US20060211789A1 - Long-wearable soft contact lens - Google Patents

Long-wearable soft contact lens Download PDF

Info

Publication number
US20060211789A1
US20060211789A1 US11/437,732 US43773206A US2006211789A1 US 20060211789 A1 US20060211789 A1 US 20060211789A1 US 43773206 A US43773206 A US 43773206A US 2006211789 A1 US2006211789 A1 US 2006211789A1
Authority
US
United States
Prior art keywords
group
mold
contact lens
lens
monomer
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.)
Abandoned
Application number
US11/437,732
Inventor
Junichi Iwata
Tsuneo Hoki
Seiichirou Ikawa
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.)
CooperVision International Ltd
Original Assignee
Asahi Kasei Aime Co Ltd
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=26580596&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=US20060211789(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Asahi Kasei Aime Co Ltd filed Critical Asahi Kasei Aime Co Ltd
Priority to US11/437,732 priority Critical patent/US20060211789A1/en
Assigned to ASAHIKASEI AIME CO., LTD. reassignment ASAHIKASEI AIME CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HOKI, TSUNEO, IKAWA, SEIICHIROU, IWATA, JUNICHI
Publication of US20060211789A1 publication Critical patent/US20060211789A1/en
Priority to US12/960,236 priority patent/US8637621B2/en
Assigned to COOPERVISION INTERNATIONAL HOLDING COMPANY, LP reassignment COOPERVISION INTERNATIONAL HOLDING COMPANY, LP ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ASAHIKASEI AIME CO., LTD.
Assigned to COOPERVISION INTERNATIONAL LIMITED reassignment COOPERVISION INTERNATIONAL LIMITED ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: COOPERVISION INTERNATIONAL HOLDING COMPANY, LP
Abandoned legal-status Critical Current

