JP2007160706A - Resin mold for polymerization - Google Patents
Resin mold for polymerization Download PDFInfo
- Publication number
- JP2007160706A JP2007160706A JP2005359893A JP2005359893A JP2007160706A JP 2007160706 A JP2007160706 A JP 2007160706A JP 2005359893 A JP2005359893 A JP 2005359893A JP 2005359893 A JP2005359893 A JP 2005359893A JP 2007160706 A JP2007160706 A JP 2007160706A
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- JP
- Japan
- Prior art keywords
- mold
- water
- weight
- resin
- 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.)
- Granted
Links
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 64
- 239000011347 resin Substances 0.000 title claims abstract description 58
- 229920005989 resin Polymers 0.000 title claims abstract description 58
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- 238000004519 manufacturing process Methods 0.000 claims abstract description 19
- -1 polytrimethylene terephthalate Polymers 0.000 claims description 92
- 238000010521 absorption reaction Methods 0.000 claims description 31
- 229920002215 polytrimethylene terephthalate Polymers 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 229920001225 polyester resin Polymers 0.000 claims description 2
- 239000004645 polyester resin Substances 0.000 claims description 2
- 229920002959 polymer blend Polymers 0.000 claims description 2
- 229920006026 co-polymeric resin Polymers 0.000 claims 1
- 239000002352 surface water Substances 0.000 abstract description 9
- 238000009736 wetting Methods 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 description 41
- 229920000642 polymer Polymers 0.000 description 39
- 239000000203 mixture Substances 0.000 description 30
- 150000002430 hydrocarbons Chemical group 0.000 description 25
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 24
- 125000004432 carbon atom Chemical group C* 0.000 description 19
- 125000005401 siloxanyl group Chemical group 0.000 description 19
- 230000000704 physical effect Effects 0.000 description 17
- 229920001296 polysiloxane Polymers 0.000 description 17
- 239000003505 polymerization initiator Substances 0.000 description 15
- 125000001424 substituent group Chemical group 0.000 description 15
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 14
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- 229910052710 silicon Inorganic materials 0.000 description 14
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- 108090000623 proteins and genes Proteins 0.000 description 13
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 229920000139 polyethylene terephthalate Polymers 0.000 description 11
- 239000005020 polyethylene terephthalate Substances 0.000 description 11
- 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 10
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 10
- 238000007626 photothermal therapy Methods 0.000 description 10
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 238000002347 injection Methods 0.000 description 9
- 239000007924 injection Substances 0.000 description 9
- 238000000465 moulding Methods 0.000 description 9
- 230000035699 permeability Effects 0.000 description 9
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 9
- 239000002202 Polyethylene glycol Substances 0.000 description 8
- 239000004743 Polypropylene Substances 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- PNLUGRYDUHRLOF-UHFFFAOYSA-N n-ethenyl-n-methylacetamide Chemical group C=CN(C)C(C)=O PNLUGRYDUHRLOF-UHFFFAOYSA-N 0.000 description 8
- 229920001223 polyethylene glycol Polymers 0.000 description 8
- 229920001155 polypropylene Polymers 0.000 description 8
- 239000003761 preservation solution Substances 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
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- 230000008859 change Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
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- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 6
- 125000003827 glycol group Chemical group 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 6
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 description 6
- 239000008363 phosphate buffer Substances 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- IEVADDDOVGMCSI-UHFFFAOYSA-N 2-hydroxybutyl 2-methylprop-2-enoate Chemical group CCC(O)COC(=O)C(C)=C IEVADDDOVGMCSI-UHFFFAOYSA-N 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- 239000004205 dimethyl polysiloxane Substances 0.000 description 5
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical group C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 5
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- 238000011282 treatment Methods 0.000 description 5
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- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 4
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical group CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229920000297 Rayon Polymers 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000002216 antistatic agent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 150000002433 hydrophilic molecules Chemical class 0.000 description 3
- 238000006459 hydrosilylation reaction Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 229940119545 isobornyl methacrylate Drugs 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 3
- 125000005647 linker group Chemical group 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 3
- 229920001230 polyarylate Polymers 0.000 description 3
- 239000008213 purified water Substances 0.000 description 3
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- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
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- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical group CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 2
- IMDPTYFNMLYSLH-UHFFFAOYSA-N 3-silylpropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC[SiH3] IMDPTYFNMLYSLH-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
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- 125000003158 alcohol group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
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- DFFZOPXDTCDZDP-UHFFFAOYSA-N naphthalene-1,5-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1C(O)=O DFFZOPXDTCDZDP-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Eyeglasses (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
Abstract
Description
本発明は、製品の表面水濡れ性が優れ、型剥離性に優れたキャスト重合製品を製造するのに適した樹脂鋳型に関するものである。 The present invention relates to a resin mold suitable for producing a cast polymerization product having excellent surface water wettability of a product and excellent mold releasability.
医療機器、例えば眼内レンズ、コンタクトレンズは表面の親水性、特に水濡れ性が要求されるためポリプロピレン樹脂鋳型内で成型して製造した後に製品の表面を親水化処理して製造されている。例えば、特表平１１−５０２９４９号公報にはポリプロピレン樹脂鋳型内でキャスト重合した後、表面をプラズマ重合処理して表面特性を改良した眼のレンズに関する記載がある。これら表面処理をしないで表面の水濡れ性に優れたコンタクトレンズを製造する方法として、ＷＯ出願 ＪＰ００／０８９１２号にはモノマーに不溶で、少なくとも１つの面が接触角６５〜８０度である樹脂、例えばポリアミド、ポリエチレンテレフタレート、エチレンビニルアルコール共重合体から選ばれた樹脂鋳型で製造する記載がある。また、特開平９−１８３１３２号公報にはポリオレフィン樹脂にワックス状添加剤、帯電防止剤等の付着力低減剤、濡れ改良剤を添加した鋳型が記載されている。 Since medical devices such as intraocular lenses and contact lenses are required to have surface hydrophilicity, particularly water wettability, they are manufactured by molding in a polypropylene resin mold and then manufacturing the surface of the product to make it hydrophilic. For example, Japanese Patent Application Laid-Open No. 11-502949 discloses an ophthalmic lens in which the surface characteristics are improved by performing cast polymerization in a polypropylene resin mold and then subjecting the surface to plasma polymerization. As a method for producing a contact lens having excellent surface water wettability without performing these surface treatments, a resin having a contact angle of 65 to 80 degrees in WO application JP00 / 08912, which is insoluble in a monomer, For example, there is a description of manufacturing with a resin mold selected from polyamide, polyethylene terephthalate, and ethylene vinyl alcohol copolymer. Japanese Patent Application Laid-Open No. 9-183132 describes a mold obtained by adding a wax-like additive, an adhesion reducing agent such as an antistatic agent, and a wetting improver to a polyolefin resin.
しかしながら、レンズを鋳型成型した後に表面処理する方法は、レンズの表裏を均一に処理する必要があり、大掛りな設備と厳密な生産工程管理を行う必要があり、製造コストが高くなるという問題点があり、さらに、これら表面処理したレンズは表面の水濡れ性が経時変化しやすいという問題がある。一方ポリアミド、ポリエチレンテレフタレート、エチレンビニルアルコール共重合体から選ばれた樹脂鋳型で製造する場合には、鋳型と製品の密着性が高いため型剥離に特別な方法が必要であったり、製品の樹脂組成によっては表面の水濡れ性が不十分となる問題があった。また、鋳型への付着を防止し、レンズの濡れ性を改良するためにポリオレフィン樹脂にワックス状添加剤、低分子量の帯電防止剤等の添加剤を添加する方法では、これら添加剤がレンズに残留する可能性があり、一方、これらの添加剤がレンズから溶出するとその性能が低下する問題があった。 However, the method of surface treatment after molding a lens requires that the front and back of the lens be uniformly treated, requiring large equipment and strict production process management, resulting in high manufacturing costs. Furthermore, these surface-treated lenses have a problem that the water wettability of the surface easily changes with time. On the other hand, when manufacturing with a resin mold selected from polyamide, polyethylene terephthalate, and ethylene vinyl alcohol copolymer, a special method is required for mold release due to high adhesion between the mold and the product. In some cases, the water wettability of the surface is insufficient. In addition, in the method of adding an additive such as a waxy additive or a low molecular weight antistatic agent to the polyolefin resin in order to prevent adhesion to the mold and improve the wettability of the lens, these additives remain in the lens. On the other hand, when these additives are eluted from the lens, there is a problem that the performance is lowered.
前記課題を解決するため、本発明者らは表面の水濡れ性が要求される医療機器、特に眼内レンズ、コンタクトレンズのキャスト重合用の鋳型の材料特性を検討し鋭意研究を重ねた結果、特定の材料特性を有する鋳型材料を使用することで、その目的を達成できることを見いだし、本発明を完成する事ができた。すなわち、本発明は吸水率が０．０１〜０．１５％の範囲内の樹脂を用いて成型した鋳型であって、その表面の水接触角が６５〜８０度の範囲内である樹脂鋳型及び当該鋳型を用いる医療機器の製造方法に関するものである。以下、本発明を詳細に説明する。 In order to solve the above-mentioned problems, the present inventors examined the material properties of a cast device for cast polymerization of medical devices, particularly intraocular lenses and contact lenses that require surface wettability, and as a result of earnest research, It has been found that the object can be achieved by using a mold material having specific material characteristics, and the present invention has been completed. That is, the present invention is a mold molded using a resin having a water absorption of 0.01 to 0.15%, and a resin mold having a water contact angle of 65 to 80 degrees on the surface thereof. The present invention relates to a method for manufacturing a medical device using the mold. Hereinafter, the present invention will be described in detail.
本発明の鋳型は、吸水率が０．０１〜０．１５％の範囲内の樹脂を用いて成型され、且つその表面、すなわちキャスト重合のための表面の水接触角が６５〜８０度の範囲内にあるものである。 The mold of the present invention is molded using a resin having a water absorption of 0.01 to 0.15%, and the water contact angle of the surface thereof, that is, the surface for cast polymerization is in the range of 65 to 80 degrees. It is what is inside.
本発明において、上記、鋳型の製造に用いられる樹脂の吸水率及び鋳型表面の水接触角は、以下の方法により測定された値として与えられる。なお、特に断りのない限り、本明細書において、数値は、全て有効数字として表される。 In the present invention, the water absorption rate of the resin used in the production of the mold and the water contact angle on the mold surface are given as values measured by the following method. In the present specification, all numerical values are expressed as significant figures unless otherwise specified.
