JPS63210114A - Oxygen-permeable material - Google Patents
Oxygen-permeable materialInfo
- Publication number
- JPS63210114A JPS63210114A JP4127587A JP4127587A JPS63210114A JP S63210114 A JPS63210114 A JP S63210114A JP 4127587 A JP4127587 A JP 4127587A JP 4127587 A JP4127587 A JP 4127587A JP S63210114 A JPS63210114 A JP S63210114A
- Authority
- JP
- Japan
- Prior art keywords
- fluorine
- atom
- fluorinated
- oxygen
- hydrocarbon group
- 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
- 239000000463 material Substances 0.000 title abstract description 13
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 48
- 229920001577 copolymer Polymers 0.000 claims abstract description 23
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 19
- -1 acrylate ester Chemical class 0.000 claims abstract description 14
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 10
- 239000011737 fluorine Substances 0.000 claims description 38
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 36
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 13
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 3
- 239000000178 monomer Substances 0.000 abstract description 11
- 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 abstract description 6
- 239000003999 initiator Substances 0.000 abstract description 4
- 238000012719 thermal polymerization Methods 0.000 abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 2
- 238000002844 melting Methods 0.000 abstract description 2
- 230000008018 melting Effects 0.000 abstract description 2
- 230000000379 polymerizing effect Effects 0.000 abstract description 2
- 150000002430 hydrocarbons Chemical group 0.000 abstract 3
- 150000001925 cycloalkenes Chemical class 0.000 abstract 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 38
- 239000001301 oxygen Substances 0.000 description 38
- 229910052760 oxygen Inorganic materials 0.000 description 38
- 230000035699 permeability Effects 0.000 description 19
- 238000006116 polymerization reaction Methods 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000002632 lipids Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- JNELGWHKGNBSMD-UHFFFAOYSA-N xanthone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3OC2=C1 JNELGWHKGNBSMD-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- DXVLAUMXGHQKAV-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-(2-hydroxypropoxy)propoxy]propoxy]propoxy]propoxy]propoxy]propoxy]propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)COC(C)COC(C)COC(C)COC(C)COC(C)COC(C)CO DXVLAUMXGHQKAV-UHFFFAOYSA-N 0.000 description 1
- HLGNMOUJXWELKK-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOCCOCCOCCOCCOCCOCCOC(=O)C(C)=C HLGNMOUJXWELKK-UHFFFAOYSA-N 0.000 description 1
- YWADTJSDSIORKX-UHFFFAOYSA-N 4-(3-cyanopropyldiazenyl)-2-phenylbutanenitrile Chemical compound C1(=CC=CC=C1)C(C#N)CCN=NCCCC#N YWADTJSDSIORKX-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
- 241000894006 Bacteria Species 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
- 241000233866 Fungi Species 0.000 description 1
- 206010020565 Hyperaemia Diseases 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 206010030113 Oedema Diseases 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 210000001742 aqueous humor Anatomy 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 210000004204 blood vessel Anatomy 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 210000004087 cornea Anatomy 0.000 description 1
- 208000021921 corneal disease Diseases 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 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
- 210000000744 eyelid Anatomy 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 210000004877 mucosa Anatomy 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- 230000000241 respiratory effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- ILLKMACMBHTSHP-UHFFFAOYSA-N tetradecaethylene glycol Chemical compound OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO ILLKMACMBHTSHP-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 150000007964 xanthones Chemical class 0.000 description 1
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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/22—Esters containing halogen
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、装用感および耐汚染性に優れた
弗素含有共重合体から形成された酸素透過体に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an oxygen permeable body formed from a fluorine-containing copolymer that has excellent oxygen permeability, wear comfort, and stain resistance.
さらに詳細にはハードコンタクトレンズなどの医療用酸
素透過体として用いると生体適合性に優れ、長時間の装
着が可能となりかつ優れた性能を発揮することのできる
酸素透過体に関する。More specifically, the present invention relates to an oxygen permeable material that has excellent biocompatibility when used as a medical oxygen permeable material such as a hard contact lens, can be worn for a long time, and exhibits excellent performance.
眼の角膜は血管のない組織であるために、その呼吸代謝
に必要な酸素は眠っている時は眼瞼粘膜や房水からの拡
散により得られているが、起きている時は大気中から取
り入れられている。Since the cornea of the eye is a tissue without blood vessels, the oxygen necessary for its respiratory metabolism is obtained by diffusion from the eyelid mucosa and aqueous humor when we are asleep, but when we are awake, it is taken in from the atmosphere. It is being
そのため、ハードコンタクトレンズであれソフトコンタ
クトレンズであれ、コンタクトレンズを装着することは
酸素供給の障害となり易く、長時間装着を行うと、充血
、浮腫およびその他の角膜障害を起こすことが多かった
。従って、コンタクトレンズ用の素材には光学的性質、
化学的性質、物理的性質、機械的性質に優れていること
に加えて、酸素透過性に優れていることが求められてい
る。Therefore, wearing contact lenses, whether hard or soft, tends to impede oxygen supply, and wearing them for a long time often causes hyperemia, edema, and other corneal disorders. Therefore, materials for contact lenses have optical properties,
In addition to having excellent chemical, physical, and mechanical properties, it is also required to have excellent oxygen permeability.
