EP0209597A1 - Lentilles a port prolonge - Google Patents

Lentilles a port prolonge

Info

Publication number
EP0209597A1
EP0209597A1 EP86901227A EP86901227A EP0209597A1 EP 0209597 A1 EP0209597 A1 EP 0209597A1 EP 86901227 A EP86901227 A EP 86901227A EP 86901227 A EP86901227 A EP 86901227A EP 0209597 A1 EP0209597 A1 EP 0209597A1
Authority
EP
European Patent Office
Prior art keywords
monomer
oxygen
hydroxy
monomers
alkyl
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP86901227A
Other languages
German (de)
English (en)
Inventor
Nick Stoyan
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bausch and Lomb Inc
Original Assignee
Bausch and Lomb Inc
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 Bausch and Lomb Inc filed Critical Bausch and Lomb Inc
Publication of EP0209597A1 publication Critical patent/EP0209597A1/fr
Withdrawn legal-status Critical Current

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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/22—Esters containing halogen
    • C08F220/24—Esters containing halogen containing perhaloalkyl radicals
    • 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
    • C08F230/00—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
    • C08F230/04—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
    • C08F230/08—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

  • the present invention is directed to eye-compatible lenses, particularly hard contact lenses having excellent oxygen permeability and wettability.
  • Contact lenses presently on the market are classified into two large groups: soft contact lenses and hard contact lenses.
  • Hard contact lenses are better able than soft contact lenses to retain visual characteristics, but are less comfortable.
  • the art has sought to increase oxygen permeability of hard contact lenses, to extend the length of time they can be worn without causing corneal damage or discomfort.
  • the object of the present invention is to overcome the deficiencies in the state of the art by offering lenses having a high degree of oxygen permeability, excellent wettability, and, if desired, ultraviolet absorption.
  • the primary benefit of UV absorptivity is the resistance to user development of cataracts.
  • the present invention is directed to eye-compatible, oxygen-permeable lenses of excellent wettability, formed of copolymers of an organosilicon monomer system which preferably comprises an organosilane or an organosiloxane of the general formula:
  • R 1 is hydrogen or methyl
  • a is 0 or 1
  • b is from 1 to about 4
  • X is an organosilicon moiety containing up to about 16 silicon atoms.
  • At least a portion, and as much as 100 percent, of the organosilicon monomer system is a hydroxyorganosilicon monomer which is a monomer having at least one hydroxyl group bonded to silicon.
  • a second component is a fluoroorgano monomer of the formula:
  • M 1 is hydrogen, alkyl, fluoroalkyl, alkyl carboxy, carboxy ester, alkyl carboxy ester, fluorinated carboxy ester, fluorinated alkyl carboxy ester, cyano, or phenyl
  • M is hydroxy alkyl, alkyl ether, or hydroxy alkyl ether
  • a is as defined above
  • c is from 0 to 4
  • y is a fluorocarbon group, preferably containing from about 2 to about 21 fluorine atoms.
  • At least one hydrophilic monomer is included, preferably an unsaturated carboxylic acid capable of inducing wettability, and is present in an amount sufficient to provide in the resultant polymer a receding contact angle of about 45° or less.
  • Methacrylic acid is preferred.
  • a UV-absorbing agent if desired, may be included.
  • the UV-absorbing agent may be a UV- absorbing monomer, preferably a hydroxybenzophenone or a benzotriazole compound of the formula:
  • R 1 , a and b are as defined above, d is 1 or 2, and Z is:
  • the UV-absorbing monomer may be a benzotriazole of the formula:
  • UV-absorbing agents may be non-reactive homopolymers and copolymers preferably containing the UV monomers which are added to the monomer system undergoing reaction, and which become physically entrained in the formed lens.
  • a final component is a crosslinking monomer which is a crosslinking agent, preferably an organosilicon monomer, present in an amount up to about 5, preferably up to about 2, percent by weight based on the total weight of the monomers.