１．吸水率
ＪＩＳ Ｋ７２０９に記載の方法、すなわち、６０Ｘ６０ｍｍ角、１ｍｍ厚みのキャビティを有する金型（ＩＳＯ ２９４−３ Ｄ１形モールド）を使用して、樹脂の適正射出条件にて射出成型した試料片について、２３℃で蒸留水に２４時間試料片を浸漬した後、その重量変化を測定して計算する。なお、適正射出条件とは、各樹脂の技術資料に記載されている推奨条件に準ずるものである。
1. Water absorption rate Using the method described in JIS K7209, that is, using a mold having a cavity of 60 × 60 mm square and 1 mm thickness (ISO 294-3 D1 mold), a sample piece injection-molded under proper injection conditions of resin, After immersing the sample piece in distilled water for 24 hours at 23 ° C., the weight change is measured and calculated. The proper injection conditions are in accordance with the recommended conditions described in the technical data for each resin.
２．水接触角
厚み１ｍｍ、８０Ｘ８０ｍｍ角の板状のキャスト重合用鋳型を成型する金型を使用して、樹脂の適正射出条件にて射出成型した鋳型試料片について、空気中の湿気の影響を防止するために、前記試料片を直ちに防湿性包装材料にて密閉包装し、当該包装形態のままで前記試料片を２３℃の恒温室内に２４時間静置して温度を平衡化させた後、試料片を取り出し、シリンジにて直径約１．８ｍｍの純水を試料片上に接触させ、その液滴と試料片が形成する角度を読み取り、計算により水接触角を求める。吸水率と同様、適正射出条件とは、各樹脂の技術資料に記載されている推奨条件に準ずるものである。
2. Using a mold for molding a plate-shaped cast polymerization mold with a water contact angle thickness of 1 mm and 80 x 80 mm square, the mold sample piece injection-molded under the appropriate resin injection conditions prevents the effects of moisture in the air. For this purpose, the sample piece is immediately sealed and packaged in a moisture-proof packaging material, and the sample piece is left in a constant temperature room at 23 ° C. for 24 hours in the packaging form to equilibrate the temperature. The pure water having a diameter of about 1.8 mm is brought into contact with the sample piece with a syringe, the angle formed by the droplet and the sample piece is read, and the water contact angle is obtained by calculation. As with the water absorption rate, the proper injection conditions are based on the recommended conditions described in the technical data for each resin.
上記の各特性において、鋳型の成型に使用する樹脂の吸水率が０．０１％未満のものは、製造される医療機器の表面水濡れ性が不十分となり好ましくないことが見出された。また、０．１５％を超える樹脂を使用して成型した鋳型を使用した場合は、該鋳型内でキャスト重合される医療機器のポリマー組成によっては表面の水濡れ性が不十分となったり、鋳型と成型品の剥離性が困難になり好ましくないことが明らかとなった。 In each of the above characteristics, it has been found that a resin having a water absorption rate of less than 0.01% used for molding a mold is not preferable because the surface water wettability of a manufactured medical device is insufficient. In addition, when a mold molded using a resin exceeding 0.15% is used, depending on the polymer composition of the medical device cast polymerized in the mold, the surface wettability may be insufficient, It became clear that the peelability of the molded product became difficult.
更に、当該吸水率を有する樹脂から成型した鋳型においてさえも、表面の水接触角が６５度未満のものは、鋳型と成型品の剥離性が低下し、甚だしくは成型品の鋳型からの剥離が著しく困難になって、とりわけコンタクトレンズ等の薄い製品では、鋳型からの剥離時に成型品に欠け、破損等が起きやすくなり好ましくない。また、８０度を超える鋳型では、それにより成型される医療機器の表面水濡れ性が不十分となり好ましくない。 Furthermore, even in a mold molded from a resin having the water absorption rate, when the water contact angle on the surface is less than 65 degrees, the peelability between the mold and the molded product is lowered, and the molded product is not peeled off from the mold. In particular, a thin product such as a contact lens becomes extremely difficult, and the molded product is likely to be chipped and damaged when peeled from the mold. In addition, a mold exceeding 80 degrees is not preferable because the surface water wettability of the medical device molded thereby becomes insufficient.
本発明の樹脂鋳型を用いて製造した医療機器、例えばコンタクトレンズの表面の水濡れ性及び鋳型からの剥離性に優れる理由は、明確には判明していないが、鋳型表面の化学組成、分子構造、表面の吸着水の構造、分布などが影響して鋳型表面への医療機器用のモノマーの相互作用が異なり、それにより得られる医療機器の表面の化学構造が水濡れ性、型剥離性に良い構造になっているのかもしれない。 The reason why the medical device manufactured using the resin mold of the present invention, for example, the contact lens surface is excellent in water wettability and peelability from the mold is not clearly understood, but the chemical composition of the mold surface, molecular structure The structure and distribution of adsorbed water on the surface affects the interaction of the monomer for medical devices on the mold surface, and the resulting chemical structure on the surface of the medical device has good wettability and mold release properties. It may be a structure.
本発明の鋳型に使用される樹脂としては、例えば、ポリトリメチレンテレフタレート（吸水率０．０４％）、液晶ＰＥＴ（吸水率０．０１％）、ポリアリレート（吸水率０．１５％）などのポリエステル樹脂があり、これらの樹脂から成型された鋳型の成型後直ちに測定した水接触角は、ポリトリメチレンテレフタレートで７３度、液晶ＰＥＴで７４度、ポリアリレートで８０度である。ここで、それらの鋳型は、空気中の湿気をその表面に吸着し、次第にその水接触角が変化する場合もあるが、いずれにせよ、上記特性が本発明に規定する範囲であれば使用可能である。好ましくは、本発明の特性を有する樹脂により鋳型を成型後、直ちに当該鋳型を使用するか、少なくともＲＨ６０％以下、好ましくはＲＨ３５％前後の乾燥雰囲気下で鋳型を取り扱い、操作し、若しくは保存するか、或いは、成型した鋳型が空気中の湿気を表面に吸着しないような環境下で保管して使用する。鋳型が空気中の湿気を表面に吸着しないような環境下での具体的な保管方法の非限定的な例示としては、成型した鋳型を、実質的に水分を透過しないようなフィルム材料、例えば、ポリエチレンにより作製したフィルム製の袋、バッグ等、或いはその他の密閉可能な容器等に収容して保管することが挙げられる。 Examples of the resin used in the mold of the present invention include polytrimethylene terephthalate (water absorption 0.04%), liquid crystal PET (water absorption 0.01%), polyarylate (water absorption 0.15%), and the like. There are polyester resins, and the water contact angles measured immediately after molding of molds molded from these resins are 73 degrees for polytrimethylene terephthalate, 74 degrees for liquid crystal PET, and 80 degrees for polyarylate. Here, these molds adsorb moisture in the air to the surface, and the water contact angle may gradually change, but in any case, it can be used as long as the above characteristics are within the range specified in the present invention. It is. Preferably, the mold should be used immediately after molding with the resin having the characteristics of the present invention, or the mold should be handled, operated or stored in a dry atmosphere of at least RH 60% or less, preferably around RH 35%. Alternatively, the molded mold is stored and used in an environment where moisture in the air is not adsorbed on the surface. Non-limiting examples of specific storage methods in an environment where the mold does not adsorb moisture in the air to the surface include a film material that does not substantially permeate the molded mold, for example, For example, it may be stored in a bag made of polyethylene, a bag made of polyethylene, or the like, or stored in another sealable container.
吸水率が０．０１〜０．１５％の範囲内の樹脂であって、表面の水接触角が６５〜７５度の範囲内の鋳型を提供する樹脂としては、例えばポリトリメチレンテレフタレート、ポリトリメチレンテレフタレート共重合体などが挙げられ、これらは、それ自体の射出成型性にも優れ、また、当該鋳型から製造される製品の表面水濡れ性、その維持安定性、鋳型剥離性、レンズ剥離性等のバランスがとれていてより好ましい。 Examples of resins that provide a mold having a water absorption of 0.01 to 0.15% and a surface water contact angle of 65 to 75 degrees include polytrimethylene terephthalate and polytrimethylene. Examples include methylene terephthalate copolymers, which are excellent in their own injection moldability. Also, surface water wettability of products manufactured from the mold, its maintenance stability, mold peelability, and lens peelability. Etc. are more preferable.
ポリトリメチレンテレフタレート及びその共重合体（以下ＰＴＴと略す）はトリメチレングリコールとテレフタル酸を主成分とするポリエステルであり、例えば特開平５−２６２８６２号公報、特開平８−３１１１７７号公報、特開２０００−１５９８７５号公報などに記載されている。また、ＰＴＴの重合度を高め、成形性を改良したり、熱安定性を高める方法、低分子量の副生物の生成を抑制する方法などが開発され、高重合度で良好な熱安定性を有するＰＴＴの製造方法が特表２００２−５４３２２７号公報に記載され、再溶融しても低分子量副生物が少ない組成物とその製造方法が特開２００３−１１９２６６号公報、および特開２００３−１５５３３５号公報に記載され、安定した溶融成型が出来るポリマーチップが特開２００３−７３４６２号公報に記載され、熱安定性が高く、低分子量の副生物の生成が少ない組成物が特開２００３−１６０６４８号公報、および特開２００３−３４２３５６号公報に記載され、重合度が高く、色調に優れ溶融成型性に優れた製造方法が特開２００４−２６９５７１号公報および特開２００５−６０５２８号公報に記載され、低分子量の副生物の生成を抑制する方法が特表２００５−５２０８９６号公報および特表２００５−５２０８９７号公報に記載されている。また、ポリトリメチレンテレフタレートの共重合体は特表２００２−５４３２２７号公報カラム００３６及び００３９、特開２００３−７３４６２号公報カラム００１４、特開２００３−１１９２６６号公報カラム００１２、特開２００３−１５５３３５号公報カラム００１０から００１１、特開２００３−１６０６４８号公報カラム００１２から００１３、特開２００３−３４２３５６号公報カラム００１７、特開２００４−１８９９７７号公報カラム０００９から００１１、特開２００５−６０５２８号公報カラム００１３等に記載されている。 Polytrimethylene terephthalate and its copolymer (hereinafter abbreviated as PTT) are polyesters mainly composed of trimethylene glycol and terephthalic acid. For example, JP-A-5-262862, JP-A-8-3111177, 2000-159875 and the like. In addition, methods have been developed to increase the degree of polymerization of PTT, improve moldability, increase thermal stability, and suppress the formation of low molecular weight by-products, and have good thermal stability at a high degree of polymerization. A method for producing PTT is described in JP-T-2002-543227, and a composition having a low molecular weight by-product even when remelted and a method for producing the same are disclosed in JP-A No. 2003-119266 and JP-A No. 2003-155335. Described in JP-A-2003-73462, and a composition having high thermal stability and low generation of low-molecular-weight by-products is disclosed in JP-A-2003-160648. JP-A-2004-269571 and JP-A-2003-342356 have disclosed a production method having a high degree of polymerization, excellent color tone and excellent melt moldability. Open 2005-60528 Patent described in Japanese, a method of suppressing the formation of by-products of low molecular weight have been described in publications and Kohyo 2005-520897 Patent JP-T-2005-520896. Further, copolymers of polytrimethylene terephthalate are disclosed in JP 2002-543227 A column 0036 and 0039, JP 2003-73462 A column 0014, JP 2003-119266 A column 0012, and JP 2003-155335 A. Columns 0010 to 0011, JP 2003-160648 A column 0012 to 0013, JP 2003-342356 A column 0017, JP 2004-189977 A column 0009 to 0011, JP 2005-60528 A column 0013, etc. Are listed.