Links

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
    • C08F226/00—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/02—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B29D11/00009—Production of simple or compound lenses
    • B29D11/00038—Production of contact lenses
    • B29D11/00125—Auxiliary operations, e.g. removing oxygen from the mould, conveying moulds from a storage to the production line in an inert atmosphere
    • 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
    • C08F226/00—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • C08F226/10—N-Vinyl-pyrrolidone
    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/061—Polyesters; Polycarbonates
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/065—Polyamides; Polyesteramides; Polyimides
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/068—Polysiloxanes
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
    • G02C7/00—Optical parts
    • G02C7/02—Lenses; Lens systems ; Methods of designing lenses
    • G02C7/04—Contact lenses for the eyes
    • 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
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1806—C6-(meth)acrylate, e.g. (cyclo)hexyl (meth)acrylate or phenyl (meth)acrylate
    • 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
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • 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
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • 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 relates to a soft contact lens superior in long-wearability (extended-wearability). More precisely, the present invention relates to a hydrogel soft contact lens having no adhesion to a cornea in wearing and superiorities iri lens movement, comfort in wearing and extended-wearability.
  • the present invention further relates to an ophthalmologic lens material comprising a hydrophilic polysiloxane copolymer.
  • the present invention still further relates to a hydrophilic copolymer superior in water wettability, oxygen permeability, deposition resistance, flexibility, optical transparency and strength useful as a soft contact lens.
  • Polysiloxane compounds such as dimethylsilicone compounds as typical examples, have conventionally been widely used industrially by themselves or as modifiers for other materials utilizing specific functions such as heat resistance, electrical insulation, flexibility, lubrication and water repellency.
  • polydimethylsiloxane with methacrylic groups at both ends which is a polymerizable polysiloxane, has been used as a polymer modifier for acrylic polymers or-polystyrene, utilizing the polymerization function.
  • Polysiloxanes are used as gas permselective membranes due to high gas permeability and also as biomaterials or medical materials due to little influence on a human body.
  • Contact lenses are fundamentally classified into a soft and a hard types. Hard contact lenses are literally hard and show an discomfort in wearing. However, a recent remarkable improvement in oxygen permeability has produced products for a continuous wearing. On the other hand, soft contact lenses have features in softness and comfortable in wearing but still have many problems. Soft contact lenses are classified, in detail, to a hydrogel and a non-hydrofel types.
  • Hydrogel soft contact lenses are composed of copolymers of hydrophilic monomers such as hydroxyethyl methacrylate and N-vinylpyrrolidone as a main-component and prepared by lathe-cutting, molding or cast molding methods, followed by a swelling treatment in a physiological saline solution to obtain a lens with water content of about 40-80%.
  • Non-hydrogel soft contact lenses include, for example, a silicone rubber lens obtained by thermal curing of a mixture of polydimethylsiloxane capped with vinyldimethylsilyl groups at both ends of its molecular chain and methylhydrogenpolysiloxane by molding method after an addition of a platinum-based catalyst, and a flexible lens with an elastic modulus between soft and hard types, composed of polyperfluoroether as a main component, linked with polymerizable groups such as methacrylic groups at both ends (JP Nos. 1278540 and 1677573).
  • Another example for manufacturing a non-hydrogel soft contact lens with comfortable in wearing is preparing a lens by lathe-cutting a hard substrate obtained by a copolymerization of (meth)acrylic acid and (meth)acrylate followed by an esterification and/or a transesterification treatment (JP No. 952157).
  • Soft contact lens of a higher water content has improved oxygen permeability to a certain extent but is not sufficient enough, and does not have a satisfactory strength for a extended-wearable lens.
  • a non-hydrogel soft contact lens also has the following problems. Silicone lens, started with a big expectation due to extremely high oxygen permeability, has poor wettability to tear owing to a hydrophobic lens surface. Although surface treatments to improve hydrophilic property such as plasma processing and grafting hydrophilic monomers have been tried but sufficient levels of hydrophilic property and durability have not been obtained. Another problem is an adhesion during wearing and deposition with proteins and lipids in tear. In order to overcome these problems, a hydrogel soft contact lens consisting of silicone hydrogel with high oxygen permeability has been proposed, but it is still insufficient in surface wettability, liable to lipid staining and thus inferior as an extended-wearable lens (for example, Japanese Patent No. 1421481, JP-A-6-503276, JP-A-7-505169, JP-A-7-508063 and JP-A-8-245737).
  • copolymers of hydrophilic siloxane monomers with amide-group-containing monomers having N-vinyl group were very useful to solve the above mentioned problems, and that contact lenses obtained in a specific polar mold were, in particular, useful to solve the above mentioned problems, and thus attained the present invention.
  • the present invention includes the following disclosures.
  • hydrogel soft contact lens according to the above 1st item or the 2nd item comprising a copolymer obtained by a polymerization of at least one kind of hydrophilic siloxane monomer.
  • hydrophilic siloxane monomer is a hydrophilic polysiloxane monomer shown by the following formula (1): wherein, X1 is a polymerizable substitutent shown by the following formula (2): wherein, R5 is a hydrogen or a methyl group; Z1 is a linking group selected from —NHCOO—, —NHCONH—, —OCONH—R6-NHCOO—, —NHCONH—R7-NHCONH— and —OCONH—R8-NHCONH—(R6, R7 and R8 are hydrocarbon groups with 2-13 carbon atoms); m is 0-10; n is 3-10; p is 0 when m is 0 and 1 when m is not less than 1; q is an integer of 0-20; R1, R2, R3 and R4 are groups selected from hydrocarbon groups with 1-12 carbon atoms or trimethylsiloxy group, respectively; and the structure [Y
  • R9 and R10 are groups selected from hydrocarbon groups with 1-12 carbon atoms, hydrocarbon groups substituted with fluorine atom(s), trimethylsiloxy group and hydrophilic substituents, and may be different from each other in the chain, and r is 7-1000.
  • hydrogel soft contact lens according to the above 5 th item wherein the structural unit [Y1] according to the above 5 th item is a polysiloxane monomer with R9 and R10 being methyl group.
  • hydrogel soft contact lens according to the above 4 th item consisting of a hydrophilic polysiloxane monomer, wherein the structural unit [Y1] according to the above 4th item comprises linked structural units (Ia) and (IIa) shown below, the linking ratio of the units (Ia) and (IIa) being 1:10-10:1, and the total number of the linking of (Ia) and (IIa) being 7-1000:
  • each of R11 and R12 is a hydrocarbon group with 1-12 carbon atoms, respectively, each of R13 and R14 is a hydrocarbon group with 1-12 carbon atoms or a hydrocarbon group substituted with fluorine atom(s), respectively, and at least one of R13 and R14 is a hydrocarbon group substituted with fluorine atom(s).
  • hydrogel soft contact lens according to the above 7 th item consisting of a hydrophilic poly-siloxane monomer, wherein R11, R12 and R13 are methyl groups and R14 is a trifluoropropyl group in the structural unit [Y1] according to the above 7 th item.
  • R15 and R16 are a group selected from hydrocarbon group with 1-12 carbon atoms, hydrocarbon group with 1-12 carbon atoms substituted with fluorine atom(s) and trimethylsiloxy group, respectively, and they may be the same or different from each other; each of R17 and R18 is a group consisting of hydrocarbon group with 1-12 carbon atoms, trimethylsiloxy group or hydrophilic groups, respectively; and at least one of R17 and R18 groups is a hydrophilic group, wherein the hydrophilic group is a linear or cyclic hydrocarbon group linked with at least one substituent selected from hydroxy group and polyoxyalkylene group.
  • hydrogel soft contact lens consisting of a hydrophilic polysiloxane monomer, wherein the structral unit [Y1] according to the above 4th item comprises linked structural units (Ic), (IIc) and (IIIc) shown by the following formulas:
  • hydrogel soft contact lens according to any one of the above 9 th -11 th items consisting of a hydrophilic polysiloxane monomer, wherein the hydrophilic substituent is shown by the following formula (4) or (5): —R2O(OH)a (4)
  • R20 is a hydrocarbon group with 3-12 carbon atoms; the group may have a group of —O—, —CO— or —COO— inserted between carbon atoms; only one OH group can be substituted on one carbon atom; and a is a number not less than 1: —R21-(OR22)b-OZ2 (5)
  • R21 is a hydrocarbon group with 3-12 carbon atoms; the group may have a group of —O—, —CO— or —COO— inserted between carbon atoms;
  • R22 is a hydrocarbon group with 2-4 carbon atoms, and the number of the carbon atoms may be different from each other when b is not less than 2;
  • b is 1-200;
  • Z2 is a group selected from hydrogen atom, hydrocarbon group with 1-12 carbon atoms and —OCOR23 (R23 is a hydrocarbon group with 1-12 carbon atoms).
  • hydrogel soft contact lens according to any one of the above 9 th -11 th items, wherein the hydrophilic substituent is selected from the group consisting of the following formulas (6), (7) and (8): —C 3 H 6 OH (6) —C 3 H 6 OCH 2 CH(OH)CH 2 OH (7) —C 3 H 6 OC 2 H 4 OH (8)
  • hydrogel soft contact lens according to the above 9 th -11 th items, wherein the hydrophilic substituent is selected from the group of the following formulas (9) and (10): —C 3 H 6 (OC 2 H 4 ) c OH (9) —C 3 H 6 (OC 2 H 4 ) d OCH 3 (10)
  • Z3 is a linking group shown by the following formula (12): -A-COHN—R30-NHCOO—R31—CONH—R30-NHCO-A- (12)
  • R30 is a hydrocarbon group with 4-20 carbon atoms and may be interrupted by oxygen atom;
  • R31 is polyoxyalkylene group or fluorine-substituted polyoxyalkylene group;
  • the structural unit [Y2] means a polysiloxane structural unit shown by any one of formulas (3), linked structure of (Ia) and (IIa), linked structure of (Ib) and (IIb) or linked structure of (Ic), (IIc) and (IIIc); a means —O— or —NH— linkage;
  • each of R24, R25, R26 and R27 is a group selected from hydrocarbon group with 1-12 carbon atoms and trimethylsiloxy group, respectively;
  • each of R28 and R29 is a hydrocarbon group with 3-12 carbon atoms and may be interrupted by oxygen atom, respectively.
  • hydrogel soft contact lens according to the above 15 th item consisting of a polymer from a hydrophilic polysiloxane monomer, wherein R30 in the Z3 liking group shown by the formula (11) according to the above 15 th item is selected from hexamethylene, tetramethylene, dicyclohexylmethane, hydrogenated xylylene and isophorone groups and R31 is selected from polyethylene glycol, polypropylene glycol and polybuitylene glycol.
  • hydrogel soft contact lens according to any one of the above 4 th -14 th item, wherein the polymerizable Z1 liking group shown by the formula (2) according to the above 4 th item is shown by the following formula(13): —B—COHN—R32-NHCOO—R33-CONH—R32-NHCO—B— (13) wherein, R32 is a hydrocarbon group with 4-20 carbon atoms and may be interrupted by oxygen atom; R33 is polyoxyalkylene or polyoxyfluoloalkylene group; B means —O— or —NH— linkage.
  • hydrogel soft contact lens consisting of a polymer from a hydrophilic polysiloxane monomer, wherein R32 in the formula (13) is selected from hexamethylene, tetramethylene, dicyclohexylmethane, hydrogenated xylylene and isophorone groups and R33 is selected from polyethylene glycol, polypropylene glycol and polybutylene glycol.
  • a hydrogel soft contact lens obtained by a copolymerization of at least 1 kind of hydrophilic polysiloxane monomer in the formula (1) with at least 1 kind of hydrophilic monomer.
  • hydrogel soft contact lens according to the above 19th item, wherein the hydrophilic monomer is an amide monomer.
  • hydrogel soft contact lens according to the above 19th item, wherein the hydrophilic monomer is an amide monomer containing N-vinyl group.
  • hydrogel soft contact lens according to any one of the above 21st-23rd items, consisting of a copolymer composed of 10-99% by weight of a hydrophilic polysiloxane monomer and 1-80% by weight of an amide monomer containing N-vinyl group.
  • hydrogel soft contact lens according to any one of the above 21st-23rd items, consisting of a copolymer composed of 30-95% by weight of a hydrophilic polysiloxane monomer and 5-60% by weight of a monomer containing an amide group with N-vinyl group.
  • hydrogel soft contact lens obtained by a polymerization of a crosslinkable monomer linked with urethane groups.
  • R34 and R35 are hydrogen or methyl group and may be the same or different from each other;
  • Z4 is —NHCOO— linking group;
  • R36 is selected from hydrocarbon groups with 2-10 carbon atoms or polyoxyethylene group shown by —(C 2 H 4 O) g C 2 H 4 — (g is 2-40);
  • f is 0-10;
  • e is 0 when f is o and 1 when f is not less than 1.
  • hydrogel soft contact lens according to any one of the 19th-28th items, wherein surface contact angel is in a range of 10-50° and 30-90° by the captive bubble method in water and by the sessile drop method in air, respectively, oxygen permeability is not less than 30 and water content is not less than 5%.
  • hydrogel soft contact lens according to the above 29th item wherein surface contact angle is in a range of 10-40° and 30-80° by captive bubble method in water and by sessile drop method in air, respectively, oxygen permeability is not less than 80 and water content is not less than 9%.
  • hydrogel soft contact lens according to any one of the above 1st-30th items, manufactured by a polymerization in a mold.
  • hydrogel soft contact lens according to the above 3rd item, wherein the hydrophilic siloxanyl monomer is shown by the following formula (16):
  • R37 is hydrogen or methyl group
  • R38 is siloxanyl alkyl group
  • h is 0-20.
  • hydrogel soft contact lens consisting of a polymer comprising at least the hydrophilic siloxanyl monomer shown by the following above (16), a hydrophilic monomer and a crosslinkable monomer.
  • hydrogel soft contact lens according to any of the above 32nd or 33rd item, wherein the hydrophilic siloxanyl monomer according to the above 32nd item is shown by the following formula (17):
  • hydrogel soft contact lens consisting of a polymer comprising at least a hydrophilic siloxanyl monomer shown by the above formula (16), a siloxanyl monomer shown by the following formula (18), a hydrophilic monomer and a crosslinkable monomer:
  • R39 is hydrogen or methyl group
  • R40 is siloxanyl alkyl group
  • j is 0-4.
  • hydrogel soft contact lens according to any of the above 33rd or 35th item, wherein the hydrophilic monomer is an amide monomer containing N-vinyl group.
  • hydrogel soft contact lens according to the above 37th item wherein the amide monomer containing N-vinyl group is N-vinyl- N-methylacetamide or N-vinyl pyrrolidone.
  • hydrogel soft contact lens prepared by processing a polymer comprising a hydrophilic siloxanyl monomer by lathe-cutting and polishing method followed by swelling with water.
  • a hydrogel soft contact lens manufactured by a polymerization in a mold, wherein a mold material is insoluble to a composition of polymerizable monomers and at least one side of the mold for forming a lens surface has a polar group.
  • hydrogel soft contact lens according to the above 40th item, wherein the mold material consists of a resin with a contact angle to water of not higher than 90° by the sessile drop method.
  • hydrogel soft contact lens according to the above 40th item, wherein the mold material consists of a resin with a contact angel to water is 65-80° by the sessile drop method.
  • hydrogel soft contact lens according to any one of the above 40th-42nd items, wherein the mold consists of a resin selected from polyamide, polyethylene terephthalate and ethylene-vinylalcohol copolymer.
  • hydrogel soft contact lens according to any one of the above 40th-42nd items, wherein the mold material consists of ethylene-vinylalcohol copolymer.
  • hydrogel soft contact lens according to any one of the above 40th-44th items, wherein contact angle of a surface is in a range of 10-50° and 30-90° by the captive bubble method in water and by the sessile-drop method in air, respectively, and water content is not less than 5%.
  • hydrogel soft contact lens according to any one of the above 40th-44th items, wherein surface contact angle is in a range of 10-40° and 30-80° by the captive bubble method in water and by the sessile drop method in air, respectively, and water content is not less than 9%.
  • a method for manufacturing a contact lens wherein the mold according to the above 48th item consists of the material according to any one of the above 40th-44th items.
  • the present invention provides a hydrogel soft contact lens with contact angle of lens surface within a range of 10-50° and 30-90° by the captive bubble method in water and the sessile drop method in air, respectively, oxygen permeability not less than 30 and water content not less than 5%, and further a hydrogel soft contact lens with contact angle of lens surface within 10-40°, preferably 10-30°, and more preferably 15-30° by the captive bubble method in water, and 30-80°, preferably 40-70° by the sessile drop method in air, oxygen permeability not less than 80, preferably not less than 100, and water content not less than 9%.
  • the present invention includes the following.
  • hydrogel soft contact lens consisting of a polymer comprising at least hydrophilic siloxanyl methacrylate shown by the general formula I, and having tensile modulus of 0.8-2 ⁇ 10 7 dyne/cm 2 :
  • m is an integer of 0-4; and RSi is siloxanyl group.
  • hydrogel soft contact lens consisting of a polymer comprising at least hydrophilic siloxanyl methacrylate shown by the general formula I, hydrophilic monomer and crosslinkable monomer.
  • hydrogel soft contact lens consisting of a polymer comprising at least hydrophilic siloxanyl methacrylate shown by the general formula I, siloxanyl methacrylate shown by the general formula I2, a hydrophilic monomer and a crosslinkable monomer:
  • m is an integer of 0-4; and RSi is siloxanyl group.
  • hydrogel soft contact lens consisting of a polymer comprising at least 5-20% by weight of hydrophilic siloxanyl methacrylate shown by the general formula I1, 15-30% by weight of tris(trimethylsiloxy)silylpropyl methacrylate, 25-35% by weight of N-vinylpyrrolidone, 20-30% by weight of N-dimethylacrylamide, 5-10% by weight of trifluoroethyl methacrylate, 5-10% by weight of 1,1,2,2-tetraethoxy-2-hydroxypropyl methacrylate and 0.2-2% by weight of ethylene glycol dimethacrylate.
  • hydrophilic siloxanyl methacrylate shown by the general formula I1, 15-30% by weight of tris(trimethylsiloxy)silylpropyl methacrylate, 25-35% by weight of N-vinylpyrrolidone, 20-30% by weight of N-dimethylacrylamide, 5-10% by weight of trifluoroethyl methacryl
  • hydrogel soft contact lens prepared by processing a polymer comprising hydrophilic siloxanyl methacrylate to lens shape by a lathe-cutting and polishing method and hydration.
  • the hydrogel soft contact lens according to any of the above mentioned (1)-(6), consisting of a polymer comprising a hydrophilic polysiloxane monomer shown by the following general formula II, a hydrophilic monomer and a crosslinkable monomer:
  • R 1 is hydrogen or methyl group
  • each of R 2 , R 3 , R 4 and R 5 is hydrocarbon group with 1-12 carbon atoms or trimethylsiloxy group
  • Y consists of the structural units (I′) and (II′) shown below, ratio of the structural unit (I′) and the structural unit (II′) being 1:10 - 10:1 and total number of the structural units (I′) and (II′) being 7-200
  • b and c are integers of i-20, being the same or different from each-other
  • p is an integer of 0-20
  • X is —NHCOO— group or —OOCNH—R 10 —NHCOO— group (R 10 is hydrocarbon group with 4-13 carbon atom
  • each of R 6 and R 7 is hydrocarbon group with 1-12 carbon atoms; each of R 8 and R 9 is hydrocarbon group with 1-12 carbon atoms or fluorine-substituted hydrocarbon group; and at least one of R 8 and R 9 is fluorine-substituted hydrocarbon group.
  • the present invention provides a hydrogel soft contact lens with contact angle of lens surface in a range of 10-50° and 30-90° by the captive bubble method in water and the sessile drop method in air, respectively, oxygen permeability not less than 30 and water content not less than 5%.
  • a contact lens which can exhibit superior water wettability of lens surface for a long wearing period, high oxygen permeability, reduced protein and lipid depositions, stable lens movement, and little adhesion to a cornea.
  • a soft contact lens enabling continuous wearing for 30 days can be realized by keeping the contact angle of lens surface in a range of 10-40°, more preferably 10-30°, still more preferably 15-30° by the captive bubble method in water, and also 30-80°, more preferably 40-70° by the sessile drop method in air, oxygen permeability not less than 80, more preferably not less than 100, and water content not less than 9%.
  • a lower limit of contact angle by the sessile drop method of the material is, in general, preferably 30° because of superior physical properties such as tensile strength.
  • Oxygen permeability lower than 30 is not desirable because of an increased load to a cornea making extended-wearing difficult.
  • Water content lower than 5% is not desirable because of significant increase in staining of a lens surface with proteins and lipids and extremely increased adhesion to a cornea.
  • composition of the contact lens of the present invention so long as the lens has characteristics described above.
  • a soft contact lens obtained from a polymer containing a hydrophilic siloxanyl methacrylate shown by the above mentioned formula I is preferable.
  • hydrophilic siloxanyl methacrylate enabled to provide a contact lens with high oxygen permeability, less depositions of proteins and lipids, superior water wettability at lens surface maintained during an extended-wearing period, stabilized lens movement and less adhesion to a cornea.
  • RSi is a siloxanyl group, and at least one kind of group selected from the groups shown by the following formula (1a), (2a) and (3a) may be used:
  • 1 is an integer of 1-10.
  • m is an integer of 0-4 and m not less than 5 is undesirable because the monomer becomes too hydrophilic to be compatible with other copolymerizable monomers, giving a cloudiness during polymerization and a difficulty in homogeneous mixing of monomers.
  • 1 is an integer of 1-10 and 1 not less than 11 is undesirable because of a reduced compatibility with other copolymerizable monomers.
  • hydrophilic siloxanyl methacrylate is synthesized by reacting 2-isocyanatoethyl methacrylate with siloxanylalkyl alcohol.
  • the soft contact lens of the present invention consists of a hydrogel polymer with water content of about 5-60%, comprising hydrophilic siloxanyl methacrylate shown by the general formula I, and having oxygen permeability not less than about 30 and tensile modulus 0.8-2 ⁇ 10 7 dyne/cm 2 .
  • the lens provides less adsorption of proteins and lipids to inner part of lens, easy lens care, little decrease in lens movement caused by stain accumulation, superior stability in lens shape, flexible and comfortable, no adhesion to a cornea during wearing caused by sucking disk effect and thus enabling an extended-wearing.
  • Water content less than 5% is undesirable due to an easy adsorption of lipids to lens, resulting in an adhesion to a cornea. On the contrary, water content over 60% is also undesirable because of giving low strength, poor scratch resistance in handling, easy fracture and high adsorption of proteins.
  • Oxygen permeability lower than 30 is undesirable due to difficulty in continuous wearing and possibility to cause diseases of a cornea by long wearing.
  • Tensile modulus less than 0.8 ⁇ 10 7 dyne/cm 2 is undesirable due to inferior stability in lens shape, difficulty in handling to wear and poor feeling in wearing together with possible damages to cornea and sclera caused by easy turning back of lens at an edge or waving on an eye surface during wearing.
  • Tensile modulus over 2 ⁇ 10 7 dyne/cm 2 is undesirable because of an increased sucking disk effect resulting in a significant decrease in lens movement and occurrence of an adhesion.
  • hydrophilic siloxanyl methacrylates shown by the general formula I used for a soft contact lens of the present invention, the structure shown by the following formula Id is preferable because of providing a well-balanced performance among water content, oxygen permeability and modulus, together with less deposition of proteins and lipids:
  • any polymer can be used for a soft contact lens of the present invention so long as it contains hydrophilic siloxanyl methacrylate described above.
  • the polymer includes copolymers with the following copolymerizable compounds: acrylic monomers such as methyl acrylate, ethyl acrylate and acrylic acid; methacrylic monomers such as methyl methacrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate and methacrylic acid; siloxane monomers such as tris(trimethylsiloxy)silylpropyl methacrylate, bis(trimethylsiloxy)methylsilylpropyl methacrylate, pentamethyldisiloxanepropyl methacrylate, tris(trimethylsiloxy)silylpropyloxyethyl methacrylate, and tris(polydimethylsiloxy)silylpropyl methacrylate; fluorosiloxane monomers such as tris(dimethyltri
  • copolymers with siloxane methacrylates, fluoroalkylsiloxane methacrylates, fluoroalkyl methacrylates, fluoroalkylether methacrylates containing hydroxyl groups, hydrophilic monomers, crosslinkable monomers with two or more unsaturated groups within a molecule and siloxane macromers with polymerizable unsaturated groups at molecular ends are preferable because of well-balanced physical properties such as oxygen permeability, stain deposition resistance and mechanical strength.
  • Preferable hydrophilic monomers in the present invention are amide monomers containing N-vinyl group, and N-vinylpyrrolidone or N-vinyl-N-methylacetamide, in particular, can provide a contact lens with superior surface wettablity.
  • An example of such contact lens comprises a polymer composed of 5-20% by weight of hydrophilic siloxanyl methacrylate shown by formula Ii, 15-30% by weight of tris(trimethylsiloxy)silylpropyl methacrylate, 25-35% by weight of N-vinylpyrrolidone, 20-30% by weight of N-dimethylacetamide, 5-10% by weight of trifluoroethyl methacrylate, 5-10% by weight of 1,1,2,2-tetrafluoroethoxy-2-hydroxypropyl methacrylate and 0.2-2% by weight of ethylene glycol dimethacrylate.
  • a contact lens of the present invention can be manufactured by conventional lens manufacturing methods.
  • the methods includes, for example, a method by lathe-cutting of polymer bock followed by polishing, a method to cast a monomer composition into a mold with corresponding lens shape followed by polymerization, and a method to form only one face of lens by casting method using a polymerization mold then finish the other face by lathe-cutting and polishing method, etc.
  • a feature of the present invention is that a contact lens can be manufactured by lathe-cutting and polishing method.
  • hydrophilic siloxanyl methacrylate shown by formula I improves a compatibility between siloxanyl monomer to raise oxygen permeability and hydrophilic monomer to enhance water wettability to give a polymer sufficiently hard for machining and polishing in dry state and a hydrous soft contact lens with superior optical transparency when swelled with water and suitable range of modulus.
  • a lens manufactured by lathe-cutting and polishing method is preferable because it has the same polymer composition in surface and inside of a lens, and exhibits a stable lens performances such as water wettability and depositions of proteins and lipids together with little change in surface characteristics during long-wearing.
  • a polymer comprising hydrophilic polysiloxane monomer shown by the general formula II can be used for a contact lens of the present invention:
  • R 1 is hydrogen or methyl group
  • each of R 2 , R 3 , R 4 and R 5 is a hydrocarbon group with 1-12 carbon atoms or trimethylsiloxy group
  • Y consists of the structural units (I′) and (II′) shown below, ratio of the structural unit (II) and the structural unit (II′) being 1:10-10:1 and total number of the structural units (I′) and (II′) being 7-200
  • each of b and c is an integer of 1-20, being the same or different from each other
  • p is an integer of 0-20
  • X is —NHCOO— group or —OOCNH—R 10 —NHCOO— group (R 10 is a hydrocarbon group with 4-13 carbon atoms).
  • each of R 6 and R 7 is a hydrocarbon group with 1-12 carbon atoms; and each of R 8 and R 9 is a hydrocarbon or fluorinated hydrocarbon group with 1-12 carbon atoms, and at least one of R 8 and R 9 being fluorinated hydrocarbon group.
  • hydrophilic polysiloxane monomer may be copolymerized with the copolymerizable monomers described above.
  • copolymers further comprising polysiloxane monomers with polymerizable unsaturated groups at molecular ends may be used,-which are described in JP-B-3-240021, JP-B-3-257420, JP-B-4-50814, JP-B-5-45612, JP No. 2592356, etc., and shown by the following formulas (4a) - (7a):
  • R 1 is hydrogen or methyl group
  • each of R 2 , R 3 , R 4 and R 5 is hydrocarbon group or trimethylsiloxy group
  • each of R 6 and R 7 is hydrocarbon group with 1-12 carbon atoms
  • each of a and c is an integer of 1-20
  • b is an integer of 10-100.
  • R 1 is hydrogen or methyl group
  • each of R 2 , R 3 , R 5 and R 5 is methyl or trimethylsiloxy group
  • each of R 6 and R 7 is a hydrocarbon group with 1-12 carbon atoms
  • each of a and c is an integer of 1-20
  • p is an integer of 0-20
  • b is an integer of 10-100
  • X is —NHCOO— group or —OOCNH—R 8 —NHCOO— group (R8 is hydrocarbon group with 4-13 carbon atoms).
  • R 1 is hydrogen or methyl group
  • each of R 2 , R 3 , R 4 and R 5 is hydrocarbon group with 1-12 carbon atoms or trimethylsiloxy group
  • Y consists of the structural units (I) and (II) shown below, ratio of the structural unit (I) and the structural unit (II) being 1:10-10:1 and total number of the structural units (I) and (II) being 7-200
  • each of b and c is an integer of 1-20, being the same or different from each other
  • p is an integer of 0-20.
  • each of R 6 and R 7 is a hydrocarbon group with 1-12 carbon atoms; and each of R 8 and R 9 is a hydrocarbon or fluorinated hydrocarbon group with 1-12 carbon atoms, and at least one of R 8 and R 9 being fluorinated hydrocarbon group.
  • X is substituent with radically polymerizable unsaturated group
  • Y is R 9 or X
  • c is 0-500
  • b is 1-500
  • each of R 3 and R 4 is a group selected from alkyl group, hydrocarbon group with 1-10 carbon atoms, halogenated alkyl group with 1-10 carbon atoms and trimethylsiloxy group, being the same or different from each other
  • R is a fluorinated substituent linked with at least one hydroxyl group
  • each of R 1 , R 2 , R 6 , R 7 , R 8 and R 9 is a group selected from fluorinated substituent with at least one hydroxyl group, alkyl group with 1-10 carbon atoms, halogenated alkyl groups with 1-10 carbon atoms and trimethylsiloxy group, being the same or different from each other, and being the same to or different from R 5 .
  • copolymers with siloxane methacrylates, fluoroalkylsiloxane methacrylates, fluoroalkyl methacrylates, fluoroalkylether methacrylates containing hydroxyl groups, hydrophilic monomers, crosslinkable monomers with two or more unsaturated groups in a molecule and polysiloxane monomers with polymerizable unsaturated groups at molecular ends are preferable because of well-balanced physical properties such as oxygen permeability, stain deposition and mechanical strength.
  • a contact lens comprising the above described polysiloxane monomer as a main component can be manufactured by conventional lens manufacturing methods such as the casting method in which a monomer composition is injected into a polymerization mold with a corresponding lens shape followed by a polymerization.
  • a lens manufactured by using a polymerization mold made of a material with polar groups at a surface such as ethylene-vinylalcohol copolymer, polyamide and polyethylene terephthalate, is particularly preferable due to formation of a thick stable hydrophilic layer at a lens surface, little change in surface characteristics during extended-wearing, together with stable performances such as superior water wettability and reduced deposition of proteins and lipids.
  • the present invention includes the following.
  • An ophthalmologic lens material obtained by copolymerization of at least one or more types of compounds of the following (a) and one or more types of compounds of the following (b).
  • X is a polymerizable substitution group shown by the formula (2b):
  • R 5 is hydrogen or methyl group
  • Z1 is a linking group selected from —NHCOO—, —NHCONH—, —OOCNH—R 6 —NHCOO—, —NHCONH—R 7 —NHCONH— and —OOCNH—R 8 —NHCONH— (R 6 , R 7 and R 8 are hydrocarbon groups with 2-13 carbon atoms);
  • m is 0-10;
  • n is 3-10;
  • p is 0 when m is 0 and 1 when m is not less than 1;
  • q is an integer of 0-20;
  • each of R 1 , R 2 , R 3 and R 4 is a hydrocarbon group with 1-12 carbon atoms or trimethylsiloxy group;
  • each of R9 and R 10 being the same or different from each other, is a group selected from hydrocarbon group with 1-12 carbon atoms, fluorinated hydrocarbon group with 1-12 carbon atoms and trimethylsiloxy group; each of R 11 and R 12 consists of hydrocarbon group with 1-12 carbon atoms, trimethylsiloxy group or hydrophilic substituent, and at least one of R 11 and R 12 being hydrophilic substituent.
  • a hydrophilic substituent in the present invention means a linear or cyclic hydrocarbon group linked with at least one substituent selected from hydroxyl group and oxyalkylene group.
  • hydrophilic substituent of hydrophilic polysilioxane monomer is expressed by the formula (3b) or the formula (4b): —R 14 (OH)a (3b)
  • R 14 is a hydrocarbon group with 3-12 carbon atoms and may have —O—, —CO— or —COO— group inserted between carbon atoms; number of hydroxyl group on the same carbon atom is limited to only one; a is larger than 1; —R 15 —(OR 16 ) b —OZ2 (4b)
  • R 15 is hydrocarbon group with 3-12 carbon atoms and may have —O—, —CO— or —COO— group inserted between carbon atoms;
  • R 16 is hydrocarbon group with 2-4 carbon atoms and number of carbon atoms may be different from each other when b is not less than 2;
  • b is 1-200;
  • Z2 is a group selected from hydrogen, hydrocarbon group with 1-12 carbon atoms and —OOCR 17 (R 17 is hydrocarbon group with 1-12 carbon atoms).
  • hydrophilic substituent is selected from the formulas (5b), (6b) and (7b): —C 3 H 5 OH (5B) —C 3 H 6 OCH 2 CH(OH)CH 2 OH (6B) C 3 H 6 OC 2 H 4 OH (7B)
  • amide-group-containing monomer having N-vinyl group is selected from N-vinyl formamide, N-vinyl acetamide, N-vinyl isopropylamide, N-vinyl-N-methyl acetamide, N-vinyl pyrrolidone and N-vinyl caprolactam.
  • each of R 16 and R 18 being the same or different from each other, is hydrogen or methyl group;
  • Z3 is urethane linking group;
  • R 17 is a group selected from hydrocarbon group with 2-10 carbon atoms and polyoxyethylene group shown by —(C 2 H 4 O) g C 2 H 4 — (g is 2-40);
  • f is 0-10;
  • e is 0 when f is 0 and 1 when f is not less than 1.
  • a soft contact lens made of an ophthalmologic lens material described in any of (1)-(13) above.
  • hydrophilic polyasiloxane monomers are expressed as a block type linkage, but the present invention also includes a random linkage type.
  • a hydrophilic substituent in the said polysiloxane monomers is a linear or cyclic hydrocarbon group linked with at least one substituent selected from hydroxyl group and oxyalkylene group, and preferably such group as shown by the following formula (3b) or (4b): —R 14 (OH) a (3b)
  • R 14 is hydrocarbon group with 3-12 carbon atoms and may have —O—, —CO— or —COO— group inserted between carbon atoms; number of hydroxyl group on the same carbon atom is limited to only one; a is not less than 1; —R 15 —(OR 16 ) b —OZ2. (4b)
  • R 15 is hydrocarbon group with 3-12 carbon atoms and may have —O—, —CO— or —COO— group inserted between carbon atoms;
  • R 16 is hydrocarbon group with 2-4 carbon atoms and number of carbon atoms may be different each other when b is not less than 2;
  • b is 1-200;
  • z2 is a group selected from hydrogen, hydrocarbon group with 1-12 carbon atoms and —OOCR 17 (R 17 is hydrocarbon group with 1-12 carbon atoms).
  • Preferable hydrophilic group includes: monohydric alcohol substituent such as —C 3 H 6 OH, —C 8 H 16 OH, —C 3 H 6 OC 2 H 4 OH, —C 3 H 6 OCH 2 CH(OH)CH 3 , —C 2 H 4 COOC 2 H 4 OH and —C 2 H 4 COOCH 2 CH(OH)C 2 H 5 ; polyhydric alcohol substituent such as —C 3 H 6 OCH 2 CH(OH)CH 2 OH, —C 2 H 4 COOCH 2 CH(OH)CH 2 OH and —C 3 H 6 OCH 2 C(CH 2 OH) 3 ; and polyoxyalkylene substituent such as —C 3 H 6 (OC 2 H 4 ) 4 OH, —C 3 H 6 (OC 2 H 4 ) 30 OH, —C 3 H 6 (OC 2 H 4 ) 10 OCH 3 and —C 3 H 6 (OC 2 H 4 ) 10 —(OC 3 H 6 ) 10 OC 4 H
  • particularly preferable groups are: alcohol substituent such as —C 3 H 6 OH, —C 3 H 6 OCH 2 CH(OH)CH 2 OH and —C 3 H 6 OC 2 H 4 OH; and polyoxyethylene substituent such as —C 3 H 6 (OC 2 H 4 )cOH and —C 3 H 6 (OC 2 H 4 )dOCH 3 (c and d are 2-40) from the viewpoints of superior hydrophilic property and oxygen permeability.
  • alcohol substituent such as —C 3 H 6 OH, —C 3 H 6 OCH 2 CH(OH)CH 2 OH and —C 3 H 6 OC 2 H 4 OH
  • polyoxyethylene substituent such as —C 3 H 6 (OC 2 H 4 )cOH and —C 3 H 6 (OC 2 H 4 )dOCH 3 (c and d are 2-40) from the viewpoints of superior hydrophilic property and oxygen permeability.
  • Fluorine-containing substituent provides staining resistance to the material, but an excess substitution impairs hydrophilic property.
  • a hydrocarbon substituent with 1-12 carbon atoms linked with fluorine atoms is preferable including: 3,3,3-trifluoropropyl group, 1,1,2,2-tetrahydroperfluorooctyl group and 1,1,2,2-tetrahydroperfluorodecyl group. Among these, 3,3,3-trifluoropropyl group is most preferable in view of hydrophilic property and oxygen permeability.
  • substituents linked to Si atom include hydrocarbon group with 1-12 carbon atoms or trimethylsiloxy group, being the same or different from each other.
  • Preferable group is alkyl group with 1-3 carbon atoms, and methyl group is particularly preferable.
  • a polysiloxane chain with small substituent such as methyl group is flexible and has good oxygen permeability.
  • Ratio of linking numbers of the siloxane structure unit [I] and the siloxane structure unit linked with hydrophilic substituent [II], [I]/[II], is 0.1-200.
  • Total number of the siloxane structure units [I] and [II] is preferably 10-1000, more preferably 20-500. Shorter polysiloxane chain lowers flexibility and oxygen permeability of the polymer. Too long -siloxane chain is undesirable due to a remarkable increase in viscosity of a polysiloxane monomer itself, which leads to difficulties in manufacturing and handling of the monomer together with lower degree of polymerization.
  • polymerizable unsaturated groups are linked to the ends of siloxane chain and structure of the unsaturated group is acrylate or methacrylate group.
  • a linking group to Si atom hydrocarbon group containing urethane or urea linkages is preferable, and may be linked to Si atom through oxyethylene group.
  • Urethane or urea linkage is highly polar and enhances hydrophilic property and strength of the polymer.
  • a structure having two groups of this linkage can be introduced by a reaction with diisocyanate compound, and a linking group between the isocyanate linkages is a hydrocarbon with 2-13 carbon atoms and may be linear, cyclic or aromatic types.
  • Diisocyanate compounds used include trimethylene diisocyanate, hexamethylene diisocyanate, cyclohexyl diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexyl diisocyanate and 2,4-torylenediisocyanate and the like.
  • hydrophilic polysiloxane monomers there are various synthesis methods for the hydrophilic polysiloxane monomers disclosed in the present invention.