  • the total organosiliconmonomer content of the polymer may range from about 10 to about 40 percent by weight, preferably from about 15 to about 35 percent by weight based on the total weight of the monomers.
  • the hydrophilic monomer may be present in an amount of from about 1 to about 15 percent by weight, preferably from about 2 to about 10 percent by weight based on the total weight of the monomers.
  • the UV-absorbing agent if present, whether monomeric or not, may be present in an amount of from about 0.1 to about 20 percent, preferably from about 2 to about 10 percent by weight based on the total weight of the monomers and/or agent, and the crosslinking monomer may be present in an amount up to about 2 percent by weight based on the total weight of the monomers.
  • the balance of the monomer system may be solely the fluoroorgano monomers. It is desired that the lens have a Shore D hardness greater than about 78, preferably from about 80 to about 85. There may be desirably included other monomers, such as acrylates, methacrylates, itaconic esters, styrenes, fluorinated styrenes, alkyl styrenes, fluorinated alkyl styrenes, and the like, present in a concentration of up to about 50 percent by weight of the concentration of the fluoroorgano monomer, typically up to about 5 percent by weight based on the total weight of the monomers which can effectively be used to modify properties such as hardness, machinability, wettability, oxygen permeability, and the like.
  • monomers such as acrylates, methacrylates, itaconic esters, styrenes, fluorinated styrenes, alkyl styrenes, fluorinated alky
  • the organosilicon content of the monomer system must be high, typically in the range of from 25 percent to 30 percent or more by weight based on the total weight of the monomers.
  • Organosilicon monomer content can be advantageously reduced, however, by inclusion of high-performance fluoroorganomonomers such as hexafluoroisopropyl esters of an unsaturated carboxylic acid containing from 2 to about 6 carbon atoms and 1 or 2 carboxyl groups, preferably hexafluoroisopropylmethacrylate.
  • high-performance fluoroorganomonomers such as hexafluoroisopropyl esters of an unsaturated carboxylic acid containing from 2 to about 6 carbon atoms and 1 or 2 carboxyl groups, preferably hexafluoroisopropylmethacrylate.
  • the present invention is directed to eye-compatible, i.e., ocular-compatible, lenses, in particular, hard contact lenses formed of an interpolymerized amount of an organosilicon monomer system containing at least one hydroxyorganosilicon monomer, at least one fluoroorgano compound, at least one monomeric unsaturated carboxylic acid hydrophilic monomer, and, if desired, a UV-absorbing agent, which may be a monomer formed of a monomer which is a benzotriazole and/or benzophenone and at least one crosslinking monomer.
  • reactive monomers such as acrylates, methacrylates, itaconic esters, styrenes, fluorinated styrenes, alkyl styrenes, fluorinated alkyl styrenes, and the like, may be included as part of the po ⁇ ymerizable composition, to achieve a lens of desired hardness for machinability, wettability, oxygen permeability, and the like, and can be present in an amount of up to about 50 percent by weight of the fluoroorgano monomer content of the polymers.
  • R 1 is hydrogen or methyl
  • a is 0 or 1
  • b is from 1 to about 4
  • X is an organosilicon moiety containing up to about 26 silicon atoms.
  • At least a portion or all of the organosilicon monomer system is a hydroxyorganosilicon monomer, namely, a monomer having at least one hydroxyl group bonded to silicon.
  • Preferred organosilicon compounds are acrylates and methacrylates of the general formula:
  • R 1 , a, and b are as defined above.
  • the representative monomers included are: tris(trimethylsiloxy)silylpropylmethacrylate, 1,3-bis( ⁇ -methacryloxypropyl)-1,1,3,3-tetra(trimethylsiloxy)disiloxane, vinyl di(trimethylsiloxy)silylpropylmethacrylate, pentamethyldisiloxy- ⁇ -methacryloxypropylsilane, trimethylsilylpropylmethacrylate, methyl di(trimethylsiloxy)silylpropylmethacrylate, and tris(trimethylsiloxy)silylpropylglycerolmethacrylate, and the like.
  • Tris(trimethylsiloxy)- ⁇ -methacryloxypropylsilane is presently preferred.
  • Another important monomer is 1,3-bis-( ⁇ -methacryloxypropyl)-1,1,3,3-tetra(trimethylsiloxy)disiloxane, as it serves as a crosslinking agent without sacrificing oxygen permeability.
