WO2003032051A1 - Lentille de contact dure permeable a l'oxygene - Google Patents

Lentille de contact dure permeable a l'oxygene Download PDF

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Publication number
WO2003032051A1
WO2003032051A1 PCT/JP2002/010345 JP0210345W WO03032051A1 WO 2003032051 A1 WO2003032051 A1 WO 2003032051A1 JP 0210345 W JP0210345 W JP 0210345W WO 03032051 A1 WO03032051 A1 WO 03032051A1
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WO
WIPO (PCT)
Prior art keywords
oxygen
lens
meth
hard contact
contact lens
Prior art date
Application number
PCT/JP2002/010345
Other languages
English (en)
Japanese (ja)
Inventor
Junko Kita
Takashi Makabe
Original Assignee
Kuraray 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
Application filed by Kuraray Co., Ltd. filed Critical Kuraray Co., Ltd.
Priority to KR10-2003-7016948A priority Critical patent/KR20040030708A/ko
Priority to JP2003534966A priority patent/JPWO2003032051A1/ja
Publication of WO2003032051A1 publication Critical patent/WO2003032051A1/fr

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Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers 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
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/22Esters containing halogen
    • GPHYSICS
    • G02OPTICS
    • G02CSPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
    • G02C7/00Optical parts
    • G02C7/02Lenses; Lens systems ; Methods of designing lenses
    • G02C7/04Contact lenses for the eyes
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/041Lenses
    • G02B1/043Contact lenses

