B2 (en) 2007-12-10 2013-08-13 Novartis Ag Method for making silicone hydrogel contact lenses
WO2011045299A1 (en) 2009-10-12 2011-04-21 Sauflon Cl Limited Method of making a contact lens
US8557940B2 (en) 2010-07-30 2013-10-15 Novartis Ag Amphiphilic polysiloxane prepolymers and uses thereof
US8987403B2 (en) 2010-07-30 2015-03-24 Novartis Ag Amphiphilic polysiloxane prepolymers and uses thereof
US9341744B2 (en) 2010-07-30 2016-05-17 Novartis Ag Amphiphilic polysiloxane prepolymers and uses thereof
US8993651B2 (en) 2010-10-06 2015-03-31 Novartis Ag Polymerizable chain-extended polysiloxanes with pendant hydrophilic groups
US9109091B2 (en) 2010-10-06 2015-08-18 Novartis Ag Polymerizable chain-extended polysiloxanes with pendant hydrophilic groups

Also Published As

Publication number Publication date
AU4087993A (en) 1993-12-13
JPH05310837A (ja) 1993-11-22

Similar Documents

Publication Publication Date Title
JP2802287B2 (ja) コンタクトレンズ材料とその製法
AU602659B2 (en) Fluorine containing polymeric compositions useful in contact lenses
US4996275A (en) Fluorine containing polymeric compositions useful in contact lenses
EP1355963B1 (en) Polymeric biomaterials containing silsesquioxane monomers
US5331067A (en) Silicone-containing contact lens polymers, oxygen permeable contact lenses and methods for making these lenses and treating patients with visual impairment
WO1993023773A1 (en) Process for preparation of oxygen permeable polymer material
GB2119951A (en) Oxygen permeable hard contact lens of silicon copolymer
GB2153371A (en) Oxygen permeable hard contact lens
JPH03207744A (ja) 酸素透過性コンタクトレンズ材料
US5855825A (en) Process for producing ocular lens and ocular lens produced by the process
GB2152522A (en) Contact lens materials
US4769431A (en) Polyacryloxyalkylsilanol lens composition, articles and method of manufacture
JP4144088B2 (ja) コンタクトレンズ用ポリマーおよびそれを用いたコンタクトレンズ
EP0387706B1 (en) Oxygen permeable hard contact lens
US5019628A (en) Silicone containing acrylic star polymers
EP0219884B1 (en) Hard contact lens material
JP2954691B2 (ja) 酸素透過性重合体の製造法
EP0478261A2 (en) Process for producing oxygen-permeable polymer
CA1103838A (en) Polymer for contact lens and contact lens made thereof
US5142009A (en) Hard contact lens material
JP2947915B2 (ja) 酸素透過性高分子材料の製造方法
EP0560620B1 (en) Maleimide polymers and contact lenses from such polymers
EP0446372B1 (en) Contact lens
JP3184211B2 (ja) 酸素透過性高分子材料の製造方法
JP2947911B2 (ja) 酸素透過性高分子材料の製造方法

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU BB BG BR CA CZ FI HU JP KR KZ LK MG MN MW NO NZ PL RO RU SD SK UA US VN

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)

Free format text: PL

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: CA