  • concentration may vary from about 0.1 to about 2 parts by weight based on the total weight of the reactants.
  • Representative hydroxyorganosilicon monomers include hydroxy-di(trimethylsiloxy)silylpropyl methacrylate, hydroxy-di(trimethylsiloxy)-y-methacryloxypropyl silane, hydroxy-methyl(trimethylsiloxy)methacryloxymethyl silane, hydroxy-methyl(trimethylsiloxy)methacryloxyethyl silane, hydroxy-methyl(trimethylsiloxy)methacryloxypropyl silane, hydroxy-di(trimethylsiloxy)-£-methacryloxyethyl silane, hydroxy-di(trimethylsiloxy)-methacryloxy methyl silane, hydroxy-(trimethylsiloxy)-(pentamethyIdisiloxy)-methacryloxy-methyl silane, hydroxy-(trimethylsiloxy)-(pentamethyldisiloxy)- ⁇ -methacryloxyethyl silane, and the like. Hydroxy-di(trimethylsiloxy)s
  • organosilicon monomers are disclosed in U.S. Patents 4,152,508 to Ellis; 4,153,641 to Deichert et al; 4,189,546 to Deichert et al; and 4,463,149 to Ellis, each incorporated herein by reference. While total concentrations of organosilicon monomers may range from about 10 to about 40 parts by weight based on the total weight of the monomers, the preferred range is from about 15 to about 35 parts by weight. Oxygen per meability (all other factors being constant) will increas with an increase in organosilicon monomer content.
  • the lens becomes more difficult to machine, requiring inclusion of monomers such as acrylates, methacrylates and the like, may be employed as part of the monomer system to yield a lens having a Shore D hardness greater than about 78, preferably from about 80 to about 85.
  • Oxygen permeability and wettability of the lens is enhanced by the presence of the hydroxyorganosilicon monomer.
  • concentration of the hydroxyorganosilicon monomer is from about 0.1 to about 10 percent by weight of the total monomer, it may be the exclusive organosilicon monomer, except for any multifunctional organosilicon monomer used as a crosslinking monomer.
  • the fluoroorgano monomers utile in the practice of the instant invention are generally compounds of the formula:
  • M 1 is hydrogen, alkyl, fluoroalkyl, alkyl carboxy, carboxy ester, alkyl carboxy ester, fluorinated carboxy ester, fluorinated alkyl carboxy ester, cyano, or phenyl
  • M is hydroxy alkyl, alkyl ether, or hydroxy alkyl ether
  • a is as defined above
  • c is from 0 to 4
  • Y is a fluorocarbon group.
  • Y has the general formula:
  • High-performance fluorinated compounds are hexafluoroisopropyl esters of unsaturated carboxylic acids containing from 2 to about 10 carbon atoms and 1 or 2 carboxyl groups.
  • Illustrative of fluoroorgano monomers are: 2,2,2-trifluoroethylmethacrylate, hexafluorobutylmethacrylate, hexafluoroisopropylmethacrylate, pentafluoro-n-propylmethacrylate, and the like.
  • Hexafluoroisopropylmethacrylate is the preferred monomer for oxygen permeability, with 2,2,2-trifluoroethylmethacrylate being preferred for cost. Perfluoro or fluorinated styrenes may also be used.
  • Hydrophilic monomers are included in the composition to induce wettability. They preferably comprise an unsaturated carboxylic acid, most preferably methacrylic acid, for compatability of monomers and wearer comfort. Acrylic acid is functional but less desirable. Other monomers such as 2-hydroxyethylmethacrylate, vinyl pyrrolidone, and the like may be used. Concentration may be from about 0.1 to about 15 or more percent by weighty preferably from about 2 to about 10 percent by weight based on the total weight of the monomers.
  • hydrophilic monomer present depends on whether a UV-absorbing agent, as described below, is employed, as the latter also has the capability of being hydrophilic. If a UV-absorbing agent is employed, whether in monomeric or polymeric form, its concentration may range from about 0.1 to about 20 percent by weight, preferably from about 2 to about 10 percent by weight based on the total weight of the monomers and agent.
  • the UV-absorbing agents used herein cooperate with the hydrophilic monomer to induce wettability and antisepticability, i.e., self-sterilizable, in consequence of hydroxy-substituted benzene moieties.
  • the UV-absorbing agents absorb in the range of from about 300nm to about 450nm, preferably with no less than about 70% UV radiation at 370nm.
