JPH02269306A - Fluorine based contact lens - Google Patents
Fluorine based contact lensInfo
- Publication number
- JPH02269306A JPH02269306A JP8972489A JP8972489A JPH02269306A JP H02269306 A JPH02269306 A JP H02269306A JP 8972489 A JP8972489 A JP 8972489A JP 8972489 A JP8972489 A JP 8972489A JP H02269306 A JPH02269306 A JP H02269306A
- Authority
- JP
- Japan
- Prior art keywords
- contact lens
- group
- formula
- monomer
- oxygen permeability
- 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.)
- Pending
Links
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title abstract description 9
- 229910052731 fluorine Inorganic materials 0.000 title abstract description 9
- 239000011737 fluorine Substances 0.000 title abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 59
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 17
- RRZIJNVZMJUGTK-UHFFFAOYSA-N 1,1,2-trifluoro-2-(1,2,2-trifluoroethenoxy)ethene Chemical compound FC(F)=C(F)OC(F)=C(F)F RRZIJNVZMJUGTK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920000642 polymer Polymers 0.000 claims abstract description 9
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 4
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 19
- 239000001301 oxygen Substances 0.000 abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 abstract description 19
- 230000035699 permeability Effects 0.000 abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 150000007942 carboxylates Chemical group 0.000 abstract 1
- 238000000034 method Methods 0.000 description 11
- -1 siloxanyl methacrylates Chemical class 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000012530 fluid Substances 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000012719 thermal polymerization Methods 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000010702 perfluoropolyether Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920002338 polyhydroxyethylmethacrylate Polymers 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- MNSWITGNWZSAMC-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-yl prop-2-enoate Chemical compound FC(F)(F)C(C(F)(F)F)OC(=O)C=C MNSWITGNWZSAMC-UHFFFAOYSA-N 0.000 description 1
- GWYSWOQRJGLJPA-UHFFFAOYSA-N 1,1,2,2-tetrafluoropropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)C(C)(F)F GWYSWOQRJGLJPA-UHFFFAOYSA-N 0.000 description 1
- LCPUCXXYIYXLJY-UHFFFAOYSA-N 1,1,2,4,4,4-hexafluorobutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)C(F)CC(F)(F)F LCPUCXXYIYXLJY-UHFFFAOYSA-N 0.000 description 1
- MHNPWFZIRJMRKC-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical compound F[C]=C(F)F MHNPWFZIRJMRKC-UHFFFAOYSA-N 0.000 description 1
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 description 1
- DZZAHLOABNWIFA-UHFFFAOYSA-N 2-butoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCCCC)C(=O)C1=CC=CC=C1 DZZAHLOABNWIFA-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- BESKSSIEODQWBP-UHFFFAOYSA-N 3-tris(trimethylsilyloxy)silylpropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC[Si](O[Si](C)(C)C)(O[Si](C)(C)C)O[Si](C)(C)C BESKSSIEODQWBP-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical group CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- LVWQVTPCZIUGSS-UHFFFAOYSA-N [3,3,3-trifluoro-2-(trifluoromethyl)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C(F)(F)F)C(F)(F)F LVWQVTPCZIUGSS-UHFFFAOYSA-N 0.000 description 1
- QWYSJTTWCUXHQO-UHFFFAOYSA-N [F].OC(=O)C=C Chemical compound [F].OC(=O)C=C QWYSJTTWCUXHQO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 210000004087 cornea Anatomy 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- FFYWKOUKJFCBAM-UHFFFAOYSA-N ethenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC=C FFYWKOUKJFCBAM-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000002504 physiological saline solution Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- RGBXDEHYFWDBKD-UHFFFAOYSA-N propan-2-yl propan-2-yloxy carbonate Chemical compound CC(C)OOC(=O)OC(C)C RGBXDEHYFWDBKD-UHFFFAOYSA-N 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
Landscapes
- Eyeglasses (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明は、酸素透過性、耐汚染性、装用感に優れたフッ
素系コンタクトレンズに関するものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a fluorine-containing contact lens that has excellent oxygen permeability, stain resistance, and wear comfort.