  • An example includes the following: A ring-opening polymerization of a mixture of cyclic siloxane with hydrosilane (Si—H), cyclic siloxane with hydrocarbon group and disiloxane with hydroxyalkyl groups at both ends, along with cyclic siloxane with fluorine-substituted hydrocarbon group in certain cases, is performed using an acidic catalyst such as sulfuric acid, trifluoromethanesulfonic acid and acidic clay to obtain hydrosilyl-group-containing polysiloxane compound having hydroxyl groups at both ends.
  • siloxane compounds with various degree of polymerization and introduction ratios of fluorine-containing substituent and hydrosilyl group can be obtained by changing feed ratios of each cyclic siloxanes and disiloxane compounds.
  • Isocyanate substituted acrylates or isocyanate substituted methacrylates are then reacted with hydroxyl groups at the ends of polysiloxane to obtain hydrosilane-containing fluorinated silixane compound with polymerizable unsaturated groups at both ends.
  • isocyanate-substituted methacrylates include such monomers as methacryloxyethylisocyanate and methacryloylisocyanate.
  • Isocyanate compounds with acrylate or methacrylate group obtained by reacting hydroxyl-group-containing acrylate or methacrylate such as hydroxyethyl methacrylate and hydroxybutyl acrylate with various diisocyanate compounds are also utilized.
  • hydrophilic polysiloxane monomers can be obtained by adding a hydrophilic compound with unsaturated hydrocarbon group to the hydrosilane using a transition metal catalyst such as chloroplatinic acid, utilizing so called hydrosilylation reaction.
  • a dehydrogenation reaction occurs as a side reaction if an active hydrogen compound such as hydroxyl group and carboxylic acid is present. Therefore, if these active hydrogen atoms are present in a hydrophilic compound to be introduced, the side reaction should be suppressed by protecting the active hydrogen atom in advance or adding buffer agents (refer to, for example, U.S. Pat. No. 3,907,851 and JP-B-62-195389).
  • hydrosilyl-group-containing polysiloxane compound having hydoxyl groups at both ends hydrophilic compound is introduced by hydrosilylation in advance, then polymerizable groups are introduced to both ends of the siloxane by reacting with isocyanate-substituted methacrylate or the like.
  • hydrophilic compound which is reactive to isocyanate
  • side reaction with isocyanate must be prevented by introducing a protective group.
  • silicate ester derivative such as dimethoxy silane or diethoxysilane compound instead of cyclic siloxane can be used as a starting raw material. Mixtures of two or more hydrophilic polysiloxane monomers thus obtained can also be used.
  • a hydrophilic monomer is indispensable as a comonomer component in addition to the hydrophilic polysiloxane monomer.
  • an amide monomer an amide monomer containing N-vinyl group among them, is useful to obtain superior transparency, staining resistance and surface wettability.
  • An amide monomer containing N-vinyl group is selected from N-vinyl formamide, N-vinyl acetamide, N-vinyl isopropylamide, N-vinyl-N-methyl acetamide, N-vinyl pyrrolidone and N-vinyl caprolactam, and mixed use of two or more kinds of monomers may be possible.
  • N-vinyl-N-methyl acetamide and N-vinyl pyrrolidone are, in particular, preferable.
  • a copolymer is preferably composed of 10-99% by weight of hydrophilic polysiloxane monomer and 1-90% by weight of amide monomer containing N-vinyl group, and more preferably composed of 30-95%. by weight of hydrophilic polysiloxane monomer and 5-70% by weight of amide monomer containing N-vinyl group. Lower content of hydrophilic polysiloxane monomer reduces oxygen permeability and flexibility. An excess content of amide monomer containing N-vinyl group increases water content and lowers strength.
  • a material disclosed in the present invention also includes copolymers obtained by addition of monomers other than the hydrophilic polysiloxane monomer and the amide monomer containing N-vinyl group.
  • Any monomer can be used in the present invention so long as it is copolymerizable, and hydrophilic monomers, among them, are useful for a hydrous material. It is because they have good compatibility with the hydrophilic polysiloxane monomer and also can further improve surface wettability of polymer and modify water content.
  • monomers containing hydroxyl group such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate and glycerol methacrylate; monomers containing fluorine-substituted group such as 3-(1,1,2, 2-tetrafluoroethoxy)-2-hydroxypropyl methacrylate; monomers containing carboxyl group such as methacrylic acid, acrylic acid and itaconic acid; monomers containing alkyl substituted amino group such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; acrylamide or methacrylamide monomers such as N,N′-dimethylacrylamide, N,N′-diethylacrylamide, N-methylacrylamide, methylenebisacrylamide and diacetoneacrylamide; monomers containing oxyalkylene group such as methoxypolyethylene glycol monomethacrylate and polypropylene glycol monometh
  • Siloxanyl acrylates are also useful comonomers to adjust oxygen permeability.
  • they include tris(trimethylsiloxy)silylpropyl methacrylate, bis(trimethylsiloxy)methylsilylpropyl methacrylate and pentamethyldisiloxanyl methacrylate.
  • Polymerizable polydimethylsiloxane substituted with methacrylate group and the like can also be used for the similar objective.
  • fluorinated monomers such as fluoroalkyl acrylates and fluoroalkyl methacrylates, for example, trifluoroethyl acrylate, tetrafluoroethyl acrylate, tetrafluoropropyl acrylate, pentafluoropropyl acrylate, hexafluorobutyl acrylate, hexafluoroisopropyl acrylate and methacrylates corresponding to these acrylates.
  • fluorinated monomers such as fluoroalkyl acrylates and fluoroalkyl methacrylates, for example, trifluoroethyl acrylate, tetrafluoroethyl acrylate, tetrafluoropropyl acrylate, pentafluoropropyl acrylate, hexafluorobutyl acrylate, hexafluoroisopropyl acrylate and methacrylates corresponding to these acryl
  • alkyl acrylate monomers and alkyl methacrylate monomers can also be used if necessary. They include, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, stearyl acrylate and methacrylates corresponding to these acrylates.
  • monomers with high glass transition temperature (Tg) such as cyclohexyl methacrylate, tert-butyl methacrylate and isobornyl methacrylate can also be used to enhance mechanical properties.
  • crosslinkable monomers other than hydrophilic polysiloxane monomers can be used to improve mechanical properties and stability and adjust water content.
  • they include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, bisphenol A dimethacrylate, vinyl methacrylate; acrylates corresponding to these methacrylates; siloxane derivatives such as 1,3-bis(3-methacryloxypropyl)tetramethyldisiloxane and the like.
  • crosslinkable monomers linked with urethane group in a polymerization composition disclosed in the present invention, were particularly superior in compatibility and hydrophilic property, together with improvement of mechanical properties.
  • Bifunctional crosslinkable monomers shown by the formula (10b) are preferable:
  • R 16 and R 18 are hydrogen or methyl group, being the same or different from each other;
  • Z3 is urethane linking group;
  • R 17 is selected from hydrocarbon group with 2-10 carbon atoms or polyoxyethylene group expressed by —(C 2 H 4 O) g C 2 H 4 — (g is 2-40);
  • f is 0-10;
  • e is 0 when f is 0 and 1 when f is not less than 1.
  • crosslinkable monomers of urethane linkage type are; 2-methacryloylcarbamoyloxyethyl methacrylate, 2-(2-methacryloxycarbamoyloxy)ethyl acrylate, 2-(2-methacryloxyethylcarbamoyloxy)propyl methacrylate, 2-methacryloxyethylcarbamoyloxytetraethylene glycol methacrylate and the like.
  • crosslinkable monomers shown by the formula (11b) are preferable:
  • crosslinkable monomers can be used alone or in combination of two or more kinds.
  • additives may further be added before or after polymerization, if necessary.
  • additives include dyes or pigments with various coloring characteristics and UV absorbers.
  • mold releasing agents such as surfactants can be added to improve separation of lens from the mold.
  • a polymer used for an ophthalmologic lens of the present invention is formed to an ophthalmologic lens by so called a mold method in which a monomer mixture comprising, for example, hydrophilic polysiloxane monomer and amide monomer containing N-vinyl group is filled into a mold, followed by a radical polymerization by the known method, or by so called a spin casting method in which a monomer mixture is fed in a rotatable hemisphere mold, followed by a polymerization.
  • a mold method in which a monomer mixture comprising, for example, hydrophilic polysiloxane monomer and amide monomer containing N-vinyl group is filled into a mold, followed by a radical polymerization by the known method, or by so called a spin casting method in which a monomer mixture is fed in a rotatable hemisphere mold, followed by a polymerization.
  • a solution of monomer mixture added with solvents in a mold is utilized to adjust degree of
  • alcohols such as ethanol and isopropanol
  • ethers such as dimethylsulfoxide, dimethylformamide, dioxane and tetrahydrofran
  • ketons such as methylethyl keton
  • esters such as ethyl acetate; and the like. Two or more of these solvents are also used in combination.
  • Any mold material can be used for mold polymerization or casting polymerization, so long as it is substantially insoluble to monomer mixture and lens can be separated after polymerization.
  • polyolefin resins such as polypropylene and polyethylene can be used, and materials having polar groups at a surface and small contact angle to water are preferable.
  • Polar group here is an atomic group with strong affinity with water and includes hydroxyl group, nitrile group, carboxyl group, polyoxyethylene group, amide group, urethane group and the like.
  • Preferrable mold material is insoluble to a polymerization monomer composition and has contact angle to water at least at the part for forming one lens surface, not higher than 90°, preferably 65-80°, by the sessile drop method.
  • a lens formed using a mold material having surface contact angle smaller than 80° shows particularly superior water wettability and stable performance in lipid deposition and the like.
  • a mold material having surface contact angle smaller than 65° is not practical because it has a difficulty in lens separation from the mold material after polymerization, resulting in minute surface damages or fractures at an edge part of lens.
  • a mold material soluble to monomer compositions is also difficult to use practically because it causes the separation problem of a lens, rough lens surface and low transparency.
  • acrylic or styrene-based resins such as methyl methacrylate copolymer and styrene copolymer can not be used because they are soluble to a composition comprising amide monomers disclosed by the present invention, although they have superior molding characteristics.
  • a mold material is a resin selected from polyamide, polyethylene terephthalate and ethylene-vinylalcohol copolymer, and ethylene-vinylalcohol copolymer is particularly more preferable from the viewpoints of an easiness in molding itself providing a dimensionally stable mold and giving stable water wettability to lens.
  • Ethylene-vinylalcohol copolymer resin to be used is available as “Soarlite” from The Japan Synthetic Chem. Ind. Co. Ltd. or “EVAL” from Kuraray Co., Ltd.
  • Various grades with ethylene copolymerization ratio of about 25-50% by mole can be used in the present invention.
  • polyethylene terephthalate with low crystallinity is difficult to be used as a mold material due to solubility problem for monomer compositions, but a grade with enhanced crystallinity can be used.
  • a drawn film of polyethylene terephthalate can be used by forming to a mold shape.
  • a photopolymerization method to polymerize by UV or visible light irradiation in the presence of photopolymerization initiators in a monomer mixture, or a radical polymerization method to thermally polymerize using azo compounds or organic peroxides may be used.
  • photopolymerization initiator examples include benzoin ethyl ether, benzyl dimethyl ketal, ⁇ , ⁇ ′-diethoxy acetophenone and 2,4,6-trimethylbenzoyl diphenyl phosphine oxide
  • examples of organic peroxide are benzoin peroxide and t-butyl peroxide
  • examples of azo compound are azobisisobutyronitorile and azobisdimethylvaleronitorile.
  • a photo-polymerization method is preferable due to providing a stable polymerization in a short cycle time.
  • Surface of molded lens may be modified, if necessary, by applying plasma treatment, ozone treatment, graft polymerization or the like.
  • the present invention further includes the following compounds as a hydrophilic polysiloxane monomer shown by the formula (1).
  • each of R 1 , R 2 , R 3 and R 4 is a group selected from —CH 3 and —CH 2 CH 2 CF 3 , being the same or different from each other; m+n is an integer of 7-1000;
  • R 5 is a group selected from hexamethylene group, tetramethylene group, dicyclohexylmethane group, hydrogenated tolylene group, hydrogenated xylylene group and isophorone group; a is an integer of 0-20; R 6 is a group selected from —(C 2 H 4 O) 1 —, —(CH 2 C(CH 3 )HO) 1 — and —(C 4 H 8 O) 1 —, 1 being an integer of 1-40.
  • each of R 7 , R 8 , R 11 , R 12 , R 13 , R 14 , R 17 and R 18 is a groups selected from —CH 3 and —CH 2 CH 2 CF 3 , being the same or different from each other; m, o, p and r are integers of 5-500; b is an integer of 0-20;
  • each of R 9 , R 10 , R 15 and R 16 is a group selected from —CH 3 and —(CH 2 CH 2 O) s CH 3 , being the same or different from each other; n and q are integers of 1-500; s is an integer of 1-40;
  • R 19 is a group selected from hexamethylene group, tetramethylene group, dicyclohexylmethane group, hydrogenated tolylene group, hydrogenated xylylene group and isophorone group;
  • R 20 is a group selected from —(C 2 H 4 O) 1 —, —(CH 2 C(CH 3 )HO) 1 — and —(C 4 H 8 O) 1 —; 1 is an integer of 1-40.
  • each of R 21 and R 22 is a group selected from —CH 3 and —CH 2 CH 2 CF 3 , at least one of them being —CH 3 ;
  • m is an integer of 5-500;
  • m+n is an integer of 7-1000;
  • c is an integer of 0-20;
  • each of R 23 and R 24 is a group selected from —CH 3 and —CH 2 CH 2 CF 3 , at least one of them being —CH 2 CH 2 CF 3 ; n is an integer of 0-500;
  • R 25 is a group selected from hexamethylene group, tetramethylene group, dicyclohexylmethane group, hydrogenated tolylene group, hydrogenated xylylene group and isophorone group;
  • R 26 is a group selected from —(C 2 H 4 O) 1 —, —(CH 2 C(CH 3 )HO) 1 — and —(C 4 H 8 O) 1 —; 1 is an integer of 1-40;
  • R 5 group in the formula (1c), R 19 group in the formula (2c) and R 25 group in the formula (3c) are residual groups of bifunctional isocyanate and include, for example, hexamethylene diisocyanate, tetramethylene diisocyanate, 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, methyl 2,6-diisocyanatecaproate, 3-isocyanatemethyl-3,5,5-trimethylcyclohexyl isocyanate, dicyclohexylmethane-4,4′-diisocyanate, hydrogenated xylene isocyanate, hydrogenated tolylene diisocyanate and isophorone diisocyanate.
  • residual groups of hexamethylene diisocyanate and isophorone diisocyanate are preferable in view of well-balanced mechanical characteristics of a lens;
  • R 6 , R 20 and R 26 groups are residual groups of polyoxyalkylene glycol and include groups such as polyethylene glycol, polypropylene glycol and polytetraethylene glycol, and those with polymerization degree of 1-40 can be used. Among them polyethylene glycol is preferable due to providing superior water wettability of lens and staining resistance performance.
  • a bifunctional organopolysiloxane monomer shown by the formula (1c) and (2c) can be obtained, for example, by reacting two molar equivalent of a diol having polysiloxane structure obtained by a ring-opening insertion reaction among 1,3-bis-(hydroxyethoxypropyl)tetramethyldisiloxane, octamethylcyclotetrasiloxane and 1,3,5-trifluoropropyltrimethylcyclotrisiloxane, with an isocyanate-modified compound at both ends of polyethylene glycol obtained, for example, by a reaction of polyethylene glycol and two molar equivalent of hexamethylene diisocyanate, together with methacryloxyethyl isocianate.
  • a bifunctional organopolysiloxane monomer shown by the formula (3c) can be obtained, for example, by reacting a diol having polysiloxane structure obtained, for example, by a ring-opening insertion reaction between 1,3-bis-(hydroxyethoxypropyl)tetramethyldisiloxane and octamethylcyclotetrasiloxane, together with, if necessary, 1,3,5-trifluoropropyltrimethylcyclotrisiloxane, with an excess amount of an isocyanate-modified compound at both ends of polyethylene glycol obtained, for example, by a reaction of two molar equivalent of hexamethylene diisocyanate, followed by reacting thus obtained product with ab excess amount of 2-hydroxyethyl methacrylate.
  • An ophthalmologic lens material obtained by copolymerization of a hydrophilic polysiloxane monomer and an amide monomer containing N-vinyl group disclosed in the present invention is superior in transparency, water wettability, oxygen permeability and staining resistance.
  • the material can be used for a hard lens such as a hard contact lens, it is useful for an application to a soft lens, in particular, a hydrogel soft contact lens.
  • the material is, of course, also useful for an intraocular lens or a cornea lens.
  • An ophthalmologic lens material disclosed by the present invention includes a hydrogel soft contact lens with contact angle in a range of 10-50° and 30-90° by the captive bubble method in water and by the sessile drop method in air, respectively, oxygen permeability of not less than 30 and water content of not less than 5%, and further a hydrogel soft contact lens with contact angle in a range of 10-40° and 30-80° by the captive bubble method in water and by the sessile drop method in air, respectively, oxygen permeability of not less than 80 and water content of not less than 9%. They provide a contact lens suitable for 30 days of continuous-wearing as described above.
  • Dk value was determined in physiological saline solution at 35° C. according to Standard Measurement Method for Dk Value by Japan Contact Lens Association, using an oxygen permeability measurement instrument for film, Model K-316-IPI manufactured by Rika Seiki Ind. Co., Ltd. An expression of Dk value; ⁇ 10 ⁇ 11 (cm 2 /sec) ⁇ (ml O 2 /ml ⁇ mmHg) (3) Tensile Modulus
  • Test pieces of about 3 mm width were cut out from a central part of lens and tensile modulus (unit; dyne/cm 2 ) was determined from a initial slop of a stress-strain curve obtained by tensile test at the rate of 100 mm/min in physiological saline-solution at 25° C., using Autograph (Model AGS-50B manufactured by Shimadzu Corp.)
  • a model soiling solution with the following composition was prepared. NaCl 0.9 weight % NaH 2 PO4 0.0184 weight % Na 2 HPO4 0.076 weight % Egg lysozyme 0.12 weight % Bovine serum albumin 0.388 weight % CaCl 2 (H 2 O) 2 0.0407 weight %
  • a lens was immersed in 2 ml of the solution at 37° C. for 24 hr, then washed by shaking in purified water for 30 min., followed by taking out and gentle wiping off of surface water.
  • the lens was then immersed in 2 ml of protein assay reagent (BCA liquid), followed by reacting at 40° C. for 5 hours, and absorption at UV 562 nm was measured using a spectrophotometer (Model V-550 manufactured by Japan Spectrophotometer Co., Ltd.)
  • An amount of protein adhered per lens was determined using a calibration line measured separately.
  • a lens was immersed in a phosphoric acid buffer dispersed solution containing 1% of olive oil and kept at 40° C. for 20 hours in a constant temperature oven.
  • the lens was immersed in 5 ml of purified water in a container, then washed by shaking for 30 sec. Washing was repeated five times.
  • the lens was extracted with a mixed solvents of chloroform/methanol: 2/1.
  • the extract was then colored with triglyceride G reagent, and absorption at 505 nm was measured using a spectrophotometer (Model V-550 manufactured by Japan Spectrophotometer Co., Ltd.). An amount of lipid deposition per lens was determined using a calibration line measured separately.
  • Water wettability of a surface of soft contact lens was evaluated by measuring contact angle. Contact angle was measured by the captive bubble method in purified water using a contact angle tester (Model CA-DT manufactured by Kyowa Kaimen Kagaku Co., Ltd.). In addition, in order to evaluate water wettability in a dry state of a lens, measurement by the sessile drop method was also carried out. The measurements of contact angle by the captive bubble method and the sessile drop method were performed at 25° C. in accordance with Journal of Japan Contact Lens Society, 25 (1), 100, 1983. Smaller value and difference in both methods mean more superior water wettability, along with little change by drying of lens.
  • Corneal curvature of a white rabbit was measured, and a lens with 13.5 mm of diameter, 0.05 mm of center thickenss, ⁇ 3.00 diopter of power and base curve larger than the measured curvature by about 0.2 mm was used for wearing test and observed for 21 days. A state of wearing was recorded and a cornea was inspected in every 7 days by visual inspection and fluorescence dying.
  • a micro hardness tester for light loading (Model MVK-IS manufactured by Akashi Seisakusyo Co., Ltd.) was used. Test piece was polished to mirror finish, stored in a silica gel desiccator, then hardness was measured at 25° C.
  • AIBN azobisisobutylonitrile
  • the mixture was poured into a test tube made of propylene with a diameter of 16mm, and polymerized for 72 hours at 90° C. resulting in a transparent polymer with Vickers Hardness of 8.4.
  • a lens with base curve: 9.0 mm, power: ⁇ 3.00 diopter, diameter: 14.0 mm and thickness at center: 0.05 mm was prepared by a lathe-cutting and polishing method.
  • a physiological saline solution for 3 hours then with a soaking solution for 16 hours at 90° C. gave a hydrogel soft lens.
  • the lens obtained showed, after dipping in purified water for 72 hours at 37° C., 46% of water content and 1.0 ⁇ 10 7 dyne/cm 2 of tensile modulus.
  • Depositions of proteins and lipids to the lens were evaluated by dipping the lens in a model soiling solution proving less deposition such as 10 ⁇ g/lens for protein and 40 ⁇ g lens for lipid.
  • oxygen permeability (Dk value) measured with a disk having a given thickness was 60, and water wettability was 22° by the captive bubble method and 60° by the sessile drop method.
  • the lenses described above were worn on eyes of a white rabbit for continuous 21 days, and showed a smooth movement without adhesion and little deposition on the lenses. In addition, it was proved that the lenses were safe enough for an extended-wearing without showing any problem on the eyes of the rabbit.
  • the recovered lenses maintained the superior water wettability, and did not show any change during use in the lens performances.
  • a transparent polymer was obtained by polymerizing according to the same method as described in the Example 1 except for using 18 parts by weight of hydrophilic siloxanyl methacrylate and 15 parts by weight of tris(tri-methylsiloxy)silylpropyl methacrylate. From the polymer thus obtained, hydrogel soft lenses having 44% of water content and 1.2 ⁇ 10 7 dyne/cm 2 of tensile modulus were prepared. Furthermore, depositions of proteins and lipids were so little as 5 ⁇ g/lens and 38 ⁇ g/lens, respectively, and Dk value was 60. Water wettability was 20° by the captive bubble method and 56° by the sessile drop method.
  • hydrophilic siloxanyl methacrylate a monomer having a fluorosiloxanyl alkyl group shown by the formula (2a) was synthesized similarly to the synthesis method in the Example 1.
  • the monomer obtained was polymerized similarly to the method in the Example 1 resulting in a polymer, from which lenses were prepared similarly to the method in the Example 1.
  • Water content and tensile modulus were 40% and 1 ⁇ 10 7 dyne/cm 2 , respectively.
  • depositions of proteins and lipids were so little as 12 ⁇ g/lens and 35 ⁇ g/lens, respectively, and Dk value was 65. Water wettability was 20° by the captive bubble method and 57° by the sessile drop method.
  • the monomer obtained was polymerized similarly to the method in the Example 1 resulting in a polymer, from which lenses were prepared similarly to the method in the Example 1.
  • Water content and tensile modulus were 40% and 0.9 ⁇ 10 7 dyne/cm 2 , respectively.
  • depositions of proteins and lipids were so little as 15 ⁇ g/lens and 45 ⁇ g/lens, respectively, and Dk value was 68.
  • Water wettability was 24° by the captive bubble method and 63° by the sessile drop method.
  • lenses were prepared by the lathe-cutting and polishing method so that they had base curve of 8.5 mm, power of ⁇ 3.00 diopter, size of 14.0 mm and center thickness of 0.05 mm.
  • the dry lenses obtained were swelled in a physiological saline solution for 3 hours then in a soaking solution for 16 hours at 90° C. to give hydrous soft lenses.
  • Water content and tensile modulus of the lenses obtained after dipping in purified water for 72 hours at 37° C. were 30% and 1.1 ⁇ 10 7 dyne/cm 2 , respectively.
  • Depositions of proteins and lipids to the lens were evaluated by dipping the lens in a model staining solution proving less deposition such as 12 ⁇ g/lens for proteins and 35 ⁇ g/lens for lipids.
  • oxygen permeation coefficient (Dk value) measured with a disk having a given thickness was 75, and water wettability was 22° by the air bubble method and 60° by the droplet method.
  • the lenses described above were worn on eyes of a white rabbit for continuous 21 days, and showed a smooth movement without adhesion and little deposition on the lenses. In addition, it was proved that the lenses were safe enough for an extended-wearing without showing any problem on the eyes of the rabbit.
  • the recovered lenses showed good water wettability, and did not show any change during use.
  • TPO 2,4,6-trimethylbenzoyl diphenylphosphin oxide
  • Water wettability was 22° by the captive bubble method and 54° by the sessile drop method showing no decrease of water wettability of a surface by drying.
  • An extended-wearing test with rabbit eyes showed less depositions and no deformation.
  • water wettability was kept in a superior state without any change during use, and the water film on a surface did not disappear when the lens was taken out from the soaking solution.
  • a polymerization was carried out according to the method described in the Example 1 except for using no hydrophilic siloxanyl methacrylate and 33 parts by weight of tris(trimethylsiloxy)silylpropyl methacrylate.
  • Button-like test pieces were prepared from the polymer thus obtained.
  • An inspection of distortion showed a slight optical distortion.
  • Hydrogel soft lenses were prepared as in the Example 1.
  • Results of the evaluation on their physical properties showed water content of 45% and Dk value of 45 both of which were similar to the results in the Example 1, but more depositions of proteins and lipids which were 20 ⁇ g/lens and 255 ⁇ g/lens, respectively.
  • Water wettability was 21° by the captive bubble method and 110° by the sessile drop method, and it became worse by drying with a remarkable change in a contact angle.
  • a long-wearing test with rabbit eyes showed more deposition and a partial deformation of the lens.
  • Recovered lenses showed poor water wettability, and showed a state in which the lens lost water film on its surface immediately when it was taken out from the soaking solution.
  • the mixture of the monomers described in the Example 6 was poured into a lens-shaped mold for casting polymerization made of polypropylene, then polymerized by an irradiation of UV ray followed by swelling to give soft contact lenses.
  • Evaluations of physical properties of the lenses carried out similarly to the Example 1 gave water content of 46% and Dk value of 60 both of which were same as in the Example 6, but showed more depositions of proteins and lipids which were 45 ⁇ g/lens and 450 ⁇ g/lens, respectively.
  • Water wettability was 26° by the captive bubble method and 115° by the sessile drop method showing a remarkable difference between them, and water wattability of a surface decreased by drying.
  • An extended-wearing test with rabbit eyes showed much deposition, a partial deformation of the lens. Water wettability also changed drastically, and the water film on a surface disappeared immediately when the lens was taken out from a soaking solution.
  • a hydrophilic polysiloxane monomer shown by the formula (8a) was synthesized by a reaction of corresponding dihydroxypropyl polysiloxane and 2-isocyanatoethyl methacrylate.
  • a mixture of monomers comprising 70 parts by weight of the hydrophilic polysiloxane monomer described above, 15 parts by weight of N-vinylpirrolidone, 15 parts by weight of N,N-dimethylacrylamide, 5 parts by weight of trifluoroethyl methacrylate, 1 part by weight of ethyleneglycol dimethacrylate and 0.5 parts by weight of TPO was poured into a lens-shaped mold for casting polymerization made of ethylene-vinylalcohol copolymer, then polymerized by an irradiation of UV ray followed by hydration to give soft contact lenses.
  • the mixture of the monomers in the Example 7 was poured into a lens-shaped mold for casting polymerization made of polypropylene, then polymerized by an irradiation of UV ray followed by hydration to give soft contact lenses.
  • Evaluations of physical properties of the lens carried out similarly to the Example 7 gave water content of 24% and Dk value of 165, and showed much adhesions of proteins and lipids which were 60 ⁇ g/lens and 350 ⁇ g/lens, respectively.
  • Water wettability was 26° by the captive bubble method and 120° by the sessile drop method, and showed a remarkable decrease of water wettability of a surface by drying.
  • Wettability to the purified water was evaluated by visual inspections. Lenses were pulled up vertically after dipping in the purified water for one day, then water wettability was ranked by a time for which water film was maintained for: 5 seconds or more; ⁇ , 1-5 seconds; ⁇ , 1 second or less; x.
  • a Lens was dipped in the purified water then taken out. After wiping off adhered water, the lens was left for 10 minutes at 25° C. After dipping in the purified water, the lens was pulled up vertically, then water wettability was evaluated and ranked by a time for which water film was maintained for: 5 seconds or more; ⁇ , 1-5 seconds; ⁇ , 1 second or less; x.
  • Measurement was performed by the electrode method using a Model K-316-IPI oxygen permeability measurement instrument for film manufactured by Rika Seiki Kogyo Co., Ltd. according to the Standard Dk Value Measuring Method of Japan Contact Lens Association.
  • As the test pieces lenses having diameter of 14 mm and thickness of about 0.1-0.5 mm were prepared using a mold to provide for the measurement.
  • the measurement was performed in a physiological saline solution at 35° C.
  • An oxygen permeability was obtained from a slope of a line of oxygen permeation amount versus sample thickness.
  • Dk value was expressed by a unit of x 10 11 [(ml ⁇ cm)/(cm 2 ⁇ sec ⁇ mmHg)].
  • Measurement was performed using Autograph AGS-50B manufactured by Shimadzu Corp. in a physiological saline solution at 25° C. Strength at break was measured with a center part having a width of 3 mm cut out from a lens. A unit is (g/mm 2 ).
  • Solubility of a mold material to a mixture of monomers was evaluated by the following method.
  • One drop of a mixture of monomers was dropped on a flat surface of various kinds of mold and sheet-like materials, and left for 1 hour at 25° C.
  • the wiped-off-surface was inspected and ranked as follows: no change at all; ⁇ , cloudy surface; ⁇ , corroded uneven surface; x.
  • the residual liquid was dissolved in isopropanol, reprecipitated with methanol, followed by removal of volatile components under the vacuum from a separated liquid to give a transparent viscous liquid.
  • the said liquid was the siloxanediol having hydrosilane groups (A1) expressed by the following formula with a yield of 98 g.
  • A1 hydrosilane groups
  • the product was the polysiloxane-dimethacrylate having alcohol groups (C2) wherein the linking group Y in the formula (B1) in the Synthesis Example 1 was shown by the following formula:
  • the product was the polysiloxane-diol having hydrosilane groups (A2) shown by the following formula:
  • a mixture of 150 g of octamethyl-cyclotetrasiloxane, 12 g of 1,3,5,7-tetramethyl-cyclotetrasiloxane, 6.8 g of 1,3-bis(2-hydroxyethyloxypropyl)tetramethyl-disiloxane, 200 g of chloroform and 1.5 g of trifluoromethane sulfonic acid was charged into a flask, and synthesized and purified similarly to the siloxanediol (A1) in the Synthesis Example 1 to give 95 g of a transparent viscous liquid.
  • the product was the polysiloxanediol having hydrosilan groups (A3) shown by the following formula:
  • MIEM the compound shown by the formula (11a)
  • VMA N-vinyl-N-methylacetoamide
  • IBM isobornyl methacrylate
  • 4ED tetraethyleneglycoldimethacrylate
  • TPO 2,4,6-trimethylbenzoyl-diphenylphosphinoxide
  • the monomer mixture was injected into a mold for forming contact lens made of an ethylene vinyl alcohol resin (hereinafter “EVOH resin”) (made by The Japan Synthetic Chem. Ind. Co., Ltd., Soarlite S), then irradiated by UV ray for 1 hour in a light exposure equipment to give a lens-shaped polymer.
  • the lens thus obtained was dipped in ethyl alcohol overnight, then dipped in water followed by heating at 90° C. for 3 hours.
  • the lens thus obtained was transparent and flexible, and showed good water wettability. Evaluation of physical properties showed water content of 10%, oxygen permeability (Dk) of 256, tensile strength of 185 g/mm 2 and lipid deposition of 40 ⁇ g.
  • contact angle of the EVOH resin used to water was 73°. Results of evaluation on its performances are shown in Table 1.
  • Comparative lenses were prepared by polymerizing and processing in the same manner in compositions and conditions as in the Example 8, except for using the polydimethylsiloxane-dimethacrylate (R1) or the polysiloxane-dimethacrylate having alcohol groups (R2) shown by the following formulas instead of the hydrophilic polysiloxane monomer. Results obtained are shown jointly in Table 1.
  • a mixture of 60 parts by weight of polysiloxane-dimethacrylate having polyoxyethylene groups (C3), 35 parts by weight of N-vinylpyrroridone (hereinafter “NVP”), 5 parts by weight of cyclohexyl methacrylate (hereinafter “CH”), 1 part by weight of ethyleneglycoldimethacrylate (hereinafter “ED”) and 0.5 parts by weight of TPO was mixed, photopolymerized in a mold made of EVOH resin in the same manner as in Example 8 to obtain a lens. Results of evaluation on the lens thus obtained are shown in Table 3.
  • a lens was prepared in the exactly same manner as in Example 8 except for using the crosslinkable monomer (“MIEM”) described in the Synthesis Example 5 instead of 4ED, and the lens obtained was evaluated. Results of the evaluation proved a transparent lens with good water wettability and improved strength, showing water content of 12%, oxygen permeability (Dk) of 245 and tensile strength of 285 g/mm 2 .
  • MIEM crosslinkable monomer
  • a lens was prepared in the exactly same manner as in Example 10 except for using the crosslinkable monomer (“MIEM”) described in the Synthesis Example 5 instead of 4ED, and the lens obtained was evaluated. Results of the evaluation showed water content of 23%, oxygen permeability (Dk) of 181 and improved tensile strength of 305 g/mm 2 .
  • MIEM crosslinkable monomer
  • a lens was prepared in the exactly same manner as in Example 8 except for using molds made of each resin shown in Table 4 instead of the mold for forming lens made of EVOH resin. Results of evaluation on solubility and contact angle of each resin material itself and on each lens are jointly shown in Table 4.
  • Contact lenses were prepared using 100 pieces of molds made of EVOH resin in the same manner in monomer composition and procedures as described in Example 19. Defectives were only 2 pieces which were partly chipped at their edges, and no defect was observed in all of other 98 lenses, proving the present invention being very useful method for an industrial manufacturing.
  • a mixture of 50 parts by weight of the hydrophilic polysiloxane monomer shown by the following structural formula (4c), 20 parts by weight of tris(trimethylsiloxy)silylpropyl methacrylate, 25 parts by weight of VMA, 5 parts by weight of CH, 1 part by weight of ED, 0.5 parts by weight of TPO and 80 parts by weight of 2-butanol was stirred, then injected into a mold made of EVOH resin, followed by an irradiation of UV ray for 1 hour.
  • the lens thus obtained was dipped in ethyl alcohol overnight. After the alcohol was replaced with water, the lens was heated at 90° C. for 3 hours. Evaluation on the hydrogel contact lens thus obtained showed water content of 32% and Dk value of 125.
  • Contact angle was 24° by the captive bubble method and 77° by the sessile drop method.
  • a house rabbit wearing test showed good lens movement, little deposition after 30 days wearing and good water wettability.
  • a mixture of 80 parts by weight of the hydrophilic polysiloxane monomer shown by the following structural formula (5c), 20 parts by weight of NVP, 1 part by weight of ED, 0.5 parts by weight of TPO and 80 parts by weight of 2-butanol was dissolved with stirring, and a contact lens was prepared similarly as in the Example 35. Evaluation on the lens showed water content of 13%, Dk value of 225, and contact angle of 24° by the captive bubble method and 70° by the sessile drop method. A house rabbit wearing test also showed good lens movement, little deposition, and maintaining of good water wettability.
  • a contact lens was prepared in the same manner as in the Example 35 except for using the monomer shown by the following structural formula (6c) as a hydrophilic polysiloxane monomer.
  • the lens thus obtained showed water content of 28%, Dk value of 166, and contact angle of 22° by the captive bubble method and 69° by the sessile drop method.
  • a rabbit wearing test showed good lens movement, little deposition after 30 days wearing and good water wettability.
  • a contact lens was prepared in the same manner as in the Example 36 except for using the monomer shown by the following structural formula (7c) as a hydrophilic polysiloxane monomer.
  • the lens thus obtained showed water content of 27%, Dk value of 285, and contact angle of 18° by the captive bubble method and 53° by the sessile drop method.
  • a rabbit wearing test showed good lens movement, little deposition after 30 days wearing and maintaining of good water wettability.
  • Example No. Transparency Wettability (%) ( ⁇ 10 ⁇ 11 ) (g/mm 2 ) ( ⁇ g)
  • Example 8 C1 (Synthesis ⁇ ⁇ 10 256 185 40 Example 1)
  • Example 9 C2 (Synthesis ⁇ ⁇ 14 218 174 32 Example 2)
  • Example 10 C3 (Synthesis ⁇ ⁇ 22 186 210 35 Example 3)
  • Example 11 C4 (Synthesis ⁇ ⁇ 12 240 235 62 Example 4)
  • Example 12 C5 (Synthesis ⁇ ⁇ 20 183 207 35 Example 5)
  • Example 13 C6 (Synthesis ⁇ ⁇ 34 145 168 20 Example 6) Comparative R1 ⁇ X 5 200 120 150
  • Example 4 Comparative R2 ⁇ ⁇ 18 195 115 65
  • Example 5 Comparative R1 ⁇ X 5 200 120 150
  • Example 4 Comparative R2 ⁇ ⁇ 18 195 115 65
  • Example 5 Comparative R1 ⁇ X 5 200 120 150
  • NVP N-Vinylpyrrolidone
  • VMA N-Vinyl-N-methylacetoamide
  • AC3 3-Tris(trimethylsiloxy)silylpropyl Methacrylate
  • MMA Methyl Methacrylate
  • DMA N,N-Dimethylacrylamide
  • HEMA 2-Hydroxyethyl Methacrylate
  • 3FM 2,2,4-Trifluoroethyl Methacrylate
  • OHF 1,1,2,2-Tetrafluoroethoxy-2-hydroxypropyl Methacrylate
  • CH Cyclohexyl Methacrylate
  • ED Ethyleneglycol-di-methacrylate
  • EVOH Ethylene-Vinylalcohol Copolymer
  • PET Polyethylene Terephthalate
  • PA Nylon 66
  • AS Acrylonitrile-Styrene (40/60)
  • Copolymer AM Acrylonitrile-Methyl Methacrylate (75/25)
  • Copolymer PP Polypropylene
  • PS Polystyrene
  • PC Polycarbonate
  • PMMA Polymethylmethacrylate
  • the present invention provides a soft contact lens showing small and stable contact angle to-water at its surface, little stain deposition in wearing, high oxygen permeability, no adhesion of the lens to cornea and superior extended-wearing characteristics.
  • a ophthalmologic lens material obtained by a copolymerization of a hydrophilic siloxane monomer and a amide-group-containing monomer having N-vinyl group of the present invention shows superior transparency, water wettability, and in particular, superior resistance to lipid deposition.
  • strength and durability are further improved by adding a crosslinkable monomer having urethane linking group.
  • polymerization in a mold comprising a resin having polar groups can give a stable water wettability to a lens. The material is useful particularly for a soft contact lens, and thus superior as a contact lens for extended-wearing.