  • Preferred UV-absorbing agents are, or are formed of, monomers of the formula:
  • R 1 is hydrogen or methyl, a is 0 or 1, b is from about 1 to about 3, d is 1 or 2, and Z is:
  • R 2 is hydrogen; an alkyl, preferably a C 1 -C 5 alkyl or hydroxyl, and c is 1 or 2.
  • R 2 is hydrogen; an alkyl, preferably a C 1 -C 5 alkyl or hydroxyl, and c is 1 or 2.
  • R 1 and R 2 are as defined above, preferably a C 1 - C 10 alkyl, and R 3 is H, alkyl, preferably a C 1 -C 10 alkyl, or hydroxyl.
  • Preferred UV-absorbing monomers for forming agents include:
  • the hard contact lenses of the instant invention are formulated to have high oxygen permeability (Dk) of at least about 15 and preferably greater than 50, as expressed in units of 10 -11 (cm 2 /sec.) (ml O 2 /ml x mm Hg) and as determined at 35°C. Values are achieved using high concentrations of the organosilicon monomer and/or selection of the fluoroorgano monomer. With compositions of high organosilicon-monomer content there are displayed increased brittleness and a reduction in capability to undergo machining.
  • Dk oxygen permeability
  • At least one crosslinking agent such as a multi-functional organosilicon monomer, a fluoroorgano monomer, an acrylate and/or a methacrylate, is employed in an amount sufficient to control hardness of the lens in the range of Shore D hardness of from about 80 to about 85.
  • a highly multi-functional organosilicon monomer is preferred, as it does not interfere with oxygen permeability.
  • Other crosslinking agents which may be used include ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, and the like.
  • Lens formation is by free radical polymerization such as azobisisobutyronitrile (AIBN) and peroxide catalysts under conditions set forth in U.S. Patent 3,808,179, incorporated herein by reference. Colorants and the like may be added prior to monomer polymerization. It is preferred to form the lens base in sheet form between layers of a non-adherent surface. The sheet is cut into smaller lense precursors from which the lens is ground to user specifications. Spin-casting, as described for instance in U.S. Patent 3,408,429, incorporated herein by reference, may also be used.
  • AIBN azobisisobutyronitrile
  • peroxide catalysts under conditions set forth in U.S. Patent 3,808,179, incorporated herein by reference. Colorants and the like may be added prior to monomer polymerization. It is preferred to form the lens base in sheet form between layers of a non-adherent surface. The sheet is cut into smaller lense precursors from which the lens is ground to user specifications. Spin-casting,
  • Oxygen permeability values were determined using a test method developed by Dr. Irving Fatt of Berkeley, California, and disclosed in the paper, entitled: "Oxygen Transmissibility and Permeability of Gas Permeable Hard Contact Lenses and Materials” by Irving Fatt, Ph.D., International Contact Lens Clinic, Vol. II, No. 3, March 1984.
  • the instrument was a polarographic cell with a curved surface for finished lenses, polarographic amplifier, recorder and a constant temperature chamber equipped with a temperature control unit. The measurements were made at 35°C and the units of oxygen permeability (Dk) are (cm /sec.) (ml O 2 /ml x mm Hg).
  • the water wettability of the contact lense material was determined by the sesile drop method using a Rame-Hart goniometer with an environmental chamber. Both the advancing and the receding contact angles were determined. The hardness was measured as Shore D at 22°C using a hardness tester, and percent light transmission was measured using a recording spectrophotometer.
  • the absorption spectra of the copolymer were determined on a "Perkin Elmer” UV-Vis spectrophotometer using 0.1-0.15mm-thin optically polished discs.
  • the amount of materials extractable from the lenses were evaluated by first storing them in a saline solution for 10 days at 35°C. The lenses were then rinsed with distilled water, dried, weighed, and placed in stoppered, 25cc volumetric flasks, again containing saline as the extracting medium.
  • the saline was analyzed daily for its extracted ultraviolet absorber by placing 4cc of the extract in a spectrophotometer cell and determining the absorption at 320nm. The absorption values were compared against the calibration curve made for the pure ultraviolet absorber.