(従来の技術)
従来、コンタクトレンズはポリメチルメタクリレート(
PMMA )を中心に、各種アクリレート系単量体の重
合物が広く用いられてきたが、このPMMA[のコンタ
クトレンズは酸素透過能力がないため、装用中の角膜の
酸素不足を解消するうえから酸素透過性の材料が用いら
れるようになってきた。これらの材料として例えばアク
リレート分子内にシロキサン結合を導入した各種シロキ
サニルメタクリレートや、フッ素を導入した含フツ素ア
クリレートを用いた重合体によるコンタクトレンズが提
案されている(USP152073号、USP3808
178号)、シかしながらこれらの重合体は、従来のP
MMAに比べれば酸素透過性は改善されているもののい
まだ十分でなく、又耐汚染性、装用感についても満足で
きるものではない。(Conventional technology) Conventionally, contact lenses were made of polymethyl methacrylate (
Polymers of various acrylate monomers, mainly PMMA), have been widely used, but since PMMA contact lenses do not have the ability to permeate oxygen, oxygen Transparent materials have come into use. As these materials, for example, contact lenses made of polymers using various siloxanyl methacrylates in which siloxane bonds are introduced into the acrylate molecules and fluorine-containing acrylates in which fluorine is introduced have been proposed (USP No. 152073, USP 3808).
178), but these polymers are similar to conventional P
Although the oxygen permeability has been improved compared to MMA, it is still not sufficient, and the stain resistance and wearing comfort are also unsatisfactory.
装用感の改善の目的でポリヒドロキシエチルメタクリレ
ート(PHEMA)やポリビニルピロリドン(PNVP
)等を成分とするハイドロゲルからなる含水性コンタク
トレンズが知られている。Polyhydroxyethyl methacrylate (PHEMA) and polyvinylpyrrolidone (PNVP) are used to improve wearing comfort.
) and other hydrogels are known.
これらの材料は、装用感は大幅に改善されているが、酸
素透過性、機械的強度が不十分で、又菌類や涙液成分に
よって汚染されやすいという問題点がある。Although these materials have greatly improved wearing comfort, they have problems in that they have insufficient oxygen permeability and mechanical strength, and are easily contaminated by fungi and lachrymal fluid components.
非含水系のシリコンラバーコンタクトレンズも酸素透過
性は優れているものの親油性が強く、涙液成分中の脂質
が付着しやすいこと、又表面撥水性のため涙液とのなじ
みが悪く、異物感を生じるなどの問題がある。Although non-hydrous silicone rubber contact lenses have excellent oxygen permeability, they are highly lipophilic, making it easy for lipids in tear fluid to adhere to them, and their surface water repellency makes them poorly compatible with tear fluid, resulting in a foreign body sensation. There are problems such as causing
ところでフッ素系コンタクトレンズとしてパーフロロビ
ニルエーテル系のもの(USP3940207号)が知
られている。By the way, perfluorovinyl ether type contact lenses (USP No. 3,940,207) are known as fluorine type contact lenses.
このものはフッ素含有重合体のもつ不活性な特性により
、耐汚染性に優れ、屈折率も涙液に近いため涙液/コン
タクトレンズの間での光学的特性が良く、コンタクトレ
ンズの角膜への適合を容易にする効果があることが知ら
れている。しかしながら、パーフロロビニルエーテル系
の単量体は該特許に示されるようにその重合法や得られ
る重合体が限られており、そこで得られた共重合体も酸
素透過性において不十分であり、そもそもコンタクトレ
ンズ材料によく使われる各種シロキサニルメタクリレー
ト単量体やメチルメタクリレート等の炭化水素系アクリ
レート単量体とは重合せず、これらの単量体との共重合
コンタクトレンズは得られていなかった。This product has excellent stain resistance due to the inert properties of the fluorine-containing polymer, and has a refractive index close to that of tear fluid, so it has good optical properties between the tear fluid and the contact lens, and the contact lens does not affect the cornea. It is known to have the effect of facilitating adaptation. However, as shown in the patent, perfluorovinyl ether monomers have limited polymerization methods and polymers that can be obtained, and the copolymers obtained therefrom also have insufficient oxygen permeability. It does not polymerize with various siloxanyl methacrylate monomers and hydrocarbon acrylate monomers such as methyl methacrylate, which are often used in contact lens materials, and no contact lenses copolymerized with these monomers have been obtained. .