また、コンタクトレンズ用の素材には涙液成分であるタ
ンパク質、脂質、ムチン質などに対する耐汚染性および
細菌や真菌に対する耐汚染性に優れていることの他に、
装用感、生体適合性に優れていることが求められている
。In addition, materials for contact lenses have excellent stain resistance against proteins, lipids, mucin, etc. that are components of tear fluid, as well as stain resistance against bacteria and fungi.
It is required to have excellent wearing comfort and biocompatibility.
従来、コンタクトレンズ用の材料としてはポリメチルメ
タクリレート（ＰＭＭＡ ）および種々メタクリル酸エ
ステル系単量体の重合体が広く用いられているが、これ
らのほとんどは酸素透過性が劣り、長時間の装着に耐え
得るものではなかった。従来のメタクリル酸エステル系
重合体の酸素透過性を改善するためにメタクリル酸エス
テル分子内にシロキサン結合を導入したシリコーンメタ
クリレート系重合体（特公昭５２−３３５０２号公報）
、酢酸酪酸セルロースを主体とする酸素透過性重合体お
よびフッ素含有メタクリレート系重合体（特開昭５７−
５１７０５号公報および特開昭６１−１４１３０８号公
報）などを用いたコンタクトレンズが提案されている。Conventionally, polymethyl methacrylate (PMMA) and polymers of various methacrylic acid ester monomers have been widely used as materials for contact lenses, but most of these have poor oxygen permeability and are difficult to wear for long periods of time. It was unbearable. A silicone methacrylate polymer in which a siloxane bond is introduced into the methacrylate ester molecule in order to improve the oxygen permeability of conventional methacrylate ester polymers (Japanese Patent Publication No. 33502/1983)
, an oxygen-permeable polymer mainly composed of cellulose acetate butyrate, and a fluorine-containing methacrylate polymer (Japanese Patent Application Laid-Open No. 1987-
51705 and Japanese Unexamined Patent Publication No. 61-141308) and the like have been proposed.
しかしながら、これらの重合体は従来のＰＭＭＡなどの
メタクリル酸エステル系重合体に比べれば、酸素透過性
は改善されているが、まだ充分ではなく、さらに酸素透
過性の改善された重合体が求められている。また、これ
らの重合体は耐汚染性、装用性などの性能においても満
足できるものではない。However, although these polymers have improved oxygen permeability compared to conventional methacrylic acid ester polymers such as PMMA, it is still not sufficient, and there is a need for polymers with further improved oxygen permeability. ing. Furthermore, these polymers are not satisfactory in terms of stain resistance, wearability, and other properties.
本発明者らは、従来の酸素透過体、とくにコンタクトレ
ンズの先行技術が上記の状況にあることを認識し、酸素
透過性、装用感および耐汚染性に優れた酸素透過体につ
いて鋭意検討を行った結果、特定の弗素含有共重合体が
前述の目的を充足することを見出し、本発明に到達した
。The present inventors recognized that the prior art of conventional oxygen permeable materials, especially contact lenses, is in the above situation, and conducted intensive studies on oxygen permeable materials that have excellent oxygen permeability, wear comfort, and stain resistance. As a result, it was discovered that a specific fluorine-containing copolymer satisfies the above-mentioned object, and the present invention was achieved.
本発明によれば、一般式（１）
〔式中、Ａ、ＢおよびＣはそれぞれ水素原子または弗素
原子または炭化水素基を示し、Ｄは弗素原子または少な
くとも１個の弗素原子が結合した酸素原子を含有してい
てもよい炭素原子数１ないし３０の弗素置換炭化水素基
を示し、ｎは０ないし２の整数を示す〕で表わされる弗
素含有環状オレフィン成分単位１ａ）が２ないし５０重
量％および一般式％式％
〔式中、Ｒｆは少なくとも３個の弗素原子が結合した酸
素原子を含有していてもよい炭素原子数１ないし３０の
弗素置換炭化水素基を示し、Ｒ１は水素原子またはメチ
ル基を示し、１はＯないし４の整数を示す〕で表わされ
る弗素含有（メタ）アクリル酸エステル系単量体成分単
位（ｂ）が５０ないし９８％からなる弗素含有共重合体
から形成される酸素透過体が提供される。According to the present invention, general formula (1) [wherein A, B and C each represent a hydrogen atom, a fluorine atom or a hydrocarbon group, and D is a fluorine atom or an oxygen atom to which at least one fluorine atom is bonded] 2 to 50% by weight of fluorine-containing cyclic olefin component units 1a) represented by a fluorine-substituted hydrocarbon group having 1 to 30 carbon atoms which may contain General formula % Formula % [In the formula, Rf represents a fluorine-substituted hydrocarbon group having 1 to 30 carbon atoms which may contain an oxygen atom to which at least 3 fluorine atoms are bonded, and R1 is a hydrogen atom or a methyl is formed from a fluorine-containing copolymer consisting of 50 to 98% of the fluorine-containing (meth)acrylic acid ester monomer component unit (b) represented by An oxygen permeable body is provided.