  • Extractables can also be determined by the Soxhlet extraction method, using water as the solvent. The amount of extractables was determined only for a few of the materials in the Examples. Based on 0.04 gr average lens weight, extractables were found, on the average, to be less than 1 x 10 -4 mc grams/lens/day.
  • the leachability-diffusibility was evaluated by cytotoxicity assayagar overlay method.
  • the assay is based on the method described by Guess, W.L., Rosenbluth, S.A., Schmidt, B., and Autian, J., in "Agar Diffusion Method for Toxicity Screening of Plastics on Cultured Cell Monolayers", J. Pharm. Sci. 54:1545-1547, 1965, incorporated herein by reference, and is designed to detect the response of a mammalian monolayer cell culture to readily diffusible components from materials or test solutions applied to the surface of an agar layer overlaying the monolayer.
  • the response of the cell monolayer is evaluated, with respect to the discoloration of the red-stained monolayer, under and around the sample when the petri dish is viewed against a white background. Loss of color of the stained cells is considered to be a physiologically significant reaction of the cells.
  • the extent of discoloration is confirmed by examination of the monolayer on an inverted microscope, and the extent of lysis of the cells within the discoloration zone is estimated. Typically, discoloration of cells precedes lysis, as manifested by a region and a region showing lysis. A sample is reported as "cytotoxic" only if lysis is observed. Examples 1-11 and Controls A-F Candidate lens compositions were formulated as shown in Table I.
  • the mixture was homogenized, degassed and placed in a polymerization cell made of two glass plates separated by a seal and held together by spring clamps. After filling, the cell was purged with nitrogen, sealed and placed in a circulating water bath at 60oC for 10 hours. After the initial polymerization period, the cell was heated at 80oC for 3 hours, 100oC for one hour, and then allowed to cool to room temperature. The clamps were then removed and the transparent sheet heated for 2 hours at 100oC. The plastic sheet, about 1/4-inch in thickness, was cut into squares, then formed to discs which were used to prepare corneal contact lenses using conventional hard-contact-lens-making equipment. The properties of the lens materials are also shown in Table I.
  • Control A was too brittle to be used as a functional lens, and brittleness was attributed to excessive organosilicon-monomer content.
  • the brittleness of the remaining control was attributed to the level of silicon monomer employed and an excessive amount of a crosslinking and/or wetting monomer.
  • Tris(Trimethylsiloxy)silylprcpylmethacrylate 26 9.5 19 29 17 17 17 19 19 17 17 1,3-bis(J-methacryloxypropyl)-l,l,3,3-tetra(- .04 0.1 0.1 0.1 0.3 0.3 0.3 0.1 0.1 0.3 0.3 trimethylsiloxyldisiloxane Vinyl di(trimethyldiloxy)silylpropylmethacrylate Pentamethyldisiloxy- ⁇ -methacryloxypropylsilane Hydroxy-di(trimethylsiloxy)silylpropylmethacrylate 3.6 0.4 0.9 0.9 2.7 2.7 2.7 0.9 0.9 2.7 2.7 2,2,2-trifluoroethylmethacrylate 85 75 65 73 73 73 75.5 75 Hexafluorobutylmethacrylate 75 Hexafluoroisopropylmethacrylate 75 Methylmethacrylate 55 n-Butylmeth
  • Example 12 Following the procedure of Examples 1-11, an oxygenpermeable copolymer was prepared from a mixture of 22 parts by weight tris(trimethylsiloxy)-3'-methacryloxypropylsilane, 2.7 parts by weight hydroxy-di (trimethylsiloxy)silylpropylmethacrylate, 0.3 parts by weight 1,3 bis(y-methacryloxypropyl)-1,1,3,3-tetra(trimethylsiloxy)disiloxane, 65 parts by weight trifluoroethylmethacrylate, 5 parts by weight 2-hydroxy-4-(2-acryloxyethoxy)benzophenone, 5 parts by weight methacrylic acid, and 0.02 parts by weight AIBN.
  • Table III The properties of this lens material are shown in Table III.
  • Examples 1-11 The procedure of Examples 1-11 was repeated, except that the formulation contained 28.5 parts by weight tris(trimethylsiloxy)- ⁇ -methacryloxypropylsilane, 1.3 parts by weight hydroxy-di (trimethylsiloxy)silylpropylmethacrylate, 0.2 parts by weight 1,3 bis ( ⁇ -methacryloxypropyl)-1,1,3,3-tetra(trimethylsiloxy)disiloxane, 65 parts by weight hexafluoroethylmethacrylate, 5 parts by weight methacrylic acid, and 0.2 parts by weight AIBN. Average oxygen permeability was 398 x 10 -11 (cm 2 /sec.) (ml O 2 /ml x mm Hg).