また、テレキーリックパーフロロポリエーテル・系コン
タクトレンズ(LJSP340473号)が知られてい
るが、ここに使われている単量体はアクリレート系であ
るため、各種アクリレート系単量体とは共重合性も改善
され、酸素透過性も大幅に向上しているが単量体の精製
において次のような問題がある。Additionally, telechelic perfluoropolyether contact lenses (LJSP340473) are known, but since the monomers used here are acrylate-based, they are copolymerized with various acrylate-based monomers. Although the properties and oxygen permeability have been improved significantly, there are the following problems in purifying the monomer.
即ち、コンタクトレンズは光学製品であり、光学的には
厳しい基準を達成しなければならない。That is, contact lenses are optical products and must meet strict optical standards.
fのために原料である単量体は高純度で、しかも重合条
件を厳しくコントロールしなければならない。For f, the raw material monomer must be of high purity, and the polymerization conditions must be strictly controlled.
上記テレキーリックパーフロロポリエーテル単量体の場
合は分子量が高く、単量体の一般的な精製法である蒸留
精製が使えず、高純度に精製するのは大変である。In the case of the above-mentioned telechelic perfluoropolyether monomer, the molecular weight is high, and distillation purification, which is a common purification method for monomers, cannot be used, and it is difficult to purify it to a high degree of purity.
(本発明が解決しようとする課題)
本発明はこのような従来の酸素透過性コンタクトレンズ
の有する欠点を克服し、優れた酸素透過性、耐汚染性、
水−性を兼ね備えた装用感の良好なコンタクトレンズを
提供することを目的とする。(Problems to be Solved by the Present Invention) The present invention overcomes the drawbacks of conventional oxygen permeable contact lenses, and provides excellent oxygen permeability, stain resistance,
The purpose of the present invention is to provide a contact lens that is water-resistant and comfortable to wear.
(課題を解決するための手段)
本発明者らは、優れた酸素透過性、耐汚染性、水−性を
兼ね備えた新規なコンタクトレンズについて鋭意研究を
重ねた結果、特定のパーフロロビニルエーテル単量体と
特定の含フツ素アクリレート単量体を必須成分とする重
合体が前期目的を達成しうろことを見い出し、この知晃
に基づいて本発明を完成するに至った。即ち、本発明は
(A)一般式
%式%(1)
(式中mは0〜2の整数、nは1〜5の整数、Mはスル
ホニル基、カルボン酸エステル基又はF基である。)
で表わされるパーフロロビニルエーテル系単量体と
(B)一般式
%式%()
(式中のR1は水素原子又はメチル基R2は直鎖状もし
くは分校状のフッ素化アルキル基である。)で表わされ
るアクリレート単量体を必須成分とする重合体からなる
酸素透過性コンタクトレンズを提供するものである。(Means for Solving the Problem) As a result of intensive research into a new contact lens that has excellent oxygen permeability, stain resistance, and water resistance, the present inventors discovered that a specific perfluorovinyl ether monomer The inventors have discovered that a polymer containing a specific fluorine-containing acrylate monomer as essential components can achieve the above object, and based on this knowledge, they have completed the present invention. That is, the present invention is based on (A) the general formula % (1) (where m is an integer of 0 to 2, n is an integer of 1 to 5, and M is a sulfonyl group, a carboxylic acid ester group, or an F group). ) Perfluorovinyl ether monomer represented by (B) general formula % formula % () (R1 in the formula is a hydrogen atom or a methyl group R2 is a linear or branched fluorinated alkyl group.) The present invention provides an oxygen-permeable contact lens made of a polymer containing an acrylate monomer represented by the following as an essential component.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明のコンタクトレンズにおいて原料単量体のIA)
成分として一般式
CF2=CF (OCF2CF) a o−(CF2)
、−M・−−・(1)―
Fs
(式中のmはO〜2の整数、 n4よ1〜5の整数。IA) of the raw material monomer in the contact lens of the present invention
General formula CF2=CF (OCF2CF) a o-(CF2) as a component
, -M・---・(1)-Fs (m in the formula is an integer of O to 2, and n4 is an integer of 1 to 5.
Mはスルホニル基、カルボン酸エステル基又41 F基
である。)
で表わされるパーフロロビニルエーテル系単量体が用い
られる。この単量体の物性及びその製法に関しては、U
SP4329434号、υ5P4329435号、SI
’390937号USP3132123号、特公45−
22327号、特開52−28586などに記載しであ
る。M is a sulfonyl group, a carboxylic acid ester group, or a 41F group. ) is used. Regarding the physical properties of this monomer and its manufacturing method, please refer to U
SP4329434, υ5P4329435, SI
'390937 USP No. 3132123, Special Publication No. 45-
No. 22327, JP-A No. 52-28586, and the like.