本発明の酸素透過体の弗素含有共重合体を構成する弗素
含有環状オレフィン成分単位＋ａ）は一般式〔式中、Ａ
、ＢおよびＣはそれぞれ水素原子または弗素原子または
炭化水素基を示し、Ｄは弗素原子または少なくとも１個
の弗素原子が結合した酸素原子を含有していてもよい炭
素原子数１ないし３０の弗素置換炭化水素基を示し、ｎ
は口ないし２の整数を示す〕で表わされる弗素含有環状
オレフィン成分である。一般式（Ｉ）においてＤは少な
くとも３個の弗素原子が結合した酸素原子を含有してい
てもよい炭素原子数１ないし１５の弗素置換炭化水素基
であることが好ましい。一般式（１）においてＤで表わ
される弗素置換炭化水素基として具体的には、たとえば
−ＣＦ、、−ＣＦｘＣＦ＋ 、（ＣＦｚ）ｓＣＦ＋、（
ＣＦｚ）？ＣＦ３、−ＣＦｚＣＦＪ、 ＣＦ２ＣＦＨ
ＣＦ！、（ＣＦｚ）６Ｈ，−ＣＨｇＯＣＦｚＣＦ２Ｈ。The fluorine-containing cyclic olefin component unit +a) constituting the fluorine-containing copolymer of the oxygen permeable body of the present invention has the general formula [wherein A
, B and C each represent a hydrogen atom, a fluorine atom, or a hydrocarbon group, and D is a fluorine substituted group having 1 to 30 carbon atoms which may contain a fluorine atom or an oxygen atom to which at least one fluorine atom is bonded. Indicates a hydrocarbon group, n
represents a fluorine-containing cyclic olefin component. In general formula (I), D is preferably a fluorine-substituted hydrocarbon group having 1 to 15 carbon atoms which may contain an oxygen atom to which at least three fluorine atoms are bonded. Specifically, the fluorine-substituted hydrocarbon group represented by D in general formula (1) includes -CF, -CFxCF+, (CFz)sCF+, (
CFz)? CF3, -CFzCFJ, CF2CFH
CF! , (CFz)6H, -CHgOCFzCF2H.
−Ｃ）ｌｚＯｃＦｚｃＦｌ（ＣＦ３、−ＣＦ（ＣＦ＋）
ｚ 、−ＣＦ（ＣｚＦｓ）ｚなどを例示することができ
る。-C)lzOcFzcFl(CF3, -CF(CF+)
Examples include -CF(CzFs)z and the like.
該一般式（１）で表わされる弗素含有環状オレフィン成
分として具体的には、たとえばなどを例示することがで
きるが、これらの弗素含有環状オレフィン成分のうちで
は
などが好ましい。Specific examples of the fluorine-containing cyclic olefin component represented by the general formula (1) include the following, but among these fluorine-containing cyclic olefin components, the following are preferred.
また、本発明の酸素透過体の弗素含有共重合体を構成す
る弗素含有（メタ）アクリル酸エステル系単量体成分単
位（ｂ）は一般式（ＩＩ）■
ＣＨオ＝ ＣＣＯ！ （ＣＨｚ）−Ｒ’
（ＩＩ ）〔式中、Ｒｔは少なくとも３個の弗素原子が
結合した酸素原子を含有していてもよい炭素原子数１な
いし３０の弗素置換炭化水素基を示し、ＲＩは水素原子
またはメチル基を示し１．は０ないし４の整数を示す〕
で表わされる弗素含有（メタ）アクリル酸エステル系単
量体である。一般式（ＩＩ）においてＲｆは少なくとも
３個の弗素原子が結合した酸素原子を含有していてもよ
い炭素原子数１ないし１５の弗素置換炭化水素基である
ことが好ましい。Further, the fluorine-containing (meth)acrylic acid ester monomer component unit (b) constituting the fluorine-containing copolymer of the oxygen permeable material of the present invention has the general formula (II) ■CHO=CCO! (CHz)-R'
(II) [In the formula, Rt represents a fluorine-substituted hydrocarbon group having 1 to 30 carbon atoms which may contain an oxygen atom to which at least three fluorine atoms are bonded, and RI represents a hydrogen atom or a methyl group. Showing 1. indicates an integer from 0 to 4]
It is a fluorine-containing (meth)acrylic acid ester monomer represented by: In general formula (II), Rf is preferably a fluorine-substituted hydrocarbon group having 1 to 15 carbon atoms which may contain an oxygen atom to which at least three fluorine atoms are bonded.