Abstract

A mold for producing a soft contact lens, wherein the mold is capable of forming both front and rear surfaces of the lens from a surface of the mold during polymerization of a monomer composition.

Description

    CROSS REFERENCE TO RELATED APPLICATION
  • This application is a division of co-pending application Ser. No. 09/737,809, filed on Dec. 18, 2000, the entire contents of which are hereby incorporated by reference.
    • TECHNICAL FIELD
  • The present invention relates to a soft contact lens superior in long-wearability (extended-wearability). More precisely, the present invention relates to a hydrogel soft contact lens having no adhesion to a cornea in wearing and superiorities iri lens movement, comfort in wearing and extended-wearability.
  • The present invention further relates to an ophthalmologic lens material comprising a hydrophilic polysiloxane copolymer. The present invention still further relates to a hydrophilic copolymer superior in water wettability, oxygen permeability, deposition resistance, flexibility, optical transparency and strength useful as a soft contact lens.
    • BACKGROUND ART
  • Polysiloxane compounds, such as dimethylsilicone compounds as typical examples, have conventionally been widely used industrially by themselves or as modifiers for other materials utilizing specific functions such as heat resistance, electrical insulation, flexibility, lubrication and water repellency. For example, polydimethylsiloxane with methacrylic groups at both ends, which is a polymerizable polysiloxane, has been used as a polymer modifier for acrylic polymers or-polystyrene, utilizing the polymerization function. Polysiloxanes are used as gas permselective membranes due to high gas permeability and also as biomaterials or medical materials due to little influence on a human body. There are many studies and patent applications on an application to a contact lens utilizing their superior oxygen permeability, flexibility and optical transparency (for example, JP-B-63-29741 and JP Nos. 1430546, 2532406 and 2716181).
  • Contact lenses are fundamentally classified into a soft and a hard types. Hard contact lenses are literally hard and show an discomfort in wearing. However, a recent remarkable improvement in oxygen permeability has produced products for a continuous wearing. On the other hand, soft contact lenses have features in softness and comfortable in wearing but still have many problems. Soft contact lenses are classified, in detail, to a hydrogel and a non-hydrofel types.
  • Hydrogel soft contact lenses are composed of copolymers of hydrophilic monomers such as hydroxyethyl methacrylate and N-vinylpyrrolidone as a main-component and prepared by lathe-cutting, molding or cast molding methods, followed by a swelling treatment in a physiological saline solution to obtain a lens with water content of about 40-80%.
  • Non-hydrogel soft contact lenses include, for example, a silicone rubber lens obtained by thermal curing of a mixture of polydimethylsiloxane capped with vinyldimethylsilyl groups at both ends of its molecular chain and methylhydrogenpolysiloxane by molding method after an addition of a platinum-based catalyst, and a flexible lens with an elastic modulus between soft and hard types, composed of polyperfluoroether as a main component, linked with polymerizable groups such as methacrylic groups at both ends (JP Nos. 1278540 and 1677573). Another example for manufacturing a non-hydrogel soft contact lens with comfortable in wearing is preparing a lens by lathe-cutting a hard substrate obtained by a copolymerization of (meth)acrylic acid and (meth)acrylate followed by an esterification and/or a transesterification treatment (JP No. 952157).
  • There are many inconveniences in handling a hydrous soft contact lens such as poor oxygen permeability, liability to fracture, inferior durability and periodical boiling sterilization required due to an easy deposition of tear components and a possibility of germ growth. Soft contact lens of a higher water content has improved oxygen permeability to a certain extent but is not sufficient enough, and does not have a satisfactory strength for a extended-wearable lens.
  • On the other hand, a non-hydrogel soft contact lens also has the following problems. Silicone lens, started with a big expectation due to extremely high oxygen permeability, has poor wettability to tear owing to a hydrophobic lens surface. Although surface treatments to improve hydrophilic property such as plasma processing and grafting hydrophilic monomers have been tried but sufficient levels of hydrophilic property and durability have not been obtained. Another problem is an adhesion during wearing and deposition with proteins and lipids in tear. In order to overcome these problems, a hydrogel soft contact lens consisting of silicone hydrogel with high oxygen permeability has been proposed, but it is still insufficient in surface wettability, liable to lipid staining and thus inferior as an extended-wearable lens (for example, Japanese Patent No. 1421481, JP-A-6-503276, JP-A-7-505169, JP-A-7-508063 and JP-A-8-245737).
    • DISCLOSURE OF THE INVENTION
  • After through studies on characteristics of the materials for a soft contact lens to solve the above mentioned problems, the inventors could accomplish the present invention by finding out that the objectives could be attained by giving specific characteristics to a lens material.
  • The inventors found out that copolymers of hydrophilic siloxane monomers with amide-group-containing monomers having N-vinyl group were very useful to solve the above mentioned problems, and that contact lenses obtained in a specific polar mold were, in particular, useful to solve the above mentioned problems, and thus attained the present invention.
  • The present invention includes the following disclosures.
  • 1. A hydrogel soft contact lens with-contact angle of a surface in a range of 10-50° and 30-90° by the captive bubble method in water and the sessile drop method in air, respectively, oxygen permeability of not less than 30 and water content of not less than 5%.
  • 2. A hydrogel soft contact lens with a surface contact angle in a range of 10-40° and 30-80° by the captive bubble method in water and the sessile drop method in air, respectively, oxygen permeability of not less than 80 and water content of not less than 9%.
  • 3. The hydrogel soft contact lens according to the above 1st item or the 2nd item, comprising a copolymer obtained by a polymerization of at least one kind of hydrophilic siloxane monomer..
  • 4. The hydrogel soft contact lens according to the above 3rd item, wherein the hydrophilic siloxane monomer is a hydrophilic polysiloxane monomer shown by the following formula (1):
    Figure US20060211789A1-20060921-C00001
    wherein, X1 is a polymerizable substitutent shown by the following formula (2):
    Figure US20060211789A1-20060921-C00002
    wherein, R5 is a hydrogen or a methyl group; Z1 is a linking group selected from —NHCOO—, —NHCONH—, —OCONH—R6-NHCOO—, —NHCONH—R7-NHCONH— and —OCONH—R8-NHCONH—(R6, R7 and R8 are hydrocarbon groups with 2-13 carbon atoms); m is 0-10; n is 3-10; p is 0 when m is 0 and 1 when m is not less than 1; q is an integer of 0-20; R1, R2, R3 and R4 are groups selected from hydrocarbon groups with 1-12 carbon atoms or trimethylsiloxy group, respectively; and the structure [Y1] shows a polysiloxane backbone comprising not less than 2 siloxane linkages.
  • 5. The hydrogel soft contact lens according to the above 4th item, wherein the structure [Y1] is a structural unit shown by the following formula (1):
    Figure US20060211789A1-20060921-C00003
  • wherein, R9 and R10 are groups selected from hydrocarbon groups with 1-12 carbon atoms, hydrocarbon groups substituted with fluorine atom(s), trimethylsiloxy group and hydrophilic substituents, and may be different from each other in the chain, and r is 7-1000.
  • 6. The hydrogel soft contact lens according to the above 5th item, wherein the structural unit [Y1] according to the above 5th item is a polysiloxane monomer with R9 and R10 being methyl group.
  • 7. The hydrogel soft contact lens according to the above 4th item consisting of a hydrophilic polysiloxane monomer, wherein the structural unit [Y1] according to the above 4th item comprises linked structural units (Ia) and (IIa) shown below, the linking ratio of the units (Ia) and (IIa) being 1:10-10:1, and the total number of the linking of (Ia) and (IIa) being 7-1000:
    Figure US20060211789A1-20060921-C00004
  • wherein, each of R11 and R12 is a hydrocarbon group with 1-12 carbon atoms, respectively, each of R13 and R14 is a hydrocarbon group with 1-12 carbon atoms or a hydrocarbon group substituted with fluorine atom(s), respectively, and at least one of R13 and R14 is a hydrocarbon group substituted with fluorine atom(s).
  • 8. The hydrogel soft contact lens according to the above 7th item consisting of a hydrophilic poly-siloxane monomer, wherein R11, R12 and R13 are methyl groups and R14 is a trifluoropropyl group in the structural unit [Y1] according to the above 7th item.
  • 9. The hydrogel soft contact lens according to the above 4th item consisting of a hydrophilic polysiloxane monomer, wherein the structural unit [Y1] according to the above 4th item comprises linked structural units (Ib) and (IIb) shown below, the linking ratio of the structural units (Ib) and (IIb) being (Ib)/(IIb)=0.1-200, and the total number of the linking of (Ib) and (IIb) being 7-1000:
    Figure US20060211789A1-20060921-C00005
  • wherein, R15 and R16 are a group selected from hydrocarbon group with 1-12 carbon atoms, hydrocarbon group with 1-12 carbon atoms substituted with fluorine atom(s) and trimethylsiloxy group, respectively, and they may be the same or different from each other; each of R17 and R18 is a group consisting of hydrocarbon group with 1-12 carbon atoms, trimethylsiloxy group or hydrophilic groups, respectively; and at least one of R17 and R18 groups is a hydrophilic group, wherein the hydrophilic group is a linear or cyclic hydrocarbon group linked with at least one substituent selected from hydroxy group and polyoxyalkylene group.
  • 10. The hydrogel soft contact lens according to the above 4th item consisting of a hydrophilic polysiloxane monomer, wherein the structral unit [Y1] according to the above 4th item comprises linked structural units (Ic), (IIc) and (IIIc) shown by the following formulas:
    Figure US20060211789A1-20060921-C00006
  • wherein, R19 is a hydrophilic substituent which is a linear or cyclic hydrocarbon group linked with at least one substituent selected from hydroxy group and polyoxyalkylene group; the linking ratio of the structural units (Ic), (IIc) and (IIIc) being ((Ic)+(IIc))/(IIIc)=0.5-100, (IIc)/(Ic)=0-1, and the total number of the linking of (Ic), (IIc) and (IIIc) being 7-1000.
  • 11. The hydrogel soft contact lens according to the above 10th item, wherein the linking ratio of the structural units (IC), (IIc) and (IIIc) in the structural unit [Y1] according to the above 10th item is ((Ic)+(IIc))/(IIIc)=1-50, (IIc)/(Ic)=0.01-0.50, and the total number of the linking of (Ic), (IIc) and (IIIc) is 20-500.
  • 12. The hydrogel soft contact lens according to any one of the above 9th-11th items consisting of a hydrophilic polysiloxane monomer, wherein the hydrophilic substituent is shown by the following formula (4) or (5):
    —R2O(OH)a   (4)
  • wherein, R20 is a hydrocarbon group with 3-12 carbon atoms; the group may have a group of —O—, —CO— or —COO— inserted between carbon atoms; only one OH group can be substituted on one carbon atom; and a is a number not less than 1:
    —R21-(OR22)b-OZ2   (5)
  • wherein, R21 is a hydrocarbon group with 3-12 carbon atoms; the group may have a group of —O—, —CO— or —COO— inserted between carbon atoms; R22 is a hydrocarbon group with 2-4 carbon atoms, and the number of the carbon atoms may be different from each other when b is not less than 2; b is 1-200; Z2 is a group selected from hydrogen atom, hydrocarbon group with 1-12 carbon atoms and —OCOR23 (R23 is a hydrocarbon group with 1-12 carbon atoms).
  • 13. The hydrogel soft contact lens according to any one of the above 9th-11th items, wherein the hydrophilic substituent is selected from the group consisting of the following formulas (6), (7) and (8):
    —C3H6OH   (6)
    —C3H6OCH2CH(OH)CH2OH   (7)
    —C3H6OC2H4OH   (8)
  • 14. The hydrogel soft contact lens according to the above 9th-11th items, wherein the hydrophilic substituent is selected from the group of the following formulas (9) and (10):
    —C3H6(OC2H4)cOH   (9)
    —C3H6(OC2H4)dOCH3   (10)
  • wherein, c and d are 1-40.
  • 15. The hydrogel soft contact lens according to the above 4th item, wherein the structural unit [Y1] in the hydrophilic polysiloxane monomer shown by the formula (1) according to the above 4th item is expressed by the following formula (11):
    Figure US20060211789A1-20060921-C00007
  • wherein, Z3 is a linking group shown by the following formula (12):
    -A-COHN—R30-NHCOO—R31—CONH—R30-NHCO-A-   (12)
  • wherein, R30 is a hydrocarbon group with 4-20 carbon atoms and may be interrupted by oxygen atom; R31 is polyoxyalkylene group or fluorine-substituted polyoxyalkylene group; the structural unit [Y2] means a polysiloxane structural unit shown by any one of formulas (3), linked structure of (Ia) and (IIa), linked structure of (Ib) and (IIb) or linked structure of (Ic), (IIc) and (IIIc); a means —O— or —NH— linkage; each of R24, R25, R26 and R27 is a group selected from hydrocarbon group with 1-12 carbon atoms and trimethylsiloxy group, respectively; each of R28 and R29 is a hydrocarbon group with 3-12 carbon atoms and may be interrupted by oxygen atom, respectively.
  • 16. The hydrogel soft contact lens according to the above 15th item consisting of a polymer from a hydrophilic polysiloxane monomer, wherein R30 in the Z3 liking group shown by the formula (11) according to the above 15th item is selected from hexamethylene, tetramethylene, dicyclohexylmethane, hydrogenated xylylene and isophorone groups and R31 is selected from polyethylene glycol, polypropylene glycol and polybuitylene glycol.
  • 17. The hydrogel soft contact lens according to any one of the above 4th-14th item, wherein the polymerizable Z1 liking group shown by the formula (2) according to the above 4th item is shown by the following formula(13):
    —B—COHN—R32-NHCOO—R33-CONH—R32-NHCO—B—  (13)
    wherein, R32 is a hydrocarbon group with 4-20 carbon atoms and may be interrupted by oxygen atom; R33 is polyoxyalkylene or polyoxyfluoloalkylene group; B means —O— or —NH— linkage.
  • 18. The hydrogel soft contact lens according to the above 17th item consisting of a polymer from a hydrophilic polysiloxane monomer, wherein R32 in the formula (13) is selected from hexamethylene, tetramethylene, dicyclohexylmethane, hydrogenated xylylene and isophorone groups and R33 is selected from polyethylene glycol, polypropylene glycol and polybutylene glycol.
  • 19. A hydrogel soft contact lens obtained by a copolymerization of at least 1 kind of hydrophilic polysiloxane monomer in the formula (1) with at least 1 kind of hydrophilic monomer.
  • 20. The hydrogel soft contact lens according to the above 19th item, wherein the hydrophilic monomer is an amide monomer.
  • 21. The hydrogel soft contact lens according to the above 19th item, wherein the hydrophilic monomer is an amide monomer containing N-vinyl group.
  • 22. The hydrogel soft contact lens according to the above 21st item, wherein the amide monomer containing N-vinyl group is selected from N-vinyl formamide, N-vinyl acetamide, N-vinyl isopropylamide, N-vinyl-N-methylacetamide, N-vinylpyrrolidone and N-vinyl caprolactam.
  • 23. The hydrogel soft contact lens according to the above 21st item, wherein the amide monomer containing N-vinyl group is N-vinyl N-methylacetamide or N-vinylpyrrolidone.
  • 24. The hydrogel soft contact lens according to any one of the above 21st-23rd items, consisting of a copolymer composed of 10-99% by weight of a hydrophilic polysiloxane monomer and 1-80% by weight of an amide monomer containing N-vinyl group.
  • 25. The hydrogel soft contact lens according to any one of the above 21st-23rd items, consisting of a copolymer composed of 30-95% by weight of a hydrophilic polysiloxane monomer and 5-60% by weight of a monomer containing an amide group with N-vinyl group.
  • 26. The hydrogel soft contact lens according to any one of the above 3rd-25th items, obtained by a polymerization of a crosslinkable monomer linked with urethane groups.
  • 27. The hydrogel soft contact lens according to the above 26th item, wherein the crosslinkable monomer is shown by the following formula (14):
    Figure US20060211789A1-20060921-C00008
  • wherein, R34 and R35 are hydrogen or methyl group and may be the same or different from each other; Z4 is —NHCOO— linking group; R36 is selected from hydrocarbon groups with 2-10 carbon atoms or polyoxyethylene group shown by —(C2H4O)gC2H4— (g is 2-40); f is 0-10; e is 0 when f is o and 1 when f is not less than 1.
  • 28. The hydrogel soft contact lens according to the-above 26th item, wherein the crosslinkable monomer is shown by the following formula (15):
    Figure US20060211789A1-20060921-C00009
  • 29. The hydrogel soft contact lens according to any one of the 19th-28th items, wherein surface contact angel is in a range of 10-50° and 30-90° by the captive bubble method in water and by the sessile drop method in air, respectively, oxygen permeability is not less than 30 and water content is not less than 5%.
  • 30. The hydrogel soft contact lens according to the above 29th item, wherein surface contact angle is in a range of 10-40° and 30-80° by captive bubble method in water and by sessile drop method in air, respectively, oxygen permeability is not less than 80 and water content is not less than 9%.
  • 31. The hydrogel soft contact lens according to any one of the above 1st-30th items, manufactured by a polymerization in a mold.
  • 32. The hydrogel soft contact lens according to the above 3rd item, wherein the hydrophilic siloxanyl monomer is shown by the following formula (16):
    Figure US20060211789A1-20060921-C00010
  • wherein, R37 is hydrogen or methyl group; R38 is siloxanyl alkyl group; and h is 0-20.
  • 33. The hydrogel soft contact lens according to the above 3rd item, consisting of a polymer comprising at least the hydrophilic siloxanyl monomer shown by the following above (16), a hydrophilic monomer and a crosslinkable monomer.
  • 34. The hydrogel soft contact lens according to any of the above 32nd or 33rd item, wherein the hydrophilic siloxanyl monomer according to the above 32nd item is shown by the following formula (17):
    Figure US20060211789A1-20060921-C00011
  • 35. The hydrogel soft contact lens according to any one of the above 32nd-34th items, consisting of a polymer comprising at least a hydrophilic siloxanyl monomer shown by the above formula (16), a siloxanyl monomer shown by the following formula (18), a hydrophilic monomer and a crosslinkable monomer:
    Figure US20060211789A1-20060921-C00012
  • wherein, R39 is hydrogen or methyl group; R40 is siloxanyl alkyl group; and j is 0-4.
  • 36. The hydrogel soft contact lens according to the above 35th item, wherein the siloxanyl monomer shown by the formula (18) is tris(trimethylsiloxy)silylpropyl methacrylate.
  • 37. The hydrogel soft contact lens according to any of the above 33rd or 35th item, wherein the hydrophilic monomer is an amide monomer containing N-vinyl group.
  • 38. The hydrogel soft contact lens according to the above 37th item, wherein the amide monomer containing N-vinyl group is N-vinyl- N-methylacetamide or N-vinyl pyrrolidone.
  • 39. The hydrogel soft contact lens according to any one of the above 32nd-38th items, prepared by processing a polymer comprising a hydrophilic siloxanyl monomer by lathe-cutting and polishing method followed by swelling with water.
  • 40. A hydrogel soft contact lens manufactured by a polymerization in a mold, wherein a mold material is insoluble to a composition of polymerizable monomers and at least one side of the mold for forming a lens surface has a polar group.
  • 41. The hydrogel soft contact lens according to the above 40th item, wherein the mold material consists of a resin with a contact angle to water of not higher than 90° by the sessile drop method.
  • 42. The hydrogel soft contact lens according to the above 40th item, wherein the mold material consists of a resin with a contact angel to water is 65-80° by the sessile drop method.
  • 43. The hydrogel soft contact lens according to any one of the above 40th-42nd items, wherein the mold consists of a resin selected from polyamide, polyethylene terephthalate and ethylene-vinylalcohol copolymer.
  • 44. The hydrogel soft contact lens according to any one of the above 40th-42nd items, wherein the mold material consists of ethylene-vinylalcohol copolymer.
  • 45. The hydrogel soft contact lens according to any one of the above 40th-44th items, wherein contact angle of a surface is in a range of 10-50° and 30-90° by the captive bubble method in water and by the sessile-drop method in air, respectively, and water content is not less than 5%.
  • 46. The hydrogel soft contact lens according to any one of the above 40th-44th items, wherein surface contact angle is in a range of 10-40° and 30-80° by the captive bubble method in water and by the sessile drop method in air, respectively, and water content is not less than 9%.
  • 47. The hydrogel soft contact lens according to any one of the above 1st-38th items, manufactured by a polymerization in a mold according to any one of the above 40th-44th items.
  • 48. A method for manufacturing a contact lens according to any one of the above 1st-38th items, wherein the method is a polymerization in a mold.
  • 49. A method for manufacturing a contact lens, wherein the mold according to the above 48th item consists of the material according to any one of the above 40th-44th items.
    • BEST MODE FOR CARRYING OUT THE INVENTION
  • The present invention provides a hydrogel soft contact lens with contact angle of lens surface within a range of 10-50° and 30-90° by the captive bubble method in water and the sessile drop method in air, respectively, oxygen permeability not less than 30 and water content not less than 5%, and further a hydrogel soft contact lens with contact angle of lens surface within 10-40°, preferably 10-30°, and more preferably 15-30° by the captive bubble method in water, and 30-80°, preferably 40-70° by the sessile drop method in air, oxygen permeability not less than 80, preferably not less than 100, and water content not less than 9%.
  • The present invention, in particular, includes the following.
  • (1) A hydrogel soft contact lens with contact angle of lens surface in a range of 10-50° and 40-70° by the captive bubble method in water and the sessile drop method in air, respectively, oxygen permeability not less than 30 and water content not less than 9%.
  • (2) The hydrogel soft contact lens according to the above mentioned (1), wherein contact angle of surface in a range of 10-30° and 50-65° by the captive bubble method in water and the sessile drop method in air, respectively, oxygen permeability not less than 100 and water content not less than 15%.
  • (3) The hydrogel soft contact lens according to the above mentioned (1) or (2), consisting of a polymer comprising at least hydrophilic siloxanyl methacrylate shown by the general formula I, and having tensile modulus of 0.8-2×107 dyne/cm2:
    Figure US20060211789A1-20060921-C00013
  • wherein, m is an integer of 0-4; and RSi is siloxanyl group.
  • (4) The hydrogel soft contact lens according to any of the above mentioned (1) - (3), consisting of a polymer comprising at least hydrophilic siloxanyl methacrylate shown by the general formula I, hydrophilic monomer and crosslinkable monomer.
  • (5) The hydrogel soft contact lens according to the above mentioned (3) or (4), wherein the hydrophilic siloxanyl methacrylate is shown by the following formula I1:
    Figure US20060211789A1-20060921-C00014
  • (6) The hydrogel soft contact lens according to any of the above mentioned (1)-(5), consisting of a polymer comprising at least hydrophilic siloxanyl methacrylate shown by the general formula I, siloxanyl methacrylate shown by the general formula I2, a hydrophilic monomer and a crosslinkable monomer:
    Figure US20060211789A1-20060921-C00015
  • wherein, m is an integer of 0-4; and RSi is siloxanyl group.
  • (7) The hydrogel soft contact lens according to any of the above mentioned (1)-(6), consisting of a polymer comprising at least 5-20% by weight of hydrophilic siloxanyl methacrylate shown by the general formula I1, 15-30% by weight of tris(trimethylsiloxy)silylpropyl methacrylate, 25-35% by weight of N-vinylpyrrolidone, 20-30% by weight of N-dimethylacrylamide, 5-10% by weight of trifluoroethyl methacrylate, 5-10% by weight of 1,1,2,2-tetraethoxy-2-hydroxypropyl methacrylate and 0.2-2% by weight of ethylene glycol dimethacrylate.
  • (8) The hydrogel soft contact lens according to any of the above mentioned (1)-(7), prepared by processing a polymer comprising hydrophilic siloxanyl methacrylate to lens shape by a lathe-cutting and polishing method and hydration.
  • (9) The hydrogel soft contact lens according to any of the above mentioned (1)-(6), consisting of a polymer comprising a hydrophilic polysiloxane monomer shown by the following general formula II, a hydrophilic monomer and a crosslinkable monomer:
    Figure US20060211789A1-20060921-C00016
    Wherein, R1 is hydrogen or methyl group; each of R2, R3, R4 and R5 is hydrocarbon group with 1-12 carbon atoms or trimethylsiloxy group; Y consists of the structural units (I′) and (II′) shown below, ratio of the structural unit (I′) and the structural unit (II′) being 1:10 - 10:1 and total number of the structural units (I′) and (II′) being 7-200; b and c are integers of i-20, being the same or different from each-other; p is an integer of 0-20; X is —NHCOO— group or —OOCNH—R10—NHCOO— group (R10 is hydrocarbon group with 4-13 carbon atoms):
    Figure US20060211789A1-20060921-C00017
  • wherein, each of R6 and R7 is hydrocarbon group with 1-12 carbon atoms; each of R8 and R9 is hydrocarbon group with 1-12 carbon atoms or fluorine-substituted hydrocarbon group; and at least one of R8 and R9 is fluorine-substituted hydrocarbon group.
  • (10) The hydrous soft contact lens according to the above mentioned (9), prepared by a polymerization of a polymerizable composition comprising a hydrophilic polysiloxane monomer shown in the general formula II in a mold having polar groups on its surface to a lens shape, followed by hydration.
    • DETAILED DESCRIPTION OF THE PRESENT INVENTION
  • Now the above mentioned invention will be explained in detail.
  • The present invention provides a hydrogel soft contact lens with contact angle of lens surface in a range of 10-50° and 30-90° by the captive bubble method in water and the sessile drop method in air, respectively, oxygen permeability not less than 30 and water content not less than 5%.
  • By controlling lens surface characteristics, it became possible to provide a contact lens which can exhibit superior water wettability of lens surface for a long wearing period, high oxygen permeability, reduced protein and lipid depositions, stable lens movement, and little adhesion to a cornea. Preferably, a soft contact lens enabling continuous wearing for 30 days can be realized by keeping the contact angle of lens surface in a range of 10-40°, more preferably 10-30°, still more preferably 15-30° by the captive bubble method in water, and also 30-80°, more preferably 40-70° by the sessile drop method in air, oxygen permeability not less than 80, more preferably not less than 100, and water content not less than 9%.
  • Surface contact angle of a contact lens of the present invention exceeding 50° by the captive bubble method in water often causes staining on a lens surface with lipid and thus not desirable. Although smaller contact angle is desirable, materials with contact angle less than 10° are not suitable due to an easy taking up of proteins of low molecular weight into lens inside and inferior physical properties such as tensile strength generally observed in such materials. On the contrary, contact angle higher than 90° by the sessile drop method in air is also undesirable due to generation of cloudiness during wearing, easy adhesion to a cornea caused by extremely increased-lipid staining and deformation of a lens.
  • Furthermore, a lower limit of contact angle by the sessile drop method of the material is, in general, preferably 30° because of superior physical properties such as tensile strength. Oxygen permeability lower than 30 is not desirable because of an increased load to a cornea making extended-wearing difficult. Water content lower than 5% is not desirable because of significant increase in staining of a lens surface with proteins and lipids and extremely increased adhesion to a cornea.
  • There is no limitation in a composition of the contact lens of the present invention so long as the lens has characteristics described above. However, a soft contact lens obtained from a polymer containing a hydrophilic siloxanyl methacrylate shown by the above mentioned formula I is preferable.
  • Use of the hydrophilic siloxanyl methacrylate enabled to provide a contact lens with high oxygen permeability, less depositions of proteins and lipids, superior water wettability at lens surface maintained during an extended-wearing period, stabilized lens movement and less adhesion to a cornea.
  • In the general formula I, RSi is a siloxanyl group, and at least one kind of group selected from the groups shown by the following formula (1a), (2a) and (3a) may be used:
    Figure US20060211789A1-20060921-C00018
  • wherein, 1 is an integer of 1-10. In the general formula I, m is an integer of 0-4 and m not less than 5 is undesirable because the monomer becomes too hydrophilic to be compatible with other copolymerizable monomers, giving a cloudiness during polymerization and a difficulty in homogeneous mixing of monomers. In the formula (3a), 1 is an integer of 1-10 and 1 not less than 11 is undesirable because of a reduced compatibility with other copolymerizable monomers.
  • The above described hydrophilic siloxanyl methacrylate is synthesized by reacting 2-isocyanatoethyl methacrylate with siloxanylalkyl alcohol.
  • The soft contact lens of the present invention consists of a hydrogel polymer with water content of about 5-60%, comprising hydrophilic siloxanyl methacrylate shown by the general formula I, and having oxygen permeability not less than about 30 and tensile modulus 0.8-2×107 dyne/cm2. The lens provides less adsorption of proteins and lipids to inner part of lens, easy lens care, little decrease in lens movement caused by stain accumulation, superior stability in lens shape, flexible and comfortable, no adhesion to a cornea during wearing caused by sucking disk effect and thus enabling an extended-wearing.
  • Water content less than 5% is undesirable due to an easy adsorption of lipids to lens, resulting in an adhesion to a cornea. On the contrary, water content over 60% is also undesirable because of giving low strength, poor scratch resistance in handling, easy fracture and high adsorption of proteins. Oxygen permeability lower than 30 is undesirable due to difficulty in continuous wearing and possibility to cause diseases of a cornea by long wearing. Tensile modulus less than 0.8×107 dyne/cm2 is undesirable due to inferior stability in lens shape, difficulty in handling to wear and poor feeling in wearing together with possible damages to cornea and sclera caused by easy turning back of lens at an edge or waving on an eye surface during wearing. Tensile modulus over 2×107 dyne/cm2 is undesirable because of an increased sucking disk effect resulting in a significant decrease in lens movement and occurrence of an adhesion.
  • Among hydrophilic siloxanyl methacrylates shown by the general formula I, used for a soft contact lens of the present invention, the structure shown by the following formula Id is preferable because of providing a well-balanced performance among water content, oxygen permeability and modulus, together with less deposition of proteins and lipids:
    Figure US20060211789A1-20060921-C00019
  • Any polymer can be used for a soft contact lens of the present invention so long as it contains hydrophilic siloxanyl methacrylate described above. For example, the polymer includes copolymers with the following copolymerizable compounds: acrylic monomers such as methyl acrylate, ethyl acrylate and acrylic acid; methacrylic monomers such as methyl methacrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate and methacrylic acid; siloxane monomers such as tris(trimethylsiloxy)silylpropyl methacrylate, bis(trimethylsiloxy)methylsilylpropyl methacrylate, pentamethyldisiloxanepropyl methacrylate, tris(trimethylsiloxy)silylpropyloxyethyl methacrylate, and tris(polydimethylsiloxy)silylpropyl methacrylate; fluorosiloxane monomers such as tris(dimethyltrifluoropropylsiloxy) silylpropyl methacrylate; perfluoroalkyl monomers such as 2,2,2-trifluoroethyl methacrylate, 2,2,3,3,3-pentafluoropropyl methacrylate and hexafluoroisopropyl methacrylate; fluoroalkyl and fluoroalkylether monomers containing hydroxyl group such as 1,1,2,2-tetrafluoroethoxy-2-hydroxypropyl methacrylate; hydrophilic monomers such as N-vinylpyrrolidone, N,N′-dimethylacrylamide and N-vinyl-N-methylacetamide; crosslinkable monomers such as ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate and tetramethyldisiloxanebis(propylmethacrylate).
  • Among these, copolymers with siloxane methacrylates, fluoroalkylsiloxane methacrylates, fluoroalkyl methacrylates, fluoroalkylether methacrylates containing hydroxyl groups, hydrophilic monomers, crosslinkable monomers with two or more unsaturated groups within a molecule and siloxane macromers with polymerizable unsaturated groups at molecular ends are preferable because of well-balanced physical properties such as oxygen permeability, stain deposition resistance and mechanical strength. Preferable hydrophilic monomers in the present invention are amide monomers containing N-vinyl group, and N-vinylpyrrolidone or N-vinyl-N-methylacetamide, in particular, can provide a contact lens with superior surface wettablity. An example of such contact lens comprises a polymer composed of 5-20% by weight of hydrophilic siloxanyl methacrylate shown by formula Ii, 15-30% by weight of tris(trimethylsiloxy)silylpropyl methacrylate, 25-35% by weight of N-vinylpyrrolidone, 20-30% by weight of N-dimethylacetamide, 5-10% by weight of trifluoroethyl methacrylate, 5-10% by weight of 1,1,2,2-tetrafluoroethoxy-2-hydroxypropyl methacrylate and 0.2-2% by weight of ethylene glycol dimethacrylate.
  • A contact lens of the present invention can be manufactured by conventional lens manufacturing methods. The methods includes, for example, a method by lathe-cutting of polymer bock followed by polishing, a method to cast a monomer composition into a mold with corresponding lens shape followed by polymerization, and a method to form only one face of lens by casting method using a polymerization mold then finish the other face by lathe-cutting and polishing method, etc. A feature of the present invention is that a contact lens can be manufactured by lathe-cutting and polishing method. Use of hydrophilic siloxanyl methacrylate shown by formula I improves a compatibility between siloxanyl monomer to raise oxygen permeability and hydrophilic monomer to enhance water wettability to give a polymer sufficiently hard for machining and polishing in dry state and a hydrous soft contact lens with superior optical transparency when swelled with water and suitable range of modulus. A lens manufactured by lathe-cutting and polishing method is preferable because it has the same polymer composition in surface and inside of a lens, and exhibits a stable lens performances such as water wettability and depositions of proteins and lipids together with little change in surface characteristics during long-wearing.
  • Also, a polymer comprising hydrophilic polysiloxane monomer shown by the general formula II can be used for a contact lens of the present invention:
    Figure US20060211789A1-20060921-C00020
  • wherein, R1 is hydrogen or methyl group; each of R2, R3, R4 and R5 is a hydrocarbon group with 1-12 carbon atoms or trimethylsiloxy group; Y consists of the structural units (I′) and (II′) shown below, ratio of the structural unit (II) and the structural unit (II′) being 1:10-10:1 and total number of the structural units (I′) and (II′) being 7-200; each of b and c is an integer of 1-20, being the same or different from each other; p is an integer of 0-20; X is —NHCOO— group or —OOCNH—R10—NHCOO— group (R10 is a hydrocarbon group with 4-13 carbon atoms).
    Figure US20060211789A1-20060921-C00021
  • wherein, each of R6 and R7 is a hydrocarbon group with 1-12 carbon atoms; and each of R8 and R9 is a hydrocarbon or fluorinated hydrocarbon group with 1-12 carbon atoms, and at least one of R8 and R9 being fluorinated hydrocarbon group.
  • The above hydrophilic polysiloxane monomer may be copolymerized with the copolymerizable monomers described above. Furthermore, copolymers further comprising polysiloxane monomers with polymerizable unsaturated groups at molecular ends may be used,-which are described in JP-B-3-240021, JP-B-3-257420, JP-B-4-50814, JP-B-5-45612, JP No. 2592356, etc., and shown by the following formulas (4a) - (7a):
    Figure US20060211789A1-20060921-C00022
  • wherein, R1 is hydrogen or methyl group; each of R2, R3, R4 and R5 is hydrocarbon group or trimethylsiloxy group; each of R6 and R7 is hydrocarbon group with 1-12 carbon atoms; each of a and c is an integer of 1-20; and b is an integer of 10-100.
    Figure US20060211789A1-20060921-C00023
  • wherein, R1 is hydrogen or methyl group; each of R2, R3, R5 and R5 is methyl or trimethylsiloxy group; each of R6 and R7 is a hydrocarbon group with 1-12 carbon atoms; each of a and c is an integer of 1-20; p is an integer of 0-20; b is an integer of 10-100; X is —NHCOO— group or —OOCNH—R8—NHCOO— group (R8 is hydrocarbon group with 4-13 carbon atoms).
    Figure US20060211789A1-20060921-C00024
  • wherein, R1 is hydrogen or methyl group; each of R2, R3, R4 and R5 is hydrocarbon group with 1-12 carbon atoms or trimethylsiloxy group; Y consists of the structural units (I) and (II) shown below, ratio of the structural unit (I) and the structural unit (II) being 1:10-10:1 and total number of the structural units (I) and (II) being 7-200; each of b and c is an integer of 1-20, being the same or different from each other; p is an integer of 0-20.
    Figure US20060211789A1-20060921-C00025
  • wherein, each of R6 and R7 is a hydrocarbon group with 1-12 carbon atoms; and each of R8 and R9 is a hydrocarbon or fluorinated hydrocarbon group with 1-12 carbon atoms, and at least one of R8 and R9 being fluorinated hydrocarbon group.
    Figure US20060211789A1-20060921-C00026
  • wherein, X is substituent with radically polymerizable unsaturated group; Y is R9 or X; c is 0-500; b is 1-500; each of R3 and R4 is a group selected from alkyl group, hydrocarbon group with 1-10 carbon atoms, halogenated alkyl group with 1-10 carbon atoms and trimethylsiloxy group, being the same or different from each other; R is a fluorinated substituent linked with at least one hydroxyl group; each of R1, R2, R6, R7, R8 and R9 is a group selected from fluorinated substituent with at least one hydroxyl group, alkyl group with 1-10 carbon atoms, halogenated alkyl groups with 1-10 carbon atoms and trimethylsiloxy group, being the same or different from each other, and being the same to or different from R5.
  • Among these, copolymers with siloxane methacrylates, fluoroalkylsiloxane methacrylates, fluoroalkyl methacrylates, fluoroalkylether methacrylates containing hydroxyl groups, hydrophilic monomers, crosslinkable monomers with two or more unsaturated groups in a molecule and polysiloxane monomers with polymerizable unsaturated groups at molecular ends are preferable because of well-balanced physical properties such as oxygen permeability, stain deposition and mechanical strength.
  • A contact lens comprising the above described polysiloxane monomer as a main component can be manufactured by conventional lens manufacturing methods such as the casting method in which a monomer composition is injected into a polymerization mold with a corresponding lens shape followed by a polymerization. A lens manufactured by using a polymerization mold made of a material with polar groups at a surface such as ethylene-vinylalcohol copolymer, polyamide and polyethylene terephthalate, is particularly preferable due to formation of a thick stable hydrophilic layer at a lens surface, little change in surface characteristics during extended-wearing, together with stable performances such as superior water wettability and reduced deposition of proteins and lipids.
  • The present invention includes the following.
  • (1) An ophthalmologic lens material obtained by copolymerization of at least one or more types of compounds of the following (a) and one or more types of compounds of the following (b).
  • (a) Hydrophilic polysiloxane monomers shown by the formula (1b):
    Figure US20060211789A1-20060921-C00027
  • wherein, X is a polymerizable substitution group shown by the formula (2b):
    Figure US20060211789A1-20060921-C00028
  • wherein, R5 is hydrogen or methyl group; Z1 is a linking group selected from —NHCOO—, —NHCONH—, —OOCNH—R6—NHCOO—, —NHCONH—R7—NHCONH— and —OOCNH—R8—NHCONH— (R6, R7 and R8 are hydrocarbon groups with 2-13 carbon atoms); m is 0-10; n is 3-10; p is 0 when m is 0 and 1 when m is not less than 1; q is an integer of 0-20;
  • each of R1, R2, R3 and R4 is a hydrocarbon group with 1-12 carbon atoms or trimethylsiloxy group; Y consists of linkage of the structural units [I] and [II] shown by the following formulas, ratio of the structural unit [I] and the structural unit [II] being [I]/[II]=0.1-200 and total number of the structural units [I] and [II] being 10-1000:
    Figure US20060211789A1-20060921-C00029
  • wherein, each of R9 and R10, being the same or different from each other, is a group selected from hydrocarbon group with 1-12 carbon atoms, fluorinated hydrocarbon group with 1-12 carbon atoms and trimethylsiloxy group; each of R11 and R12 consists of hydrocarbon group with 1-12 carbon atoms, trimethylsiloxy group or hydrophilic substituent, and at least one of R11 and R12 being hydrophilic substituent. A hydrophilic substituent in the present invention means a linear or cyclic hydrocarbon group linked with at least one substituent selected from hydroxyl group and oxyalkylene group.
  • (b) Amide-group-containing monomers having N-vinyl group
  • (2) An ophthalmologic lens material described in (1) above, wherein the structural unit Y consists of a linkage of the structural units [I′], [II′] and [III′] shown by the following formulas:
    Figure US20060211789A1-20060921-C00030
  • wherein, R13 is a hydrophilic substituent which is linear or cyclic hydrocarbon group linked with at least one substituent selected from hydroxyl group and oxyalkylene group; linking ratio of the structural units [I′], [II′] and [III′] is ([I′]+[II′])/[III′]=0.5-100 and [II′] [I′]=0-1 and total number of [I′], [II′] and [III′] is 10-1000.
  • (3) An ophthalmologic lens material described in (2) above, wherein the structure Y consists of a linkage of the structural units [I′], [II′] and [III′], linking ratio of structural units. [I′] [II′] and [III′] being ([I′]+[II′])/[III′]=1-50 and [II′]/[I′]=0.01-0.5, and total number of [I′] [II′] and [III′] being 20-500.
  • (4) An ophthalmologic lens material according to (1) above, wherein hydrophilic substituent of hydrophilic polysilioxane monomer is expressed by the formula (3b) or the formula (4b):
    —R14 (OH)a   (3b)
  • wherein, R14 is a hydrocarbon group with 3-12 carbon atoms and may have —O—, —CO— or —COO— group inserted between carbon atoms; number of hydroxyl group on the same carbon atom is limited to only one; a is larger than 1;
    —R15—(OR16)b—OZ2   (4b)
  • wherein, R15 is hydrocarbon group with 3-12 carbon atoms and may have —O—, —CO— or —COO— group inserted between carbon atoms; R16 is hydrocarbon group with 2-4 carbon atoms and number of carbon atoms may be different from each other when b is not less than 2; b is 1-200; Z2 is a group selected from hydrogen, hydrocarbon group with 1-12 carbon atoms and —OOCR17 (R17 is hydrocarbon group with 1-12 carbon atoms).
  • (5) An ophthalmologic lens material described in (4) above, wherein hydrophilic substituent is selected from the formulas (5b), (6b) and (7b):
    —C3H5OH   (5B)
    —C3H6OCH2CH(OH)CH2OH   (6B)
    C3H6OC2H4OH   (7B)
  • (6) An ophthalmologic lens material described in (4) above, wherein hydrophilic substituent is selected from the formulas (8b) and (9b):
    —C3H6(OC2H4)cOH   (8b)
    —C3H6(OC2H4)dOCH3   (9b)
  • wherein, c and d are 2-40.
  • (7) An ophthalmologic lens material described in (1) above, wherein the amide-group-containing monomer having N-vinyl group is selected from N-vinyl formamide, N-vinyl acetamide, N-vinyl isopropylamide, N-vinyl-N-methyl acetamide, N-vinyl pyrrolidone and N-vinyl caprolactam.
  • (8) An ophthalmologic lens material-described in (7) above, wherein the amide-group-containing monomer having N-vinyl group is N-methyl acetamide or N-vinyl pyrrolidone.
  • (9) An ophthalmologic lens material described in any of (1)-(8) above, consisting of a copolymer comprising at least 10-99% by weight of hydrophilic polysiloxane monomer and 1-90% by weight of amide-group-containing monomer having N-vinyl group.
  • (10) An ophthalmologic lens material described in (9) above, consisting of a copolymer comprising at least 30-95% by weight of hydrophilic polysiloxane monomer and 5-70% by weight of amide-group-containing monomer having N-vinyl group.
  • (11) An ophthalmologic lens material described in (1)-(10) above, consisting of a copolymer copolymerized further comprising a crosslinkable monomer linked with urethane group.
  • (12) An ophthalmologic lens material described in (11) above, prepared by copolymerization of monomers comprising a crosslinkable monomer shown by the formula (10b)
    Figure US20060211789A1-20060921-C00031
  • wherein, each of R16 and R18 being the same or different from each other, is hydrogen or methyl group; Z3 is urethane linking group; R17 is a group selected from hydrocarbon group with 2-10 carbon atoms and polyoxyethylene group shown by —(C2H4O)gC2H4— (g is 2-40); f is 0-10; e is 0 when f is 0 and 1 when f is not less than 1.
  • (13) An ophthalmologic lens material described in (11) or (12) above, wherein a crosslinkable monomer is shown by the formula (11b):
    Figure US20060211789A1-20060921-C00032
  • (14) A soft contact lens made of an ophthalmologic lens material described in any of (1)-(13) above.
  • (15) A method for manufacturing an ophthalmologic lens in a mold using an ophthalmologic lens material described in any of (1)-(14) above, characterized by that the said mold is made of a material with polar group.
  • (16) The method for manufacturing an ophthalmologic lens described in (15) above, characterized by that the mold material is insoluble to a composition of polymerizable monomers and at least one side of the mold for forming lens surface has contact angle to water not higher than 90°.
  • (17) The method for manufacturing an ophthalmologic lens described in (15) or (16) above, wherein the mold material is a resin selected from polyamide, polyethylene terephthalate and ethylene-vinylalcohol copolymer.
  • (18) The method for manufacturing an ophthalmologic lens described in (17) above, wherein the mold material is ethylene-vinylalcohol copolymer.
  • (19) The method for manufacturing an ophthalmologic lens described in any of (15)-(18) above, characterized by a polymerization by means of an irradiation of UV ray or visible light.
  • (20) The method for manufacturing an ophthalmologic lens described in any of (15)-(19) above, wherein the ophthalmologic lens is a soft contact lens.
  • In this specification, the structure units of [I] and [II] of hydrophilic polyasiloxane monomers are expressed as a block type linkage, but the present invention also includes a random linkage type. A hydrophilic substituent in the said polysiloxane monomers is a linear or cyclic hydrocarbon group linked with at least one substituent selected from hydroxyl group and oxyalkylene group, and preferably such group as shown by the following formula (3b) or (4b):
    —R14(OH)a   (3b)
  • wherein, R14 is hydrocarbon group with 3-12 carbon atoms and may have —O—, —CO— or —COO— group inserted between carbon atoms; number of hydroxyl group on the same carbon atom is limited to only one; a is not less than 1;
    —R15—(OR16)b—OZ2.   (4b)
  • wherein, R15 is hydrocarbon group with 3-12 carbon atoms and may have —O—, —CO— or —COO— group inserted between carbon atoms; R16 is hydrocarbon group with 2-4 carbon atoms and number of carbon atoms may be different each other when b is not less than 2; b is 1-200; z2 is a group selected from hydrogen, hydrocarbon group with 1-12 carbon atoms and —OOCR17 (R17 is hydrocarbon group with 1-12 carbon atoms).
  • Preferable hydrophilic group includes: monohydric alcohol substituent such as —C3H6OH, —C8H16OH, —C3H6OC2H4OH, —C3H6OCH2CH(OH)CH3, —C2H4COOC2H4OH and —C2H4COOCH2CH(OH)C2H5; polyhydric alcohol substituent such as —C3H6OCH2CH(OH)CH2OH, —C2H4COOCH2CH(OH)CH2OH and —C3H6OCH2C(CH2OH)3; and polyoxyalkylene substituent such as —C3H6(OC2H4)4OH, —C3H6 (OC2H4)30OH, —C3H6(OC2H4)10OCH3 and —C3H6(OC2H4)10—(OC3H6)10OC4H9. Among these, particularly preferable groups are: alcohol substituent such as —C3H6OH, —C3H6OCH2CH(OH)CH2OH and —C3H6OC2H4OH; and polyoxyethylene substituent such as —C3H6(OC2H4)cOH and —C3H6(OC2H4)dOCH3 (c and d are 2-40) from the viewpoints of superior hydrophilic property and oxygen permeability.
  • Fluorine-containing substituent provides staining resistance to the material, but an excess substitution impairs hydrophilic property. A hydrocarbon substituent with 1-12 carbon atoms linked with fluorine atoms is preferable including: 3,3,3-trifluoropropyl group, 1,1,2,2-tetrahydroperfluorooctyl group and 1,1,2,2-tetrahydroperfluorodecyl group. Among these, 3,3,3-trifluoropropyl group is most preferable in view of hydrophilic property and oxygen permeability. Besides the hydrophilic substituent and the fluorine-containing substituent, substituents linked to Si atom include hydrocarbon group with 1-12 carbon atoms or trimethylsiloxy group, being the same or different from each other. Preferable group is alkyl group with 1-3 carbon atoms, and methyl group is particularly preferable. A polysiloxane chain with small substituent such as methyl group is flexible and has good oxygen permeability.
  • Ratio of linking numbers of the siloxane structure unit [I] and the siloxane structure unit linked with hydrophilic substituent [II], [I]/[II], is 0.1-200. When the ratio of the siloxane structure unit [I] decreases, flexibility and oxygen permeability of the siloxane chain decreases, whereas reduced content of the hydrophilic substituent lowers hydrophilic property and deteriorates surface water wettability. Total number of the siloxane structure units [I] and [II] is preferably 10-1000, more preferably 20-500. Shorter polysiloxane chain lowers flexibility and oxygen permeability of the polymer. Too long -siloxane chain is undesirable due to a remarkable increase in viscosity of a polysiloxane monomer itself, which leads to difficulties in manufacturing and handling of the monomer together with lower degree of polymerization.
  • It is preferable from the viewpoint of polymerization that polymerizable unsaturated groups are linked to the ends of siloxane chain and structure of the unsaturated group is acrylate or methacrylate group. As a linking group to Si atom, hydrocarbon group containing urethane or urea linkages is preferable, and may be linked to Si atom through oxyethylene group. Urethane or urea linkage is highly polar and enhances hydrophilic property and strength of the polymer. A structure having two groups of this linkage can be introduced by a reaction with diisocyanate compound, and a linking group between the isocyanate linkages is a hydrocarbon with 2-13 carbon atoms and may be linear, cyclic or aromatic types. Aliphatic hydrocarbon is more preferable due to superior light resistance. Diisocyanate compounds used include trimethylene diisocyanate, hexamethylene diisocyanate, cyclohexyl diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexyl diisocyanate and 2,4-torylenediisocyanate and the like.
  • There are various synthesis methods for the hydrophilic polysiloxane monomers disclosed in the present invention. An example includes the following: A ring-opening polymerization of a mixture of cyclic siloxane with hydrosilane (Si—H), cyclic siloxane with hydrocarbon group and disiloxane with hydroxyalkyl groups at both ends, along with cyclic siloxane with fluorine-substituted hydrocarbon group in certain cases, is performed using an acidic catalyst such as sulfuric acid, trifluoromethanesulfonic acid and acidic clay to obtain hydrosilyl-group-containing polysiloxane compound having hydroxyl groups at both ends. In this case, siloxane compounds with various degree of polymerization and introduction ratios of fluorine-containing substituent and hydrosilyl group can be obtained by changing feed ratios of each cyclic siloxanes and disiloxane compounds.
  • Isocyanate substituted acrylates or isocyanate substituted methacrylates are then reacted with hydroxyl groups at the ends of polysiloxane to obtain hydrosilane-containing fluorinated silixane compound with polymerizable unsaturated groups at both ends. Here, isocyanate-substituted methacrylates include such monomers as methacryloxyethylisocyanate and methacryloylisocyanate. Isocyanate compounds with acrylate or methacrylate group obtained by reacting hydroxyl-group-containing acrylate or methacrylate such as hydroxyethyl methacrylate and hydroxybutyl acrylate with various diisocyanate compounds are also utilized.
  • Then, hydrophilic polysiloxane monomers can be obtained by adding a hydrophilic compound with unsaturated hydrocarbon group to the hydrosilane using a transition metal catalyst such as chloroplatinic acid, utilizing so called hydrosilylation reaction. In the hydrosilylation reaction, it is known that a dehydrogenation reaction occurs as a side reaction if an active hydrogen compound such as hydroxyl group and carboxylic acid is present. Therefore, if these active hydrogen atoms are present in a hydrophilic compound to be introduced, the side reaction should be suppressed by protecting the active hydrogen atom in advance or adding buffer agents (refer to, for example, U.S. Pat. No. 3,907,851 and JP-B-62-195389).
  • Another rout of synthesis is the following method: After synthesis of hydrosilyl-group-containing polysiloxane compound having hydoxyl groups at both ends, hydrophilic compound is introduced by hydrosilylation in advance, then polymerizable groups are introduced to both ends of the siloxane by reacting with isocyanate-substituted methacrylate or the like.
  • In this case also, if active hydrogel, which is reactive to isocyanate, is present in the hydrophilic compound, side reaction with isocyanate must be prevented by introducing a protective group. Alternatively, silicate ester derivative such as dimethoxy silane or diethoxysilane compound instead of cyclic siloxane can be used as a starting raw material. Mixtures of two or more hydrophilic polysiloxane monomers thus obtained can also be used.
  • In a copolymer as a material for an ophthalmologic lens, in particular, as a material for a hydrogel soft contact lens of the present invention, a hydrophilic monomer is indispensable as a comonomer component in addition to the hydrophilic polysiloxane monomer. Preferably an amide monomer, an amide monomer containing N-vinyl group among them, is useful to obtain superior transparency, staining resistance and surface wettability. Although a reason for superiority of the amide monomer containing N-vinyl group is not clear, it is supposed that a microwisely phase-separated structure may be formed in the copolymerization with the hydrophilic polysiloxane monomer disclosed in the present invention due to remarkably different copolymerizability, molecular weight and polarity of these monomers resulting in providing stable staining resistance and hydrophilic property to lens surface while maintaining transparency.
  • An amide monomer containing N-vinyl group is selected from N-vinyl formamide, N-vinyl acetamide, N-vinyl isopropylamide, N-vinyl-N-methyl acetamide, N-vinyl pyrrolidone and N-vinyl caprolactam, and mixed use of two or more kinds of monomers may be possible. N-vinyl-N-methyl acetamide and N-vinyl pyrrolidone are, in particular, preferable.
  • As for a composition of copolymerization, a copolymer is preferably composed of 10-99% by weight of hydrophilic polysiloxane monomer and 1-90% by weight of amide monomer containing N-vinyl group, and more preferably composed of 30-95%. by weight of hydrophilic polysiloxane monomer and 5-70% by weight of amide monomer containing N-vinyl group. Lower content of hydrophilic polysiloxane monomer reduces oxygen permeability and flexibility. An excess content of amide monomer containing N-vinyl group increases water content and lowers strength.