例えば、ポリトリメチレンテレフタレートの共重合モノマーとしては、イソフタル酸、オルトフタル酸、１，５−ナフタレンジカルボン酸、２，５−ナフタレンジカルボン酸、２，６−ナフタレンジカルボン酸、ビフェニル−２，２’−ジカルボン酸、ビフェニル−３，３’−ジカルボン酸、ビフェニル−４，４’−ジカルボン酸、ビス（４，４’−カルボキシフェニル）メタン、アントラセンジカルボン酸、４，４’−ジフェニルエーテルジカルボン酸などの芳香族ジカルボン酸、５−ナトリウムスルホイソフタル酸、５−カリウムスルホイソフタル酸、３，５−ジカルボン酸ベンゼンスルホン酸テトラブチルホスホニウム塩、３，５−ジカルボン酸ベンゼンスルホン酸トリブチルメチルホスホニウム塩などの塩、１，４−シクロヘキサンジカルボン酸、４，４’−ジシクロヘキシルジカルボン酸などの脂環族ジカルボン酸、アジピン酸、セバシン酸、アゼライン酸、ダイマー酸などの脂肪族ジカルボン酸類およびそれらのエステル誘導体類、並びにエチレングリコール、テトラメチレングリコール、１，５−ペンタンジオール、１，６−ヘキサンジオール、ネオペンチルグリコール、デカメチレングリコール、１、４−シクロヘキサンジオール、シクロヘキサンジメタノール、４，４’−ジシクロヘキシルヒドロキシメタン、４，４’−ジシクロヘキシルヒドロキシプロパン、ビスフェノールＡのエチレンオキシド付加ジオール、グリセリン、トリメチロールプロパンなどのトリオール類などが挙げられるが、これらに限定されない。 For example, copolymer monomers of polytrimethylene terephthalate include isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, biphenyl-2,2′- Fragrances such as dicarboxylic acid, biphenyl-3,3′-dicarboxylic acid, biphenyl-4,4′-dicarboxylic acid, bis (4,4′-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid Salts such as aliphatic dicarboxylic acid, 5-sodium sulfoisophthalic acid, 5-potassium sulfoisophthalic acid, 3,5-dicarboxylic acid benzenesulfonic acid tetrabutylphosphonium salt, 3,5-dicarboxylic acid benzenesulfonic acid tributylmethylphosphonium salt, 1 , 4-cyclohexane Carboxylic acids, alicyclic dicarboxylic acids such as 4,4′-dicyclohexyldicarboxylic acid, aliphatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid, dimer acid and their ester derivatives, and ethylene glycol and tetramethylene glycol 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, decamethylene glycol, 1,4-cyclohexanediol, cyclohexanedimethanol, 4,4′-dicyclohexylhydroxymethane, 4,4′-dicyclohexylhydroxy Examples include, but are not limited to, propane, trioxides such as bisphenol A ethylene oxide addition diol, glycerin, and trimethylolpropane.
更に、本発明の樹脂鋳型は、これらＰＴＴにその性質を大きく変えない範囲、例えば５〜３０重量％の範囲内で他の熱可塑性樹脂たとえばポリエチレンテレフタレート、イオノマーなどを溶融混練したポリマーブレンド体も使用可能である。ＰＴＴは商業的にはサンデルタ株式会社製、商品名：サンビスロン、シェルケミカルズ社製、商品名：コルテラが知られている。これらのうち、サンビスロン Ａ０１２０が射出成型性に優れ好ましい。 Furthermore, the resin mold of the present invention uses a polymer blend in which other thermoplastic resins such as polyethylene terephthalate and ionomer are melt-kneaded within the range in which the properties of these PTTs are not greatly changed, for example, in the range of 5 to 30% by weight. Is possible. PTT is commercially available from Sun Delta, Inc., trade name: Sanvislon, Shell Chemicals, trade name: Cortera. Of these, Sanbislon A0120 is preferable because of its excellent injection moldability.
液晶ＰＥＴとしては、ポリエチレンテレフタレートとパラヒドロキシ安息香酸共重合体が知られており、三菱エンジニアリングプラスチックス社製、商品名：ノバキュレート、ユニチカ社製、商品名：ロッドランなどがある。 Polyethylene terephthalate and parahydroxybenzoic acid copolymer are known as liquid crystal PET, and include Mitsubishi Engineering Plastics, trade names: Novacurate, Unitika, trade names: Rod Run.
ポリアリレートとしては、ビスフェノールＡとフタル酸との共重合体が知られており、ユニチカ社製、商品名：Ｕポリマーなどがある。 As polyarylate, a copolymer of bisphenol A and phthalic acid is known, and there is a product name: U polymer manufactured by Unitika Ltd.
本発明の樹脂鋳型に使用する樹脂には、その目的により熱安定剤、酸化防止剤、帯電防止剤、結晶核剤、滑剤、離型剤、顔料、フィラー、補強剤等を適宜添加することが出来る。 The resin used for the resin mold of the present invention may be appropriately added with a heat stabilizer, an antioxidant, an antistatic agent, a crystal nucleating agent, a lubricant, a release agent, a pigment, a filler, a reinforcing agent and the like depending on the purpose. I can do it.
本発明の樹脂鋳型は、その目的に応じてさまざまな形態の鋳型に使用が可能であり、例えば特開昭５２−１１７６４７号公報、特開昭６２−２９７１２０号公報、特開平９−１８３１３２号公報に例示されているコンタクトレンズのキャスト重合用の鋳型、あるいは特開昭６３−３９１０号公報、特表平８−５０５０９５号公報に例示されている片面ないしは両面切削加工によりコンタクトレンズを製造する材料を重合する重合型などに使用が可能である。 The resin mold of the present invention can be used in various forms of molds depending on the purpose, for example, Japanese Patent Laid-Open Nos. 52-117647, 62-297120, and 9-183132. Or a material for producing a contact lens by one-sided or double-sided cutting as exemplified in JP-A-63-3910 and JP-A-8-505095. It can be used in a polymerization type for polymerization.
本発明の樹脂鋳型を使用して製造される医療機器は、製品の表面が親水性であることが要求されるもので、人工心臓、人工心臓弁、埋込型ペースメーカー、血液回路、眼内レンズ、コンタクトレンズ、カテーテルガイドなどがあり、特にコンタクトレンズではその表面の親水性および水濡れ性が、汚れ付着防止、視機能維持、感染症防止、装用感向上等において重要である。 The medical device manufactured using the resin mold of the present invention is required to have a hydrophilic surface. The artificial heart, the artificial heart valve, the implantable pacemaker, the blood circuit, and the intraocular lens There are contact lenses, catheter guides, etc. In particular, the hydrophilicity and water wettability of the surface of contact lenses are important in preventing dirt adhesion, maintaining visual function, preventing infectious diseases, improving wearing feeling, and the like.
本発明の樹脂鋳型を使用して製造されるコンタクトレンズには、ヒドロキシエチルメタクリレート、ｎ−ビニルピロリドンなどを主成分とする含水ソフトコンタクトレンズ、シリコン系モノマーを共重合したシリコン系非含水ソフトコンタクトレンズまたはシリコン系含水ソフトコンタクトレンズなどが含まれる。これらのうち、シリコン系含水ソフトコンタクトレンズは酸素透過性が高く、眼に対してより安全なコンタクトレンズであり好ましい。シリコン系含水ソフトコンタクトレンズとしては、例えばポリシロキサンマクロマーと親水性モノマーを主成分とするポリマーからなり、ポリシロキサンマクロマーが７０〜３０重量％、親水性モノマーの合計が３０〜７０重量％であるポリマーからなる含水性のレンズがあげられる。さらに具体的には、ポリシロキサンマクロマーとしては分子末端に重合性の不飽和基を有するシリコン系マクロマー、そのパーフロロ変性マクロマー、またはポリアルキレングリコール変性マクロマーなどのシリコン系マクロマーなどが使用できる。その具体例は特開平３−２４００２１号公報、特開平３−２５７４２０号公報、特開平４−５０８１４号公報、特願平３−２０２１０６号、特願平３−３３０２６号、ＷＯ出願 ＪＰ００／０８９１２号などに記載されている。 The contact lens manufactured using the resin mold of the present invention includes a hydrous soft contact lens mainly composed of hydroxyethyl methacrylate, n-vinyl pyrrolidone, etc., and a silicon non-hydrous soft contact lens copolymerized with a silicon monomer. Alternatively, silicon-containing water-containing soft contact lenses are included. Of these, the silicon-based water-containing soft contact lens is preferable because it has high oxygen permeability and is safer for the eyes. Examples of the silicon-containing water-containing soft contact lens include a polymer mainly composed of a polysiloxane macromer and a hydrophilic monomer, wherein the polysiloxane macromer is 70 to 30% by weight and the total of the hydrophilic monomers is 30 to 70% by weight. And a water-containing lens. More specifically, as the polysiloxane macromer, a silicon-based macromer having a polymerizable unsaturated group at the molecular terminal, a perfluoro-modified macromer thereof, or a silicon-based macromer such as a polyalkylene glycol-modified macromer can be used. Specific examples thereof include JP-A-3-240021, JP-A-3-257420, JP-A-4-50814, Japanese Patent Application 3-202106, Japanese Patent Application 3-33026, and WO Application JP00 / 08912. It is described in.