また、一般式(1)で表わされる置換基Mとしてはスル
ホニル基の場合はS Oz F 、カルボン酸エステル
基としてはカルボン酸メチル、カルボン酸エチル勢のカ
ルボン酸アルキルエステル基が好ましい、その好ましい
具体例としては
CFz−CF OCF2OF −0−(CF2) 2C
OOCH3CF 3
CF2■CF OCFzc F2OOOC)(3CF2
四〇FO(CF2)3COOCH3CFz=CFO(C
F2)4COOCR3F3
CF2=CFO(CF2)ssOzF、CFt箇CFO
(CF、)gcF3などがある。Further, as the substituent M represented by the general formula (1), in the case of a sulfonyl group, S Oz F is preferable, and as the carboxylic acid ester group, a carboxylic acid alkyl ester group such as methyl carboxylate or ethyl carboxylate group is preferable. An example is CFz-CF OCF2OF -0-(CF2) 2C
OOCH3CF 3 CF2■CF OCFzc F2OOOC) (3CF2
40FO(CF2)3COOCH3CFz=CFO(C
F2) 4COOCR3F3 CF2=CFO (CF2)ssOzF, CFt CFO
(CF,) gcF3, etc.
これらパーフロロビニルエーテル系単量体は、それぞれ
単独で用いてもよいし、2種類以上を組み合わせてもよ
い。These perfluorovinyl ether monomers may be used alone or in combination of two or more.
この単量体はコンタクトレンズに柔軟性と、酸素透過性
を寄与する役割を果たす。This monomer plays a role in contributing flexibility and oxygen permeability to contact lenses.
末端にスルホニル基やカルボン酸エステル基を持ったパ
ーフロロビニルエーテル系単量体を用いた共重合コンタ
クトレンズの場合は、公知の方法により例えば5%水酸
化ナトリウム水溶液中に短時間浸漬して1表面上に50
3 Na、COONa基を生成することによって、ホー
性を付与することもできる。In the case of copolymerized contact lenses using perfluorovinylether monomers having a sulfonyl group or a carboxylic acid ester group at the end, one surface of the contact lens is immersed for a short time in a 5% aqueous sodium hydroxide solution using a known method. 50 on top
By generating 3 Na and COONa groups, it is also possible to impart ho properties.
本発明のコンタクトレンズにおいて、原料(B)成分と
して用いられる含フツ素アクリレート単量体は(B)一
般式
(式中のR1及びR2は前記とv4シ意味をもつ、)で
表わされる構造を有する公知の単量体で、このものは該
(A)単量体との相港性が^く、前記(A)単量体の酸
素透過性と柔軟性付与効果をそこなうことなく、かつ前
記(^)単量体の欠点である炭化水素系アクリレート単
量体や、シロキサン結合を有するアクリレート単量体と
の共重合を可能にせしめる効果がある。In the contact lens of the present invention, the fluorine-containing acrylate monomer used as the raw material (B) component has a structure represented by the general formula (B) (in which R1 and R2 have the meanings as above). This monomer is compatible with the monomer (A), does not impair the oxygen permeability and flexibility imparting effect of the monomer (A), and has the (^) It has the effect of making it possible to copolymerize with hydrocarbon-based acrylate monomers, which are drawbacks of monomers, and with acrylate monomers having siloxane bonds.
前記式(rl)で表わされる倉フッ素アクリレート単量
体の具体例としてはトリフルオロエチルメタクリレート
、テトラフルオロプロピルメタクリレート、ヘキサフル
オロブチルメタクリレート、ヘキサフルオロイソブnビ
ルメタ゛クリレートなどのメタクリレート類及びこれら
に対応するアクリレ−子類をあげることができる。これ
らのアクリレート単量体は、それぞれ単独で用いても真
いし。Specific examples of the fluorine acrylate monomer represented by the above formula (rl) include methacrylates such as trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, hexafluorobutyl methacrylate, and hexafluoroisobutyl methacrylate; Corresponding acrylic children can be mentioned. Each of these acrylate monomers may be used alone.
2種類以上を組み合わせても真い。It is also true that two or more types are combined.
本発明のコンタクトレンズにおいては、前記(^)単量
体と(B)単量体の使用割合は5:95ないし50:5
0.好ましくは5二95ないし35:65の範囲で選ば
れる。In the contact lens of the present invention, the ratio of the monomer (^) to the monomer (B) is 5:95 to 50:5.