Definitions

  • the present invention relates to an oxygen-permeable hard contact lens.
  • the oxygen-permeable hard contact lens of the present invention has a small center thickness of the lens, a high ability to supply oxygen to the cornea, is excellent in safety, has less damage during use, and has high durability.
  • Contact lenses are vision correction tools that are used in direct contact with the eye (cornea). Therefore, it is essential that the contact lenses not only have excellent optical characteristics but also have sufficient safety. .
  • the cornea is a bloodless tissue, and the supply of oxygen from the atmosphere is indispensable for maintaining the corneal cell's metabolic activity. Therefore, as a result of the development of materials for improving oxygen permeability, various contact lens materials and contact lenses having a high oxygen permeability coefficient have been developed.
  • Japanese Patent Laying-Open No. 6-41242 proposes an ophthalmic lens material containing a silicon-containing styrene derivative and a fluorinated alkyl ester-containing styrene derivative as essential components.
  • the present invention has been made in view of the above conventional technology, and an object of the present invention is to provide an oxygen-permeable hard contact lens capable of supplying physiologically sufficient oxygen to the cornea and having excellent durability. To provide. Disclosure of the invention
  • the oxygen permeability coefficient of 20 X 1 0- 11 cm 3 ⁇ cm / cm 2 ⁇ sec ⁇ m mHg consists in that the polymer or more and the lens center thickness 0.0 1 0-0 of. 1 25
  • the present invention relates to an oxygen-permeable hard contact lens having a vertex refractive power value of ⁇ 6.0D or more, which is characterized in that it is mm.
  • the oxygen-permeable hard contact lens of the present invention has a center thickness in the range of 0.010 to 0.125 mm and a vertex refractive power value of not less than 6.00 D. It is.
  • the “center thickness of the lens” in this specification means the thickness of the center portion (optical center) of the optical part of the lens, and the “value of the vertex power” means the refractive index of the lens. .
  • the value of the apex power decreases, the difference in curvature between the front surface and the rear surface of the lens increases, and the thickness of the peripheral portion of the lens inevitably increases. Therefore, even if the center thickness is reduced in order to reduce the thickness of the entire lens, the strength of the lens is maintained by the thickness of the peripheral portion.
  • the oxygen permeability coefficient of 20 X 1 0- 11 cm 3 ( STP) - central thickness of cm / cm 2 ⁇ sec ⁇ mmH g or more at which consist material contact lens When the value is set in the above range, there is no shortage of strength that causes a problem in practical use, but rather the lens is easily bent, and the stress is dispersed and shrunk throughout the lens, so that the lens is resistant to the stress repeatedly applied to the lens. It was found that durability (durability in actual use environment) was significantly improved.
  • the center thickness of the lens is preferably in the range of 0.050 to 0.120 mm, and preferably in the range of 0.070 to 0.105 mm, from the viewpoints of vision correction ability and durability against repeated stress. Is more preferred.
  • the Vickers hardness which is an index of the flexibility of the lens (the rigidity of the lens) is 5 to 15 from the viewpoint of the ability to correct visual acuity and the durability against repeated stress. It is preferably within the range, more preferably within the range of 5-10.
  • the compression elastic modulus of the oxygen-permeable hard contact lens of the present invention is preferably in the range of 100 to 100 gf, and more preferably in the range of 20 to 90 gf. More preferred.
  • the compression elastic modulus is an index of the flexibility of a lens. The smaller the value, the easier the lens is to bend, and the larger the value, the higher the rigidity of the lens.
  • the oxygen permeability coefficient of the polymer used for the oxygen-permeable hard contact lens of the present invention is 20 ⁇ 10 ⁇ 11 cm 3 -cm / cm 2 ⁇ sec ⁇ mmHg or more.
  • oxygen permeability coefficient as used in this specification is expressed as the product of the solubility coefficient of oxygen in a polymer and the diffusion coefficient of oxygen in the polymer. Standard method means the value measured by the "Oxygen permeability measurement method for hard contact lenses".
  • the oxygen permeability coefficient of the polymer is less than 20 X 1 (T 11 cm 3 -cm / cm 2 -sec-mm Hg, it will not be possible to supply physiologically sufficient oxygen to the cornea, Oxygen deficiency in the lens may cause eye damage, and as the oxygen permeability coefficient of the polymer increases, the stain resistance tends to decrease.
  • the oxygen permeability coefficient of the polymer is 20 X 1 0- 11 ⁇ 2 0 0 X 1 0 _11 cm 3 - preferably in the range of cm / cm 2 ⁇ sec ⁇ mmH g, 20 x 1 0- 11 ⁇ 1 50 x 1 0- 11 cm 3 - cm / cm 2 'sec' range of mmHg, more preferably, 20 X 1 0 ⁇ 11 ⁇ 1 00 X 1 0- 11 cm 3 - cm / cm 2 ⁇ sec ⁇ mmHg Is more preferable.
  • the polymer constituting the oxygen-permeable hard contact lens of the present invention may be appropriately selected from known ones used for oxygen-permeable hard contact lenses, and has a high oxygen permeability coefficient.
  • those containing a monomer unit having a siloxanyl group are preferred.
  • Examples of such a monomer include tris (trimethylsiloxy) silylpropyl (meth) acrylate, heptanemethyltrisiloxanylethyl (meth) acrylate, pentamethyldisiloxanyl (meth) acrylate, and isobutylhexamethyl.