  • A material disclosed in the present invention also includes copolymers obtained by addition of monomers other than the hydrophilic polysiloxane monomer and the amide monomer containing N-vinyl group. Any monomer can be used in the present invention so long as it is copolymerizable, and hydrophilic monomers, among them, are useful for a hydrous material. It is because they have good compatibility with the hydrophilic polysiloxane monomer and also can further improve surface wettability of polymer and modify water content. They include, for example, monomers containing hydroxyl group such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate and glycerol methacrylate; monomers containing fluorine-substituted group such as 3-(1,1,2, 2-tetrafluoroethoxy)-2-hydroxypropyl methacrylate; monomers containing carboxyl group such as methacrylic acid, acrylic acid and itaconic acid; monomers containing alkyl substituted amino group such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; acrylamide or methacrylamide monomers such as N,N′-dimethylacrylamide, N,N′-diethylacrylamide, N-methylacrylamide, methylenebisacrylamide and diacetoneacrylamide; monomers containing oxyalkylene group such as methoxypolyethylene glycol monomethacrylate and polypropylene glycol monomethacrylate; and the like.
  • Siloxanyl acrylates are also useful comonomers to adjust oxygen permeability. For example, they include tris(trimethylsiloxy)silylpropyl methacrylate, bis(trimethylsiloxy)methylsilylpropyl methacrylate and pentamethyldisiloxanyl methacrylate. Polymerizable polydimethylsiloxane substituted with methacrylate group and the like can also be used for the similar objective.
  • Other monomers, which can be utilized, include fluorinated monomers such as fluoroalkyl acrylates and fluoroalkyl methacrylates, for example, trifluoroethyl acrylate, tetrafluoroethyl acrylate, tetrafluoropropyl acrylate, pentafluoropropyl acrylate, hexafluorobutyl acrylate, hexafluoroisopropyl acrylate and methacrylates corresponding to these acrylates.
  • Furthermore, alkyl acrylate monomers and alkyl methacrylate monomers can also be used if necessary. They include, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, stearyl acrylate and methacrylates corresponding to these acrylates. In addition, monomers with high glass transition temperature (Tg) such as cyclohexyl methacrylate, tert-butyl methacrylate and isobornyl methacrylate can also be used to enhance mechanical properties.
  • Moreover, crosslinkable monomers other than hydrophilic polysiloxane monomers can be used to improve mechanical properties and stability and adjust water content. For example, they include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, bisphenol A dimethacrylate, vinyl methacrylate; acrylates corresponding to these methacrylates; siloxane derivatives such as 1,3-bis(3-methacryloxypropyl)tetramethyldisiloxane and the like.
  • The inventor of the present invention found out that crosslinkable monomers linked with urethane group, in a polymerization composition disclosed in the present invention, were particularly superior in compatibility and hydrophilic property, together with improvement of mechanical properties. Bifunctional crosslinkable monomers shown by the formula (10b) are preferable:
    Figure US20060211789A1-20060921-C00033
  • wherein, R16 and R18 are hydrogen or methyl group, being the same or different from each other; Z3 is urethane linking group; R17 is selected from hydrocarbon group with 2-10 carbon atoms or polyoxyethylene group expressed by —(C2H4O)gC2H4— (g is 2-40); f is 0-10; e is 0 when f is 0 and 1 when f is not less than 1.
  • Although reasons for a superiority of the above compounds as a crosslinkable monomer are not clear, it is considered that they have good compatibilities and copolymerizability and contribute to strength improvement by intermolecular interaction because the hydrophilic polysiloxane monomers disclosed in the present invention have a similar urethane group backbone. Examples of crosslinkable monomers of urethane linkage type are; 2-methacryloylcarbamoyloxyethyl methacrylate, 2-(2-methacryloxycarbamoyloxy)ethyl acrylate, 2-(2-methacryloxyethylcarbamoyloxy)propyl methacrylate, 2-methacryloxyethylcarbamoyloxytetraethylene glycol methacrylate and the like.
  • Particularly, crosslinkable monomers shown by the formula (11b) are preferable:
    Figure US20060211789A1-20060921-C00034
  • These crosslinkable monomers can be used alone or in combination of two or more kinds.
  • In order to improve a balance of characteristics of a hydrophilic material such as optical characteristics, oxygen permeability, mechanical strength, recovery from deformation, staining resistance in wearing, dimensional stability in tear and these durability, mixed monomers of these copolymerizable monomers can be used, various additives may further be added before or after polymerization, if necessary. Examples of additives include dyes or pigments with various coloring characteristics and UV absorbers. Furthermore, when a lens is manufactured using a mold, mold releasing agents such as surfactants can be added to improve separation of lens from the mold.
  • A polymer used for an ophthalmologic lens of the present invention is formed to an ophthalmologic lens by so called a mold method in which a monomer mixture comprising, for example, hydrophilic polysiloxane monomer and amide monomer containing N-vinyl group is filled into a mold, followed by a radical polymerization by the known method, or by so called a spin casting method in which a monomer mixture is fed in a rotatable hemisphere mold, followed by a polymerization. In these cases, polymerization of a solution of monomer mixture added with solvents in a mold is utilized to adjust degree of polymerization or lens swelling ratio. As the solvents to be added, those dissolving monomers well are used. Their examples include alcohols such as ethanol and isopropanol; ethers such as dimethylsulfoxide, dimethylformamide, dioxane and tetrahydrofran; ketons such as methylethyl keton; esters such as ethyl acetate; and the like. Two or more of these solvents are also used in combination.
  • Any mold material can be used for mold polymerization or casting polymerization, so long as it is substantially insoluble to monomer mixture and lens can be separated after polymerization. For example, polyolefin resins such as polypropylene and polyethylene can be used, and materials having polar groups at a surface and small contact angle to water are preferable. Polar group here is an atomic group with strong affinity with water and includes hydroxyl group, nitrile group, carboxyl group, polyoxyethylene group, amide group, urethane group and the like. Preferrable mold material is insoluble to a polymerization monomer composition and has contact angle to water at least at the part for forming one lens surface, not higher than 90°, preferably 65-80°, by the sessile drop method. A lens formed using a mold material having surface contact angle smaller than 80° shows particularly superior water wettability and stable performance in lipid deposition and the like. A mold material having surface contact angle smaller than 65° is not practical because it has a difficulty in lens separation from the mold material after polymerization, resulting in minute surface damages or fractures at an edge part of lens. A mold material soluble to monomer compositions is also difficult to use practically because it causes the separation problem of a lens, rough lens surface and low transparency. For example, acrylic or styrene-based resins such as methyl methacrylate copolymer and styrene copolymer can not be used because they are soluble to a composition comprising amide monomers disclosed by the present invention, although they have superior molding characteristics.
  • More preferably, a mold material is a resin selected from polyamide, polyethylene terephthalate and ethylene-vinylalcohol copolymer, and ethylene-vinylalcohol copolymer is particularly more preferable from the viewpoints of an easiness in molding itself providing a dimensionally stable mold and giving stable water wettability to lens. Ethylene-vinylalcohol copolymer resin to be used is available as “Soarlite” from The Japan Synthetic Chem. Ind. Co. Ltd. or “EVAL” from Kuraray Co., Ltd. Various grades with ethylene copolymerization ratio of about 25-50% by mole can be used in the present invention. In addition, polyethylene terephthalate with low crystallinity is difficult to be used as a mold material due to solubility problem for monomer compositions, but a grade with enhanced crystallinity can be used. For example, a drawn film of polyethylene terephthalate can be used by forming to a mold shape.
  • As a method for initiating polymerization in lens molding, a photopolymerization method to polymerize by UV or visible light irradiation in the presence of photopolymerization initiators in a monomer mixture, or a radical polymerization method to thermally polymerize using azo compounds or organic peroxides, may be used. Examples of photopolymerization initiator are benzoin ethyl ether, benzyl dimethyl ketal, α,α′-diethoxy acetophenone and 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, examples of organic peroxide are benzoin peroxide and t-butyl peroxide, and examples of azo compound are azobisisobutyronitorile and azobisdimethylvaleronitorile. Among them, a photo-polymerization method is preferable due to providing a stable polymerization in a short cycle time.
  • Surface of molded lens may be modified, if necessary, by applying plasma treatment, ozone treatment, graft polymerization or the like.
  • The present invention further includes the following compounds as a hydrophilic polysiloxane monomer shown by the formula (1).
  • (1) A bifunctional orgonosiloxane monomer shown by the following formula (1c):
    Figure US20060211789A1-20060921-C00035
  • wherein, each of R1, R2, R3 and R4 is a group selected from —CH3 and —CH2CH2CF3, being the same or different from each other; m+n is an integer of 7-1000;
  • R5 is a group selected from hexamethylene group, tetramethylene group, dicyclohexylmethane group, hydrogenated tolylene group, hydrogenated xylylene group and isophorone group; a is an integer of 0-20; R6 is a group selected from —(C2H4O)1—, —(CH2C(CH3)HO)1— and —(C4H8O)1—, 1 being an integer of 1-40.
  • (2) A bifunctional organosiloxane monomer shown by the following formula (2c):
    Figure US20060211789A1-20060921-C00036
  • wherein, each of R7, R8, R11, R12, R13, R14, R17 and R18 is a groups selected from —CH3 and —CH2CH2CF3, being the same or different from each other; m, o, p and r are integers of 5-500; b is an integer of 0-20;
  • each of R9, R10, R15 and R16 is a group selected from —CH3 and —(CH2CH2O)sCH3, being the same or different from each other; n and q are integers of 1-500; s is an integer of 1-40;
  • R19 is a group selected from hexamethylene group, tetramethylene group, dicyclohexylmethane group, hydrogenated tolylene group, hydrogenated xylylene group and isophorone group;
  • R20 is a group selected from —(C2H4O)1—, —(CH2C(CH3)HO)1— and —(C4H8O)1—; 1 is an integer of 1-40.
  • (3) A-bifunctional organopolysiloxane monomer shown by the following formula (3c):
    Figure US20060211789A1-20060921-C00037
  • wherein, each of R21 and R22 is a group selected from —CH3 and —CH2CH2CF3, at least one of them being —CH3; m is an integer of 5-500; m+n is an integer of 7-1000; c is an integer of 0-20;
  • each of R23 and R24 is a group selected from —CH3 and —CH2CH2CF3, at least one of them being —CH2CH2CF3; n is an integer of 0-500;
  • R25 is a group selected from hexamethylene group, tetramethylene group, dicyclohexylmethane group, hydrogenated tolylene group, hydrogenated xylylene group and isophorone group;
  • R26 is a group selected from —(C2H4O)1—, —(CH2C(CH3)HO)1— and —(C4H8O)1—; 1 is an integer of 1-40;
  • R5 group in the formula (1c), R19 group in the formula (2c) and R25 group in the formula (3c) are residual groups of bifunctional isocyanate and include, for example, hexamethylene diisocyanate, tetramethylene diisocyanate, 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, methyl 2,6-diisocyanatecaproate, 3-isocyanatemethyl-3,5,5-trimethylcyclohexyl isocyanate, dicyclohexylmethane-4,4′-diisocyanate, hydrogenated xylene isocyanate, hydrogenated tolylene diisocyanate and isophorone diisocyanate. Among them, residual groups of hexamethylene diisocyanate and isophorone diisocyanate are preferable in view of well-balanced mechanical characteristics of a lens;
  • R6, R20 and R26 groups are residual groups of polyoxyalkylene glycol and include groups such as polyethylene glycol, polypropylene glycol and polytetraethylene glycol, and those with polymerization degree of 1-40 can be used. Among them polyethylene glycol is preferable due to providing superior water wettability of lens and staining resistance performance.
  • A bifunctional organopolysiloxane monomer shown by the formula (1c) and (2c) can be obtained, for example, by reacting two molar equivalent of a diol having polysiloxane structure obtained by a ring-opening insertion reaction among 1,3-bis-(hydroxyethoxypropyl)tetramethyldisiloxane, octamethylcyclotetrasiloxane and 1,3,5-trifluoropropyltrimethylcyclotrisiloxane, with an isocyanate-modified compound at both ends of polyethylene glycol obtained, for example, by a reaction of polyethylene glycol and two molar equivalent of hexamethylene diisocyanate, together with methacryloxyethyl isocianate.
  • Furthermore, a bifunctional organopolysiloxane monomer shown by the formula (3c) can be obtained, for example, by reacting a diol having polysiloxane structure obtained, for example, by a ring-opening insertion reaction between 1,3-bis-(hydroxyethoxypropyl)tetramethyldisiloxane and octamethylcyclotetrasiloxane, together with, if necessary, 1,3,5-trifluoropropyltrimethylcyclotrisiloxane, with an excess amount of an isocyanate-modified compound at both ends of polyethylene glycol obtained, for example, by a reaction of two molar equivalent of hexamethylene diisocyanate, followed by reacting thus obtained product with ab excess amount of 2-hydroxyethyl methacrylate.
  • An ophthalmologic lens material obtained by copolymerization of a hydrophilic polysiloxane monomer and an amide monomer containing N-vinyl group disclosed in the present invention is superior in transparency, water wettability, oxygen permeability and staining resistance. Although the material can be used for a hard lens such as a hard contact lens, it is useful for an application to a soft lens, in particular, a hydrogel soft contact lens. The material is, of course, also useful for an intraocular lens or a cornea lens. An ophthalmologic lens material disclosed by the present invention includes a hydrogel soft contact lens with contact angle in a range of 10-50° and 30-90° by the captive bubble method in water and by the sessile drop method in air, respectively, oxygen permeability of not less than 30 and water content of not less than 5%, and further a hydrogel soft contact lens with contact angle in a range of 10-40° and 30-80° by the captive bubble method in water and by the sessile drop method in air, respectively, oxygen permeability of not less than 80 and water content of not less than 9%. They provide a contact lens suitable for 30 days of continuous-wearing as described above.
  • Hereinbelow, the present invention will be further explained in detail using Examples, but the present invention should not be limited by these Examples.
  • Evaluation methods for lens characteristics in the Examples 1-7 and the Comparative Examples 1-3 are as follows.
  • (1) Water Content
  • A soft contact lens was immersed in purified water at 37° C. for 72 hours. After taking out and quick wiping off of surface water, the lens was weighed precisely. The lens was then dried at 80° C. in a vacuum dryer to a constant weight. Water content was calculated from a weight change as follows.
    water content=(weight difference/weight before drying)×100(%)
    (2) Oxygen Permeability (Dk Value)
  • Dk value was determined in physiological saline solution at 35° C. according to Standard Measurement Method for Dk Value by Japan Contact Lens Association, using an oxygen permeability measurement instrument for film, Model K-316-IPI manufactured by Rika Seiki Ind. Co., Ltd.
    An expression of Dk value;×10−11(cm2/sec)·(ml O2/ml×mmHg)
    (3) Tensile Modulus
  • Test pieces of about 3 mm width were cut out from a central part of lens and tensile modulus (unit; dyne/cm2) was determined from a initial slop of a stress-strain curve obtained by tensile test at the rate of 100 mm/min in physiological saline-solution at 25° C., using Autograph (Model AGS-50B manufactured by Shimadzu Corp.)
  • (4) Protein Deposition
  • A model soiling solution with the following composition was prepared.
    NaCl 0.9 weight %
    NaH2PO4 0.0184 weight %
    Na2HPO4 0.076 weight %
    Egg lysozyme 0.12 weight %
    Bovine serum albumin 0.388 weight %
    CaCl2(H2O)2 0.0407 weight %
  • A lens was immersed in 2 ml of the solution at 37° C. for 24 hr, then washed by shaking in purified water for 30 min., followed by taking out and gentle wiping off of surface water.
  • The lens was then immersed in 2 ml of protein assay reagent (BCA liquid), followed by reacting at 40° C. for 5 hours, and absorption at UV 562 nm was measured using a spectrophotometer (Model V-550 manufactured by Japan Spectrophotometer Co., Ltd.)
  • An amount of protein adhered per lens was determined using a calibration line measured separately.
  • (5) Lipid Deposition
  • A lens was immersed in a phosphoric acid buffer dispersed solution containing 1% of olive oil and kept at 40° C. for 20 hours in a constant temperature oven. The lens was immersed in 5 ml of purified water in a container, then washed by shaking for 30 sec. Washing was repeated five times. After vacuum drying, the lens was extracted with a mixed solvents of chloroform/methanol: 2/1. The extract was then colored with triglyceride G reagent, and absorption at 505 nm was measured using a spectrophotometer (Model V-550 manufactured by Japan Spectrophotometer Co., Ltd.). An amount of lipid deposition per lens was determined using a calibration line measured separately.
  • (6) Water Wettability
  • Water wettability of a surface of soft contact lens was evaluated by measuring contact angle. Contact angle was measured by the captive bubble method in purified water using a contact angle tester (Model CA-DT manufactured by Kyowa Kaimen Kagaku Co., Ltd.). In addition, in order to evaluate water wettability in a dry state of a lens, measurement by the sessile drop method was also carried out. The measurements of contact angle by the captive bubble method and the sessile drop method were performed at 25° C. in accordance with Journal of Japan Contact Lens Society, 25 (1), 100, 1983. Smaller value and difference in both methods mean more superior water wettability, along with little change by drying of lens. On a recovered lens after wearing, water wettabilty was also evaluated by visual inspection on a state of water film maintained on a lens surface when it was pulled up from storage liquid. A case when wet state was maintained in whole surface for not less than 30 sec. was ranked as “superior”, a case when wet state was lost even partly within one sec. was ranked as “poor”, and a case when wet state was maintained for a time between them was ranked as “good”.
  • (7) Wearing Test on a Rabbit Eye
  • Corneal curvature of a white rabbit was measured, and a lens with 13.5 mm of diameter, 0.05 mm of center thickenss, −3.00 diopter of power and base curve larger than the measured curvature by about 0.2 mm was used for wearing test and observed for 21 days. A state of wearing was recorded and a cornea was inspected in every 7 days by visual inspection and fluorescence dying.
  • (8) Measurement of Vickers hardness
  • A micro hardness tester for light loading (Model MVK-IS manufactured by Akashi Seisakusyo Co., Ltd.) was used. Test piece was polished to mirror finish, stored in a silica gel desiccator, then hardness was measured at 25° C.
    • EXAMPLE 1 Synthesis of Hydrophilic Siloxanyl Methacrylate
  • A solution of 12.4 g of 2-isocyanatoethyl methacrylate in 30 ml of cyclohexane was prepared, then said solution was added dropwisely into a solution of 30 g of tris (trimethylsiloxy)silyl propyloxyethyl alcohol in 50 ml of cyclohexane added with 0.03 g of dibutyltin laurate, followed by reacting for 24 hours at 50° C. After finishing the reaction by confirming disappearance of isocyanate group by an infrared spectrum, the reaction mixture was stirred with adding water, and further stirred with adding 500 ml of n-hexane, then about 1000 ml of saturated aqueous NaCl solution. The organic layer was separated, and dried by adding magnesium sulfate. Removal of the solvent under a reduced pressure gave 32 g of hydrophilic siloxanyl methacrylate shown by the following formula I1:
    Figure US20060211789A1-20060921-C00038
    [Preparation of Lens]
  • A mixture of 9.5 parts by weight of thus obtained hydrophilic siloxanyl methacrylate, 23.5 parts by weight of tris(trimethylsiloxy)silylpropyl methacrylate, 30.5 parts by weight of N-vinylpyrrolidone, 23.5 parts by weight of N-dimethyl acrylamide, 7 parts by weight of trifluoroethyl methacrylate, 5 parts by weight of 1,1,2,2-tetrafluoroethoxy-2-hydroxypropyl methacrylate, 0.9 parts by weight of ethyleneglycol dimethacrylate and 0.1 parts by weight of azobisisobutylonitrile (hereinafter “AIBN”) was dissolved and mixed under nitrogen atmosphere.
  • The mixture was poured into a test tube made of propylene with a diameter of 16mm, and polymerized for 72 hours at 90° C. resulting in a transparent polymer with Vickers Hardness of 8.4.
  • From the polymer thus obtained, a lens with base curve: 9.0 mm, power: −3.00 diopter, diameter: 14.0 mm and thickness at center: 0.05 mm was prepared by a lathe-cutting and polishing method. By swelling the dry lens obtained with a physiological saline solution for 3 hours then with a soaking solution for 16 hours at 90° C. gave a hydrogel soft lens. The lens obtained showed, after dipping in purified water for 72 hours at 37° C., 46% of water content and 1.0×107 dyne/cm2 of tensile modulus. Depositions of proteins and lipids to the lens were evaluated by dipping the lens in a model soiling solution proving less deposition such as 10 μg/lens for protein and 40 μg lens for lipid. In addition, oxygen permeability (Dk value) measured with a disk having a given thickness was 60, and water wettability was 22° by the captive bubble method and 60° by the sessile drop method.
  • The lenses described above were worn on eyes of a white rabbit for continuous 21 days, and showed a smooth movement without adhesion and little deposition on the lenses. In addition, it was proved that the lenses were safe enough for an extended-wearing without showing any problem on the eyes of the rabbit. The recovered lenses maintained the superior water wettability, and did not show any change during use in the lens performances.
    • EXAMPLE 2
  • A transparent polymer was obtained by polymerizing according to the same method as described in the Example 1 except for using 18 parts by weight of hydrophilic siloxanyl methacrylate and 15 parts by weight of tris(tri-methylsiloxy)silylpropyl methacrylate. From the polymer thus obtained, hydrogel soft lenses having 44% of water content and 1.2×107 dyne/cm2 of tensile modulus were prepared. Furthermore, depositions of proteins and lipids were so little as 5 μg/lens and 38 μg/lens, respectively, and Dk value was 60. Water wettability was 20° by the captive bubble method and 56° by the sessile drop method.
    • EXAMPLE 3
  • As a hydrophilic siloxanyl methacrylate, a monomer having a fluorosiloxanyl alkyl group shown by the formula (2a) was synthesized similarly to the synthesis method in the Example 1. The monomer obtained was polymerized similarly to the method in the Example 1 resulting in a polymer, from which lenses were prepared similarly to the method in the Example 1. Water content and tensile modulus were 40% and 1×107 dyne/cm2, respectively. In addition, depositions of proteins and lipids were so little as 12 μg/lens and 35 μg/lens, respectively, and Dk value was 65. Water wettability was 20° by the captive bubble method and 57° by the sessile drop method.
    • EXAMPLE 4
  • As a hydrophilic siloxanyl methacrylate, a monomer having a siloxanyl alkyl group (1=10) shown by the formula (3a) was synthesized similarly to the synthesis method in the Example 1. The monomer obtained was polymerized similarly to the method in the Example 1 resulting in a polymer, from which lenses were prepared similarly to the method in the Example 1. Water content and tensile modulus were 40% and 0.9×107 dyne/cm2, respectively. In addition, depositions of proteins and lipids were so little as 15 μg/lens and 45 μg/lens, respectively, and Dk value was 68. Water wettability was 24° by the captive bubble method and 63° by the sessile drop method.
    • EXAMPLE 5
  • A mixture of 15 parts by weight of hydrophilic siloxanyl methacrylate, 25 parts by weight of tris(trimethylsiloxy)silylpropyl, methacrylate, 27 parts by weight of N-vinylpirrolidone, 20 parts by weight of N-dimethylacrylamide, 7 parts by weight of trifluoroethyl methacrylate, 5 parts by weight of 1,1,2,2-tetrafluoroethoxy-2-hydroxypropyl methacrylate, 0.9 parts by weight of ethyleneglycol dimethacrylate and 0.1 parts by weight of AIBN was polymerized similarly as in the Example 1 giving a transparent polymer having a Vicker Hardness of 7.5.
  • From the polymer obtained, lenses were prepared by the lathe-cutting and polishing method so that they had base curve of 8.5 mm, power of −3.00 diopter, size of 14.0 mm and center thickness of 0.05 mm. The dry lenses obtained were swelled in a physiological saline solution for 3 hours then in a soaking solution for 16 hours at 90° C. to give hydrous soft lenses. Water content and tensile modulus of the lenses obtained after dipping in purified water for 72 hours at 37° C. were 30% and 1.1×107 dyne/cm2, respectively. Depositions of proteins and lipids to the lens were evaluated by dipping the lens in a model staining solution proving less deposition such as 12 μg/lens for proteins and 35 μg/lens for lipids. In addition, oxygen permeation coefficient (Dk value) measured with a disk having a given thickness was 75, and water wettability was 22° by the air bubble method and 60° by the droplet method.
  • The lenses described above were worn on eyes of a white rabbit for continuous 21 days, and showed a smooth movement without adhesion and little deposition on the lenses. In addition, it was proved that the lenses were safe enough for an extended-wearing without showing any problem on the eyes of the rabbit. The recovered lenses showed good water wettability, and did not show any change during use.
    • EXAMPLE 6
  • The mixture of the monomers used in the Example 1 except for changing AIBN to 2,4,6-trimethylbenzoyl diphenylphosphin oxide (hereinafter “TPO”) was poured into a lens-shaped mold made of ethylene-vinylalcohol copolymer for casting polymerization, then polymerized by an irradiation of UV-ray followed by hydration to give soft contact lenses. Evaluations of physical properties of the lens carried out similarly to the Example 1 gave water content of 46% and Dk value of 60 both of which were same as in the Example 1, and proved that depositions of proteins and lipids were so little as 18 μg/lens and 150 μg/lens, respectively. Water wettability was 22° by the captive bubble method and 54° by the sessile drop method showing no decrease of water wettability of a surface by drying. An extended-wearing test with rabbit eyes showed less depositions and no deformation. Also water wettability was kept in a superior state without any change during use, and the water film on a surface did not disappear when the lens was taken out from the soaking solution.
    • COMPARATIVE EXAMPLE 1
  • A polymerization was carried out according to the method described in the Example 1 except for using no hydrophilic siloxanyl methacrylate and 33 parts by weight of tris(trimethylsiloxy)silylpropyl methacrylate. Button-like test pieces were prepared from the polymer thus obtained. An inspection of distortion showed a slight optical distortion. Hydrogel soft lenses were prepared as in the Example 1. Results of the evaluation on their physical properties showed water content of 45% and Dk value of 45 both of which were similar to the results in the Example 1, but more depositions of proteins and lipids which were 20 μg/lens and 255 μg/lens, respectively. Water wettability was 21° by the captive bubble method and 110° by the sessile drop method, and it became worse by drying with a remarkable change in a contact angle.
  • A long-wearing test with rabbit eyes showed more deposition and a partial deformation of the lens. Recovered lenses showed poor water wettability, and showed a state in which the lens lost water film on its surface immediately when it was taken out from the soaking solution.
    • COMPARATIVE EXAMPLE 2
  • The mixture of the monomers described in the Example 6 was poured into a lens-shaped mold for casting polymerization made of polypropylene, then polymerized by an irradiation of UV ray followed by swelling to give soft contact lenses. Evaluations of physical properties of the lenses carried out similarly to the Example 1 gave water content of 46% and Dk value of 60 both of which were same as in the Example 6, but showed more depositions of proteins and lipids which were 45 μg/lens and 450 μg/lens, respectively. Water wettability was 26° by the captive bubble method and 115° by the sessile drop method showing a remarkable difference between them, and water wattability of a surface decreased by drying. An extended-wearing test with rabbit eyes showed much deposition, a partial deformation of the lens. Water wettability also changed drastically, and the water film on a surface disappeared immediately when the lens was taken out from a soaking solution.
    • EXAMPLE 7
  • A hydrophilic polysiloxane monomer shown by the formula (8a) was synthesized by a reaction of corresponding dihydroxypropyl polysiloxane and 2-isocyanatoethyl methacrylate.
  • A mixture of monomers comprising 70 parts by weight of the hydrophilic polysiloxane monomer described above, 15 parts by weight of N-vinylpirrolidone, 15 parts by weight of N,N-dimethylacrylamide, 5 parts by weight of trifluoroethyl methacrylate, 1 part by weight of ethyleneglycol dimethacrylate and 0.5 parts by weight of TPO was poured into a lens-shaped mold for casting polymerization made of ethylene-vinylalcohol copolymer, then polymerized by an irradiation of UV ray followed by hydration to give soft contact lenses. Evaluations of physical properties of the lenses carried out similarly to the Example 1 gave water content of 23% and Dk value of 160, and little depositions of proteins and lipids which were 18 μg/lens and 50 μg/lens, respectively. Water wettability was 21° by the captive bubble method and 54° by the sessile drop method showing no decrease of water wettability of a surface by drying.
  • An extended-wearing test with rabbit eyes showed little depbsitioins and no deformation. Water wettability was also maintained in a superior state without any change during use, and a water film on a surface did not disappear for 60 seconds when the lens was taken out from a soaking solution.
    Figure US20060211789A1-20060921-C00039
    • COMPARATIVE EXAMPLE 3
  • The mixture of the monomers in the Example 7 was poured into a lens-shaped mold for casting polymerization made of polypropylene, then polymerized by an irradiation of UV ray followed by hydration to give soft contact lenses. Evaluations of physical properties of the lens carried out similarly to the Example 7 gave water content of 24% and Dk value of 165, and showed much adhesions of proteins and lipids which were 60 μg/lens and 350 μg/lens, respectively. Water wettability was 26° by the captive bubble method and 120° by the sessile drop method, and showed a remarkable decrease of water wettability of a surface by drying.
  • An extended-wearing test with rabbit eyes resulted in that the lenses became cloudy due to much depositions and also were deformed. Water wettability varied during use and water screen of a surface disappeared immediately when they were taken out from a storage liquid.
  • The present invention will be further explained in more detail with the following Synthesis Examples, Examples 8-22 and Comparative Examples 4-14. However, the present invention is not limited by these Examples. Each evaluation item was measured as follows.
  • (1) Optical Transparency
  • Evaluation was performed by visual inspections and results were ranked as follows: finely transparent without cloudiness; ◯, translucent with cloudiness; Δ, opaque with cloudiness; x
  • (2) Water Wettability
  • Wettability to the purified water was evaluated by visual inspections. Lenses were pulled up vertically after dipping in the purified water for one day, then water wettability was ranked by a time for which water film was maintained for: 5 seconds or more; ◯, 1-5 seconds; Δ, 1 second or less; x.
  • (3) Water Wettability in Dry State
  • A Lens was dipped in the purified water then taken out. After wiping off adhered water, the lens was left for 10 minutes at 25° C. After dipping in the purified water, the lens was pulled up vertically, then water wettability was evaluated and ranked by a time for which water film was maintained for: 5 seconds or more; ◯, 1-5 seconds; Δ, 1 second or less; x.
  • (4) Contact Angle
  • Contact angle of a water drop on a surface of mold material was measured using a contact angle measuring instrument (manufactured by Kyowa Kaimen Kagaku Co., Ltd., Model CA-DT) at 25° C. (by the sessile drop method in air).
  • (5) Water Content
  • Measurement was performed according to the method as described in the Example 1-7.
  • (6) Oxygen Permeability (Dk Value)
  • Measurement was performed by the electrode method using a Model K-316-IPI oxygen permeability measurement instrument for film manufactured by Rika Seiki Kogyo Co., Ltd. according to the Standard Dk Value Measuring Method of Japan Contact Lens Association. As the test pieces, lenses having diameter of 14 mm and thickness of about 0.1-0.5 mm were prepared using a mold to provide for the measurement. The measurement was performed in a physiological saline solution at 35° C. An oxygen permeability was obtained from a slope of a line of oxygen permeation amount versus sample thickness. Dk value was expressed by a unit of x 1011[(ml×cm)/(cm2×sec×mmHg)].
  • (7) Tensile Strength
  • Measurement was performed using Autograph AGS-50B manufactured by Shimadzu Corp. in a physiological saline solution at 25° C. Strength at break was measured with a center part having a width of 3 mm cut out from a lens. A unit is (g/mm2).
  • (8) Lipid Deposition
  • Measurement was performed according to the method as described in the Examples 1-7.
  • (9) Solubility
  • Solubility of a mold material to a mixture of monomers was evaluated by the following method. One drop of a mixture of monomers was dropped on a flat surface of various kinds of mold and sheet-like materials, and left for 1 hour at 25° C. After wiping off the mixture of monomers with a soft cloth, the wiped-off-surface was inspected and ranked as follows: no change at all; ◯, cloudy surface; Δ, corroded uneven surface; x.
    • SYNTHESIS EXAMPLE 1 Synthesis of Polysiloxanediol having Hydrosilane Groups (A1)
  • A mixture of 150 g of octamethylcyclotetrasiloxane, 22.6 g of 1,3,5-trimethyltrifluoropropylcyclotrisiloxane, 17.4 g of 1,3,5,7-tetramethylcyclotetrasiloxane, 7.2 g of 1,3-bis(4-hydroxypropyl)tetramethyldisiloxane, 200 g of chloroform and 1.5 g of trifluoromethane sulfonic acid was stirred for 24 hours at 25° C., then washed repeatedly with purified water until a pH of the mixture became neutral. After water was separated, chloroform was distilled off under the reduced pressure. The residual liquid was dissolved in isopropanol, reprecipitated with methanol, followed by removal of volatile components under the vacuum from a separated liquid to give a transparent viscous liquid. The said liquid was the siloxanediol having hydrosilane groups (A1) expressed by the following formula with a yield of 98 g. Here, although the structural formula of the linking group Y is shown as a block structure composed of each siloxane unit, actually it contains random structures, and this formula shows only a ratio of each siloxane unit. This is also the same in the following Synthesis Examples.
    Figure US20060211789A1-20060921-C00040
    • Synthesis of Polysiloxane-Dimethacrylate having Hydrosilane Groups (B1)
  • A mixture of 50 g of the siloxanediol described above, 3.9 g of methacryloyloxyethyl isocyanate, 100 g of dry acetone and 0.02 g of dibutyltin dilaurate was poured in a brown-colored flask and stirred for 24 hours at 25° C., then further stirred after an addition of 1.4 g of purified water. Subsequently, acetone was distilled off under the reduced pressure, and the resulting liquid was washed with methanol followed by removal of volatile components under the vacuum again to give a transparent viscous liquid. The said liquid was the polysiloxane-dimethacrylate having hydrosilane groups (B1) expressed by the following formula with a yield of 48.7 g:
    Figure US20060211789A1-20060921-C00041
    • Synthesis of Polysiloxane-Dimethacrylate having Alcohol Groups (C1)
  • A mixture of 48 g of the polysiloxane-dimethacrylate (B1) described above, 11.6 g of allyl alcohol, 96 g of isopropyl alcohol, 0.04 g of potassium acetate, 10 mg of chloroplatinic acid and 10 mg of di-t-butylcresol was charged into a flask with a reflux condenser and heated with stirring for 3 hours at 50° C. The reaction mixture was filtered, then isopropanol was distilled off under the reduced pressure, followed by washing with a mixture of methanol/water. Further removal of volatile components under the vacuum gave a transparent viscous liquid. The said liquid was the polysiloxane-di-methacrylate having alcohol groups (C1) shown by the following formula:
    Figure US20060211789A1-20060921-C00042
    • SYNTHESIS EXAMPLE 2 Synthesis of Polysiloxane-Dimethacrylate having Alcohol Groups (C2)
  • A mixture of 35 g of the polysiloxane-dimethacrylate having hydrosilane groups (B1) described in the Synthesis Example 1, 15 g of 3-allyloxy-1,2-propanediol, 80 g of isopropyl alcohol, 0.03 g of potassium acetate, 6 mg of chloroplatinic acid and 7 mg of di-t-butylcresol was charged into a flask with a reflux condenser, and reacted and purified similarly as in the synthesis of (C1) in the Synthesis Example 1 to give 33 g of a transparent viscous liquid. The product was the polysiloxane-dimethacrylate having alcohol groups (C2) wherein the linking group Y in the formula (B1) in the Synthesis Example 1 was shown by the following formula:
    Figure US20060211789A1-20060921-C00043
    • SYNTHESIS EXAMPLE 3 Synthesis of Polysiloxane-Diol having Hydrosilane Groups (A2)
  • A mixture of 190 g of octamethyl-cyclotetrasiloxane, 100 g of 1,3,5-trimethyltrifluoropropyl-cyclotrisiloxane, 7.7 g of 1,3,5,7-tetramethyl-cyclotetasiloxane, 14.4 g of 1,3-bis (2-hydroxyethyloxypropyl) tetramethyl-disiloxane, 300 g of chloroform and 2.3 g of trifluoromethane sulfonic acid was charged into a flask, and synthesized and purified similarly to the siloxane-diol (A1) in the Synthesis Example 1 to give 110 g of a transparent viscous liquid. As a result of an analysis, the product was the polysiloxane-diol having hydrosilane groups (A2) shown by the following formula:
    Figure US20060211789A1-20060921-C00044
    • Synthesis of Polysiloxanediol having Polyoxyethylene Groups (D1)
  • A mixture of 35 g of the polysiloxanediol having hydrosilane groups (A2) described above, 14 g of polyoxyethylene allylmethyl ether (molecular weight approximately 400), 100 g of isopropyl alcohol, 0.03 g of potassium acetate and 6 mg of chloroplatinic acid was charged into a flask with a reflux condenser and refluxed for 3 hours under the nitrogen atmosphere. The reaction mixture was filtered, then isopropanol was distilled off under the reduced pressure followed by washing with a mixture of methanol/water. Further removal of volatile components under the vacuum gave 42 g of a transparent viscous liquid. As a result of an analysis, the product was the polysiloxanediol having terminal methoxy type polyoxyethylene groups (D1) shown by the following formula:
    Figure US20060211789A1-20060921-C00045
    • Synthesis of Polysiloxane-Dimethacrylate having Polyoxyethylene Groups (C3)
  • A mixture of 40 g of the polysiloxanediol having polyoxyethylene groups (D1) obtained and 85 g of dry acetone was charged into a brown-colored flask and dissolved. The solution was then added with 2.0 g of methacryloxyethyl isocyanate, and stirred for 3 hours at 25° C. After adding 1.4 g of purified water, the solution was stirred for further 2 hours, followed by distilling off of acetone under the reduced pressure. The residual liquid was washed with a mixture of methanol/water followed by a removal of volatile components under the vacuum again to give 48.7 g of a transparent viscous liquid. As a result of an analysis, the product was the polysiloxane-dimethacrylate having terminal methoxy type polyoxyethylene groups (C3) as shown by the following formula:
    Figure US20060211789A1-20060921-C00046
    • SYNTHESIS EXAMPLE 4 Synthesis of Polysiloxanediol having Hydrosilan Groups (A3)
  • A mixture of 150 g of octamethyl-cyclotetrasiloxane, 12 g of 1,3,5,7-tetramethyl-cyclotetrasiloxane, 6.8 g of 1,3-bis(2-hydroxyethyloxypropyl)tetramethyl-disiloxane, 200 g of chloroform and 1.5 g of trifluoromethane sulfonic acid was charged into a flask, and synthesized and purified similarly to the siloxanediol (A1) in the Synthesis Example 1 to give 95 g of a transparent viscous liquid. As a result of an analysis, the product was the polysiloxanediol having hydrosilan groups (A3) shown by the following formula:
    Figure US20060211789A1-20060921-C00047
    • Synthesis of Polysiloxane-Dimethacrylate having Hydrosilans (B2)
  • A mixture of 50 g of the polysiloxanediol (A3) described above, 10 g of hexamethylene-diisocyanate, 100 g of dry acetone, 0.02 g of dibutyltin laurate and 2 mg of di-t-butylcresol was charged into a flask with a reflux condenser and refluxed for 2 hours under the nitrogen stream. The reaction mixture was added with 20 g of 2-hydroxyethyl methacrylate, then refluxed for further 2 hours. After adding 6 g of purified water, the mixture was left overnight at room temperature. Subsequently acetone was distilled-off under the reduced pressure. Further removal of volatile components under the vacuum gave a transparent viscous liquid. The product was 36 g of polysiloxane-dimethacrylate having hydrosilane groups (B2) shown by the following formula:
    Figure US20060211789A1-20060921-C00048
    • Synthesis of Polysiloxane-Dimethacrylate having Alcohol Groups (C4)
  • A mixture of 30 g of the polysiloxane-dimethacrylate described above, 12 g of 2-allyloxyethanol, 60 g of isopropyl alcohol, 0.03 g of potassium acetate, 6 mg of chloroplatinic acid and 3 mg of di-t-butylcresol was charged into a flask with a reflux condenser and heated with stirring at 50° C. for 3 hours under the nitrogen atmosphere. The reaction mixture was filtered, then isopropanol was distilled off under the reduced pressure followed by washing with a mixture of methanol/water. Further removal of volatile components under the vacuum gave 24 g of a transparent viscous liquid. The product was the polysiloxane-dimethacrylate having alcohol groups (C4) with the linking group Y in the structural formula (B2) shown-by the following formula:
    Figure US20060211789A1-20060921-C00049
    • SYNTHESIS EXAMPLE 5 Synthesis of Polysiloxane-Dimethacrylate having Hydrosilane Groups (B3)
  • A mixture of 50 g of the polysiloxanediol (A2) described in the Synthesis Example 3, 3.9 g of methacryloyloxyethylisocyanate, 100 g of dry acetone and 0.02 g of dibutyltin dilaurate was charged into a brown-colored flask and stirred at 25° C. for 24 hours under the nitrogen atmosphere. After adding 1.4 g of purified water, the mixture was stirred for further 3 hours. Acetone was distilled off under the reduced pressure, and the residual liquid was washed with methanol. Removal of volatile components under the vacuum again gave a transparent viscous liquid. The product was 46 g of the polysiloxane-dimethacrylate having hydrosilane groups (B3) shown by the following formula:
  • Synthesis of Polysiloxane-dimethacrylate having polyoxy-ethylene groups (C5).
    Figure US20060211789A1-20060921-C00050
  • A mixture of 40 g of the polysiloxanediol having hydrosilane groups obtained, 20 g of polyoxyethylene allylether (molecular weight approximately 400), 80 g of isopropyl alcohol, 0.04 g of potassium acetate and 8 mg of chloroplatinic acid was charged into a flask with a reflux condenser and refluxed for 3 hours under the nitrogen atmosphere. The reaction mixture was filtered, then isopropanol was distilled off under the reduced pressure followed by washing with a mixture of methanol/water. Further removal of volatile components under the vaccuum gave 42 g of a transparent viscous liquid. As a result of an analysis, the product was the polysiloxane-dimethacrylate having terminal hydroxyl group type polyoxyethylene groups (C5), wherein the linking group Y in the structural formula (B3) was shown by the following formula:
    Figure US20060211789A1-20060921-C00051
    • SYNTHESIS EXAMPLE 6 Synthesis of Polysiloxane-Dimethacrylate having Polyoxyethylene Groups (C6)
  • A mixture of 40 g of the polysiloxanediol having hydrosilane groups (B3) obtained in the Synthesis Example 5, 40 g of polyoxyethylene allylmethylether (molecular weight approximately 1500), 120 g of isopropyl alcohol, 0.04 g of potassium acetate and 8 mg of chloroplatinic acid was charged into a flask with a reflux condenser and refluxed for 3 hours under the nitrogen atmosphere. The reaction mixture was filtered, then isopropanol was distilled off under the reduced pressure followed by washing with a mixture of methanol/water. Further removal of volatile components under the vacuum gave 38 g of a transparent viscous liquid. As a result of an analysis, the product was the polysiloxane-dimethacrylate having terminal methoxy type polyoxyethylene groups (C6), wherein the linking group Y in the structural formula (B3) was shown by the following formula:
    Figure US20060211789A1-20060921-C00052
    • SYNTHESIS EXAMPLE 7 Synthesis of 2-(2-methacryloxyethylcarbamoyloxy)ethyl methacrylate
  • A mixture of 13 g of 2-hydroxyethyl methacrylate dried with dessicating agent, 15.6 g of methacryloxyethylisocyanate, 60 g of dry acetone was reacted similarly as in Synthesis Example 5 to give the compound shown by the formula (11a) (hereinafter “MIEM”):
    Figure US20060211789A1-20060921-C00053
    • EXAMPLE 8
  • A mixture of 80 parts by weight of polysiloxane-dimethacrylate having alcohol groups (C1) described in the Synthesis Example 1, 10 parts by weight of N-vinyl-N-methylacetoamide (hereinafter “VMA”), 6 parts by weight of isobornyl methacrylate (hereinafter “IBM”), 4 parts by weight of tetraethyleneglycoldimethacrylate (hereinafter “4ED”) and 0.5 parts by weight of 2,4,6-trimethylbenzoyl-diphenylphosphinoxide (hereinafter “TPO”) was mixed with stiring. Then, the monomer mixture was injected into a mold for forming contact lens made of an ethylene vinyl alcohol resin (hereinafter “EVOH resin”) (made by The Japan Synthetic Chem. Ind. Co., Ltd., Soarlite S), then irradiated by UV ray for 1 hour in a light exposure equipment to give a lens-shaped polymer. The lens thus obtained was dipped in ethyl alcohol overnight, then dipped in water followed by heating at 90° C. for 3 hours. The lens thus obtained was transparent and flexible, and showed good water wettability. Evaluation of physical properties showed water content of 10%, oxygen permeability (Dk) of 256, tensile strength of 185 g/mm2 and lipid deposition of 40 μg. In addition, contact angle of the EVOH resin used to water was 73°. Results of evaluation on its performances are shown in Table 1.
    • EXAMPLES 9-13
  • Lenses were obtained using hydrophilic polysiloxane monomers described in the Synthesis Examples 2-6 by polymerizing and processing in the same manner in compositions and conditions as in the Example 8. Results of evaluation on its performances are described in Table 1.
    • COMPARATIVE EXAMPLES 4 AND 5
  • Comparative lenses were prepared by polymerizing and processing in the same manner in compositions and conditions as in the Example 8, except for using the polydimethylsiloxane-dimethacrylate (R1) or the polysiloxane-dimethacrylate having alcohol groups (R2) shown by the following formulas instead of the hydrophilic polysiloxane monomer. Results obtained are shown jointly in Table 1.
    Figure US20060211789A1-20060921-C00054
    • EXAMPLE 14
  • A mixture of 60 parts by weight of polysiloxane-dimethacrylate having polyoxyethylene groups (C3), 35 parts by weight of N-vinylpyrroridone (hereinafter “NVP”), 5 parts by weight of cyclohexyl methacrylate (hereinafter “CH”), 1 part by weight of ethyleneglycoldimethacrylate (hereinafter “ED”) and 0.5 parts by weight of TPO was mixed, photopolymerized in a mold made of EVOH resin in the same manner as in Example 8 to obtain a lens. Results of evaluation on the lens thus obtained are shown in Table 3.
    • EXAMPLES 15-18 AND COMPARATIVE EXAMPLES 6-8
  • Monomer mixtures of the compositions shown in Table 2 were photopolymerized in the same manner as in Example 12 to obtain lenses. Results of evaluation are shown in Table 3.
    • EXAMPLE 19
  • A lens was prepared in the exactly same manner as in Example 8 except for using the crosslinkable monomer (“MIEM”) described in the Synthesis Example 5 instead of 4ED, and the lens obtained was evaluated. Results of the evaluation proved a transparent lens with good water wettability and improved strength, showing water content of 12%, oxygen permeability (Dk) of 245 and tensile strength of 285 g/mm2.
    • EXAMPLE 20
  • A lens was prepared in the exactly same manner as in Example 10 except for using the crosslinkable monomer (“MIEM”) described in the Synthesis Example 5 instead of 4ED, and the lens obtained was evaluated. Results of the evaluation showed water content of 23%, oxygen permeability (Dk) of 181 and improved tensile strength of 305 g/mm2.
    • EXAMPLES 21-22 AND COMPARATIVE EXAMPLES9-14
  • A lens was prepared in the exactly same manner as in Example 8 except for using molds made of each resin shown in Table 4 instead of the mold for forming lens made of EVOH resin. Results of evaluation on solubility and contact angle of each resin material itself and on each lens are jointly shown in Table 4.
  • The present invention will be further explained with Examples 23-38 and Comparative Examples 15-19, but the present invention is not limited by these Examples. Furthermore, each evaluation item was measured as follows.
  • (1) Water content, (2) Oxygen permeability (Dk value) and (3) Water wettability (contact angle) were measured by the methods according to the Examples 1-7. (4) Rabbit eyes wearing test was carried out for 30 days by the method of the wearing test according to the Examples 1-7 with the same inspections.
    • EXAMPLES23-26
  • The contact lens wearing tests described in the Examples 1, 5, 6 and 7 were performed again by extending the period to 30 days. All lenses showed good movements, little stain depositions, no abnormality on the rabbit eyes, and proved that they were safe enough for long period.
    • EXAMPLE 27
  • Contact angle of the hydrogel contact lens obtained in the Example 8 was measured resulting in 18° by the captive bubble method and 57° by the sessile drop method. Furthermore, a rabbit eyes wearing test for 30 days also showed no lens adhesion and no abnormality on the house rabbit eyes.
    • EXAMPLES 28-33 AND COMPARATIVE EXAMPLES 15-17
  • The contact lenses prepared in the Example 10, Examples 14-18 and Comparative Examples 6, 8 and 11 were evaluated by the rabbit wearing test similarly as in the Example 18. Results are shown in Table 5.
    • EXAMPLE 34
  • Contact lenses were prepared using 100 pieces of molds made of EVOH resin in the same manner in monomer composition and procedures as described in Example 19. Defectives were only 2 pieces which were partly chipped at their edges, and no defect was observed in all of other 98 lenses, proving the present invention being very useful method for an industrial manufacturing.
    • COMPARATIVE EXAMPLE 18
  • Using the same monomer composition as in the Example 44, a preparation of 100 pieces of lenses was tried with molds made of AS resin [acrylonitrilestyrene (40/60) copolymer]. None of good lens could be obtained with 35 pieces fractured to fragments, and the others having chippings at edges or damages on surfaces.
    • COMPARATIVE EXAMPLE 19
  • In the same manner as in the Comparative Example 18, a preparation of 100 pieces of contact lenses was tried with molds made of AM resin (acrylonitrile-methyl acrylate copolymer, Barex-210 supplied by Mitsui Toatsu Chemicals Inc.). However, 90 pieces failed to keep lens shapes due to fractures to fragments in a mold separation, the other 10 pieces also had breaks or chippings in edges, and none of good lens could be obtained.
    • EXAMPLE 35
  • A mixture of 50 parts by weight of the hydrophilic polysiloxane monomer shown by the following structural formula (4c), 20 parts by weight of tris(trimethylsiloxy)silylpropyl methacrylate, 25 parts by weight of VMA, 5 parts by weight of CH, 1 part by weight of ED, 0.5 parts by weight of TPO and 80 parts by weight of 2-butanol was stirred, then injected into a mold made of EVOH resin, followed by an irradiation of UV ray for 1 hour. The lens thus obtained was dipped in ethyl alcohol overnight. After the alcohol was replaced with water, the lens was heated at 90° C. for 3 hours. Evaluation on the hydrogel contact lens thus obtained showed water content of 32% and Dk value of 125. Contact angle was 24° by the captive bubble method and 77° by the sessile drop method. A house rabbit wearing test showed good lens movement, little deposition after 30 days wearing and good water wettability.
    Figure US20060211789A1-20060921-C00055
    • EXAMPLE 36
  • A mixture of 80 parts by weight of the hydrophilic polysiloxane monomer shown by the following structural formula (5c), 20 parts by weight of NVP, 1 part by weight of ED, 0.5 parts by weight of TPO and 80 parts by weight of 2-butanol was dissolved with stirring, and a contact lens was prepared similarly as in the Example 35. Evaluation on the lens showed water content of 13%, Dk value of 225, and contact angle of 24° by the captive bubble method and 70° by the sessile drop method. A house rabbit wearing test also showed good lens movement, little deposition, and maintaining of good water wettability.
    Figure US20060211789A1-20060921-C00056
    • EXAMPLE 37
  • A contact lens was prepared in the same manner as in the Example 35 except for using the monomer shown by the following structural formula (6c) as a hydrophilic polysiloxane monomer. The lens thus obtained showed water content of 28%, Dk value of 166, and contact angle of 22° by the captive bubble method and 69° by the sessile drop method. A rabbit wearing test showed good lens movement, little deposition after 30 days wearing and good water wettability.
    Figure US20060211789A1-20060921-C00057
    • EXAMPLE 38
  • A contact lens was prepared in the same manner as in the Example 36 except for using the monomer shown by the following structural formula (7c) as a hydrophilic polysiloxane monomer. The lens thus obtained showed water content of 27%, Dk value of 285, and contact angle of 18° by the captive bubble method and 53° by the sessile drop method. A rabbit wearing test showed good lens movement, little deposition after 30 days wearing and maintaining of good water wettability.
    Figure US20060211789A1-20060921-C00058
    TABLE 1
    Polysiloxane
    Monomer Water Oxygen Tensile Lipid
    (Synthesis Water Content Permeability Strength Deposition
    Example No. Example No.) Transparency Wettability (%) (×10−11) (g/mm2) (μg)
    Example 8 C1 (Synthesis ◯ ◯ 10 256 185 40
    Example 1)
    Example 9 C2 (Synthesis ◯ ◯ 14 218 174 32
    Example 2)
    Example 10 C3 (Synthesis ◯ ◯ 22 186 210 35
    Example 3)
    Example 11 C4 (Synthesis ◯ ◯ 12 240 235 62
    Example 4)
    Example 12 C5 (Synthesis ◯ ◯ 20 183 207 35
    Example 5)
    Example 13 C6 (Synthesis ◯ ◯ 34 145 168 20
    Example 6)
    Comparative R1 Δ X 5 200 120 150
    Example 4
    Comparative R2 ◯ Δ 18 195 115 65
    Example 5
  • TABLE 2
    (unit: parts by weight)
    Polysiloxane
    Example No. (C3) NVP VMA AC3 MMA DMA HEMA 3FM OHF CH ED
    Example 14 60 35 5 1
    Example 15 50 15 15 20 5 1
    Example 16 50 15 20 15 5 1
    Example 17 60 35 5 1
    Example 18 40 20 20 10 10 5 1
    Comparative 60 35 5 1
    Example 6
    Comparative 60 35 5 1
    Example 7
    Comparative 60 20 15 5 1
    Example 8