これらのうち、特に下記式（１）で表される親水性ポリシロキサンマクロマーがレンズの表面水濡れ性、酸素透過性、機械的強度並びに弾性率などの特性バランスに優れるため好ましい。 Among these, the hydrophilic polysiloxane macromer represented by the following formula (1) is particularly preferable because of excellent balance of characteristics such as surface water wettability, oxygen permeability, mechanical strength, and elastic modulus.
−ＯＣＯＮＨ−Ｒ６−ＮＨＣＯＯ−、−ＮＨＣＯＮＨ−Ｒ７−ＮＨＣＯＮＨ−
および−ＯＣＯＮＨ−Ｒ８−ＮＨＣＯＮＨ−から選ばれた基（Ｒ６、Ｒ７、Ｒ８は炭素数２〜１３の炭化水素基）であり、ｍは０〜１０、ｎは３〜１０、
ｐはｍが０のとき０であり、ｍが１以上のとき１である。ｑは０〜２０の整数である。）
-OCONH-R 6 -NHCOO -, - NHCONH-R 7 -NHCONH-
And —OCONH—R 8 —NHCONH— (R 6 , R 7 , R 8 are hydrocarbon groups having 2 to 13 carbon atoms), m is 0 to 10, n is 3 to 10,
p is 0 when m is 0, and 1 when m is 1 or more. q is an integer of 0-20. )
構造Ｙは下記式で表される構造単位［Ｉ］および［II］が結合してなり、
構造単位［Ｉ］と［II］の結合数の比率は［Ｉ］／［II］＝０．１〜２００
であり、［Ｉ］と［II］の合計数は１０〜１０００である。
Structure Y is formed by combining structural units [I] and [II] represented by the following formula:
The ratio of the number of bonds between the structural units [I] and [II] is [I] / [II] = 0.1 to 200
The total number of [I] and [II] is 10 to 1000.
ここで親水性ポリシロキサンマクロマーの構造単位［Ｉ］は、Ｒ９及びＲ１０が炭化水素基のみのもの［Ｉａ］、少なくとも一つがトリメチルシロキシ基であるもの［Ｉｂ］、少なくとも一つがフッ素置換炭化水素基であるもの［Ｉｃ］からなるもの、あるいはこれらから選ばれた２以上を含む構造であってもよく、構造単位［Ｉ］および［II］の結合形式はブロック的に結合しているもの、ランダム的に結合しているもの、それらが混合しているものを含んでいても良い。該ポリシロキサンマクロマーの構造単位［II］における親水性置換基は水酸基、オキシアルキレン基から選ばれた置換基が少なくとも１個結合してなる鎖状または環状の炭化水素基であるが、式（３）または式（４）で表される基であるものが好ましい。 Here, the structural unit [I] of the hydrophilic polysiloxane macromer is such that R 9 and R 10 are only hydrocarbon groups [Ia], at least one is a trimethylsiloxy group [Ib], and at least one is fluorine-substituted carbonized It may be a hydrogen group [Ic] or a structure containing two or more selected from these, and the structural units [I] and [II] are connected in block form , Randomly bonded ones, or a mixture of them may be included. The hydrophilic substituent in the structural unit [II] of the polysiloxane macromer is a chain or cyclic hydrocarbon group formed by bonding at least one substituent selected from a hydroxyl group and an oxyalkylene group. ) Or a group represented by the formula (4) is preferable.
さらに好ましくは親水性基が、-Ｃ３Ｈ６ＯＨ、-Ｃ８Ｈ１６ＯＨ、-Ｃ３Ｈ６ＯＣ２Ｈ４ＯＨ、-Ｃ３Ｈ６ＯＣＨ２ＣＨ（ＯＨ）ＣＨ３、-Ｃ２Ｈ４ＣＯＯＣ２Ｈ４ＯＨ、-Ｃ２Ｈ４ＣＯＯＣＨ２ＣＨ（ＯＨ）Ｃ２Ｈ５などの１価アルコール置換基、-Ｃ３Ｈ６ＯＣＨ２ＣＨ（ＯＨ）ＣＨ２ＯＨ、-Ｃ２Ｈ４ＣＯＯＣＨ２ＣＨ（ＯＨ）ＣＨ２ＯＨ、-Ｃ３Ｈ６ＯＣＨ２Ｃ（ＣＨ２ＯＨ）３などの多価アルコール置換基、-Ｃ３Ｈ６（ＯＣ２Ｈ４）４ＯＨ、-Ｃ３Ｈ６（ＯＣ２Ｈ４）３０ＯＨ、-Ｃ３Ｈ６（ＯＣ２Ｈ４）１０ＯＣＨ３、-Ｃ３Ｈ６（ＯＣ２Ｈ４）１０-（ＯＣ３Ｈ６）１０ＯＣ４Ｈ９などのポリオキシアルキレン基から選ばれたものがある。これらの中で特に、−Ｃ３Ｈ６ＯＨ、 −Ｃ３Ｈ６ＯＣＨ２ＣＨ（ＯＨ）ＣＨ２ＯＨ、 −Ｃ３Ｈ６ＯＣ２Ｈ４ＯＨなどのアルコール置換基、 −Ｃ３Ｈ６（ＯＣ２Ｈ４）cＯＨ −Ｃ３Ｈ６（ＯＣ２Ｈ４）dＯＣＨ３ （ ｃ、ｄは２〜４０でる）などのポリオキシエチレン基であるものが親水性、酸素透過性のバランスがとれている点で優れている。 More preferably the hydrophilic group, -C 3 H 6 OH, -C 8 H 16 OH, -C 3 H 6 OC 2 H 4 OH, -C 3 H 6 OCH 2 CH (OH) CH 3, -C 2 H 4 COOC 2 H 4 OH, -C 2 H 4 COOCH 2 CH (OH) 1 monohydric alcohol substituent, such as C 2 H 5, -C 3 H 6 OCH 2 CH (OH) CH 2 OH, -C 2 H 4 COOCH 2 CH (OH) CH 2 OH, polyhydric alcohol substituents such as —C 3 H 6 OCH 2 C (CH 2 OH) 3 , —C 3 H 6 (OC 2 H 4 ) 4 OH, —C 3 H 6 (OC 2 H 4) 3 0OH, -C 3 H 6 (OC 2 H 4) 10 OCH 3, -C 3 H 6 (OC 2 H 4) 10 - (OC 3 H 6) 10 OC 4 H 9 There are those selected from polyoxyalkylene groups such as Among these, alcohol substituents such as —C 3 H 6 OH, —C 3 H 6 OCH 2 CH (OH) CH 2 OH, —C 3 H 6 OC 2 H 4 OH, —C 3 H 6 ( What is a polyoxyethylene group such as OC 2 H 4 ) c OH —C 3 H 6 (OC 2 H 4 ) d OCH 3 (where c and d are 2 to 40) has a balance between hydrophilicity and oxygen permeability. It is excellent in that it is taken.
Ｒ９またはＲ１０としてのフッ素置換炭化水素基は材料に耐汚染性を付与するが、フッ素原子が多すぎると親水性を低下させるため、炭化水素の水素原子の４０〜８５％がフッ素原子に置換した炭素数１〜１２の置換基が好ましく、例えば、３，３，３-トリフルオロプロピル基、１，１，２，２−テトラヒドロパーフルオロオクチル基、１，１，２，２−テトラヒドロパーフルオロデシル基等があり、なかでも３，３，３-トリフルオロプロピル基が親水性、酸素透過性のバランスが優れる点で好ましい。また親水性置換基およびフッ素置換炭化水素基のほかにＲ９またはＲ１０としてＳｉ原子に結合してもよい置換基或いはＲ１１またはＲ１２としてＳｉ原子に結合する置換基としては炭素数１〜１２の炭化水素基またはトリメチルシロキシ基であり、それらは互いに同一でも異なっていても良く、好ましくは炭素数１〜３のアルキル基で、柔軟性に富み、酸素透過性も良好であることからメチル基が特に好ましい。 The fluorine-substituted hydrocarbon group as R 9 or R 10 imparts contamination resistance to the material. However, when too many fluorine atoms are present, the hydrophilicity is lowered. Therefore, 40 to 85% of hydrocarbon hydrogen atoms are converted to fluorine atoms. Substituted substituents having 1 to 12 carbon atoms are preferred, such as 3,3,3-trifluoropropyl group, 1,1,2,2-tetrahydroperfluorooctyl group, 1,1,2,2-tetrahydroper There are fluorodecyl groups and the like. Among them, 3,3,3-trifluoropropyl group is preferable in terms of excellent balance between hydrophilicity and oxygen permeability. In addition to the hydrophilic substituent and the fluorine-substituted hydrocarbon group, R 9 or R 10 may be bonded to an Si atom or R 11 or R 12 may be bonded to an Si atom as a substituent having 1 to 1 carbon atoms. 12 hydrocarbon groups or trimethylsiloxy groups, which may be the same as or different from each other, preferably an alkyl group having 1 to 3 carbon atoms, which has high flexibility and good oxygen permeability. The group is particularly preferred.
シロキサン構造単位［Ｉ］、親水性置換基が結合したシロキサン構造単位［II］の比率は［Ｉ］／［II］で０．１〜２００であり、シロキサン構造単位［Ｉ］の割合が少ないとシロキサン鎖の柔軟性と酸素透過性が低下する一方、親水性置換基が少なすぎると、親水性が低下し表面濡れ性が悪化する。さらにシロキサン構造単位［Ｉ］と［II］の合計数は１０〜１０００が良いが、より好ましくは２０〜５００である。ポリシロキサン鎖が短いと重合体の柔軟性、酸素透過性が低下する。又、シロキサン鎖が長すぎると単量体自体でも粘度が著しく大きくなり、モノマーの製造や取扱いが困難となるとともに、重合性が低下し好ましくない。 The ratio of the siloxane structural unit [I] and the siloxane structural unit [II] to which the hydrophilic substituent is bonded is 0.1 to 200 in terms of [I] / [II], and the ratio of the siloxane structural unit [I] is small. While the flexibility and oxygen permeability of the siloxane chain are reduced, if the hydrophilic substituent is too small, the hydrophilicity is reduced and the surface wettability is deteriorated. Furthermore, the total number of the siloxane structural units [I] and [II] is preferably 10 to 1000, more preferably 20 to 500. When the polysiloxane chain is short, the flexibility and oxygen permeability of the polymer are lowered. On the other hand, if the siloxane chain is too long, the viscosity of the monomer itself is remarkably increased, making it difficult to produce and handle the monomer, and decreasing the polymerizability.