  • (Meth) acryl amide having a siloxanyl group (meth) acrylamide having a siloxanyl group is preferred from the viewpoint of durability against repeated stress and stain resistance, and N- [tris (trimethylcycoxy) silylpropyl] (meth) acryla is preferred. Mid is more preferred.
  • the monomer having a siloxanyl group only one type may be used, or two or more types may be used in combination.
  • (meth) acrylate means “acrylate J and / or“ methacrylate ”.
  • (Meth) acryloxymethylsilane means “acryloxymethylsilane” and / or “methacryloxymethylsilane”.
  • ⁇ (meth) acrylamide means “acrylamide J and / or“ methacrylamide j ”.
  • the oxygen permeation coefficient and the oxygen permeation rate are high, and the contamination resistance is also excellent. As a result, contact lenses with excellent total balance can be obtained.
  • Examples of the monomer having a fluorine atom include 2,2,2-trifluoroethyl (meth) acrylate, 2,2,2,2,2,2′-hexafluoroisopropyl (meth) acrylate, 2,2 2,3,3,4,4,4-heptafluorobutyl (meth) acrylate, 2, 2, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 8-penta Decafluorooctyl (meth) acrylate, 2, 2, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 9, 9-hexadecafluorononyl (meth) acrylate Fluoroalkyl (meth) acrylate, and one or more of these can be used.
  • a monomer unit having a siloxanyl group In order to obtain a polymer having a desired oxygen permeability coefficient, a monomer unit having a siloxanyl group It is preferable that the weight ratio of the monomer unit having a fluorine atom to the monomer unit is within a range of 70:30 to 30:70, and the monomer unit having a siloxanyl group and the fluorine atom are included. Preferably, the total amount of the monomer units is 30 to 70% by weight based on the total weight of the polymer.
  • the polymer constituting the oxygen-permeable hard contact lens of the present invention preferably contains a monomer unit having at least two polymerizable groups in the molecule from the viewpoint of shape stability.
  • Monomers having at least two polymerizable groups in the molecule include alkylene glycol di (meth) acrylates such as ethylene glycol di (meth) acrylate and diethylene glycol di (meth) acrylate, and trimethylolpropane tri ( Examples thereof include (meth) acrylate and tetra or tri (meth) acrylate of pentaerythritol. These monomers having at least two polymerizable groups may be used alone or in combination of two or more.
  • the content of the monomer unit is preferably from 0.1 to 20% by weight based on the total weight of the polymer. . When the content of the monomer unit is less than 0.1% by weight, the shape stability of the obtained lens tends to decrease, and when it exceeds 20% by weight, the obtained lens becomes brittle. Tend.
  • the polymer constituting the oxygen-permeable hard contact lens of the present invention preferably contains a hydrophilic monomer unit from the viewpoint of improving wettability with water.
  • hydrophilic monomer examples include hydroxyl-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate; acrylic acid, methacrylic acid.
  • Unsaturated carboxylic acids such as acid, itaconic acid, fumaric acid, maleic acid, and cinnamic acid; (meth) acrylamides such as acrylamide, methacrylamide, dimethylacrylamide, and getylacrylamide Alkylene oxide (meth) acrylates such as glycidyl (meth) acrylate; polyethylene glycol mono (meth) acrylate Alkylene glycol (meth) acrylates such as acrylate and polypropylene glycol mono (meth) acrylate; N-vinyl-2-piperidone, N-vinyl-12-pyrrolidone, N-vinyl-6-hexanelactam, N-vinyl-1-3- Methyl-2-pyrrolidone, N-vinyl-1-methyl-piperidone, N-vinyl-1-methyl-6-hexanelactam, N-vinyl-14-methyl-2-pyrrolidone, N-vinyl-14-methyl-2-
  • the content of the monomer unit is preferably from 0.1 to 20% by weight based on the total weight of the polymer.
  • the content of the monomer unit is less than 0.1% by weight, the water wettability of the obtained lens tends to decrease, and when it exceeds 20% by weight, the water absorption of the obtained lens is high. And the strength decreases.
  • the polymer constituting the oxygen-permeable hard contact lens of the present invention preferably contains an alkyl (meth) acrylate unit from the viewpoint of increasing the strength.
  • alkyl (meth) acrylate examples include methyl (meth) acrylate
  • the content of the alkyl (meth) acrylate unit is preferably from 0.1 to 20% by weight based on the total weight of the polymer.
  • the content of the monomer unit is less than 0.1% by weight, the strength of the obtained lens tends to decrease, and when it exceeds 20% by weight, the oxygen permeability of the obtained lens decreases.
  • the polymer constituting the oxygen-permeable hard contact lens of the present invention contains, if necessary, a monomer unit other than the above together with the above-mentioned monomer unit as long as the object of the present invention is not impaired. You may. Examples of such a monomer unit include units derived from fatty acid vinyl such as vinyl acetate, vinyl butyrate, and laurate; and units derived from diester diester such as dimethyl itaconate and getyl itaconate. These monomer units may be used alone or in combination of two or more. When these monomer units are contained in the polymer, the content of the monomer units should be about 10% by weight or less based on the total weight of the polymer. Preferred for obtaining coalesced and oxygen permeable hard contact lenses.
  • a pigment may be contained for the purpose of obtaining a colored oxygen-permeable hard contact lens.
  • An oxygen-permeable hard contact lens can be produced by polymerizing a polymerizable composition containing the above-described monomer in a desired ratio and molding the polymer into a contact lens shape.
  • the polymerization method is commonly used to polymerize polymerizable monomers Five