0. Preferably, it is selected in the range of 5295 to 35:65.
本発明のコンタクトレンズにおいては、機械的強度や酸
素透過性やホー性等を向上させる目的で前記(A)(B
)単量体に加えて、炭化水素系のアクリレート単量体や
シロキサン緒合奄有するアクリレート単量体や親水基敬
有する単量体が用いられる。In the contact lens of the present invention, the above-mentioned (A) and (B)
) In addition to the monomers, hydrocarbon-based acrylate monomers, acrylate monomers containing siloxane, and monomers containing hydrophilic groups are used.
これらの各種の単量体の具体例のうち、炭化水素系アク
リレートとしてはメタクリル酸メチル、メダクリル酸n
−ブチル、アクリル酸nブチル。Among the specific examples of these various monomers, hydrocarbon acrylates include methyl methacrylate and medacrylic acid n.
-butyl, n-butyl acrylate.
メタクリル駿n−ヘキシルなどがあり、又シロキサニル
結合を有するアクリレート単量体としては例えば、一般
式
ただし式中XおよびYはCユ〜C5のアルキル基フェニ
ル基およびZ基からなる群から選ばれ、Zは構造式
%式%)
をもつ基でありAは00〜C5のアルキル基およびフェ
ニル基およびZ基からなる群から選ばれ、Rは水素原子
又はメチル基から選ばれ、mは1〜5の整数であり、n
は1〜3の整数である。)をもつシロキサニル結合を有
するアクリレート単量体であり(持分52−33502
号)、好ましくはトリス(トリメチルシロキシ)シリル
プロピルメタクリレート、ベシタメチルジシロキサニル
メチルメタクリレート、ヘプタメチルシロキサニルエチ
ルアクリレート等がある。親水基を有する単量体として
はβ−ヒドロキシエチルアクリレート、β−ヒドロオキ
シエチルメタクリレート、N−ビニルピロリドン、メタ
アクリル酸等がある。Examples of acrylate monomers having a siloxanyl bond include methacryl and n-hexyl, and examples include the general formula, where X and Y are selected from the group consisting of a C to C5 alkyl group, a phenyl group, and a Z group; Z is a group having the structural formula (%), A is selected from the group consisting of 00 to C5 alkyl groups, phenyl groups, and Z groups, R is selected from hydrogen atoms or methyl groups, and m is 1 to 5. is an integer of n
is an integer from 1 to 3. ) is an acrylate monomer with a siloxanyl bond (equity 52-33502
), preferably tris(trimethylsiloxy)silylpropyl methacrylate, becitamethyldisiloxanylmethyl methacrylate, heptamethylsiloxanyl ethyl acrylate, etc. Examples of monomers having hydrophilic groups include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, N-vinylpyrrolidone, and methacrylic acid.
これら上記の単量体は、それぞれ単独で用いても良いし
、2種以上を組み合わせても良い、これら上記(A)(
B)単量体に加えられる単量体は。These above-mentioned monomers may be used alone or in combination of two or more, and these monomers (A) (
B) What monomers are added to the monomer?
通常単量体全量の重量につき3〜50%の範囲が選ばれ
る。又、これらと共に該コンタクトレンズの機械的強度
を向上させる目的で、例えばエチレングリコールジメタ
クリレート、トリメチロールプロパン、トリメタクリレ
ート、メタクリル酸ビニル等の架橋剤をlO重量%程度
の範囲で併用することもできる。Usually, a range of 3 to 50% by weight of the total amount of monomers is selected. In addition, in addition to these, for the purpose of improving the mechanical strength of the contact lens, a crosslinking agent such as ethylene glycol dimethacrylate, trimethylolpropane, trimethacrylate, vinyl methacrylate, etc. can also be used in a range of about 10% by weight. .