    Abbreviations in the Table exhibit the following monomers.

    NVP: N-Vinylpyrrolidone

    VMA: N-Vinyl-N-methylacetoamide

    AC3: 3-Tris(trimethylsiloxy)silylpropyl Methacrylate

    MMA: Methyl Methacrylate

    DMA: N,N-Dimethylacrylamide

    HEMA: 2-Hydroxyethyl Methacrylate

    3FM: 2,2,4-Trifluoroethyl Methacrylate

    OHF: 1,1,2,2-Tetrafluoroethoxy-2-hydroxypropyl Methacrylate

    CH: Cyclohexyl Methacrylate

    ED: Ethyleneglycol-di-methacrylate
  • TABLE 3
    Oxygen Lipid
    Water Water Content permeability deposition
    Example No. Transparency Wettability (%) (×10−11) (μg)
    Example 14 ◯ ◯ 38 81 85
    Example 15 ◯ ◯ 24 148 65
    Example 16 ◯ ◯ 27 154 50
    Example 17 ◯ ◯ 33 108 28
    Example 18 ◯ ◯ 31 94 44
    Comparative ◯ X 7 132 446
    Example 6
    Comparative Δ Δ 26 118 385
    Example 7
    Comparative ◯ ◯ 32 115 295
    Example 8
  • TABLE 4
    Lens Performance
    Resin Water
    Kind of Mold Resin Contact Water Wettability
    Example No. Resin Solubility Angle(°) Transparency Wettability in Dry State
    Example 8 EVOH ◯ 73 ◯ ◯ ◯
    Example 21 PET ◯ 75 ◯ ◯ ◯
    Example 22 PA ◯ 68 ◯ ◯ Δ
    Comparative AS Δ 77 ◯ ◯ Δ
    Example 9
    Comparative AM Δ 61 ◯ ◯ Δ
    Example 10
    Comparative PP ◯ 110 ◯ Δ X
    Example 11
    Comparative PS X 92 Δ X X
    Example 12
    Comparative PC X 76 Δ Δ X
    Example 13
    Comparative PMMA X 65 Δ Δ X
    Example 14

    Abbreviations in the Table exhibit the following resins.

    EVOH: Ethylene-Vinylalcohol Copolymer

    PET: Polyethylene Terephthalate

    PA: Nylon 66

    AS: Acrylonitrile-Styrene (40/60) Copolymer

    AM: Acrylonitrile-Methyl Methacrylate (75/25) Copolymer

    PP: Polypropylene

    PS: Polystyrene

    PC: Polycarbonate

    PMMA: Polymethylmethacrylate
  • TABLE 5
    Contact Angle (°) Rabbit Wearing Test
    Captive (30 days)
    Lens Preparation Bubble Sessile Adhesion Stain Water
    Example No. Example Method Drop Method to Cornea Deposition Wettability
    Example 28 Example 10 26 48 no little superior
    Example 29 Example 14 23 63 no little superior
    Example 30 Example 15 28 75 no little superior
    Example 31 Example 16 28 77 no little superior
    Example 32 Example 17 17 55 no little superior
    Example 33 Example 18 23 66 no little superior
    Comparative Comparative 36 95 occurred much poor
    Example 15 Example 6
    Comparative Comparative 27 98 occurred much poor
    Example 16 Example 8
    Comparative Comparative 55 110 occurred much poor
    Example 17 Example 11
    • INDUSTRIAL APPLICABILITY
  • The present invention provides a soft contact lens showing small and stable contact angle to-water at its surface, little stain deposition in wearing, high oxygen permeability, no adhesion of the lens to cornea and superior extended-wearing characteristics. In addition, a ophthalmologic lens material obtained by a copolymerization of a hydrophilic siloxane monomer and a amide-group-containing monomer having N-vinyl group of the present invention shows superior transparency, water wettability, and in particular, superior resistance to lipid deposition. Furthermore, strength and durability are further improved by adding a crosslinkable monomer having urethane linking group. Moreover, polymerization in a mold comprising a resin having polar groups can give a stable water wettability to a lens. The material is useful particularly for a soft contact lens, and thus superior as a contact lens for extended-wearing.

Claims (23)

1. A mold for producing a contact lens, wherein said mold is capable of forming both front and rear surfaces of said contact lens from a surface of said mold during polymerization of a monomer composition in said mold and comprises a resin of polyethylene terephthalate.
2. A mold for producing a contact lens, wherein said mold is capable of forming both front and rear surfaces of said contact lens from a surface of said mold during polymerization of a monomer composition in said mold and comprises a resin of an ethylene-vinylalcohol copolymer with an ethylene copolymerization ratio of about 25-50% by mole.
3. A Contact lens produced by the mold according to claim 1, wherein said contact lens is a hydrogel soft contact lens manufactured by a polymerization of at least one kind of siloxane monomer.
4. A Contact lens produced by the mold according to claim 1, wherein said contact lens is a hydrogel soft contact lens manufactured by a copolymerization of at least one kind of hydrophilic polysiloxane monomer of the formula (1) and at least one kind of a hydrophilic monomer:
Figure US20060211789A1-20060921-C00059
wherein, X1 is a polymerizable substituent shown by the following formula (2);
Figure US20060211789A1-20060921-C00060
wherein, R5 is a hydrogen or a methyl group; Z1 is a linking group selected from —NHCOO—, —NHCONH—, —OCONH—R6-NHCOO—, —NHCONH—R7-NHCONH— and —OCONH—R8-NHCONH— (R6, R7 and R8 are hydrocarbon groups with 2-13 carbon atoms); m is 0-10; n is 3-10; p is 0 when m is 0 and 1 when m is not less than 1; q is an integer of 0-20; R1, R2, R3 and R4 are groups independently selected from hydrocarbon groups with 1-12 carbon atoms or trimethylsiloxy group; and the structure [Y1] shows a polysiloxane backbone comprising not less than 2 siloxane linkages.
5. A Contact lens produced by the mold according to claim 1, wherein said contact lens is a contact lens manufactured by a copolymerization of at least a kind of siloxane group-containing monomer and at least one kind of hydrophilic monomer.
6. A method for producing a hydrogel soft contact lens comprising polymerizing at least one siloxane monomer, said mold comprising a resin selected from the group consisting of nylon 66, nylon 6, polyethylene terephthalate and ethylene-vinyl alcohol copolymer.
7. The method according to claim 6, wherein said mold comprises ethylene-vinyl alcohol copolymer.
8. A method for producing a contact lens comprising copolymerizing at least one siloxane monomer and at least one hydrophilic monomer, said mold comprising a resin selected from the group consisting of nylon 66, nylon 6, polyethylene terephthalate and ethylene-vinyl alcohol copolymer.
9. The method according to claim 8, wherein said mold comprises ethylene-vinyl alcohol copolymer.
10. The mold according to claim 1, which comprises an enhanced crystallinity polyethylene terephthalate.
11. The mold according to claim 1, which comprises a drawn film of polyethylene terephthalate.
12. A method for producing a contact lens comprising photopolymerization by irradiating said mold with a light, said mold comprising a resin selected from the group consisting of nylon 66,-nylon 6, polyethylene terephthalate and ethylene-vinyl alcohol copolymer.
13. The method according to claim 12, wherein said mold comprises ethylene-vinyl alcohol copolymer.
14. A mold for directly producing a contact lens, comprising a surface capable of forming both front and rear surfaces of said contact lens during polymerization of a monomer composition, and wherein the mold material is a resin selected from the group consisting of polyamide, polyethylene terephthalate and ethylene-vinyl alcohol copolymer, and wherein at least one side of the mold for forming the lens surface has a contact angle to water not higher than 90°.
15. A hydrophilic polysiloxane monomer represented by the formula (1):
Figure US20060211789A1-20060921-C00061
wherein X is a polymerizable substituent shown by the formula (2):
Figure US20060211789A1-20060921-C00062
wherein R5 is hydrogen or a methyl group; Z1 is a linking group selected from —NHCOO—, —NHCONH—, —OCONH—R6-NHCOO—, NHCONH—R7-NHCONH— and —OCONH—R8-NHCONH— wherein R6, R7 and R8 are hydrocarbon groups with 2-13 carbon atoms; m is 1-10, n is 3-10, q is an integer of 0-20; R1, R2, R3 and R4 are independently groups selected from hydrocarbon groups with 1-12 carbon atoms or trimethylsiloxy group, the structural unit [Y1] comprises linked structural unit (Ic), (IIc) and (IIIc) shown by the following formulas:
Figure US20060211789A1-20060921-C00063
wherein R19 is selected from the groups of the following formulas (3) and (4):

—C3H6(OC2H4)OH   (3)
—C3H6(OC2H4)dOCH3   (4)
wherein c and d are 2-40,
the linkage ratio of the structural units (Ic), (IIc) and (IIIC) being ((Ic)+(IIc))/(IIIc)=0.5-100, (IIc)/(Ic)=0-1, and the total number of the units (Ic), (IIc) and (IIIC) being 10-1000.
16. The hydrophilic polysiloxane monomer according to claim 15, wherein the linkage ratio of the structural units (Ic), (IIc) and (IIIc) is ((Ic)+(IIc))/(IIIc)=1-50, (IIc)/(Ic)=0.01-0.5, and the total number of the units (Ic), (IIc) and (IIIc) is 20-500.
17. The hydrophilic polysiloxane monomer according to claim 15, wherein said Z1 in the formula (2) in claim 15 is —NHCOO—.
18. The hydrophilic polysiloxane monomer according to claim 15, wherein m in formula (2) is 2.
19. The hydrophilic polysiloxane monomer according to claim 15, wherein said n in formula (2) in is 3.
20. The hydrophilic polysiloxane monomer according to claim 15, wherein said q in formula (2) is 1.
21. The hydrophilic polysiloxane monomer according to claim 15, wherein the average of d in formula (4) is about 7.
22. An ophthalmic lens materials comprising the monomer according to claim 15.
23. A contact lens materials comprising the monomer according to claim 15.
US11/437,732 1999-12-16 2006-05-22 Long-wearable soft contact lens Abandoned US20060211789A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US11/437,732 US20060211789A1 (en) 1999-12-16 2006-05-22 Long-wearable soft contact lens
US12/960,236 US8637621B2 (en) 1999-12-16 2010-12-03 Long-wearable soft contact lens

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
JP11-357376 1999-12-16
JP35737699 1999-12-16
JP35869999 1999-12-17
JP11-358699 1999-12-17
US09/737,809 US6867245B2 (en) 1999-12-16 2000-12-18 Long wearable soft contact lens
US10/804,161 US20040192872A1 (en) 1999-12-16 2004-03-19 Long-wearable soft contact lens
US11/437,732 US20060211789A1 (en) 1999-12-16 2006-05-22 Long-wearable soft contact lens