一般式（ＩＩ）においてＲｔで表わされる弗素置換炭化
水素基として具体的には、たとえば−ＣＦ２、−ＣＦｚ
ＣＦｓ、−（Ｃｈ）ｓｃＦｓ、−（Ｃｈ）ｔｃＦｓ、−
（ｃｐｓ） ＊ＣＦｓ、−（ＣＦオ）＋＋ＣＦｓ 、−
ＣＦ（ＣＦｓ）ｇ 、−（ＣＦｘ）ｓＣ（ＣＦｓ）ｉ、
−（ＣＦｚ）ｓＣＨ（ＣｇＦｓ）ｘ、−ＣＦｔＣＦＨＣ
Ｆｓ、−（Ｃｈ）ｉＨｌ−（ＣＦｉ）＋。Ｈなどを例示
することができる。Specifically, the fluorine-substituted hydrocarbon group represented by Rt in general formula (II) includes, for example, -CF2, -CFz
CFs, -(Ch)scFs, -(Ch)tcFs, -
(cps) *CFs, - (CF o)++ CFs, -
CF(CFs)g, -(CFx)sC(CFs)i,
-(CFz)sCH(CgFs)x, -CFtCFHC
Fs, -(Ch)iHl-(CFi)+. Examples include H.
該一般式（Ｉｌ）で表わされる弗素含有（メタ）アクリ
ル酸エステル系単量体成分として具体的には、たとえば
ＣＨ３ＣＨ３
ＣＨ。Specifically, the fluorine-containing (meth)acrylic acid ester monomer component represented by the general formula (Il) is, for example, CH3CH3CH.
ＣＨｚ＝ＣＣＯＣＨｚＣＦｆＣＦｚＣＦＪ 。CHz=CCOCHzCFfCFzCFJ.
ＣＨ。CH.
■
Ｃ１ｈ＝ＣＣＯＣＨｚＣＨｚ （Ｃｈ）３ｃＨ（ＣｚＦ
ｓ） ２、などを例示することができるが、これらの弗
素含有（メタ）アクリル酸エステル系単量体成分のうち
では、
Ｃ１，ＣＨ３
ＣＩ。■ C1h=CCOCHzCHz (Ch)3cH(CzF
Among these fluorine-containing (meth)acrylic acid ester monomer components, C1, CH3 CI.
ＣＨ２＝ＣＣ０ＣＨＣＨ２Ｃ６ＦＩ ａ などが好ま
しい。CH2=CC0CHCH2C6FI a and the like are preferred.
＋１ １
０ ＣＨｚＯＣＣｓＦ＋ｔ
本発明の酸素透過体を形成する弗素含有共重合体は前記
一般式（１）で表わされる弗素含有環状オレフィン成分
単位（８１を２ないし５０重量％、好ましくは２ないし
４０重量％、とくに好ましくは５ないし３５重量％の範
囲および一般式（Ｉ［）で表わされる弗素含有（メタ）
アクリル酸エステル成分単位（ｂｌを５０ないし９８重
量％、好ましくは６０ないし９８重量％、とくに好まし
くは６５ないし９５重量％の範囲で含有していればよい
。該弗素含有共重合体は該弗素含有環状オレフィン成分
単位Ｔａ）および該弗素含有（メタ）アクリル酸エステ
ル成分単位（ｂ）の二成分のみから成っていてもよいし
、これらの必須の二成分に加えて酸素透過体の性能を損
ねない範囲で他の共重合成分が共重合されていてもよい
。+1 1 0 CHzOCCsF+t The fluorine-containing copolymer forming the oxygen permeable body of the present invention contains 2 to 50% by weight, preferably 2 to 40% by weight of the fluorine-containing cyclic olefin component unit (81) represented by the above general formula (1). , particularly preferably in the range of 5 to 35% by weight and fluorine-containing (meth) represented by the general formula (I[)
The fluorine-containing copolymer may contain the acrylic acid ester component unit (BL) in an amount of 50 to 98% by weight, preferably 60 to 98% by weight, particularly preferably 65 to 95% by weight. It may be composed of only two components, the cyclic olefin component unit Ta) and the fluorine-containing (meth)acrylic acid ester component unit (b), or in addition to these two essential components, it may not impair the performance of the oxygen permeable body. Other copolymerization components may be copolymerized within a certain range.
たとえば、エチレングリコールジメタクリレート、ノナ
エチレングリコールジメタクリレート、テトラデカエチ
レングリコールジメタクリレート、ノナプロピレングリ
コールジメタクリレート、アリルメタクリレート、トリ
メチロールプロパントリメタクリレートなどの多官能性
単量体を架橋剤として任意の割合で添加することもでき
る。For example, polyfunctional monomers such as ethylene glycol dimethacrylate, nonaethylene glycol dimethacrylate, tetradecaethylene glycol dimethacrylate, nonapropylene glycol dimethacrylate, allyl methacrylate, and trimethylolpropane trimethacrylate can be used as a crosslinking agent in any proportion. It can also be added.
また、本発明の酸素透過体を形成する重合体または、重
合前の段階に各種の安定剤、顔料、増粘剤などの添加物
も任意の割合で添加することもできる。Further, additives such as various stabilizers, pigments, thickeners, etc. can also be added in arbitrary proportions to the polymer forming the oxygen permeable body of the present invention or at a stage before polymerization.