重合可能な不飽和部分を含む重合性置換基（Ｘ）はシロキサン鎖の末端に結合しており、該不飽和部位の構造としてはアクリレート基あるいはメタクリレート基が重合性の観点から好ましい。該不飽和部分は炭素数０〜１０の炭化水素架橋を介してＳｉ原子との連結部分基に結合してよい。Ｓｉ原子との連結部分基としてはウレタン結合またはウレア結合を含む炭化水素基が好ましく、該ウレタン結合またはウレア結合（Ｚ1）は、更にオキシエチレン基を介して炭化水素に結合し、そこに含まれていても良い。ウレタン結合およびウレア結合は極性が高く、重合体の親水性を増加させるとともに、強度を大きくする。上記ウレタン結合またはウレア結合は、Ｓｉ原子との連結部分基で２個存在することも可能である。例えば、−ＯＣＯＮＨ−Ｒ６−ＮＨＣＯＯ−、−ＮＨＣＯＮＨ−Ｒ７−ＮＨＣＯＮＨ−および−ＯＣＯＮＨ−Ｒ８−ＮＨＣＯＮＨ−（Ｒ６、Ｒ７、Ｒ８は炭素数２〜１３の炭化水素基）を例示できる。これらの構造はジイソシアナート化合物との反応により導入され、両イソシアナートは炭素数２〜１３の炭化水素基により相互に結合され得、該炭化水素基は鎖状、環状あるいは芳香族化炭化水素基であってもよい。より好ましくは耐光性の良好な脂肪族炭化水素基がよい。使用できるジイソシアナート化合物の例としては、トリメチレンジイソシアネート、ヘキサメチレンジイソシアネート、シクロヘキシルジイソシアネート、イソホロンジイソシアネート、４，４’-ジシクロヘキシルメタンジイソシアネート、２，４-トリレンジイソシアナートなどがある。 The polymerizable substituent (X) containing a polymerizable unsaturated moiety is bonded to the end of the siloxane chain, and the structure of the unsaturated site is preferably an acrylate group or a methacrylate group from the viewpoint of polymerizability. The unsaturated moiety may be bonded to a linking moiety group with an Si atom via a hydrocarbon bridge having 0 to 10 carbon atoms. As the linking moiety group with the Si atom, a hydrocarbon group containing a urethane bond or a urea bond is preferable, and the urethane bond or urea bond (Z 1 ) is further bonded to a hydrocarbon via an oxyethylene group and contained therein. It may be. Urethane bonds and urea bonds are highly polar, increasing the hydrophilicity of the polymer and increasing the strength. Two urethane bonds or urea bonds may be present as a linking moiety group with an Si atom. For example, —OCONH—R 6 —NHCOO—, —NHCONH—R 7 —NHCONH— and —OCONH—R 8 —NHCONH— (wherein R 6 , R 7 and R 8 are hydrocarbon groups having 2 to 13 carbon atoms) are exemplified. it can. These structures are introduced by a reaction with a diisocyanate compound, and both isocyanates can be connected to each other by a hydrocarbon group having 2 to 13 carbon atoms, and the hydrocarbon group is a chain, cyclic or aromatized hydrocarbon. It may be a group. More preferred is an aliphatic hydrocarbon group having good light resistance. Examples of diisocyanate compounds that can be used include trimethylene diisocyanate, hexamethylene diisocyanate, cyclohexyl diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 2,4-tolylene diisocyanate, and the like.
Ｓｉ原子との連結部分基中、オキシエチレン基を介してウレタン結合またはウレア結合が結合してもよい炭化水素基、つまりウレタン結合またはウレア結合を含む炭化水素基における炭化水素には３〜１０個の炭素原子が含まれ得る。 3 to 10 hydrocarbons in a hydrocarbon group containing a urethane bond or a urea bond, that is, a urethane bond or a urea bond to which a urethane bond or a urea bond may be bonded via an oxyethylene group in a connecting partial group with an Si atom. Of carbon atoms may be included.
本発明で開示した親水性ポリシロキサンマクロマーの合成方法は種々考えられるが、例えばヒドロシラン（Ｓｉ-Ｈ）を有する環状シロキサン、炭化水素基を有する環状シロキサンおよび両末端にヒドロキシアルキル基を有するジシロキサン、場合によりフッ素置換炭化水素基を有する環状シロキサンを加えた混合物を硫酸、トリフルオロメタンスルホン酸、酸性白土などの酸性触媒を用いて開環重合し、両末端に水酸基を有し、ヒドロシリル基含有ポリシロキサン化合物を得る。その際、それぞれの環状シロキサンとジシロキサン化合物の仕込み比率を変えることで重合度およびフッ素置換基、ヒドロシリル基の導入割合が異なったシロキサン化合物が得られる。次にイソシアネート基含有アクリレート、あるいはイソシアネート基含有メタクリレートをシロキサン末端の水酸基と反応させ両末端に重合性置換基を有するヒドロシラン含有含フッ素シロキサン化合物を得る。ここで、イソシアネート基含有メタクリレート化合物としては、例えばメタクリロキシエチルイソシアネート、メタクリロイルイソシアネートなどがあり、さらにヒドロキシエチルメタクリレート、ヒドロキシブチルアクリレートなどの水酸基含有アクリレートあるいは水酸基含有メタクリレートと種々のジイソシアネート化合物と反応させて得られるアクリレート基あるいはメタクリレート基含有イソシアナート化合物も利用できる。次に、不飽和炭化水素基を有する親水性化合物を塩化白金酸など遷移金属触媒を用いヒドロシランに付加反応させる、いわゆるヒドロシリル化反応を利用することで親水性ポリシロキサンマクロマーを得ることができる。ここでヒドロシリル化反応の際に、水酸基、カルボン酸などの活性水素化合物が存在すると副反応として脱水素反応を起こすことが知られていて、あらかじめ活性水素を保護したり、バッファー剤を添加し、副反応を抑える方法が、例えば、米国特許第３９０７８５１号、特開昭６２−１９５３８９号公報に記載されている。また別の合成ルートとしては両末端に水酸基を有するヒドロシリル基含有ポリシロキサン化合物の合成後、先にヒドロシリル化による親水性化合物の導入を行い、その後にイソシアネート基含有メタクリレートなどを反応させ、シロキサン末端に重合性置換基を導入する方法もある。この場合にも親水性化合物中にイソシアネートと反応しうる活性水素が存在する場合には保護基を導入し、イソシアネートとの反応を防止する方法が知られている。また出発原料に環状シロキサンに代わって、ジメトキシシラン化合物やジエトキシシラン化合物などの珪酸エステル誘導体を用いることもできる。こうして得られる親水性ポリシロキサンマクロマーの２種以上を混合して使用する事もできる。 There are various methods for synthesizing the hydrophilic polysiloxane macromer disclosed in the present invention. For example, a cyclic siloxane having hydrosilane (Si-H), a cyclic siloxane having a hydrocarbon group, and a disiloxane having a hydroxyalkyl group at both ends, In some cases, a mixture obtained by adding a cyclic siloxane having a fluorine-substituted hydrocarbon group is subjected to ring-opening polymerization using an acidic catalyst such as sulfuric acid, trifluoromethanesulfonic acid, acidic clay, etc., having hydroxyl groups at both ends, and containing a hydrosilyl group-containing polysiloxane A compound is obtained. In this case, siloxane compounds having different degrees of polymerization and introduction ratios of fluorine substituents and hydrosilyl groups can be obtained by changing the charging ratio of each cyclic siloxane and disiloxane compound. Next, an isocyanate group-containing acrylate or an isocyanate group-containing methacrylate is reacted with a hydroxyl group at the siloxane end to obtain a hydrosilane-containing fluorine-containing siloxane compound having a polymerizable substituent at both ends. Here, examples of the isocyanate group-containing methacrylate compound include methacryloxyethyl isocyanate, methacryloyl isocyanate, etc., and further obtained by reacting a hydroxyl group-containing acrylate such as hydroxyethyl methacrylate or hydroxybutyl acrylate or a hydroxyl group-containing methacrylate with various diisocyanate compounds. An acrylate group or methacrylate group-containing isocyanate compound can also be used. Next, a hydrophilic polysiloxane macromer can be obtained by utilizing a so-called hydrosilylation reaction in which a hydrophilic compound having an unsaturated hydrocarbon group is subjected to an addition reaction with hydrosilane using a transition metal catalyst such as chloroplatinic acid. Here, in the hydrosilylation reaction, if an active hydrogen compound such as a hydroxyl group or carboxylic acid is present, it is known to cause a dehydrogenation reaction as a side reaction, and the active hydrogen is protected in advance or a buffer agent is added, Methods for suppressing side reactions are described, for example, in US Pat. No. 3,907,851 and JP-A-62-195389. As another synthesis route, after synthesizing a hydrosilyl group-containing polysiloxane compound having hydroxyl groups at both ends, a hydrophilic compound is first introduced by hydrosilylation, and then reacted with an isocyanate group-containing methacrylate, etc. There is also a method of introducing a polymerizable substituent. Also in this case, there is known a method for preventing a reaction with an isocyanate by introducing a protective group when an active hydrogen capable of reacting with an isocyanate is present in the hydrophilic compound. Further, in place of the cyclic siloxane, a silicate derivative such as a dimethoxysilane compound or a diethoxysilane compound can be used as a starting material. Two or more kinds of hydrophilic polysiloxane macromers obtained in this manner can be mixed and used.
これら親水性ポリシロキサンマクロマーの具体例としては下記のものがある。 Specific examples of these hydrophilic polysiloxane macromers include the following.