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US10/804,161 Continuation US20040192872A1 (en) 1999-12-16 2004-03-19 Long-wearable soft contact lens

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US12/960,236 Continuation US8637621B2 (en) 1999-12-16 2010-12-03 Long-wearable soft contact lens

Publications (1)

Publication Number Publication Date
US20060211789A1 true US20060211789A1 (en) 2006-09-21

Family

ID=26580596

Family Applications (5)

Application Number Title Priority Date Filing Date
US09/737,809 Expired - Lifetime US6867245B2 (en) 1999-12-16 2000-12-18 Long wearable soft contact lens
US09/737,809 Granted US20020016383A1 (en) 1999-12-16 2001-07-02 Long wearable soft contact lens
US10/804,161 Abandoned US20040192872A1 (en) 1999-12-16 2004-03-19 Long-wearable soft contact lens
US11/437,732 Abandoned US20060211789A1 (en) 1999-12-16 2006-05-22 Long-wearable soft contact lens
US12/960,236 Expired - Fee Related US8637621B2 (en) 1999-12-16 2010-12-03 Long-wearable soft contact lens

Family Applications Before (3)

Application Number Title Priority Date Filing Date
US09/737,809 Expired - Lifetime US6867245B2 (en) 1999-12-16 2000-12-18 Long wearable soft contact lens
US09/737,809 Granted US20020016383A1 (en) 1999-12-16 2001-07-02 Long wearable soft contact lens
US10/804,161 Abandoned US20040192872A1 (en) 1999-12-16 2004-03-19 Long-wearable soft contact lens

Family Applications After (1)

Application Number Title Priority Date Filing Date
US12/960,236 Expired - Fee Related US8637621B2 (en) 1999-12-16 2010-12-03 Long-wearable soft contact lens

Country Status (12)

Country Link
US (5) US6867245B2 (en)
EP (1) EP1243960B2 (en)
JP (3) JP5148794B2 (en)
KR (1) KR100522339B1 (en)
CN (1) CN100374881C (en)
AT (1) ATE441132T1 (en)
AU (1) AU779729B2 (en)
CA (1) CA2394939C (en)
DE (1) DE60042841D1 (en)
ES (1) ES2328009T5 (en)
TW (1) TWI269912B (en)
WO (1) WO2001044861A1 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080048350A1 (en) * 2006-06-15 2008-02-28 Charlie Chen Wettable Silicone Hydrogel Contact Lenses and Related Compositions and Methods
US20090234089A1 (en) * 2008-02-08 2009-09-17 Asahi Kasei Aime Co., Ltd. Hydrophilic Polysiloxane Macromonomer, and Production and Use of the same
CN103237850A (en) * 2010-10-15 2013-08-07 柏格阿莫菲克索录森斯有限公司 Coating compositions with anticorrosion properties
US8939577B2 (en) 2010-07-30 2015-01-27 Novartis Ag Silicone hydrogel lenses with water-rich surfaces
US11256003B2 (en) 2017-12-13 2022-02-22 Alcon Inc. Weekly and monthly disposable water gradient contact lenses

Families Citing this family (311)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6822016B2 (en) 2001-09-10 2004-11-23 Johnson & Johnson Vision Care, Inc. Biomedical devices containing internal wetting agents
US7052131B2 (en) 2001-09-10 2006-05-30 J&J Vision Care, Inc. Biomedical devices containing internal wetting agents
US6849671B2 (en) 1998-03-02 2005-02-01 Johnson & Johnson Vision Care, Inc. Contact lenses
US20070043140A1 (en) * 1998-03-02 2007-02-22 Lorenz Kathrine O Method for the mitigation of symptoms of contact lens related dry eye
US7461937B2 (en) * 2001-09-10 2008-12-09 Johnson & Johnson Vision Care, Inc. Soft contact lenses displaying superior on-eye comfort
ATE441132T1 (en) * 1999-12-16 2009-09-15 Asahikasei Aime Co Ltd SOFT CONTACT LENSES SUITABLE FOR LONG-TERM WEAR
JP4438162B2 (en) * 2000-02-24 2010-03-24 東レ株式会社 Method for producing polymer for ophthalmic lens and ophthalmic lens
JP4854130B2 (en) * 2001-05-01 2012-01-18 クーパーヴィジョン インターナショナル ホウルディング カンパニー リミテッド パートナーシップ Contact lens material comprising hydrophilic polysiloxane monomer and copolymer thereof, and contact lens
DE60143171D1 (en) * 2001-08-17 2010-11-11 Johnson & Johnson Vision Care METHOD FOR PRODUCING A POLYMER FOR AN EYOOPTIC LENS AND EYOOPOTIC LENS
US20070138692A1 (en) * 2002-09-06 2007-06-21 Ford James D Process for forming clear, wettable silicone hydrogel articles
US20080299179A1 (en) * 2002-09-06 2008-12-04 Osman Rathore Solutions for ophthalmic lenses containing at least one silicone containing component
US20040150788A1 (en) * 2002-11-22 2004-08-05 Ann-Margret Andersson Antimicrobial lenses, processes to prepare them and methods of their use
EP2180366B1 (en) * 2003-01-10 2013-09-25 Menicon Co., Ltd. Silicone-containing ocular lens material with high safety and preparing method thereof
JP4070637B2 (en) * 2003-03-05 2008-04-02 富士フイルム株式会社 Polymerizable composition, compound used therefor, image forming material used therefor and photosensitive lithographic printing plate
US8097565B2 (en) * 2003-06-30 2012-01-17 Johnson & Johnson Vision Care, Inc. Silicone hydrogels having consistent concentrations of multi-functional polysiloxanes
US7416737B2 (en) * 2003-11-18 2008-08-26 Johnson & Johnson Vision Care, Inc. Antimicrobial lenses, processes to prepare them and methods of their use
US7786185B2 (en) * 2004-03-05 2010-08-31 Johnson & Johnson Vision Care, Inc. Wettable hydrogels comprising acyclic polyamides
DE202004008321U1 (en) * 2004-05-25 2004-07-29 Acri.Tec Gesellschaft für ophthalmologische Produkte mbH Device for protecting the eyes of an animal against UV radiation
US7247689B2 (en) 2004-05-28 2007-07-24 Advanced Medical Optics, Inc. Biocompatible polymeric compositions for use in making anterior chamber intraocular lenses
US20060004165A1 (en) * 2004-06-30 2006-01-05 Phelan John C Silicone hydrogels with lathability at room temperature
US9322958B2 (en) * 2004-08-27 2016-04-26 Coopervision International Holding Company, Lp Silicone hydrogel contact lenses
EP1789821B1 (en) * 2004-08-27 2019-04-10 CooperVision International Holding Company, LP Silicone hydrogel contact lenses
US20060142525A1 (en) * 2004-12-29 2006-06-29 Bausch & Lomb Incorporated Hydrogel copolymers for biomedical devices
CA2597672C (en) 2005-02-14 2013-11-19 Johnson & Johnson Vision Care, Inc. A comfortable ophthalmic device and methods of its production
US20060227287A1 (en) * 2005-04-08 2006-10-12 Frank Molock Photochromic ophthalmic devices made with dual initiator system
US8158037B2 (en) 2005-04-08 2012-04-17 Johnson & Johnson Vision Care, Inc. Photochromic materials having extended pi-conjugated systems and compositions and articles including the same
US9052438B2 (en) 2005-04-08 2015-06-09 Johnson & Johnson Vision Care, Inc. Ophthalmic devices comprising photochromic materials with reactive substituents
US20060226402A1 (en) * 2005-04-08 2006-10-12 Beon-Kyu Kim Ophthalmic devices comprising photochromic materials having extended PI-conjugated systems
US7297160B2 (en) * 2005-06-15 2007-11-20 Bausch & Lomb Incorporated High refractive-index, hydrophilic, arylsiloxy-containing macromonomers and polymers, and ophthalmic devices comprising such polymers
MX2008001763A (en) * 2005-08-09 2008-04-07 Coopervision Inc Compositions and methods for producing silicone hydrogel contact lenses.
US9102110B2 (en) * 2005-08-09 2015-08-11 Coopervision International Holding Company, Lp Systems and methods for removing lenses from lens molds
US7785092B2 (en) 2005-08-09 2010-08-31 Coopervision International Holding Company, Lp Systems and methods for producing contact lenses from a polymerizable composition
US7799249B2 (en) * 2005-08-09 2010-09-21 Coopervision International Holding Company, Lp Systems and methods for producing silicone hydrogel contact lenses
US7426993B2 (en) * 2005-08-09 2008-09-23 Coopervision International Holding Company, Lp Contact lens package
MY141143A (en) * 2005-08-11 2010-03-15 Coopervision Int Holding Co Lp Contact lenses and methods for reducing conjunctival pressure in contact lens wearers
ATE461227T1 (en) * 2005-09-01 2010-04-15 Abbott Medical Optics Inc BIOCOMPATIBLE POLYMER COMPOSITIONS FOR USE IN THE MANUFACTURING OF ANTERIOR CHAMBER INTRAOCULAR LENSES
US8153726B2 (en) 2005-09-30 2012-04-10 The Lagado Corporation Highly oxygen permeable rigid contact lenses from polyacetylenes
US7329001B2 (en) 2005-11-01 2008-02-12 Synergeyes, Inc. Methods for improving the hydrophilicity of contact lenses and contact lenses having the same
EP1785153A3 (en) * 2005-11-09 2007-06-27 CooperVision Inc. Method of sterilizing silicone hydrogel contact lenses
US20070138668A1 (en) * 2005-12-21 2007-06-21 Yu-Chin Lai Process for Extracting Biomedical Devices
US20070185014A1 (en) * 2006-02-09 2007-08-09 The Schepens Eye Research Institute, Inc. Methods and compositions for modulating conjunctival goblet cells
US9052529B2 (en) 2006-02-10 2015-06-09 Johnson & Johnson Vision Care, Inc. Comfortable ophthalmic device and methods of its production
CA2646659C (en) * 2006-03-20 2013-05-14 Coopervision International Holding Company, Lp Demolding aids for silicone hydrogels and related methods
US8414804B2 (en) * 2006-03-23 2013-04-09 Johnson & Johnson Vision Care, Inc. Process for making ophthalmic lenses
US20070222095A1 (en) * 2006-03-23 2007-09-27 Diana Zanini Process for making ophthalmic lenses
US7731872B2 (en) * 2006-05-31 2010-06-08 Coopervision International Holding Company, Lp Methods and systems for forming ophthalmic lens mold assemblies
US7811483B2 (en) * 2006-06-01 2010-10-12 Coopervision International Holding Company, Lp Delensing of ophthalmic lenses using gas
US7540609B2 (en) * 2006-06-15 2009-06-02 Coopervision International Holding Company, Lp Wettable silicone hydrogel contact lenses and related compositions and methods
US8231218B2 (en) 2006-06-15 2012-07-31 Coopervision International Holding Company, Lp Wettable silicone hydrogel contact lenses and related compositions and methods
TWI512017B (en) * 2006-06-15 2015-12-11 Coopervision Int Holding Co Lp Wettable silicone hydrogel contact lenses and related compositions and methods
CN101473263B (en) * 2006-06-15 2011-01-05 库柏维景国际控股公司 Wettable silicone hydrogel contact lenses and related compositions and methods
US7468397B2 (en) * 2006-06-30 2008-12-23 Bausch & Lomb Incorporated Polymerizable siloxane-quaternary amine copolymers
US8569538B2 (en) * 2006-06-30 2013-10-29 Johnson & Johnson Vision Care, Inc. Acryloyl materials for molded plastics
US7960465B2 (en) * 2006-06-30 2011-06-14 Johnson & Johnson Vision Care, Inc. Antimicrobial lenses, processes to prepare them and methods of their use
US8053539B2 (en) 2006-06-30 2011-11-08 Johnson & Johnson Vision Care Inc. Siloxanyl materials for molded plastics
US8287782B2 (en) * 2006-08-08 2012-10-16 Coopervision International Holding Company, Lp Interference fitting polar resin ophthalmic lens molding devices and related methods
US7838698B2 (en) * 2006-09-29 2010-11-23 Johnson & Johnson Vision Care, Inc. Hydrolysis-resistant silicone compounds
US20080081850A1 (en) * 2006-09-29 2008-04-03 Kazuhiko Fujisawa Process for producing hydrolysis-resistant silicone compounds
US9056880B2 (en) 2006-09-29 2015-06-16 Johnson & Johnson Vision Care, Inc. Process for producing hydrolysis-resistant silicone compounds
US7968650B2 (en) 2006-10-31 2011-06-28 Johnson & Johnson Vision Care, Inc. Polymeric compositions comprising at least one volume excluding polymer
US8507577B2 (en) * 2006-10-31 2013-08-13 Johnson & Johnson Vision Care, Inc. Process for forming clear, wettable silicone hydrogel articles
GB0623299D0 (en) 2006-11-22 2007-01-03 Sauflon Cl Ltd Contact lens
US20080119627A1 (en) * 2006-11-22 2008-05-22 Masataka Nakamura Methods for purifying siloxanyl monomers
US8080622B2 (en) 2007-06-29 2011-12-20 Johnson & Johnson Vision Care, Inc. Soluble silicone prepolymers
US20090146329A1 (en) * 2007-12-06 2009-06-11 Changhong Yin Lens release
US20090168013A1 (en) * 2007-12-27 2009-07-02 Kunzler Jay F Trimethylsilyl-Capped Polysiloxane Macromonomers Containing Polar Fluorinated Side-Chains
US7897654B2 (en) * 2007-12-27 2011-03-01 Johnson & Johnson Vision Care Inc. Silicone prepolymer solutions
WO2009094368A1 (en) * 2008-01-25 2009-07-30 Bausch & Lomb Incorporated Contact lens
US20090244479A1 (en) * 2008-03-31 2009-10-01 Diana Zanini Tinted silicone ophthalmic devices, processes and polymers used in the preparation of same
US20090295004A1 (en) * 2008-06-02 2009-12-03 Pinsly Jeremy B Silicone hydrogel contact lenses displaying reduced protein uptake
US8440738B2 (en) 2008-07-09 2013-05-14 Timothy Higgs Silicone hydrogels and methods of manufacture
US7939579B1 (en) * 2008-07-09 2011-05-10 Contamac Limited Hydrogels and methods of manufacture
US20100081772A1 (en) * 2008-09-30 2010-04-01 Diana Zanini Process for forming silicone hydrogel articles having improved optical properties
US8470906B2 (en) 2008-09-30 2013-06-25 Johnson & Johnson Vision Care, Inc. Ionic silicone hydrogels having improved hydrolytic stability
US20130203812A1 (en) 2008-09-30 2013-08-08 Johnson & Johnson Vision Care, Inc. Ionic silicone hydrogels comprising pharmaceutical and/or nutriceutical components and having improved hydrolytic stability
JP2010095589A (en) * 2008-10-15 2010-04-30 Shin-Etsu Chemical Co Ltd Silicone for producing ophthalmological devices
US20100109176A1 (en) 2008-11-03 2010-05-06 Chris Davison Machined lens molds and methods for making and using same
SG174349A1 (en) * 2009-03-13 2011-10-28 Cognis Ip Man Gmbh Monomers and macromers for forming hydrogels
US8043369B2 (en) * 2009-06-16 2011-10-25 Bausch & Lomb Incorporated Biomedical devices
US8313675B2 (en) * 2009-08-31 2012-11-20 Coopervision International Holding Company, Lp Demolding of ophthalmic lenses during the manufacture thereof
US8646907B2 (en) * 2009-09-22 2014-02-11 Coopervision International Holding Company, Lp Materials for use in ophthalmic applications and methods
BR112012007373B1 (en) * 2009-10-01 2020-11-03 Coopervision International Holding Company, Lp silicone hydrogel contact lenses and methods for making silicone hydrogel contact lenses
JP2013509963A (en) 2009-11-09 2013-03-21 スポットライト テクノロジー パートナーズ エルエルシー Fragmented hydrogel
WO2011057131A1 (en) 2009-11-09 2011-05-12 Spotlight Technology Partners Llc Polysaccharide based hydrogels
JP5764925B2 (en) * 2009-12-28 2015-08-19 東レ株式会社 Method for producing silicone prepolymer
JP5720103B2 (en) * 2010-03-18 2015-05-20 東レ株式会社 Silicone hydrogels, ophthalmic lenses and contact lenses
US8697770B2 (en) 2010-04-13 2014-04-15 Johnson & Johnson Vision Care, Inc. Pupil-only photochromic contact lenses displaying desirable optics and comfort
US8877103B2 (en) 2010-04-13 2014-11-04 Johnson & Johnson Vision Care, Inc. Process for manufacture of a thermochromic contact lens material
US9522980B2 (en) 2010-05-06 2016-12-20 Johnson & Johnson Vision Care, Inc. Non-reactive, hydrophilic polymers having terminal siloxanes and methods for making and using the same
MY164884A (en) 2010-07-09 2018-01-30 Coopervision Int Holding Co Lp Ophthalmic lens molds with low levels of uv light transmittance, ophthalmic lenses molded therein, and related methods
US9193118B2 (en) 2010-07-30 2015-11-24 Coopervision International Holding Company, Lp Ophthalmic lens molds, ophthalmic lenses molded therein, and related methods
WO2012013945A1 (en) 2010-07-30 2012-02-02 Neil Goodenough Ophthalmic device molds and related methods
US9612363B2 (en) 2010-11-04 2017-04-04 Johnson & Johnson Vision Care, Inc. Silicone hydrogel reactive mixtures comprising borates
TWI517861B (en) 2011-02-08 2016-01-21 諾華公司 Low-tack, hydrophobic ophthalmic device materials
TWI421306B (en) * 2011-02-21 2014-01-01 Far Eastern New Century Corp Silicone hydrogel with high water content
KR101742351B1 (en) 2011-02-28 2017-05-31 쿠퍼비젼 인터내셔날 홀딩 캄파니, 엘피 Phosphine-containing hydrogel contact lenses
MY161209A (en) 2011-02-28 2017-04-14 Coopervision Int Holding Co Lp Silicone hydrogel contact lenses and related compositions and methods
SG192244A1 (en) 2011-02-28 2013-09-30 Coopervision Int Holding Co Lp Silicone hydrogel contact lenses
SG192231A1 (en) 2011-02-28 2013-09-30 Coopervision Int Holding Co Lp Wettable silicone hydrogel contact lenses
WO2012118677A1 (en) * 2011-02-28 2012-09-07 Coopervison International Holding Company, Lp Low modulus silicon hydrogel contact lenses
TWI509313B (en) 2011-02-28 2015-11-21 Coopervision Int Holding Co Lp Silicone hydrogel contact lenses
EP2492719B1 (en) 2011-02-28 2014-12-03 CooperVision International Holding Company, LP Dimensionally stable silicone hydrogel contact lenses
ES2802005T3 (en) 2011-02-28 2021-01-15 Silicone hydrogel contact lenses
GB2502755B (en) 2011-02-28 2014-03-26 Coopervision Int Holding Co Lp Dimensionally stable silicone hydrogel contact lenses
ES2719850T3 (en) 2011-02-28 2019-07-16 Coopervision Int Holding Co Lp Silicone hydrogel contact lenses that have acceptable levels of energy loss
ES2441385T3 (en) 2011-02-28 2014-02-04 Coopervision International Holding Company, Lp Wettable silicone hydrogel contact lenses
US8871016B2 (en) * 2011-08-03 2014-10-28 The Johns Hopkins University Cellulose-based hydrogels and methods of making thereof
US9175153B2 (en) 2011-03-08 2015-11-03 The Johns Hopkins University Cellulose hydrogel compositions and contact lenses for corneal applications
US9170349B2 (en) 2011-05-04 2015-10-27 Johnson & Johnson Vision Care, Inc. Medical devices having homogeneous charge density and methods for making same
US20130203813A1 (en) 2011-05-04 2013-08-08 Johnson & Johnson Vision Care, Inc. Medical devices having homogeneous charge density and methods for making same
US20120283381A1 (en) 2011-05-04 2012-11-08 Ryuta Tamiya Macroinitiator containing hydrophobic segment
EP2746836B1 (en) * 2011-08-17 2021-05-26 Toray Industries, Inc. Soft ocular lens having low moisture content, and method for manufacturing same
US10591749B2 (en) * 2011-08-17 2020-03-17 Toray Industries, Inc. Medical device, combination of coating solutions, and method for producing medical device
US20130083286A1 (en) 2011-09-30 2013-04-04 Johnson & Johnson Vision Care, Inc. Method of creating a visible mark on lens using a leuco dye
US20130083287A1 (en) 2011-09-30 2013-04-04 Johnson & Johnson Vision Care, Inc. Method of creating a visible mark on lens using a leuco dye
US9188702B2 (en) 2011-09-30 2015-11-17 Johnson & Johnson Vision Care, Inc. Silicone hydrogels having improved curing speed and other properties
HUE029018T2 (en) 2011-10-12 2017-02-28 Novartis Ag Method for making uv-absorbing ophthalmic lenses by coating
KR101369381B1 (en) * 2011-11-04 2014-03-06 에스케이이노베이션 주식회사 Coating composition for low refractive layer comprising fluorine-containing compound, anti-reflection film using the same, polarizer and image displaying device comprising said anti-reflection film
US9588258B2 (en) 2011-12-23 2017-03-07 Johnson & Johnson Vision Care, Inc. Silicone hydrogels formed from zero diluent reactive mixtures
US8937110B2 (en) * 2011-12-23 2015-01-20 Johnson & Johnson Vision Care, Inc. Silicone hydrogels having a structure formed via controlled reaction kinetics
US9156934B2 (en) * 2011-12-23 2015-10-13 Johnson & Johnson Vision Care, Inc. Silicone hydrogels comprising n-vinyl amides and hydroxyalkyl (meth)acrylates or (meth)acrylamides
US9140825B2 (en) 2011-12-23 2015-09-22 Johnson & Johnson Vision Care, Inc. Ionic silicone hydrogels
US8937111B2 (en) * 2011-12-23 2015-01-20 Johnson & Johnson Vision Care, Inc. Silicone hydrogels comprising desirable water content and oxygen permeability
US9125808B2 (en) 2011-12-23 2015-09-08 Johnson & Johnson Vision Care, Inc. Ionic silicone hydrogels
CN103183803B (en) * 2011-12-29 2015-02-11 晶硕光学股份有限公司 Preparation method for hydrophilic silicone prepolymer
TWI488892B (en) 2011-12-29 2015-06-21 Pegavision Corp Method of manufacturing hydrophilic silicone prepolymer
US8940812B2 (en) 2012-01-17 2015-01-27 Johnson & Johnson Vision Care, Inc. Silicone polymers comprising sulfonic acid groups
EP2807198A1 (en) * 2012-01-27 2014-12-03 Contamac Limited Silicone hydrogels and methods for manufacture
JP6250026B2 (en) 2012-03-22 2017-12-20 モメンティブ パフォーマンス マテリアルズ インコーポレイテッド Polymerizable amide-containing organosilicon compound, silicon-containing polymer and biomedical device using the same
IN2014MN01864A (en) 2012-03-22 2015-07-03 Momentive Performance Mat Inc
JP6502246B2 (en) 2012-03-22 2019-04-17 モメンティブ パフォーマンス マテリアルズ インコーポレイテッドＭｏｍｅｎｔｉｖｅ Ｐｅｒｆｏｒｍａｎｃｅ Ｍａｔｅｒｉａｌｓ Ｉｎｃ． Hydrophilic silicone monomer, process for preparing the same and thin film containing the same
EP2828337B1 (en) 2012-03-22 2023-08-02 Momentive Performance Materials Inc. Hydrophilic macromers and hydrogels comprising the same
KR20140143194A (en) 2012-03-22 2014-12-15 모멘티브 퍼포먼스 머티리얼즈 인크. Organo-modified silicone polymers and hydrogels comprising the same
US10209534B2 (en) 2012-03-27 2019-02-19 Johnson & Johnson Vision Care, Inc. Increased stiffness center optic in soft contact lenses for astigmatism correction
JP6183616B2 (en) * 2012-03-29 2017-08-23 日産化学工業株式会社 Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
US9297929B2 (en) 2012-05-25 2016-03-29 Johnson & Johnson Vision Care, Inc. Contact lenses comprising water soluble N-(2 hydroxyalkyl) (meth)acrylamide polymers or copolymers
US10073192B2 (en) 2012-05-25 2018-09-11 Johnson & Johnson Vision Care, Inc. Polymers and nanogel materials and methods for making and using the same
US9244196B2 (en) 2012-05-25 2016-01-26 Johnson & Johnson Vision Care, Inc. Polymers and nanogel materials and methods for making and using the same
RU2640593C2 (en) 2012-05-25 2018-01-10 Джонсон Энд Джонсон Вижн Кэа, Инк. Contact lenses containing water-soluble polymers or copolymers of n-(2-hydroxyalkyl)methacrylamide
GB2503037A (en) * 2012-06-15 2013-12-18 Dealtforce Ltd Mould and method for forming a Contact Lens
US9423528B2 (en) 2012-06-25 2016-08-23 Johnson & Johnson Vision Care, Inc. Method of making silicone containing contact lens with reduced amount of diluents
US20130341811A1 (en) 2012-06-25 2013-12-26 Johnson & Johnson Vision Care, Inc. Lens comprising low and high molecular weight polyamides
US9395468B2 (en) 2012-08-27 2016-07-19 Ocular Dynamics, Llc Contact lens with a hydrophilic layer
CN104641261B (en) 2012-08-28 2016-07-20 库柏维景国际控股公司 With the contact lens that HEMA compatibility polysiloxane macromers is made
EP2931733B1 (en) 2012-12-14 2016-10-05 Novartis AG Tris(trimethyl siloxy)silane vinylic monomers and uses thereof
MY172901A (en) 2012-12-17 2019-12-13 Alcon Inc Method for making improved uv-absorbing ophthalmic lenses
US9498035B2 (en) 2012-12-21 2016-11-22 Coopervision International Holding Company, Lp Silicone hydrogel contact lenses for sustained release of beneficial polymers
US20140178327A1 (en) 2012-12-21 2014-06-26 Coopervision International Holding Company, Lp Antimicrobial Ophthalmic Devices
US9161598B2 (en) 2012-12-21 2015-10-20 Coopervision International Holding Company, Lp Ophthalmic devices for delivery of beneficial agents
US9248928B2 (en) 2012-12-21 2016-02-02 Coopervision International Holding Company, Lp Methods of manufacturing contact lenses for delivery of beneficial agents
EP2951242B1 (en) 2013-01-31 2019-09-11 Momentive Performance Materials Inc. Water soluble silicone material
TWI535793B (en) * 2013-01-31 2016-06-01 明基材料股份有限公司 Material for contact lenses, method for manufacturing contact lenses and contact lenses obtained thereby
CN103070742A (en) * 2013-02-16 2013-05-01 宫新建 Contact lens wearing assistor
US9250357B2 (en) 2013-03-15 2016-02-02 Johnson & Johnson Vision Care, Inc. Silicone-containing contact lens having reduced amount of silicon on the surface
US20140268028A1 (en) 2013-03-15 2014-09-18 Johnson & Johnson Vision Care, Inc. Silicone-containing contact lens having clay treatment applied thereto
JP6178108B2 (en) * 2013-04-30 2017-08-09 帝人フィルムソリューション株式会社 Silicone release film
EP3570093B1 (en) 2013-11-15 2021-09-15 Tangible Science, Inc. Contact lens with a hydrophilic layer
US9296764B2 (en) 2013-12-10 2016-03-29 Momentive Performance Materials Inc. Hydrophilic silicone composition
EP3083216B1 (en) 2013-12-17 2018-01-31 Novartis AG A silicone hydrogel lens with a crosslinked hydrophilic coating
US9459377B2 (en) 2014-01-15 2016-10-04 Johnson & Johnson Vision Care, Inc. Polymers comprising sulfonic acid groups
EP3090007B1 (en) 2014-02-28 2017-06-07 CooperVision International Holding Company, LP Contact lenses made with hema-compatible polysiloxane macromers
AU2015201321A1 (en) 2014-03-31 2015-10-15 Johnson & Johnson Vision Care, Inc. Silicone acrylamide copolymer
JP6351384B2 (en) 2014-06-03 2018-07-04 株式会社メニコン Contact lens and manufacturing method thereof
JP6351385B2 (en) 2014-06-03 2018-07-04 株式会社メニコン Contact lens manufacturing method
JP6173260B2 (en) * 2014-06-12 2017-08-02 信越化学工業株式会社 Monomers for ophthalmic device manufacturing
JP6356635B2 (en) * 2014-06-12 2018-07-11 信越化学工業株式会社 Monomers for ophthalmic device manufacturing
EP3171836A4 (en) * 2014-07-21 2018-05-30 Tangible Science, LLC Contact lenses and methods of making contact lenses
MY183678A (en) 2014-08-26 2021-03-08 Alcon Inc Method for applying stable coating on silicone hydrogel contact lenses
US9789654B2 (en) 2014-12-05 2017-10-17 Coopervision International Holding Company, Lp Method of manufacturing wettable silicone hydrogel contact lenses
US10525170B2 (en) 2014-12-09 2020-01-07 Tangible Science, Llc Medical device coating with a biocompatible layer
EP3268804B1 (en) 2015-03-11 2020-11-04 University of Florida Research Foundation, Inc. Mesh size control of lubrication in gemini hydrogels
US9851472B2 (en) 2015-03-27 2017-12-26 Momentive Performance Materials Inc. Silicone-based hydrophilic copolymer and hydrogel compositions comprising the same
JP6333211B2 (en) * 2015-04-23 2018-05-30 信越化学工業株式会社 Silicone for ophthalmic device manufacturing
CN107614230B (en) * 2015-06-15 2020-01-14 三井化学株式会社 Method and apparatus for manufacturing plastic lens
TWI541291B (en) 2015-06-18 2016-07-11 明基材料股份有限公司 Material for contact lenses, method for manufacturing contact lenses and contact lenses obtained thereby
US10081697B2 (en) 2015-12-15 2018-09-25 Novartis Ag Hydrophilized polydiorganosiloxane vinylic crosslinkers and uses thereof
SG11201803724TA (en) 2015-12-15 2018-06-28 Novartis Ag Method for producing contact lenses with a lubricious surface
EP3391101B1 (en) 2015-12-15 2020-07-08 Alcon Inc. Method for applying stable coating on silicone hydrogel contact lenses
WO2017103791A1 (en) 2015-12-15 2017-06-22 Novartis Ag Polymerizable polysiloxanes with hydrophilic substituents
EP3391100B1 (en) 2015-12-15 2020-08-12 Alcon Inc. Amphiphilic branched polydiorganosiloxane macromers
US10216008B2 (en) 2015-12-31 2019-02-26 International Business Machines Corporation Saccade and vergence tracking for distance auto focus adjustment
US20190154879A1 (en) 2016-02-22 2019-05-23 Coopervision International Holding Company, Lp Silicone Hydrogel Contact Lenses Having Improved Lubricity
JP7208345B2 (en) * 2016-03-11 2023-01-18 イノベーガ，インコーポレイテッド contact lens
JP6956633B2 (en) * 2016-04-04 2021-11-02 株式会社シード Soft contact lenses
US10139521B2 (en) 2016-04-20 2018-11-27 Coopervision International Holding Company, Lp Silicone elastomer-hydrogel hybrid contact lenses
US11125916B2 (en) 2016-07-06 2021-09-21 Johnson & Johnson Vision Care, Inc. Silicone hydrogels comprising N-alkyl methacrylamides and contact lenses made thereof
KR102494793B1 (en) 2016-07-06 2023-02-03 존슨 앤드 존슨 비젼 케어, 인코포레이티드 Central optic of increased stiffness in soft contact lenses for astigmatism correction
US10371865B2 (en) 2016-07-06 2019-08-06 Johnson & Johnson Vision Care, Inc. Silicone hydrogels comprising polyamides
US10370476B2 (en) 2016-07-06 2019-08-06 Johnson & Johnson Vision Care, Inc. Silicone hydrogels comprising high levels of polyamides
US10422927B2 (en) 2016-07-14 2019-09-24 Coopervision International Holding Company, Lp Method of manufacturing silicone hydrogel contact lenses having reduced rates of evaporation
US11021558B2 (en) 2016-08-05 2021-06-01 Johnson & Johnson Vision Care, Inc. Polymer compositions containing grafted polymeric networks and processes for their preparation and use
JP6615070B2 (en) * 2016-08-30 2019-12-04 信越化学工業株式会社 Both-end modified polysiloxane macromonomer and method for producing the same
CN109690360B (en) 2016-09-20 2023-04-25 爱尔康公司 Method for producing contact lenses having durable lubricious coatings thereon
US10676575B2 (en) 2016-10-06 2020-06-09 Johnson & Johnson Vision Care, Inc. Tri-block prepolymers and their use in silicone hydrogels
JP6859432B2 (en) 2016-10-11 2021-04-14 アルコン インク． Chain Extension Polydimethylsiloxane Vinyl Crosslinker and Its Use
EP3526277B1 (en) 2016-10-11 2020-08-12 Alcon Inc. Polymerizable polydimethylsiloxane-polyoxyalkylene block copolymers
WO2018097608A2 (en) * 2016-11-22 2018-05-31 주식회사 인터로조 Siloxane monomer having excellent wettability, polymeric composition comprising same, and silicone hydrogel lenses manufactured by using same
US20180169905A1 (en) 2016-12-16 2018-06-21 Coopervision International Holding Company, Lp Contact Lenses With Incorporated Components
US11254789B2 (en) 2017-02-16 2022-02-22 Momentive Performance Materials Inc. Ionically modified silicones, compositions, and medical devices formed therefrom
WO2018207644A1 (en) 2017-05-11 2018-11-15 東レ株式会社 Method for producing medical device
EP3635450A1 (en) * 2017-06-07 2020-04-15 Alcon Inc. Silicone hydrogel contact lenses
HUE055667T2 (en) 2017-06-07 2021-12-28 Alcon Inc Method for producing silicone hydrogel contact lenses
US10875967B2 (en) 2017-06-07 2020-12-29 Alcon Inc. Silicone hydrogel contact lenses
US10752720B2 (en) 2017-06-26 2020-08-25 Johnson & Johnson Vision Care, Inc. Polymerizable blockers of high energy light
US10723732B2 (en) 2017-06-30 2020-07-28 Johnson & Johnson Vision Care, Inc. Hydroxyphenyl phenanthrolines as polymerizable blockers of high energy light
US10526296B2 (en) 2017-06-30 2020-01-07 Johnson & Johnson Vision Care, Inc. Hydroxyphenyl naphthotriazoles as polymerizable blockers of high energy light
EP3447475B1 (en) 2017-08-24 2020-06-17 Alcon Inc. Method and apparatus for determining a coefficient of friction at a test site on a surface of a contact lens
WO2019043577A1 (en) 2017-08-29 2019-03-07 Novartis Ag Cast-molding process for producing contact lenses
WO2019112255A1 (en) * 2017-12-05 2019-06-13 주식회사 인터로조 Silicone hydrogel lens having excellent physical properties
EP3743270B1 (en) 2018-01-22 2022-06-08 Alcon Inc. Cast-molding process for producing uv-absorbing contact lenses
US10961341B2 (en) 2018-01-30 2021-03-30 Johnson & Johnson Vision Care, Inc. Ophthalmic devices derived from grafted polymeric networks and processes for their preparation and use
US11034789B2 (en) 2018-01-30 2021-06-15 Johnson & Johnson Vision Care, Inc. Ophthalmic devices containing localized grafted networks and processes for their preparation and use
JP7019058B2 (en) 2018-02-26 2022-02-14 アルコン インク． Silicone hydrogel contact lenses
US10935695B2 (en) 2018-03-02 2021-03-02 Johnson & Johnson Vision Care, Inc. Polymerizable absorbers of UV and high energy visible light
US20210061934A1 (en) 2019-08-30 2021-03-04 Johnson & Johnson Vision Care, Inc. Contact lens displaying improved vision attributes
US10996491B2 (en) 2018-03-23 2021-05-04 Johnson & Johnson Vision Care, Inc. Ink composition for cosmetic contact lenses
WO2019186426A1 (en) 2018-03-28 2019-10-03 Alcon Inc. Method for making silicone hydrogel contact lenses
CN112041059A (en) * 2018-04-27 2020-12-04 信越化学工业株式会社 Hydrophilic silicone resin microchannel
SG11202009915VA (en) 2018-06-04 2020-12-30 Alcon Inc Method for producing silicone hydrogel contact lenses
HUE063073T2 (en) 2018-06-04 2023-12-28 Alcon Inc Method for making silicone hydrogel contact lenses
SG11202009916RA (en) 2018-06-04 2020-12-30 Alcon Inc Method for producing silicone hydrogel contact lenses
US11046636B2 (en) 2018-06-29 2021-06-29 Johnson & Johnson Vision Care, Inc. Polymerizable absorbers of UV and high energy visible light
US10932902B2 (en) 2018-08-03 2021-03-02 Johnson & Johnson Vision Care, Inc. Dynamically tunable apodized multiple-focus opthalmic devices and methods
US20200073145A1 (en) 2018-09-05 2020-03-05 Johnson & Johnson Vision Care, Inc. Vision care kit
US11493668B2 (en) 2018-09-26 2022-11-08 Johnson & Johnson Vision Care, Inc. Polymerizable absorbers of UV and high energy visible light
WO2020100090A1 (en) 2018-11-15 2020-05-22 Alcon Inc. Contact lens with phosphorylcholine-modified polyvinylalcohols therein
EP3890952B1 (en) 2018-12-03 2023-07-05 Alcon Inc. Method for making coated silicone hydrogel contact lenses
HUE062555T2 (en) 2018-12-03 2023-11-28 Alcon Inc Method for coated silicone hydrogel contact lenses
US11724471B2 (en) 2019-03-28 2023-08-15 Johnson & Johnson Vision Care, Inc. Methods for the manufacture of photoabsorbing contact lenses and photoabsorbing contact lenses produced thereby
US11648583B2 (en) 2019-04-10 2023-05-16 Alcon Inc. Method for producing coated contact lenses
US11542353B2 (en) 2019-05-13 2023-01-03 Alcon Inc. Method for producing photochromic contact lenses
US11584097B2 (en) 2019-05-28 2023-02-21 Alcon Inc. Method for making opaque colored silicone hydrogel contact lenses
EP3976381A1 (en) 2019-05-28 2022-04-06 Alcon Inc. Pad transfer printing instrument and method for making colored contact lenses
US11578176B2 (en) 2019-06-24 2023-02-14 Johnson & Johnson Vision Care, Inc. Silicone hydrogel contact lenses having non-uniform morphology
US20200407337A1 (en) 2019-06-28 2020-12-31 Johnson & Johnson Vision Care, Inc. Photostable mimics of macular pigment
US20200407324A1 (en) 2019-06-28 2020-12-31 Johnson & Johnson Vision Care, Inc. Polymerizable fused tricyclic compounds as absorbers of uv and visible light
US20210003754A1 (en) 2019-07-02 2021-01-07 Johnson & Johnson Vision Care, Inc. Core-shell particles and methods of making and using thereof
US11543683B2 (en) 2019-08-30 2023-01-03 Johnson & Johnson Vision Care, Inc. Multifocal contact lens displaying improved vision attributes
US11891526B2 (en) 2019-09-12 2024-02-06 Johnson & Johnson Vision Care, Inc. Ink composition for cosmetic contact lenses
CN114502362B (en) 2019-11-04 2024-03-26 爱尔康公司 Contact lenses with surfaces of different softness
AU2020408087B2 (en) 2019-12-16 2023-10-05 Alcon Inc. Wettable silicone hydrogel contact lenses
US11360240B2 (en) 2019-12-19 2022-06-14 Johnson & Johnson Vision Care, Inc. Contact lens containing photosensitive chromophore and package therefor
CN113021738B (en) * 2019-12-24 2023-06-27 烟台爱博诺德医用材料有限公司 Process for the preparation of ophthalmic materials
WO2021181307A1 (en) 2020-03-11 2021-09-16 Alcon Inc. Photochromic polydiorganosiloxane vinylic crosslinkers
US20210301088A1 (en) 2020-03-18 2021-09-30 Johnson & Johnson Vision Care, Inc. Ophthalmic devices containing transition metal complexes as high energy visible light filters
CN115298573A (en) 2020-03-19 2022-11-04 爱尔康公司 High refractive index silicone insert materials for embedded contact lenses
CN115298574A (en) 2020-03-19 2022-11-04 爱尔康公司 Embedded silicone hydrogel contact lenses
JP2023518031A (en) 2020-03-19 2023-04-27 アルコン インク． Insert material with high oxygen permeability and high refractive index
EP4121279A1 (en) 2020-03-19 2023-01-25 Alcon Inc. Method for producing embedded or hybrid hydrogel contact lenses
US11754753B2 (en) 2020-04-27 2023-09-12 Coopervision International Limited Antioxidant contact lens
US20210347929A1 (en) 2020-05-07 2021-11-11 Alcon Inc. Method for producing silicone hydrogel contact lenses
EP4158392A1 (en) 2020-06-02 2023-04-05 Alcon Inc. Method for making photochromic contact lenses
US11853013B2 (en) 2020-06-15 2023-12-26 Johnson & Johnson Vision Care, Inc. Systems and methods for indicating the time elapsed since the occurrence of a triggering event
US20210388142A1 (en) 2020-06-16 2021-12-16 Johnson & Johnson Vision Care, Inc. Amino acid-based polymerizable compounds and ophthalmic devices prepared therefrom
US20210388141A1 (en) 2020-06-16 2021-12-16 Johnson & Johnson Vision Care, Inc. Imidazolium zwitterion polymerizable compounds and ophthalmic devices incorporating them
TWI803920B (en) 2020-07-28 2023-06-01 瑞士商愛爾康公司 Coated contact lens and method for making the same
US11782297B2 (en) 2020-08-28 2023-10-10 Coopervision International Limited Dimpled contact lens
US20220075210A1 (en) 2020-09-10 2022-03-10 Coopervision International Limited Contact lens
TW202231215A (en) 2020-09-14 2022-08-16 美商壯生和壯生視覺關懷公司 Single touch contact lens case
TW202225787A (en) 2020-09-14 2022-07-01 美商壯生和壯生視覺關懷公司 Single touch contact lens package
US20220113558A1 (en) 2020-10-13 2022-04-14 Johnson & Johnson Vision Care, Inc. Contact lens position and rotation control using the pressure of the eyelid margin
US11945181B2 (en) 2020-10-28 2024-04-02 Alcon Inc. Method for making photochromic contact lenses
WO2022097048A1 (en) 2020-11-04 2022-05-12 Alcon Inc. Method for making photochromic contact lenses
US20220134692A1 (en) 2020-11-04 2022-05-05 Alcon Inc. Method for making photochromic contact lenses
JP2024502390A (en) 2020-12-13 2024-01-19 ジョンソン・アンド・ジョンソン・ビジョン・ケア・インコーポレイテッド Contact lens packaging and opening method
US20220187620A1 (en) 2020-12-15 2022-06-16 Coopervision International Limited Oleic acid-releasing contact lens
US20220183433A1 (en) 2020-12-15 2022-06-16 Coopervision International Limited Cationic contact lens
WO2022130089A1 (en) 2020-12-18 2022-06-23 Johnson & Johnson Vision Care, Inc. Photostable mimics of macular pigment
CN112812247B (en) * 2020-12-31 2023-03-24 江苏海伦隐形眼镜有限公司 High-oxygen-permeability silicone hydrogel, corneal contact lens and preparation method thereof
US20220220417A1 (en) 2021-01-12 2022-07-14 Johnson & Johnson Vision Care, Inc. Compositions for Ophthalmologic Devices
EP4291601A1 (en) 2021-02-09 2023-12-20 Alcon Inc. Hydrophilized polydiorganosiloxane vinylic crosslinkers
TW202235254A (en) 2021-03-08 2022-09-16 瑞士商愛爾康公司 Method for making photofunctional contact lenses
CN116888193A (en) 2021-03-23 2023-10-13 爱尔康公司 Polysiloxane vinyl cross-linking agent with high refractive index
KR20230132841A (en) 2021-03-24 2023-09-18 알콘 인코포레이티드 Method for manufacturing intraocular hydrogel contact lenses
US20220326412A1 (en) 2021-04-01 2022-10-13 Alcon Inc. Method for making embedded hydrogel contact lenses
US11833771B2 (en) 2021-04-01 2023-12-05 Alcon Inc. Method for making photochromic contact lenses
WO2022208447A1 (en) 2021-04-01 2022-10-06 Alcon Inc. Embedded hydrogel contact lenses
US20220350163A1 (en) 2021-04-29 2022-11-03 Coopervision International Limited Ws12-releasing contact lens
WO2022263994A1 (en) 2021-06-14 2022-12-22 Alcon Inc. Multifocal diffractive silicone hydrogel contact lenses
US20230037781A1 (en) 2021-06-30 2023-02-09 Johnson & Johnson Vision Care, Inc. Transition metal complexes as visible light absorbers
CA3173598A1 (en) 2021-09-13 2023-03-13 Johnson & Johnson Vision Care, Inc. Contact lens packages and methods of handling and manufacture
US11912800B2 (en) 2021-09-29 2024-02-27 Johnson & Johnson Vision Care, Inc. Amide-functionalized polymerization initiators and their use in the manufacture of ophthalmic lenses
US11708209B2 (en) 2021-11-05 2023-07-25 Johnson & Johnson Vision Care, Inc. Touchless contact lens packages and methods of handling
TW202335928A (en) 2021-12-08 2023-09-16 美商壯生和壯生視覺關懷公司 Contact lens packages having lens lifting arms and methods of handling
WO2023105470A1 (en) 2021-12-08 2023-06-15 Johnson & Johnson Vision Care, Inc. Slotted contact lens packages and methods of handling
TW202340053A (en) 2021-12-13 2023-10-16 美商壯生和壯生視覺關懷公司 Contact lens packages with sliding or tilting lens transfer and methods of handling
TW202332416A (en) 2021-12-14 2023-08-16 美商壯生和壯生視覺關懷公司 Contact lens packages having twisting or thimble levers and methods of handling
WO2023111851A1 (en) 2021-12-15 2023-06-22 Johnson & Johnson Vision Care, Inc. Solutionless contact lens packages and methods of manufacture
WO2023111852A1 (en) 2021-12-15 2023-06-22 Johnson & Johnson Vision Care, Inc. No-touch contact lens packages and methods of handling
TW202337346A (en) 2021-12-16 2023-10-01 美商壯生和壯生視覺關懷公司 Pressurized or vacuum-sealed contact lens packages
WO2023111941A1 (en) 2021-12-16 2023-06-22 Johnson & Johnson Vision Care, Inc. No-touch contact lens packages and methods of handling
WO2023111947A1 (en) 2021-12-17 2023-06-22 Johnson & Johnson Vision Care, Inc. Contact lens dispenser
WO2023111943A1 (en) 2021-12-17 2023-06-22 Johnson & Johnson Vision Care, Inc. Contact lens packages having a pivot mechanism and methods of handling
US20230296807A1 (en) 2021-12-20 2023-09-21 Johnson & Johnson Vision Care, Inc. Contact lenses containing light absorbing regions and methods for their preparation
US20230339149A1 (en) 2022-04-26 2023-10-26 Alcon Inc. Method for making embedded hydrogel contact lenses
US20230339148A1 (en) 2022-04-26 2023-10-26 Alcon Inc. Method for making embedded hydrogel contact lenses
WO2023209631A1 (en) 2022-04-28 2023-11-02 Alcon Inc. Method for making uv and hevl-absorbing ophthalmic lenses
US20230350228A1 (en) 2022-04-28 2023-11-02 Coopervision International Limited Contact lens
US20230348718A1 (en) 2022-04-28 2023-11-02 Johnson & Johnson Vision Care, Inc. Light-filtering materials for biomaterial integration and methods thereof
US20230350230A1 (en) 2022-04-28 2023-11-02 Johnson & Johnson Vision Care, Inc. Using particles for light filtering
US20230350099A1 (en) 2022-04-28 2023-11-02 Johnson & Johnson Vision Care, Inc. Shape engineering of particles to create a narrow spectral filter against a specific portion of the light spectrum
US20230348717A1 (en) 2022-04-28 2023-11-02 Johnson & Johnson Vision Care, Inc. Particle surface modification to increase compatibility and stability in hydrogels
US11733440B1 (en) 2022-04-28 2023-08-22 Johnson & Johnson Vision Care, Inc. Thermally stable nanoparticles and methods thereof
TW202402513A (en) 2022-04-29 2024-01-16 瑞士商愛爾康公司 Method for making silicone hydrogel contact lenses
US20230357478A1 (en) 2022-05-09 2023-11-09 Alcon Inc. Method for making embedded hydrogel contact lenses
US20230374225A1 (en) 2022-05-23 2023-11-23 Alcon Inc. Method for making hevl-filtering contact lenses
US20230374306A1 (en) 2022-05-23 2023-11-23 Alcon Inc. Uv/hevl-filtering contact lenses
JP2023175283A (en) * 2022-05-30 2023-12-12 信越化学工業株式会社 Hydrophilic copolymer and hydrophilic composition
GB2619780A (en) 2022-06-13 2023-12-20 Coopervision Int Ltd Cationic lens having improved stability
WO2023242688A1 (en) 2022-06-16 2023-12-21 Johnson & Johnson Vision Care, Inc. Ophthalmic devices containing photostable mimics of macular pigment and other visible light filters
WO2024038390A1 (en) 2022-08-17 2024-02-22 Alcon Inc. A contact lens with a hydrogel coating thereon