本発明に従えば、このコンタクトレンズはモールド(鋳
型)に原料単量体混合液と重合触媒を入れて、ラジカル
重合させる公知の方法により製造することができる。こ
の方法には特に制限はなくラジカル重合法において慣用
されている方法1例えば、熱重合法や紫外線照射による
光重合法などを用いることができる。WI熱重重合法お
いては、通常熱重合開始剤として例えば、アゾビスイソ
ブチロニトリル、過酸化ベンゾイル、ジイソプロピルパ
ーオキシカーボネート、クメンヒドロパーオキシドなど
を単量体全量に対して0.01〜5重量%割合で添加し
、この混合物を25〜120℃の範囲の温度において5
〜100時間程重合反応行なうことによって、所望の共
重合体からコンタクトレンズを得ることが出来る。According to the present invention, this contact lens can be manufactured by a known method of placing a raw material monomer mixture and a polymerization catalyst in a mold and carrying out radical polymerization. This method is not particularly limited, and methods commonly used in radical polymerization, such as thermal polymerization and photopolymerization using ultraviolet irradiation, can be used. In the WI thermal polymerization method, a thermal polymerization initiator such as azobisisobutyronitrile, benzoyl peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, etc. is usually used in an amount of 0.01 to 5% based on the total amount of monomers. % by weight, and the mixture was heated at a temperature ranging from 25 to 120°C for 50 minutes.
Contact lenses can be obtained from the desired copolymer by carrying out the polymerization reaction for about 100 hours.
一方光重合法においては通常熱重合開始剤として例えば
ベンゾインエチルエーテル、ベンゾインn−ブチルエ、
−チル、ベンジルジメチルケタール、アセトフェノン、
α、α′−ジェトキシアセトフェノン、アントラキノン
などを単量体全量に対して0.05〜3重量%割合で添
加し、この混合物を紫外線透過性のコンタクトレンズ形
状の鋳型に注入し紫外線を照射して重合反応を行なわせ
た後鋳型からコンタクトレンズを得ることが出来る。On the other hand, in the photopolymerization method, thermal polymerization initiators are usually used, such as benzoin ethyl ether, benzoin n-butyl ether,
-thyl, benzyl dimethyl ketal, acetophenone,
α, α′-Jethoxyacetophenone, anthraquinone, etc. are added at a ratio of 0.05 to 3% by weight based on the total amount of monomers, and this mixture is poured into an ultraviolet-transparent contact lens-shaped mold and irradiated with ultraviolet rays. After a polymerization reaction is carried out, a contact lens can be obtained from the mold.
(発明の効果)
本発明のコンタクトレンズは酸素透過性に優れ、強度、
柔軟性、水濡性も良好であって、コンタクトレンズとし
て、極めて好適である。(Effect of the invention) The contact lens of the invention has excellent oxygen permeability, strength,
It has good flexibility and water wettability, making it extremely suitable for use as contact lenses.
(実施例)
次に実施例により本発明をさらに詳細に説明するが、本
発明はこれらの例によってなんら限定されるものではな
い。(Examples) Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way.
実施例1゜
CF2−CF20CF2CFOCF2CF2COOCH
3(F−1)CF。Example 1゜CF2-CF20CF2CFOCF2CF2COOCH
3(F-1) CF.
10重量部へキサフルオロイソプロピルアクリレート9
0重量部さらにベンジルジメチルケタール1重量部をよ
く混合して、混合物を紫外線透過性のコンタクトレンズ
鋳型に注入してケミカルランプ8mw/cm2で1時間
照射し、さらに80℃で1時間加熱処理した。10 parts by weight hexafluoroisopropyl acrylate 9
0 parts by weight and 1 part by weight of benzyl dimethyl ketal were thoroughly mixed, and the mixture was poured into an ultraviolet-transparent contact lens mold, irradiated with a chemical lamp of 8 mw/cm2 for 1 hour, and further heat-treated at 80°C for 1 hour.
このレンズは柔軟性があり、透明で、同一重合条件で作
成した307μmのフィルムを用いて圧力法(真空法)
により酸素透過性を測定したところ、 51 X 1
0−10cm’(STP) ・am/ am2・se
c−cmHgを示し、かつ引張強度は369g / m
m2、伸びは438%であった。気泡法により水に対
する接触角を測定したところ48度であリ・水濡性良好
であった。接触角の測定の前処理として試料フィルムは
界面活性剤で表面を洗い、該フィルムを生理食塩水に2
4時間浸積したのち接触角の測定を行なった。This lens is flexible and transparent, and is produced using a pressure method (vacuum method) using a 307 μm film made under the same polymerization conditions.
When oxygen permeability was measured by
0-10cm'(STP) ・am/ am2・se
c-cmHg, and the tensile strength is 369g/m
m2, elongation was 438%. The contact angle with water was measured by the bubble method and was 48 degrees, indicating good water wettability. As a pretreatment for contact angle measurement, the surface of the sample film was washed with a surfactant, and the film was soaked in physiological saline for 2 hours.