医療機器、特にコンタクトレンズは、上記のポリシロキサンマクロマーから選ばれた少なくとも１種が７０〜３０重量％、親水性モノマーが３０〜７０重量％のものが使用され、ポリシロキサンマクロマーが６５〜４０重量％、親水性モノマーの合計が３５〜６０重量％のものが上記諸特性のバランスが取れている事から好ましい。 For medical devices, particularly contact lenses, at least one selected from the above polysiloxane macromers is used in an amount of 70 to 30% by weight, and hydrophilic monomers are used in an amount of 30 to 70% by weight, and the polysiloxane macromer is 65 to 40% by weight. %, And a total of 35 to 60% by weight of the hydrophilic monomers is preferable because the above properties are balanced.
ポリシロキサンマクロマーが３０重量％未満であると必要とする酸素透過性が得られず好ましくない。親水性モノマーが３０重量％未満では必要とされる水濡れ性が低下する為好ましくなく、また、７０重量％を超えると酸素透過性が低下する為好ましくない。 If the polysiloxane macromer is less than 30% by weight, the required oxygen permeability cannot be obtained, which is not preferable. If the hydrophilic monomer is less than 30% by weight, the required water wettability is lowered, and if it exceeds 70% by weight, the oxygen permeability is lowered.
本発明で使用できる親水性モノマーは、２−ヒドロキシエチルメタアクリレート、２−ヒドロキシプロピルメタアクリレート、ヒドロキシブチルメタアクリレート、グリセリルメタアクリレートなどのヒドロキシ基を含有する（メタ）アクリレート、Ｎ−ビニル−Ｎ−メチルアセトアミド、Ｎ−ビニルアセトアミド、Ｎ−ビニル−フォルムアミド、アクリルアミド、Ｎ−メチルアクリルアミド、Ｎ−メチロールアクリルアミド、２−ビニルピリジン、Ｎ−メチルイタコンイミド、Ｎ−ビニルピロリドン、Ｎ，Ｎ−ジメチルアクリルアミド、Ｎ−ビニルイミダゾール、Ｎ−オクタデシルアクリルアミド、１−ビニル−２−メチルイミダゾール、Ｎ−ビニルカルバゾール、Ｎ−ビニルオキサゾリドン、Ｎ−ビニルスクシンイミドなどのＮ原子含有モノマーなどがあり、ポリシロキサンマクロマーとの溶解性、得られるポリマーの物性のバランスなどから好ましくは２−ヒドロキシエチルメタアクリレート、２−ヒドロキシプロピルメタアクリレート、ヒドロキシブチルメタアクリレート、Ｎ−ビニル−Ｎ−メチルアセトアミド、Ｎ−ビニルアセトアミド、Ｎ−ビニル−フォルムアミド、アクリルアミド、Ｎ−メチルアクリルアミド、Ｎ−ビニルピロリドン、Ｎ，Ｎ−ジメチルアクリルアミドから選ばれた１種以上が使用さる。 Hydrophilic monomers that can be used in the present invention include (meth) acrylates containing hydroxy groups such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, hydroxybutyl methacrylate, glyceryl methacrylate, N-vinyl-N- Methylacetamide, N-vinylacetamide, N-vinylformamide, acrylamide, N-methylacrylamide, N-methylolacrylamide, 2-vinylpyridine, N-methylitaconimide, N-vinylpyrrolidone, N, N-dimethylacrylamide, Contains N atoms such as N-vinylimidazole, N-octadecylacrylamide, 1-vinyl-2-methylimidazole, N-vinylcarbazole, N-vinyloxazolidone, N-vinylsuccinimide Preferably 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, hydroxybutyl methacrylate, N-vinyl-N-methyl from the standpoint of solubility with polysiloxane macromer, balance of physical properties of the obtained polymer, etc. One or more selected from acetamide, N-vinylacetamide, N-vinylformamide, acrylamide, N-methylacrylamide, N-vinylpyrrolidone, and N, N-dimethylacrylamide are used.
上記のコンタクトレンズは、その実用性能を維持する目的でさらに共重合可能なモノマーを使用する事が可能である。その構成物に制限は無いが、例えば、メチルアクリレート、エチルアクリレート、アクリル酸などのアクリル系モノマー、メチルメタアクリレート、エチルメタアクリレートなどのメタアクリル系モノマー、トリス（トリメチルシロキシ）シリルプロピルメタアクリレート、ビス（トリメチルシロキシ）メチルシリルプロピルメタアクリレート、ペンタメチルジシロキサンプロピルメタアクリレート、トリス（トリメチルシロキシ）シリルプロピルオキシエチルメタアクリレート、トリス（ポリジメチルシロキシ）シリルプロピルメタアクリレートなどのシリコン系モノマー、シロキサニル基とメタアクリレート基の間にウレタン結合、グリセリル基、ポリアルキレングリコール基など親水性基を有するもの、あるいはシロキサニル基の一部を末端ヒドロキシ基あるいはポリアルキレングリコール基で置換した親水性シロキサニルメタアクリレート、トリス（ジメチルトリフロロプロピルシロキシ）シリルプロピルメタアクリレートなどのフルオロシリコン系モノマー、2、2、2−トリフロロエチルメタアクリレート、2、2、3、3、3−ペンタフロロプロピルメタアクリレート、ヘキサフロロイソプロピルメタアクリレートなどのパーフロロアルキル系モノマー、1、1、2、2−テトラフロロエトキシ−２−ヒドロキシプロピルメタアクリレートなどの水酸基を有するフロロアルキル系及びフロロアルキルエーテル系モノマー、エチレングリコールジメタアクリレート、テトラエチレングリコールジメタアクリレート、テトラメチルジシロキサンビス（プロピルメタアクリレート）などの架橋性モノマーなど共重合可能な化合物との共重合物がある。 The above contact lens can use a copolymerizable monomer for the purpose of maintaining its practical performance. The composition is not limited, but for example, acrylic monomers such as methyl acrylate, ethyl acrylate and acrylic acid, methacrylic monomers such as methyl methacrylate and ethyl methacrylate, tris (trimethylsiloxy) silylpropyl methacrylate, bis Silicon monomers such as (trimethylsiloxy) methylsilylpropyl methacrylate, pentamethyldisiloxanepropyl methacrylate, tris (trimethylsiloxy) silylpropyloxyethyl methacrylate, tris (polydimethylsiloxy) silylpropyl methacrylate, siloxanyl group and meta Those having a hydrophilic group such as urethane bond, glyceryl group, polyalkylene glycol group between acrylate groups, or part of siloxanyl group Hydrophilic siloxanyl methacrylate substituted with terminal hydroxy group or polyalkylene glycol group, fluorosilicone monomer such as tris (dimethyltrifluoropropylsiloxy) silylpropyl methacrylate, 2,2,2-trifluoroethyl methacrylate, Perfluoroalkyl monomers such as 2,2,3,3,3-pentafluoropropyl methacrylate and hexafluoroisopropyl methacrylate; hydroxyl groups such as 1,1,2,2-tetrafluoroethoxy-2-hydroxypropyl methacrylate Fluoroalkyl and fluoroalkyl ether monomers having ethylene, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetramethyldisiloxane bis (propyl methacrylate), etc. It is a copolymer of such sexual monomer copolymerizable compounds.
上記のコンタクトレンズは、上記モノマー及びマクロマーから選ばれた混合物に、熱、ＵＶ、電子線あるいは放射線などにより重合を開始する重合開始剤を添加して重合したポリマーから製造される。その目的に応じて染料、顔料、ＵＶ吸収剤などの添加物を加える事も可能である。 The contact lens is produced from a polymer obtained by adding a polymerization initiator that initiates polymerization by heat, UV, electron beam, radiation, or the like to a mixture selected from the monomer and macromer. It is also possible to add additives such as dyes, pigments and UV absorbers depending on the purpose.
上記のコンタクトレンズは、そのポリマーのミクロ構造、マクロ構造を本発明の目的に合うようにコントロールする為に、上記モノマーおよびマクロマーから選ばれた混合物にさらにモノマー混合物に可溶で、低級アルコールあるいは水に可溶の有機溶媒を０．２〜５０重量％の範囲で添加する事ができる。これら有機溶剤としては、メタノール、エタノール、イソプロピルアルコール、ブチルアルコール、エチレングリコール、エトキシエタノール、グリセリン、ジメチルアセトアミド、ジメチルフォルムアミド、テトラヒドロフラン、リン酸アルキルエステル、ピロリドンなどが使用できる。 In order to control the microstructure and macrostructure of the polymer so as to meet the object of the present invention, the above contact lens is further soluble in a monomer mixture in a mixture selected from the above monomers and macromers, and is made of a lower alcohol or water. Soluble organic solvent can be added in the range of 0.2 to 50% by weight. As these organic solvents, methanol, ethanol, isopropyl alcohol, butyl alcohol, ethylene glycol, ethoxyethanol, glycerin, dimethylacetamide, dimethylformamide, tetrahydrofuran, alkyl phosphate ester, pyrrolidone and the like can be used.
上記のコンタクトレンズは、本発明の鋳型を用いることを除いて、従来のレンズ製造方法で製造でき、例えば、レンズの形状に相当する重合鋳型の中にモノマー混合物を注入して重合するキャスト法で製造できる。なお、キャスト重合で製造した後にレンズ表面をオゾン処理、プラズマ照射処理する事により表面特性特に水濡れ性などをさらに改良する事も可能である。例えば、具体的な例の１つとして、上記ポリシキサンマクロマーおよび親水性モノマーを含む混合物に重合開始剤を加え、本発明の鋳型に注入して加熱重合し、製造することができる。 The above contact lens can be manufactured by a conventional lens manufacturing method except that the mold of the present invention is used. For example, a cast method in which a monomer mixture is injected into a polymerization mold corresponding to the shape of the lens and polymerized. Can be manufactured. It is also possible to further improve the surface characteristics, particularly water wettability, by subjecting the lens surface to ozone treatment and plasma irradiation treatment after production by cast polymerization. For example, as one specific example, it can be produced by adding a polymerization initiator to the mixture containing the polysiloxane macromer and the hydrophilic monomer, and injecting the mixture into the mold of the present invention to heat polymerization.
以下、実施例により本発明を説明するが、本発明が実施例により限定されることはないことは言うまでもない。 EXAMPLES Hereinafter, although an Example demonstrates this invention, it cannot be overemphasized that this invention is not limited by an Example.
（実施例）
実施例における鋳型成型に用いた樹脂の評価方法は以下の通りである。
(Example)
The evaluation method of the resin used for mold molding in the examples is as follows.