  • a method of adding one or both of a heat-activated polymerization initiator and an energy ray-activated polymerization initiator (eg, light) to the polymerizable composition and performing heat polymerization or photopolymerization is used. Is used. Among these, it is preferable to heat-polymerize the above-mentioned polymerizable composition using a heat-activated polymerization initiator from the viewpoint of obtaining a contact lens having no optical distortion.
  • heat-activated polymerization initiator In heating and polymerizing the polymerizable composition using a heat-activated polymerization initiator, it is preferable to use a thermostat, a hot-air circulation heating device or the like, which can easily control the temperature.
  • the heat-activated polymerization initiator include peroxide-based heat-activated polymerization initiators such as benzoyl peroxide, isopropyl peroxide, lauroyl peroxide, and methyl ethyl ketone peroxide; Zobisisobutyronitrile, 2,2'-azobismethylisobutyrate, 2,2'-azobisdimethylvaleronitrile, 2,2'-azobisisobutylamide, 2,2'-azobisiso Examples include azo-based heat-activated polymerization initiators such as dimethyl butyrate, and one or more of these heat-activated polymerization initiators can be used.
  • the amount of the polymerization initiator is not particularly limited, but is usually about 0.001 to 2 parts by weight based on 100 parts by weight of the whole polymerizable composition used for the polymerization.
  • contact lenses In the production of contact lenses, methods conventionally used for the production of plastic contact lenses, for example, (1) polymerizing and molding a polymerizable composition, and cutting and polishing the obtained molded product to obtain contact lenses (2) Filling the polymerizable composition into a mold having mold cavities corresponding to contact lenses and polymerizing and molding in the mold to produce a contact lens, (3) Rotation A spin casting method in which a polymerizable composition is dropped onto a mold surface that rotates at a high speed around an axis, and the polymerizable composition is radially cast and diffused on the mold surface, and simultaneously polymerized and molded to manufacture a contact lens.
  • a polymerizable composition is filled in a mold having a mold cavity capable of molding one surface of a contact lens, and polymerized and molded in the mold, and the other surface is molded.
  • Blank mold method for manufacturing contact lenses by cutting and polishing Can be adopted, and there is no particular limitation.
  • the center thickness of the lens is
  • the lens diameter, the diameter of the optical part of the lens, the thickness of the optical part other than the optical center, and the radius of the peripheral part of the lens on the front curve side are not particularly limited and can be determined as appropriate.
  • the diameter of the lens is 8.0-11.1 Omm
  • the diameter of the optical section is 5.0-10.5 mm
  • the radius (curvature radius) of the lens at the front curve side is 6 mm. .0-
  • the radius of the base curve should be 7.0 to 10.0 mm
  • the bevel curve radius should be 8.0 to 12.0 mm
  • the bevel width should be 0 to 2 mm. Is preferred.
  • the present invention will be described specifically with reference to Examples and the like, but the present invention is not limited thereto.
  • the Vickers hardness, oxygen permeability coefficient, oxygen permeability, compression modulus, compression bending strength, and durability against cyclic stress of the oxygen-permeable hard contact lens were measured or evaluated as follows.
  • the Vickers hardness of the oxygen-permeable hard contact lenses obtained in the following Examples and Comparative Examples was measured with a Pickers hardness tester (AKASHI).
  • the oxygen permeability coefficient of the copolymers obtained in the following Examples and Comparative Examples was measured using a Sikaken-type film oxygen permeability meter (manufactured by Rika Seiki Kogyo Co., Ltd.) as a standard test method for hard contact lenses. Measurement of Oxygen Permeability " The value obtained by dividing the thus obtained oxygen permeability coefficient by the center thickness of the lens was defined as the oxygen permeability.
  • the compression bending test was performed according to the standard test method for contact lens association “Compression bending test method for contact lenses” except that the amount was changed from 20 O mmZ to 10 mm / min.
  • the stress when the tangent to the deformation start point of the stress-strain curve obtained when performing the compression bending test was extended to the diameter of the lens was defined as the compression modulus.
  • the test used was “Autograph 1100” manufactured by Shimadzu Corporation. [Compression bending strength]
  • the oxygen-permeable hard contact lenses obtained in the following Examples and Comparative Examples were subjected to a compression bending test in accordance with the standard test method for contact lenses of Japan, "Test Method for Compression Bending of Contact Lenses".
  • “Autograph I M-100” manufactured by Shimadzu Corporation was used.
  • Table 1 shows the abbreviations of the polymerizable monomers used in the following Examples, Comparative Examples and Tables. table 1
  • Example 1 4 0 3 0 1 0 1 0 1 0 0
  • Example 2 4 0 3 0 1 0 1 0 1 0
  • Example 3 4 0 3 0 1 0 1 0 1 0
  • Example 4 5 0 2 0 1 0 1 0 1 0
  • the oxygen-permeable hard contact lenses of Examples 1 to 8 withstand repeated stress of 800 times or more, Regarding also the oxygen permeability, all day wear 30 X 1 necessary (J- 9 cm 3 • c / cm 2 ⁇ sec ⁇ mmH g ⁇ cm higher than values obtained les, Ru.
  • an oxygen-permeable hard contact lens capable of supplying physiologically sufficient oxygen to the cornea and having excellent durability.