After 4 hours of immersion, the contact angle was measured.
実施例2〜5゜
実施例1における単量体組成を次表に示すように変えた
以外は、実施例1と同様にして重合してコンタクトレン
ズおよびフィルムを作成し、物性を求めた。単量体の相
溶性および物性を談表に示す。Examples 2 to 5 Contact lenses and films were prepared by polymerization in the same manner as in Example 1, except that the monomer composition in Example 1 was changed as shown in the following table, and their physical properties were determined. Monomer compatibility and physical properties are shown in the table.
比較例1. 2
実施例1における単量体組成を、次表に示すように変え
た場合の単量体の相溶性および物性な該表に示す。Comparative example 1. 2 The following table shows the compatibility and physical properties of the monomers when the monomer composition in Example 1 was changed as shown in the table below.
以下余白Margin below
Claims (1)
ホニル基、カルボン酸エステル基又はF基を表わす。) で表わされるパーフロロビニルエーテル系単量体と(B
)一般式 ▲数式、化学式、表等があります▼‥‥‥(II) (式中R_1は水素原子又はメチル基、R_2は直鎖状
もしくは分枝状のフッ素化アルキル基を表わす。)で表
わされるアクリレート単量体を必須成分とする重合体か
らなるコンタクトレンズ。[Claims] (A) General formula▲ Numerical formulas, chemical formulas, tables, etc.▼……(I) (In the formula, m is an integer of 0 to 2, n is an integer of 1 to 5, M is a sulfonyl group , represents a carboxylic acid ester group or F group) and a perfluorovinyl ether monomer represented by (B
) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼‥‥‥(II) (In the formula, R_1 represents a hydrogen atom or a methyl group, and R_2 represents a linear or branched fluorinated alkyl group.) A contact lens made of a polymer containing acrylate monomer as an essential component.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8972489A JPH02269306A (en) | 1989-04-11 | 1989-04-11 | Fluorine based contact lens |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8972489A JPH02269306A (en) | 1989-04-11 | 1989-04-11 | Fluorine based contact lens |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH02269306A true JPH02269306A (en) | 1990-11-02 |
Family
ID=13978713
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP8972489A Pending JPH02269306A (en) | 1989-04-11 | 1989-04-11 | Fluorine based contact lens |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH02269306A (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5134211A (en) * | 1990-01-31 | 1992-07-28 | E. I. Du Pont De Nemours And Company | Hydroxy containing fluorovinyl compounds and polymers thereof |
US5196494A (en) * | 1990-01-31 | 1993-03-23 | E. I. Du Pont De Nemours And Company | Hydroxy containing fluorovinyl compounds and polymers thereof |
US5237026A (en) * | 1990-06-04 | 1993-08-17 | E. I. Du Pont De Nemours And Company | Functionalized trifluorovinyl ethers and polymers therefrom |
US5301254A (en) * | 1989-04-13 | 1994-04-05 | Hoechst Aktiengesellschaft | Transparent thermoplastic molding compound and use thereof |
WO2007005356A1 (en) * | 2005-07-01 | 2007-01-11 | Bausch & Lomb Incorporated | Biomedical devices |
-
1989
- 1989-04-11 JP JP8972489A patent/JPH02269306A/en active Pending
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5301254A (en) * | 1989-04-13 | 1994-04-05 | Hoechst Aktiengesellschaft | Transparent thermoplastic molding compound and use thereof |
US5134211A (en) * | 1990-01-31 | 1992-07-28 | E. I. Du Pont De Nemours And Company | Hydroxy containing fluorovinyl compounds and polymers thereof |
US5196494A (en) * | 1990-01-31 | 1993-03-23 | E. I. Du Pont De Nemours And Company | Hydroxy containing fluorovinyl compounds and polymers thereof |
US5237026A (en) * | 1990-06-04 | 1993-08-17 | E. I. Du Pont De Nemours And Company | Functionalized trifluorovinyl ethers and polymers therefrom |
WO2007005356A1 (en) * | 2005-07-01 | 2007-01-11 | Bausch & Lomb Incorporated | Biomedical devices |
US7534836B2 (en) | 2005-07-01 | 2009-05-19 | Bausch & Lomb Incorporated | Biomedical devices |
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