１．吸水率
ＪＩＳ Ｋ７２０９に記載の方法、すなわち、６０Ｘ６０ｍｍ角、１ｍｍ厚みのキャビティを有する金型（ＩＳＯ ２９４−３ Ｄ１形モールド）を使用して、各樹脂の技術資料に記載されている推奨条件にて射出成型した試料片について、２３℃で蒸留水に２４時間試料片を浸漬した後、その重量変化を測定して計算した。
1. Water absorption rate Using the method described in JIS K7209, that is, a mold having a cavity of 60 × 60 mm square and 1 mm thickness (ISO 294-3 D1 type mold), under the recommended conditions described in the technical data of each resin The injection-molded sample piece was immersed in distilled water at 23 ° C. for 24 hours, and then its weight change was measured and calculated.
実施例において成型した鋳型の評価方法は以下のとおりである。 The evaluation method of the mold molded in the examples is as follows.
２．水接触角
厚み１ｍｍ、８０Ｘ８０ｍｍ角の板状のキャスト重合用鋳型を成型する金型を使用して、各樹脂の技術資料に記載されている推奨条件にて射出成型した鋳型試料片について、協和界面科学株式会社製 Ｃｏｎｔａｃｔ Ａｎｇｌｅ Ｍｅｔｅｒ ＣＡ−Ａ を用いて２３℃で測定した。試料片は射出成型して直ちに空気中の湿気の影響を防止する目的で、防湿性包装材料（ポリエチレン袋等）にて密閉包装し、測定の前に２３℃の恒温室内に包装形態のままで２４時間静置して温度を一定にした後取り出し、シリンジにて直径約１．８ｍｍの純水を試料片上に接触させ、その液滴と試料片が形成する角度を読み取り、計算により求めた。
2. Using a mold that molds a plate-shaped cast polymerization mold with a water contact angle of 1 mm thickness and 80 x 80 mm square, a mold sample piece injection-molded under the recommended conditions described in the technical data of each resin The measurement was performed at 23 ° C. using Contact Angle Meter CA-A manufactured by Kagaku Corporation. For the purpose of preventing the influence of moisture in the air immediately after injection molding, the sample piece is hermetically sealed with a moisture-proof packaging material (polyethylene bag, etc.) and kept in a packaged condition in a constant temperature room at 23 ° C before measurement. The sample was left to stand for 24 hours to make the temperature constant, and then taken out. Pure water having a diameter of about 1.8 mm was brought into contact with the sample piece with a syringe, and the angle formed by the droplet and the sample piece was read and calculated.
実施例におけるキャスト重合した試料の評価方法は以下の通りである。 The evaluation method of the cast polymerized sample in the examples is as follows.
３−１．含水率
試料片を精製水に入れ３７℃で７２時間静置した後、試料片を取り出し表面の付着水を手早く拭き取ってその重量を精秤した後、真空乾燥機で恒量になるまで乾燥して、その重量変化から求めた。
含水率＝（重量変化量／乾燥前重量）×１００ （％）
3-1. Moisture content After placing the sample piece in purified water and allowing to stand at 37 ° C. for 72 hours, take out the sample piece, quickly wipe off the water adhering to the surface, accurately weigh its weight, and then dry to a constant weight with a vacuum dryer. It was obtained from the weight change.
Water content = (weight change / weight before drying) × 100 (%)
３−２．水接触角
試料片を純水に入れ２３℃で２４時間静置した後、試料片を取り出し表面の付着水を手早く拭き取って、協和界面科学株式会社製 Ｃｏｎｔａｃｔ Ａｎｇｌｅ Ｍｅｔｅｒ ＣＡ−Ａ を用いて２３℃で、シリンジにて直径約１．８ｍｍの純水を試料片上に接触させ、その液滴と試料片が形成する角度を読み取り、計算により求めた。
3-2. Water contact angle After placing the sample piece in pure water and leaving it to stand at 23 ° C. for 24 hours, the sample piece is taken out and the surface adhering water is quickly wiped off, and the contact angle meter CA-A manufactured by Kyowa Interface Science Co., Ltd. is used. Then, pure water having a diameter of about 1.8 mm was brought into contact with the sample piece with a syringe, and the angle formed by the droplet and the sample piece was read and obtained by calculation.
３−３．水濡れ性
試料片を保存液から引き上げた時のレンズ表面の水層の維持状況を観察して水濡れ性を評価した。
3-3. Water wettability The water wettability was evaluated by observing the maintenance of the water layer on the lens surface when the sample piece was pulled up from the preservation solution.
３−４．酸素透過係数（Ｄｋ値）
コンタクトレンズ協会標準Ｄｋ値測定法に準じて理化精機工業(株)社製Ｋ３１６ ＩＰ
Ｉ型フィルム酸素透過測定器を使用して電極法により測定した。
Ｄｋ値の表示は×１０１１（ｃｍ２／ｓｅｃ）・（ｍｌＯ２／ｍｌ×ｍｍＨｇ）で示した。
3-4. Oxygen transmission coefficient (Dk value)
K316 IP manufactured by Rika Seiki Co., Ltd. according to the Contact Lens Association Standard Dk Value Measurement Method
Measurements were made by the electrode method using a type I film oxygen transmission meter.
The display of the Dk value was indicated by × 10 11 (cm 2 / sec) · (mlO 2 / ml × mmHg).
３−５．引っ張り弾性率
試料片から約３ｍｍ幅のサンプルを切り出し、万能試験機（島津製作所製 ＡＧＳ−５０Ｂ型）で１００ｍｍ／ｍｉｎの速度で引っ張り試験を行い、初期の傾きから求めた。値はｄｙｎｅ／ｃｍ２で示した。
3-5. Tensile elastic modulus A sample having a width of about 3 mm was cut out from the specimen, and a tensile test was performed at a speed of 100 mm / min with a universal testing machine (AGS-50B model, manufactured by Shimadzu Corporation). The value was indicated in dyne / cm 2 .
３−６．タンパク質付着性 3-6. Protein adhesion
この液２ｍｌに約０．２ｍｍ厚み、約１５ｍｍ直径の試料片１枚を入れ、温度３７℃で２４時間浸せきし、精製水中に試料片を入れて３０分間振とうして洗浄する。試料片を取り出し表面水を軽くふき取る。 A sample piece having a thickness of about 0.2 mm and a diameter of about 15 mm is placed in 2 ml of this liquid, immersed in a temperature of 37 ° C. for 24 hours, and the sample piece is placed in purified water and shaken for 30 minutes for washing. Remove the sample piece and gently wipe off the surface water.
その試料片をＳＤＳ／炭酸ナトリウム溶液に６０℃で１５時間浸漬し、その浸漬液をプロテイン分析試薬（ＢＣＡ液）液中に添加し６０℃で１時間反応後、ＵＶ５６２ｎｍにて分光光度計（日本分光（株）社製 Ｖ−５５０型）で測定した。 The sample piece was immersed in an SDS / sodium carbonate solution at 60 ° C. for 15 hours, the immersion solution was added to a protein analysis reagent (BCA solution) solution, reacted at 60 ° C. for 1 hour, and then a spectrophotometer at UV562 nm (Japan) Spectroscopic Co., Ltd. V-550 type).
別途求めた検量線から、試料片１ｃｍ平方当りの付着タンパク質量を求めた。 From the separately obtained calibration curve, the amount of attached protein per 1 cm square of the sample piece was determined.
３−７．脂質付着性
オリーブオイル０．１％のリン酸緩衝液を撹拌混合して、約０．２ｍｍ厚み、約１５ｍｍ直径の試料片を入れ４０℃の恒温槽中で２０時間浸せきした。５ｍｌの精製水を入れた容器内に試料片を入れ３０秒間振り洗いをして、これを５回繰り返して洗浄した。
3-7. Lipid Adhesive Phosphate buffer solution of olive oil 0.1% was stirred and mixed, and a sample piece having a thickness of about 0.2 mm and a diameter of about 15 mm was placed and immersed in a constant temperature bath at 40 ° C. for 20 hours. A sample piece was placed in a container containing 5 ml of purified water, shaken for 30 seconds, and this was repeated 5 times for washing.
この試料片を真空乾燥した後クロロフォルム／メタノール ２／１混合溶媒で抽出し、トリグリセライドＧ試験液で発色してその吸光度を分光光度計（日本分光（株）社製 Ｖ−５５０型）で測定した。別に求めた検量線から試料片１ｃｍ平方当りの脂質付着量を求めた。 The sample piece was vacuum dried, extracted with a chloroform / methanol 2/1 mixed solvent, colored with a triglyceride G test solution, and the absorbance was measured with a spectrophotometer (V-550, manufactured by JASCO Corporation). . From the separately obtained calibration curve, the lipid adhesion amount per 1 cm square of the sample piece was determined.
分子側鎖にヒドロキシプロピル基、トリフロロプロピル基を有する平均分子量約６０００の両末端ヒドロキシプロピル基を有するポリジメチルシロキサン（シロキサン骨格において、ヒドロキシプロピル基置換シロキサン単位、トリフロロプロピル基置換シロキサン単位の含有比率がそれぞれ約４．４モル％、２２モル％）と、２−イソシアナトエチルメタアクリレートとの反応により親水性シロキサニルマクロマーを合成した。 Polydimethylsiloxane having a hydroxypropyl group and a trifluoropropyl group in the molecular side chain and having a hydroxypropyl group at both ends with an average molecular weight of about 6000 (including propylene group-substituted siloxane units and hydroxypropyl group-substituted siloxane units in the siloxane skeleton) Hydrophilic siloxanyl macromers were synthesized by reaction of 2-isocyanatoethyl methacrylate with a ratio of about 4.4 mol% and 22 mol%, respectively.