本発明の酸素透過体を形成する弗素含有共重合体を製造
する方法としては、前記弗素含有環状オレフィン、前記
弗素含有（メタ）アクリル酸エステル系単量体および必
要に応じて加えられる他の共重合成分からなる単量体混
合物および重合開始剤からなる混合物を反応させる方法
を挙げることができる。重合開始剤のうちで、熱重合用
ラジカル開始剤は、アゾビスイソブチロニトリル、アゾ
ビスシクロヘキサンカルボニトリル、フェニルアゾビス
ブチロニトリル、アゾビスジメチルバレロニトリル、ベ
ンゾイルパーオキサイド、ジ−ｔ−ブチルパーオキサイ
ド、ｔ−ブチルハイドロパーオキサイドなどを例示する
ことができ、また重合開始剤のうちで光重合開始剤とし
て具体的には、イソブチルなどのベンゾインエーテル類
、ベンゾフェノンやベンゾエートなどのベンゾフェノン
類、キサントン、チオキサントンなどのキサントン類、
る。熱重合の際の温度は通常４０ないし２００℃、好ま
しくは４５ないし１２０℃の範囲であり、重合に要する
時間は通常０．５ないし５０００分、好ましくは３０な
いし２０００分である。The method for producing the fluorine-containing copolymer forming the oxygen permeable body of the present invention includes the above-mentioned fluorine-containing cyclic olefin, the above-mentioned fluorine-containing (meth)acrylate monomer, and other copolymers added as necessary. A method may be mentioned in which a monomer mixture consisting of a polymerization component and a mixture consisting of a polymerization initiator are reacted. Among polymerization initiators, radical initiators for thermal polymerization include azobisisobutyronitrile, azobiscyclohexanecarbonitrile, phenylazobisbutyronitrile, azobisdimethylvaleronitrile, benzoyl peroxide, di-t-butyl Examples of photopolymerization initiators include benzoin ethers such as isobutyl, benzophenones such as benzophenone and benzoate, and xanthone. , xanthones such as thioxanthone,
Ru. The temperature during thermal polymerization is usually in the range of 40 to 200°C, preferably 45 to 120°C, and the time required for polymerization is usually 0.5 to 5000 minutes, preferably 30 to 2000 minutes.
光重合による場合は、重合に必要な時間は使用するモノ
マーおよび光重合開始剤の種類や量によっても、また使
用する光源の種類によっても相違場合は、ＵＶ照射によ
り、数秒ないし数分間の範囲の時間で実用上充分な強度
の重合体が得られる。In the case of photopolymerization, the time required for polymerization varies depending on the type and amount of monomers and photopolymerization initiators used, as well as the type of light source used. A polymer with sufficient strength for practical use can be obtained in a short period of time.
本発明の酸素透過体を製造する方法としては、上記の方
法で得られた弗素含有共重合体を溶融条件下に所望の形
状に成形する方法を採用することもできるし、前記単量
体混合物および重合開始剤からなる混合物を重合型枠内
で重合させることにより所望の形状の弗素含有共重合体
を得る方法を採用することもできる。As a method for producing the oxygen permeable material of the present invention, a method may be adopted in which the fluorine-containing copolymer obtained by the above method is molded into a desired shape under melting conditions, or a method may be adopted in which the fluorine-containing copolymer obtained by the above method is molded into a desired shape. It is also possible to adopt a method of obtaining a fluorine-containing copolymer in a desired shape by polymerizing a mixture consisting of a polymerization initiator and a polymerization initiator in a polymerization mold.
該弗素含有共重合体の酢酸エチル中で３０°Ｃで測定し
た極限粘度〔η〕は通常０．１ないし３．０ｄｌ／ｇで
ある。該弗素含有共重合体中の弗素含有率が高い場合に
は溶媒不溶性となり極限粘度〔η〕が測定できないこと
もあるが、この場合にも本発明の酸素透過体に利用する
ことができる。The intrinsic viscosity [η] of the fluorine-containing copolymer measured in ethyl acetate at 30°C is usually 0.1 to 3.0 dl/g. If the fluorine content in the fluorine-containing copolymer is high, it may become insoluble in solvents and the intrinsic viscosity [η] may not be measurable, but even in this case it can be used in the oxygen permeable material of the present invention.
該弗素含有共重合体の示差走査熱量計（ＤＳＣ）で測定
したガラス転移温度（Ｔｇ）は通常−８０ないし２００
℃、好ましくは一５０℃ないし２００’ｃの範囲である
。The glass transition temperature (Tg) of the fluorine-containing copolymer measured with a differential scanning calorimeter (DSC) is usually -80 to 200.
°C, preferably in the range of -50 °C to 200 °C.