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Eyeglasses (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Lentilles a port prolongé réalisées par la polymérisation d'un système monomère d'organosilicone, dont au moins une partie est un monomère d'hydroxyorganosilicone, d'un fluoro-organo-monomère, d'un monomère hydrophile et d'un agent de réticulation. Un agent absorbant les rayons UV peut être incorporé.
EP86901227A 1985-01-29 1986-01-28 Lentilles a port prolonge Withdrawn EP0209597A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US69601485A 1985-01-29 1985-01-29
US696014 1985-01-29
US72212185A 1985-04-10 1985-04-10
US722121 1985-04-10
US73538185A 1985-05-17 1985-05-17
US735381 1985-05-17

Publications (1)

Publication Number Publication Date
EP0209597A1 true EP0209597A1 (fr) 1987-01-28

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP86901227A Withdrawn EP0209597A1 (fr) 1985-01-29 1986-01-28 Lentilles a port prolonge

Country Status (3)

Country Link
EP (1) EP0209597A1 (fr)
CA (1) CA1295078C (fr)
WO (1) WO1986004343A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61227509A (ja) * 1985-04-02 1986-10-09 G C Dental Ind Corp 歯科用修復材
AU1156688A (en) * 1987-01-07 1988-07-27 Mei-Zyh Chang Wettable, hydrophilic, soft and oxygen permeable copolymer compositions
WO1991005285A1 (fr) * 1989-09-30 1991-04-18 Hoya Corporation Lentille de contact
GB2249551B (en) * 1990-09-28 1995-03-08 Kansai Paint Co Ltd Cationically electrodepositable finely divided gelled polymers and processes for producing the same
JP3108550B2 (ja) * 1992-11-11 2000-11-13 株式会社メニコン 軟質眼用レンズ材料
JP4066497B2 (ja) * 1998-03-23 2008-03-26 ダイキン工業株式会社 含フッ素共重合体を含んでなる化粧品

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US35080A (en) * 1862-04-29 Improvement in dampers
US4390676A (en) * 1976-11-15 1983-06-28 Schering Corporation Ultraviolet absorbing lenses
AU546039B2 (en) * 1982-05-08 1985-08-08 Menicon Co., Ltd Oxygen permeable hard contact lens
US4419505A (en) * 1982-07-14 1983-12-06 Paragon Optical, Inc. Contact lens composition, article and method of manufacture
US4535138A (en) * 1982-11-01 1985-08-13 Paragon Optical, Inc. Silane ester contact lens composition, article and method of manufacture

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO8604343A1 *

Also Published As

Publication number Publication date
CA1295078C (fr) 1992-01-28
WO1986004343A1 (fr) 1986-07-31

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