Citations (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4062627A (en) * 1973-08-06 1977-12-13 Essilor International (Compagnie Generale D'optique S.A.) Flexible contact lens
US4121896A (en) * 1976-03-24 1978-10-24 Shepherd Thomas H Apparatus for the production of contact lenses
US4136250A (en) * 1977-07-20 1979-01-23 Ciba-Geigy Corporation Polysiloxane hydrogels
US4153596A (en) * 1976-09-21 1979-05-08 Bayer Aktiengesellschaft Permanently stabilized polymers produced by after-treatment with piperidine compounds
US4208365A (en) * 1978-12-20 1980-06-17 National Patent Development Corporation Method and apparatus for molding toric contact lenses
US4259467A (en) * 1979-12-10 1981-03-31 Bausch & Lomb Incorporated Hydrophilic contact lens made from polysiloxanes containing hydrophilic sidechains
US4260725A (en) * 1979-12-10 1981-04-07 Bausch & Lomb Incorporated Hydrophilic contact lens made from polysiloxanes which are thermally bonded to polymerizable groups and which contain hydrophilic sidechains
US4440918A (en) * 1982-01-18 1984-04-03 Minnesota Mining And Manufacturing Company Contact lens containing a fluorinated telechelic polyether
US4605712A (en) * 1984-09-24 1986-08-12 Ciba-Geigy Corporation Unsaturated polysiloxanes and polymers thereof
US4703097A (en) * 1986-04-10 1987-10-27 Bayer Aktiengesellschaft Optical contact objects
US4711943A (en) * 1985-04-26 1987-12-08 Sola U.S.A. Inc. Hydrophilic siloxane monomers and dimers for contact lens materials, and contact lenses fabricated therefrom
US4786444A (en) * 1985-12-19 1988-11-22 Minnesota Mining And Manufacturing Company Method and apparatus for making optical devices
US4879072A (en) * 1987-07-07 1989-11-07 Essilor International Cie Generale D'optique Method of manufacturing natural protein polymer contact lenses by molding and cross-linking
US4954586A (en) * 1989-01-17 1990-09-04 Menicon Co., Ltd Soft ocular lens material
US5023305A (en) * 1986-09-30 1991-06-11 Hoya Corporation Oxygen-permeable hard contact lens material with excellent impact resistance
US5070169A (en) * 1988-02-26 1991-12-03 Ciba-Geigy Corporation Wettable, flexible, oxygen permeable contact lens containing block copolymer polysiloxane-polyoxyalkylene backbone units and use thereof
US5158717A (en) * 1990-11-27 1992-10-27 Bausch & Lomb Incorporated Method of molding shaped polymeric articles
US5264465A (en) * 1991-01-31 1993-11-23 Hoya Corporation Contact lens material and contact lens
US5274008A (en) * 1990-11-27 1993-12-28 Bausch & Lomb Incorporated Mold materials for silicone containing lens materials
US5312690A (en) * 1989-12-05 1994-05-17 Shin-Etsu Chemical Co., Ltd. Self-adhesive silicone rubber composition and silicone rubber coated-fabric material
US5321108A (en) * 1993-02-12 1994-06-14 Bausch & Lomb Incorporated Fluorosilicone hydrogels
US5358995A (en) * 1992-05-15 1994-10-25 Bausch & Lomb Incorporated Surface wettable silicone hydrogels
US5486579A (en) * 1991-11-05 1996-01-23 Bausch & Lomb Incorporated Wettable silicone hydrogel compositions and methods for their manufacture
US5760100A (en) * 1994-09-06 1998-06-02 Ciba Vision Corporation Extended wear ophthalmic lens
US5807944A (en) * 1996-06-27 1998-09-15 Ciba Vision Corporation Amphiphilic, segmented copolymer of controlled morphology and ophthalmic devices including contact lenses made therefrom
US5945498A (en) * 1995-04-04 1999-08-31 Novartis Ag Polysiloxane-comprising perfluoroalkyl ethers and the preparation and use thereof
US6158861A (en) * 1998-03-09 2000-12-12 Menicon Co., Ltd. Prism ballast type contact lens, method of producing the same, and mold assembly used in producing the lens
US6867245B2 (en) * 1999-12-16 2005-03-15 Asahikasei Aime Co., Ltd. Long wearable soft contact lens

Family Cites Families (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA983230A (en) 1972-01-03 1976-02-10 Lawrence Stark Physiologically compatible plastic contact lenses and a method for their production
JPS603342B2 (en) * 1977-12-13 1985-01-28 信越化学工業株式会社 How to make silicone contact lenses
EP0267158B1 (en) * 1986-11-06 1992-01-02 Ciba-Geigy Ag Substantially non-swellable contact lens containing block copolymer polysiloxane-polyoxyalkylene backbone units
DE3889769T2 (en) 1987-04-30 1994-10-20 Ciba Geigy Ag Macromers containing terminal vinyl groups, derived polymers and contact lenses.
JP2503028B2 (en) 1987-09-26 1996-06-05 ホーヤ株式会社 Contact lens manufacturing method
EP0330617B1 (en) 1988-02-26 1991-07-03 Ciba-Geigy Ag Wettable, flexible, oxygen permeable contact lens containing block copolymer polysiloxane-polyoxyalkylene backbone units
EP0330616B1 (en) 1988-02-26 1991-06-05 Ciba-Geigy Ag Wettable, flexible, oxygen permeable contact lens containing block copolymer polysiloxane-polyoxyalkylene backbone units, and use thereof
EP0362137A3 (en) * 1988-09-28 1991-09-04 Ciba-Geigy Ag Molded polymers with hydrophilic surfaces, and process for making them
DE9006868U1 (en) * 1990-06-19 1990-10-04 Venator Inc., Victor, Id., Us
JPH0519214A (en) * 1991-07-15 1993-01-29 Asahi Chem Ind Co Ltd Contact lens free from contamination
US5352714A (en) 1991-11-05 1994-10-04 Bausch & Lomb Incorporated Wettable silicone hydrogel compositions and methods for their manufacture
JP2774233B2 (en) 1992-08-26 1998-07-09 株式会社メニコン Ophthalmic lens materials
JPH06106552A (en) * 1992-09-29 1994-04-19 Hoya Corp Manufacturing mold of contact lens
JPH06170857A (en) 1992-12-03 1994-06-21 Seiko Epson Corp Production of contact lens and mold therefor
JPH07266443A (en) 1994-03-30 1995-10-17 Hoya Corp Manufacture of soft contact lens
JPH0825378A (en) 1994-07-20 1996-01-30 Seiko Epson Corp Resin mold for producing contact lens and production of contact lens
JP3901749B2 (en) † 1995-02-21 2007-04-04 株式会社メニコン Surface treatment method for hydrous contact lenses and hydrous contact lenses obtained thereby
JP3406112B2 (en) * 1995-03-10 2003-05-12 旭化成アイミー株式会社 Manufacturing method of ophthalmic lens material
JP3441024B2 (en) * 1995-03-10 2003-08-25 旭化成アイミー株式会社 Ophthalmic lens material comprising hydrophilic fluorine-containing siloxane monomer and its resin
JPH08304746A (en) * 1995-04-28 1996-11-22 Asahi Chem Ind Co Ltd Ocular lens material
US6020445A (en) * 1997-10-09 2000-02-01 Johnson & Johnson Vision Products, Inc. Silicone hydrogel polymers
US6310116B1 (en) 1997-10-09 2001-10-30 Kuraray Co., Ltd. Molded polymer article having a hydrophilic surface and process for producing the same
JPH11320571A (en) * 1998-05-15 1999-11-24 Menicon Co Ltd Mold for eye lens, its manufacture and manufacture of the lens using the mold
JPH11320699A (en) * 1998-05-21 1999-11-24 Seiko Epson Corp Manufacture of contact lens

Patent Citations (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4062627A (en) * 1973-08-06 1977-12-13 Essilor International (Compagnie Generale D'optique S.A.) Flexible contact lens
US4121896A (en) * 1976-03-24 1978-10-24 Shepherd Thomas H Apparatus for the production of contact lenses
US4153596A (en) * 1976-09-21 1979-05-08 Bayer Aktiengesellschaft Permanently stabilized polymers produced by after-treatment with piperidine compounds
US4136250A (en) * 1977-07-20 1979-01-23 Ciba-Geigy Corporation Polysiloxane hydrogels
US4208365A (en) * 1978-12-20 1980-06-17 National Patent Development Corporation Method and apparatus for molding toric contact lenses
US4259467A (en) * 1979-12-10 1981-03-31 Bausch & Lomb Incorporated Hydrophilic contact lens made from polysiloxanes containing hydrophilic sidechains
US4260725A (en) * 1979-12-10 1981-04-07 Bausch & Lomb Incorporated Hydrophilic contact lens made from polysiloxanes which are thermally bonded to polymerizable groups and which contain hydrophilic sidechains
US4440918A (en) * 1982-01-18 1984-04-03 Minnesota Mining And Manufacturing Company Contact lens containing a fluorinated telechelic polyether
US4605712A (en) * 1984-09-24 1986-08-12 Ciba-Geigy Corporation Unsaturated polysiloxanes and polymers thereof
US4711943A (en) * 1985-04-26 1987-12-08 Sola U.S.A. Inc. Hydrophilic siloxane monomers and dimers for contact lens materials, and contact lenses fabricated therefrom
US4786444A (en) * 1985-12-19 1988-11-22 Minnesota Mining And Manufacturing Company Method and apparatus for making optical devices
US4703097A (en) * 1986-04-10 1987-10-27 Bayer Aktiengesellschaft Optical contact objects
US5023305A (en) * 1986-09-30 1991-06-11 Hoya Corporation Oxygen-permeable hard contact lens material with excellent impact resistance
US4879072A (en) * 1987-07-07 1989-11-07 Essilor International Cie Generale D'optique Method of manufacturing natural protein polymer contact lenses by molding and cross-linking
US5070169A (en) * 1988-02-26 1991-12-03 Ciba-Geigy Corporation Wettable, flexible, oxygen permeable contact lens containing block copolymer polysiloxane-polyoxyalkylene backbone units and use thereof
US4954586A (en) * 1989-01-17 1990-09-04 Menicon Co., Ltd Soft ocular lens material
US5312690A (en) * 1989-12-05 1994-05-17 Shin-Etsu Chemical Co., Ltd. Self-adhesive silicone rubber composition and silicone rubber coated-fabric material
US5158717A (en) * 1990-11-27 1992-10-27 Bausch & Lomb Incorporated Method of molding shaped polymeric articles
US5274008A (en) * 1990-11-27 1993-12-28 Bausch & Lomb Incorporated Mold materials for silicone containing lens materials
US5264465A (en) * 1991-01-31 1993-11-23 Hoya Corporation Contact lens material and contact lens
US5486579A (en) * 1991-11-05 1996-01-23 Bausch & Lomb Incorporated Wettable silicone hydrogel compositions and methods for their manufacture
US5358995A (en) * 1992-05-15 1994-10-25 Bausch & Lomb Incorporated Surface wettable silicone hydrogels
US5387632A (en) * 1992-05-15 1995-02-07 Bausch & Lomb Incorporated Surface wettable silicone hydrogels
US5321108A (en) * 1993-02-12 1994-06-14 Bausch & Lomb Incorporated Fluorosilicone hydrogels
US5760100A (en) * 1994-09-06 1998-06-02 Ciba Vision Corporation Extended wear ophthalmic lens
US5760100B1 (en) * 1994-09-06 2000-11-14 Ciba Vision Corp Extended wear ophthalmic lens
US5945498A (en) * 1995-04-04 1999-08-31 Novartis Ag Polysiloxane-comprising perfluoroalkyl ethers and the preparation and use thereof
US5807944A (en) * 1996-06-27 1998-09-15 Ciba Vision Corporation Amphiphilic, segmented copolymer of controlled morphology and ophthalmic devices including contact lenses made therefrom
US6158861A (en) * 1998-03-09 2000-12-12 Menicon Co., Ltd. Prism ballast type contact lens, method of producing the same, and mold assembly used in producing the lens
US6867245B2 (en) * 1999-12-16 2005-03-15 Asahikasei Aime Co., Ltd. Long wearable soft contact lens

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8476337B2 (en) 2006-06-15 2013-07-02 Coopervision International Holding Company, Lp Wettable silicone hydrogel contact lenses and related compositions and methods
US7572841B2 (en) * 2006-06-15 2009-08-11 Coopervision International Holding Company, Lp Wettable silicone hydrogel contact lenses and related compositions and methods
US20080048350A1 (en) * 2006-06-15 2008-02-28 Charlie Chen Wettable Silicone Hydrogel Contact Lenses and Related Compositions and Methods
US8524850B2 (en) 2008-02-08 2013-09-03 Coopervision International Holding Company, Lp Hydrophilic polysiloxane macromonomer, and production and use of the same
US8129442B2 (en) 2008-02-08 2012-03-06 Coopervision International Holding Company, Lp Hydrophilic polysiloxane macromonomer, and production and use of the same
US20090234089A1 (en) * 2008-02-08 2009-09-17 Asahi Kasei Aime Co., Ltd. Hydrophilic Polysiloxane Macromonomer, and Production and Use of the same
US8939577B2 (en) 2010-07-30 2015-01-27 Novartis Ag Silicone hydrogel lenses with water-rich surfaces
US9244200B2 (en) 2010-07-30 2016-01-26 Novartis Ag Silicone hydrogel lenses with water-rich surfaces
US9411171B2 (en) 2010-07-30 2016-08-09 Novartis Ag Silicone hydrogel lenses with water-rich surfaces
US9816009B2 (en) 2010-07-30 2017-11-14 Novartis Ag Silicone hydrogel lenses with water-rich surfaces
US10781340B2 (en) 2010-07-30 2020-09-22 Alcon Inc. Silicone hydrogel lenses with water-rich surfaces
CN103237850A (en) * 2010-10-15 2013-08-07 柏格阿莫菲克索录森斯有限公司 Coating compositions with anticorrosion properties
US11256003B2 (en) 2017-12-13 2022-02-22 Alcon Inc. Weekly and monthly disposable water gradient contact lenses

Also Published As

Publication number Publication date
JP4988025B2 (en) 2012-08-01
US6867245B2 (en) 2005-03-15
JP5148794B2 (en) 2013-02-20
US20040192872A1 (en) 2004-09-30
JP2013020259A (en) 2013-01-31
US20020016383A1 (en) 2002-02-07
EP1243960B1 (en) 2009-08-26
TWI269912B (en) 2007-01-01
CA2394939C (en) 2007-10-30
ATE441132T1 (en) 2009-09-15
AU1892001A (en) 2001-06-25
KR20020070324A (en) 2002-09-05
CN1409829A (en) 2003-04-09
WO2001044861A1 (en) 2001-06-21
ES2328009T5 (en) 2013-12-12
EP1243960B2 (en) 2013-10-16
AU779729B2 (en) 2005-02-10
JP2011070207A (en) 2011-04-07
EP1243960A1 (en) 2002-09-25
CA2394939A1 (en) 2001-06-21
CN100374881C (en) 2008-03-12
DE60042841D1 (en) 2009-10-08
KR100522339B1 (en) 2005-10-20
EP1243960A4 (en) 2003-04-16
US20110211158A1 (en) 2011-09-01
ES2328009T3 (en) 2009-11-06
US8637621B2 (en) 2014-01-28

Similar Documents

Publication Publication Date Title
US6867245B2 (en) Long wearable soft contact lens
US8614261B2 (en) Silicone hydrogel contact lens
US10465047B2 (en) Polymerizable polydimethylsiloxane-polyoxyalkylene block copolymers
CA2122251C (en) Wettable silicone hydrogel compositions and methods for their manufacture
US9529119B2 (en) Method for fabricating silicone-containing copolymer molded article having hydrophilic surface and silicone-hydrogel contact lens having hydrophilic surface
EP1235866B1 (en) Soft contact lenses
TWI665263B (en) Silicone hydrogel contact lenses
US20180100053A1 (en) Chain-extended polydimethylsiloxane vinylic crosslinkers and uses thereof
US9322958B2 (en) Silicone hydrogel contact lenses
CN109416414B (en) Increased hardness central optic zone in soft contact lenses for astigmatism correction

Legal Events

Date Code Title Description
AS Assignment

Owner name: ASAHIKASEI AIME CO., LTD., JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:IWATA, JUNICHI;HOKI, TSUNEO;IKAWA, SEIICHIROU;REEL/FRAME:017920/0018

Effective date: 20010321

AS Assignment

Owner name: COOPERVISION INTERNATIONAL HOLDING COMPANY, LP, BA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:ASAHIKASEI AIME CO., LTD.;REEL/FRAME:025444/0639

Effective date: 20101201

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION

AS Assignment

Owner name: COOPERVISION INTERNATIONAL LIMITED, UNITED KINGDOM

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:COOPERVISION INTERNATIONAL HOLDING COMPANY, LP;REEL/FRAME:054370/0631

Effective date: 20201102