また、該弗素含有共重合体は酸素透過性に優れており、
その酸素透過係数は（ＤＫ値Ｘ １０− ” ｃｃ （
ＳＴＰ）ｃｍ ／ ａｆｔ−ｓｅｃ−ｍ＋ｓＨｇ）は通
常は１０以上で、好ましくは１５以上、とくに好ましく
は２０以上である。ここで、該弗素含有共重合体の酸素
透過係数は製科研式のフィルム酸素透過率計を用いて測
定した。In addition, the fluorine-containing copolymer has excellent oxygen permeability,
Its oxygen permeability coefficient is (DK value x 10-” cc (
STP)cm/aft-sec-m+sHg) is usually 10 or more, preferably 15 or more, and particularly preferably 20 or more. Here, the oxygen permeability coefficient of the fluorine-containing copolymer was measured using a film oxygen permeability meter manufactured by Seikan.
該弗素含有共重合体はたんばく質、脂質またはムチン質
などの涙液成分に対する耐汚染性に優れている。The fluorine-containing copolymer has excellent stain resistance against lachrymal fluid components such as proteins, lipids, and mucin.
本発明の弗素含有共重合体からなる酸素透過体は装用感
、耐汚染性に優れており、酸素透過性に著しく優れてお
りかつ生体適合性に優れているので、生体用酸素透過体
たとえばハードコンタクト Ｃ
レンズ、または、各種の分離膜などの用途に適している
。と（に、本発明の酸素透過体をハードコンタクトレン
ズとして用いると、従来のものにくらべて酸素透過性、
装用感、涙液成分に対する耐汚染性に優れ、生体適合性
に優れているので、長時間の装着が可能となるという利
点がある。The oxygen permeable body made of the fluorine-containing copolymer of the present invention has excellent wearing comfort and stain resistance, and has extremely high oxygen permeability and biocompatibility. Suitable for applications such as contact C lenses and various separation membranes. (In addition, when the oxygen permeable material of the present invention is used as a hard contact lens, the oxygen permeability is higher than that of conventional lenses.
It has the advantage of being comfortable to wear, excellent in stain resistance to tear fluid components, and excellent in biocompatibility, so it can be worn for a long time.
次に実施例によって本発明の酸素透過体を具体的に説明
する。Next, the oxygen permeable body of the present invention will be specifically explained with reference to Examples.
参考例１
内容積２００ｍｆｆ１のオートクレーブにジシクロペン
タジェン２０．２ｇ、ヘキサフルオロプロピレン５１．
０ ｇを仕込み密閉し、窒素２０ｋｇ／ｃｄｌを圧入し
た後、かくはんしながら、２００℃で３時間反応した。Reference Example 1 20.2 g of dicyclopentadiene and 51 g of hexafluoropropylene were placed in an autoclave with an internal volume of 200 mff1.
After charging 0 g of the reactor and sealing the reactor, 20 kg/cdl of nitrogen was introduced under pressure, and the reactor was reacted at 200° C. for 3 hours with stirring.
反応後、オートクレーブを室温まで冷却し、ガスをゆつ
（リパージした後オートクレーブを解放し、反応液６０
．５ｇを抜き出した。After the reaction, the autoclave was cooled to room temperature, the gas was removed (repurged), the autoclave was released, and the reaction solution was
．． 5g was taken out.
これを蒸留して沸点１４１”Ｃ、ガスクロマトグラフィ
ー分析純度９６％の２−トリフルオロメチル−２、３，
３，−トリフルオロビシクロ−（ Ｌ２，２ ）−ヘプ
テン３８．８ ｇを得た。This was distilled to give 2-trifluoromethyl-2,3, which had a boiling point of 141"C and a purity of 96% as analyzed by gas chromatography.
38.8 g of 3,-trifluorobicyclo-(L2,2)-heptene was obtained.
引き続き、減圧蒸留して、沸点１１３〜ｂ／１６龍Ｈｇ
の留分、ガスクロマトグラフィー分析純実施例１
３０部と１．１，２．２−テトラヒドロパーフルオロデ
シルＣＨ’ｓ
■
メククリレート ＣＨ２＝ＣＣＯＯＣ）ＩＺＣ）Ｉ２Ｃ
，Ｆｌ？ ７０部にアゾビスイソブチロニトリル０．５
部を加え、十分に攪拌混合して、１０分間真空脱気した
。この溶液を窒素雰囲気下で、２００μのテフロンバッ
キングをスペーサーとした２枚のガラス板間中に流し込
み、締具で固定した後、恒温槽に入れ、６０”Ｃ２４時
間、７０℃、８０℃、９０℃で各２時間ずつ加熱し重合
を行った。Subsequently, distilled under reduced pressure to obtain a boiling point of 113-b/16 Dragon Hg.
fraction, gas chromatography analysis Pure Example 1 30 parts and 1.1,2.2-tetrahydroperfluorodecyl CH's ■ Meccrylate CH2=CCOOC)IZC)I2C
, Fl? 0.5 parts of azobisisobutyronitrile to 70 parts
of the mixture was added, thoroughly stirred and mixed, and degassed under vacuum for 10 minutes. This solution was poured in a nitrogen atmosphere between two glass plates with a 200μ Teflon backing as a spacer, fixed with fasteners, and placed in a constant temperature bath at 60"C for 24 hours at 70℃, 80℃, and 90℃. Polymerization was carried out by heating at ℃ for 2 hours each.