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

Abstract

Cette invention se rapporte à une lentille de contact dure perméable à l'oxygène qui est capable d'amener suffisamment d'oxygène à la cornée par voie physiologique et avec une excellente durabilité. Cette lentille est constituée d'un polymère ayant une perméabilité à l'oxygène de 20 X 10-11 cm3. cm/cm2.sec.mmHg. L'épaisseur du centre de la lentille est comprise entre 0,010 et 0,125 mm et la puissance frontale est supérieure à -6,00 D.
PCT/JP2002/010345 2001-10-09 2002-10-04 Lentille de contact dure permeable a l'oxygene WO2003032051A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR10-2003-7016948A KR20040030708A (ko) 2001-10-09 2002-10-04 산소 투과성 하드 콘택트 렌즈
JP2003534966A JPWO2003032051A1 (ja) 2001-10-09 2002-10-04 酸素透過性ハードコンタクトレンズ

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2001-311107 2001-10-09
JP2001311107 2001-10-09

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WO2003032051A1 true WO2003032051A1 (fr) 2003-04-17

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JP (1) JPWO2003032051A1 (fr)
KR (1) KR20040030708A (fr)
CN (1) CN1537249A (fr)
TW (1) TWI232972B (fr)
WO (1) WO2003032051A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007241233A (ja) * 2006-02-08 2007-09-20 Toray Ind Inc コンタクトレンズ
JP2013525512A (ja) * 2010-03-18 2013-06-20 東レ株式会社 シリコーン(メタ)アクリルアミドモノマー、ポリマー、眼用レンズおよびコンタクトレンズ

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9835765B2 (en) 2011-09-27 2017-12-05 Canon Kabushiki Kaisha Optical element and method for manufacturing the same
CN106749877B (zh) * 2016-12-20 2018-12-28 无锡蕾明视康科技有限公司 一种高透氧性光学透镜材料及其制备方法
KR20210064198A (ko) * 2018-09-25 2021-06-02 니치유 가부시키가이샤 콘택트 렌즈용 모노머 조성물 및 콘택트 렌즈용 중합체, 그리고 콘택트 렌즈 및 그 제조 방법
CN114516942A (zh) * 2020-11-18 2022-05-20 亨泰光学股份有限公司 硬式透氧隐形眼镜高分子材料及其聚合方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5162391A (en) * 1989-03-10 1992-11-10 Kuraray Co., Ltd. Oxygen permeable hard contact lens
JPH04360120A (ja) * 1991-06-06 1992-12-14 Tokyo Keikaku:Kk 防眩用ハードコンタクトレンズ
JPH0534647A (ja) * 1991-07-30 1993-02-12 Tokyo Keikaku:Kk 紫外線吸収剤の溶出のないハ−ドコンタクトレンズ
US5194542A (en) * 1989-09-30 1993-03-16 Hoya Corporation Contact lens
JPH05100190A (ja) * 1991-10-08 1993-04-23 Tokyo Keikaku:Kk 鉛含有ハ−ドコンタクトレンズ
JPH0943549A (ja) * 1995-07-25 1997-02-14 Tokyo Keikaku:Kk ハードコンタクトレンズ
US6190651B1 (en) * 1998-08-03 2001-02-20 Menicon Co., Ltd. Solution for preserving contact lenses for shipping and method for preserving contact lenses for shipping employing it

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5162391A (en) * 1989-03-10 1992-11-10 Kuraray Co., Ltd. Oxygen permeable hard contact lens
US5194542A (en) * 1989-09-30 1993-03-16 Hoya Corporation Contact lens
JPH04360120A (ja) * 1991-06-06 1992-12-14 Tokyo Keikaku:Kk 防眩用ハードコンタクトレンズ
JPH0534647A (ja) * 1991-07-30 1993-02-12 Tokyo Keikaku:Kk 紫外線吸収剤の溶出のないハ−ドコンタクトレンズ
JPH05100190A (ja) * 1991-10-08 1993-04-23 Tokyo Keikaku:Kk 鉛含有ハ−ドコンタクトレンズ
JPH0943549A (ja) * 1995-07-25 1997-02-14 Tokyo Keikaku:Kk ハードコンタクトレンズ
US6190651B1 (en) * 1998-08-03 2001-02-20 Menicon Co., Ltd. Solution for preserving contact lenses for shipping and method for preserving contact lenses for shipping employing it

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007241233A (ja) * 2006-02-08 2007-09-20 Toray Ind Inc コンタクトレンズ
JP2013525512A (ja) * 2010-03-18 2013-06-20 東レ株式会社 シリコーン(メタ)アクリルアミドモノマー、ポリマー、眼用レンズおよびコンタクトレンズ

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CN1537249A (zh) 2004-10-13
TWI232972B (en) 2005-05-21
KR20040030708A (ko) 2004-04-09
JPWO2003032051A1 (ja) 2005-01-27

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