重合終了後、生成した透明なフィルムをガラス板よりは
がし、酸素透過係数を測定した。結果を表１に示す。After the polymerization was completed, the produced transparent film was peeled off from the glass plate and the oxygen permeability coefficient was measured. The results are shown in Table 1.
実施例２〜３
と１．１，２．２−テトラヒドロパーフルオロデシルメ
タＣ８゜
クリレート ＣＨ２”ＣＣ００Ｃ）ＩＺＣＨ２Ｃ８Ｆ＋
７ ノ混合割合を変えて実施例１と同様な操作で重合し
、酸素透過係数を測定した。結果を表１に示す。Examples 2-3 and 1.1,2.2-tetrahydroperfluorodecyl methacrylate CH2”CC00C)IZCH2C8F+
Polymerization was carried out in the same manner as in Example 1 by changing the mixing ratio of 7 and the oxygen permeability coefficient was measured. The results are shown in Table 1.
実施例４〜６
参考例１で得た２−トリフルオロメチル−２，３，３−
トリフルオロビシクロ（１，２，２）−へブテン ｑ
ＣＨ３
オロデシルメタクリレート ＣＪ＝ＣＣＯＯＣＨｚＣ）
ＩｚＣｓＦ＋ ’１の混合割合を変えて、実施例１と同
様な操作で重合を行い、酸素透過係数を測定した。結果
を表１に示す。Examples 4 to 6 2-trifluoromethyl-2,3,3- obtained in Reference Example 1
Trifluorobicyclo(1,2,2)-hebutene q CH3 orodecyl methacrylate CJ=CCOOCHzC)
Polymerization was carried out in the same manner as in Example 1 by changing the mixing ratio of IzCsF+ '1, and the oxygen permeability coefficient was measured. The results are shown in Table 1.
参考例２
ヘキサフルオロプロピレンの代わりに８Ｈ−パーフルオ
ロオクテンを用いた以外は参考例１と同様な方法で２−
６Ｈ−パーフルオロヘキシル−２，３，３−トリフルオ
ロビシクロ−（１，２，２）−ヘフテンを合成した。Reference Example 2 2-
6H-perfluorohexyl-2,3,3-trifluorobicyclo-(1,2,2)-heftene was synthesized.
実施例７〜８
参考例２で得た２−６Ｈ−パーフルオロヘキシル−２，
３，３−）リフルオロビシクロ−（１，２，２）−ヘプ
用いて、それぞれを１．１，２．２−テトラヒドロパー
ツＨ３
ルオロデシルメタクリレートＣＨｚ＝ＣＣＯＯＣＨｚＣ
）ＩｚＣｓＦ＋ ７と３０部／７０部の割合で混合し、
実施例１と同様な操作で重合し、それぞれの酸素透過係
数を測定した。結果を表１に示す。Examples 7-8 2-6H-perfluorohexyl-2 obtained in Reference Example 2,
Using 3,3-)lifluorobicyclo-(1,2,2)-hep, each of
) mixed with IzCsF+ 7 at a ratio of 30 parts/70 parts,
Polymerization was performed in the same manner as in Example 1, and the oxygen permeability coefficient of each was measured. The results are shown in Table 1.
比較例Ｉ
ＣＨ２
メチルメタクリレートＣＨｚ＝ＣＣＯＯＣＨ＋のみを用
いて実施例１と同様な操作で重合を行い、酸素透過係数
を測定した。結果を表１に示す。Comparative Example I Polymerization was carried out in the same manner as in Example 1 using only CH2 methyl methacrylate CHz=CCOOCH+, and the oxygen permeability coefficient was measured. The results are shown in Table 1.
比較例２
１．１，２．２−テトラヒドロバーフルオロデシルメＣ
Ｉ。Comparative Example 2 1.1,2.2-tetrahydroverfluorodecylme C
I.
■
タフリレートＣＨｔ＝ＣＣＯＯＣＨｔＣＨｚＣＪｒｑの
みを用いて実施例１と同様な操作で重合し、酸素透過係
数を測定した。結果を表１に示す。(2) Polymerization was carried out in the same manner as in Example 1 using only tafrylate CHt=CCOOCHtCHzCJrq, and the oxygen permeability coefficient was measured. The results are shown in Table 1.
Claims (1)
原子または炭化水素基を示し、Ｄは弗素原子または少な
くとも１個の弗素原子が結合した酸素原子を含有してい
てもよい炭素原子数１ないし３０の弗素置換炭化水素基
を示し、ｎは０ないし２の整数を示す〕で表わされる弗
素含有環状オレフィン成分単位（ａ）が２ないし５０重
量％および一般式〔II〕 ▲数式、化学式、表等があります▼〔II〕 〔式中、Ｒ＾ｆは少なくとも３個の弗素原子が結合した
酸素原子を含有していてもよい炭素原子数１ないし３０
の弗素置換炭化水素基を示し、Ｒ＾１は水素原子または
メチル基を示し、ｍは０ないし４の整数を示す〕で表わ
される弗素含有（メタ）アクリル酸エステル系単量体成
分単位（ｂ）が５０ないし９８重量％からなる弗素含有
共重合体から形成される酸素透過体。(1) General formula [I] ▲Mathematical formulas, chemical formulas, tables, etc.▼[I] [In the formula, A, B, and C each represent a hydrogen atom, a fluorine atom, or a hydrocarbon group, and D represents a fluorine atom or at least A fluorine-containing cyclic olefin component represented by a fluorine-substituted hydrocarbon group having 1 to 30 carbon atoms which may contain an oxygen atom to which one fluorine atom is bonded, where n is an integer of 0 to 2. 2 to 50% by weight of unit (a) and general formula [II] ▲Mathematical formulas, chemical formulas, tables, etc.▼[II] [In the formula, R^f contains an oxygen atom to which at least three fluorine atoms are bonded 1 to 30 carbon atoms, which may be
a fluorine-substituted hydrocarbon group, R^1 represents a hydrogen atom or a methyl group, and m represents an integer of 0 to 4]. ) is formed from a fluorine-containing copolymer comprising 50 to 98% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4127587A JPS63210114A (en) | 1987-02-26 | 1987-02-26 | Oxygen-permeable material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4127587A JPS63210114A (en) | 1987-02-26 | 1987-02-26 | Oxygen-permeable material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63210114A true JPS63210114A (en) | 1988-08-31 |
Family
ID=12603893
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4127587A Pending JPS63210114A (en) | 1987-02-26 | 1987-02-26 | Oxygen-permeable material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63210114A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991000880A1 (en) * | 1989-07-07 | 1991-01-24 | Daikin Industries, Ltd. | Fluorinated copolymer and method of producing the same |
| US5229473A (en) * | 1989-07-07 | 1993-07-20 | Daikin Industries Ltd. | Fluorine-containing copolymer and method of preparing the same |
| JP2002012623A (en) * | 2000-04-27 | 2002-01-15 | Shin Etsu Chem Co Ltd | High-molecular compound, chemical amplification resist material, and method for forming pattern |
| US20100160600A1 (en) * | 2008-12-22 | 2010-06-24 | Fujifilm Corporation | Resin composition for optical material and its shaped article, optical component and lens |
| WO2011024421A1 (en) * | 2009-08-26 | 2011-03-03 | 三井化学株式会社 | Fluorine-containing cyclic olefin polymer composition, transcript obtained from said composition, and manufacturing method therefor |
| JP2019089714A (en) * | 2017-11-10 | 2019-06-13 | 三井化学株式会社 | Manufacturing method of fluorine-containing cyclic olefin monomer |
| JP2019131658A (en) * | 2018-01-30 | 2019-08-08 | 三井化学株式会社 | Fluorine-containing cyclic olefin copolymer and molded body |
-
1987
- 1987-02-26 JP JP4127587A patent/JPS63210114A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991000880A1 (en) * | 1989-07-07 | 1991-01-24 | Daikin Industries, Ltd. | Fluorinated copolymer and method of producing the same |
| US5177166A (en) * | 1989-07-07 | 1993-01-05 | Daikin Industries Ltd. | Fluorine-containing copolymer and method of preparing the same |
| US5229473A (en) * | 1989-07-07 | 1993-07-20 | Daikin Industries Ltd. | Fluorine-containing copolymer and method of preparing the same |
| JP2002012623A (en) * | 2000-04-27 | 2002-01-15 | Shin Etsu Chem Co Ltd | High-molecular compound, chemical amplification resist material, and method for forming pattern |
| US20100160600A1 (en) * | 2008-12-22 | 2010-06-24 | Fujifilm Corporation | Resin composition for optical material and its shaped article, optical component and lens |
| WO2011024421A1 (en) * | 2009-08-26 | 2011-03-03 | 三井化学株式会社 | Fluorine-containing cyclic olefin polymer composition, transcript obtained from said composition, and manufacturing method therefor |
| US9056938B2 (en) | 2009-08-26 | 2015-06-16 | Mitsui Chemicals, Inc. | Fluorine-containing cyclic olefin polymer composition, imprint product obtained using the composition, and method for producing the same |
| US10000633B2 (en) | 2009-08-26 | 2018-06-19 | Mitsui Chemicals, Inc. | Fluorine-containing cyclic olefin polymer composition, imprint product obtained using the composition, and method for producing the same |
| JP2019089714A (en) * | 2017-11-10 | 2019-06-13 | 三井化学株式会社 | Manufacturing method of fluorine-containing cyclic olefin monomer |
| JP2019131658A (en) * | 2018-01-30 | 2019-08-08 | 三井化学株式会社 | Fluorine-containing cyclic olefin copolymer and molded body |
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