上記親水性シロキサニルマクロマー６０重量部、Ｎ−ビニルピロリドン２１重量部、Ｎ−ビニル−Ｎ−メチルアセトアミド１０重量部、トリフロロエチルメタアクリレート９重量部、エチレングリコールジメタアクリレート１重量部のモノマー混合物に重合開始剤として２，２’-アゾビス（２，４-ジメチルバレロニトリル）０．１重量部を加えＰＴＴ樹脂（サンデルタ株式会社製 サンビスロンＴＭ Ａ０１２０ 吸水率０．０４％）を射出成型して作成したキャスト重合用鋳型（成型後直ちに使用したもの、使用前の水接触角７４度）に注入し、８０℃で1時間加熱して重合した。重合直後の鋳型は、手で容易に剥離可能で、ポリマーシートも鋳型から容易に剥離できた。試料片を燐酸バッファーのコンタクトレンズ保存液で膨潤して含水ポリマーシートを得た。物性を評価した結果、含水率は３０％、Ｄｋ値は１５０で、タンパク質及び脂質の付着性はそれぞれ１０μｇ／ｃｍ平方、３０μｇ／ｃｍ平方と少なかった。水濡れ性はランク３で優れていた。また、引っ張り弾性率は１．２×１０７ｄｙｎｅ／ｃｍ２であった。含水ポリマーシート表面の水を拭き取った後に再度水濡れ性を評価した結果、ランク３で変化無かった。 Monomer of 60 parts by weight of the above hydrophilic siloxanyl macromer, 21 parts by weight of N-vinylpyrrolidone, 10 parts by weight of N-vinyl-N-methylacetamide, 9 parts by weight of trifluoroethyl methacrylate, and 1 part by weight of ethylene glycol dimethacrylate To the mixture, 0.1 part by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator was added, and PTT resin (Sun bislon TM A0120 water absorption 0.04% manufactured by Sun Delta Co., Ltd.) was injection molded. It was poured into the prepared casting polymerization mold (used immediately after molding, water contact angle 74 degrees before use) and polymerized by heating at 80 ° C. for 1 hour. The mold immediately after polymerization was easily peelable by hand, and the polymer sheet was also easily peeled from the mold. The sample piece was swollen with a phosphate buffer contact lens preservation solution to obtain a water-containing polymer sheet. As a result of evaluating the physical properties, the water content was 30%, the Dk value was 150, and the adhesion of proteins and lipids was as low as 10 μg / cm 2 and 30 μg / cm 2, respectively. Water wettability was excellent at rank 3. Moreover, the tensile elastic modulus was 1.2 × 10 7 dyne / cm 2 . As a result of evaluating the wettability again after wiping off the water on the surface of the water-containing polymer sheet, there was no change in rank 3.
分子側鎖に重合度１０のメチル基末端のポリエチレングリコール基、トリフロロプロピル基を有する平均分子量約６０００の両末端ヒドロキシエトキシプロピル基を有するポリジメチルシロキサン（シロキサン骨格において、ポリエチレングリコール基置換シロキサン単位、トリフロロプロピル基置換シロキサン単位の含有比率がそれぞれ約３．９モル％、６．４モル％）と、２−イソシアナトエチルメタアクリレートとの反応により親水性シロキサニルマクロマーを合成した。 Polydimethylsiloxane having a methyl group-terminated polyethylene glycol group having a polymerization degree of 10 in the molecular side chain and a trifluoropropyl group having both terminal hydroxyethoxypropyl groups having an average molecular weight of about 6000 (in the siloxane skeleton, a polyethylene glycol group-substituted siloxane unit, Hydrophilic siloxanyl macromers were synthesized by reaction of trifluoropropyl group-substituted siloxane units with a content ratio of about 3.9 mol% and 6.4 mol%, respectively, and 2-isocyanatoethyl methacrylate.
上記親水性シロキサニルマクロマー５５重量部、Ｎ−ビニルピロリドン１５重量部、Ｎ−ビニル−Ｎ−メチルアセトアミド２０重量部、トリフロロエチルメタアクリレート９重量部、エチレングリコールジメタアクリレート１重量部のモノマー混合物に重合開始剤として２，２’-アゾビス（２，４-ジメチルバレロニトリル）０．１重量部を添加し、ＰＴＴ樹脂（サンデルタ株式会社製 サンビスロンＴＭ Ａ０１２０ 吸水率０．０４％）を射出成型して製造したキャスト重合用鋳型（ポリエチレン袋で保管したもので、使用前の水接触角７３度）に注入し、８０℃で1時間加熱して重合した。重合直後の鋳型は、手で容易に剥離可能で、ポリマーシートも鋳型から容易に剥離できた。試料片を燐酸バッファーのコンタクトレンズ保存液で膨潤して含水ポリマーシートを得た。実施例１と同様にして物性を評価した結果、含水率は３９％、Ｄｋ値は１２５で、タンパク質及び脂質の付着性はそれぞれ３３μｇ／ｃｍ平方、９μｇ／ｃｍ平方と少なかった。水濡れ性はランク３で優れていた。また、引っ張り弾性率は１．１×１０７ｄｙｎｅ／ｃｍ２であった。含水ポリマーシート表面の水を拭き取った後に再度水濡れ性を評価した結果、ランク３で変化無かった。 Monomer of 55 parts by weight of the above hydrophilic siloxanyl macromer, 15 parts by weight of N-vinylpyrrolidone, 20 parts by weight of N-vinyl-N-methylacetamide, 9 parts by weight of trifluoroethyl methacrylate, and 1 part by weight of ethylene glycol dimethacrylate 0.12 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) is added to the mixture as a polymerization initiator, and PTT resin (Sunbislon TM A0120 water absorption 0.04%, manufactured by Sun Delta Co., Ltd.) is injection molded. The polymer was cast into a cast polymerization mold (stored in a polyethylene bag and had a water contact angle of 73 ° before use) and heated at 80 ° C. for 1 hour for polymerization. The mold immediately after polymerization was easily peelable by hand, and the polymer sheet was also easily peeled from the mold. The sample piece was swollen with a phosphate buffer contact lens preservation solution to obtain a water-containing polymer sheet. The physical properties were evaluated in the same manner as in Example 1. As a result, the water content was 39%, the Dk value was 125, and the adhesion of protein and lipid was 33 μg / cm 2 and 9 μg / cm 2, respectively. Water wettability was excellent at rank 3. Moreover, the tensile elastic modulus was 1.1 × 10 7 dyne / cm 2 . As a result of evaluating the wettability again after wiping off the water on the surface of the water-containing polymer sheet, there was no change in rank 3.
分子側鎖に重合度７のメチル基末端のポリエチレングリコール基、トリフロロプロピル基を有する平均分子量約１００００の両末端ヒドロキシエトキシプロピル基を有するポリジメチルシロキサン（シロキサン骨格において、ポリエチレングリコール基置換シロキサン単位、トリフロロプロピル基置換シロキサン単位の含有比率がそれぞれ約３．９モル％、６．４モル％）と、２−イソシアナトエチルメタアクリレートとの反応により親水性シロキサニルマクロマーを合成した。 Polydimethylsiloxane having both molecular end chain hydroxyethylenepropyl groups having an average molecular weight of about 10,000 having a polyethylene glycol group having a polymerization degree of 7 in the molecular side chain and a trifluoropropyl group (in the siloxane skeleton, a polyethylene glycol group-substituted siloxane unit, Hydrophilic siloxanyl macromers were synthesized by reaction of trifluoropropyl group-substituted siloxane units with a content ratio of about 3.9 mol% and 6.4 mol%, respectively, and 2-isocyanatoethyl methacrylate.
上記親水性シロキサニルマクロマー４９重量部、Ｎ−ビニルピロリドン２２重量部、Ｎ−ビニル−フォルムアミド１１重量部、ヒドロキシブチルメタアクリレート１１重量部、イソボルニルメタアクリレート６．７重量部、トリアリルイソシアヌレート０．７重量部のモノマー混合物にエトキシエタノール３０重量部を加え、これに重合開始剤として２，２’-アゾビス（２，４-ジメチルバレロニトリル）０．１重量部を添加し、ＰＴＴ樹脂（サンデルタ株式会社製 サンビスロンＴＭ Ａ０１２０ 吸水率０．０４％）で射出成型したキャスト重合用鋳型（ポリエチレン袋で３日間保管したもので、水接触角７３度）に注入し、８０℃で1時間加熱して重合した。重合直後の鋳型は、手で容易に剥離可能で、ポリマーシートも鋳型から容易に剥離できた。試料片を燐酸バッファーのコンタクトレンズ保存液で膨潤して含水ポリマーシートを得た。得られた含水ポリマーシートの物性を評価した結果、含水率は４１％、水接触角６０度。水濡れ性はランク３で優れていた。また、含水ポリマーシートを、１２１℃で６０分間オートクレーブ滅菌処理した後に測定した水接触角は６０度、水濡れ性はランク３で処理前と同じであった。 49 parts by weight of the above hydrophilic siloxanyl macromer, 22 parts by weight of N-vinylpyrrolidone, 11 parts by weight of N-vinyl-formamide, 11 parts by weight of hydroxybutyl methacrylate, 6.7 parts by weight of isobornyl methacrylate, triallyl 30 parts by weight of ethoxyethanol was added to a monomer mixture of 0.7 parts by weight of isocyanurate, 0.1 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added as a polymerization initiator, and PTT was added. It was poured into a cast polymerization mold (stored in a polyethylene bag for 3 days, water contact angle 73 degrees) injection-molded with resin (Sun bislon TM A0120 water absorption 0.04%, manufactured by Sun Delta Co., Ltd.), and at 80 ° C. for 1 hour Polymerized by heating. The mold immediately after polymerization was easily peelable by hand, and the polymer sheet was also easily peeled from the mold. The sample piece was swollen with a phosphate buffer contact lens preservation solution to obtain a water-containing polymer sheet. As a result of evaluating the physical properties of the obtained water-containing polymer sheet, the water content was 41% and the water contact angle was 60 degrees. Water wettability was excellent at rank 3. The water contact angle measured after autoclaving the water-containing polymer sheet at 121 ° C. for 60 minutes was 60 degrees, and the water wettability was rank 3 and the same as before the treatment.
分子側鎖に重合度７のメチル基末端のポリエチレングリコール基、トリフロロプロピル基を有する平均分子量約９０００の両末端ヒドロキシエトキシプロピル基を有するポリジメチルシロキサン（シロキサン骨格において、ポリエチレングリコール基置換シロキサン単位、トリフロロプロピル基置換シロキサン単位の含有比率がそれぞれ約３．９モル％、６．４モル％）と、２−イソシアナトエチルメタアクリレートとの反応により親水性シロキサニルマクロマーを合成した。 Polydimethylsiloxane having both molecular weights of about 9 000 having an average molecular weight of about 9000 having a polyethylene glycol group having a polymerization degree of 7 in the molecular side chain and a trifluoropropyl group (in the siloxane skeleton, a polyethylene glycol group-substituted siloxane unit, Hydrophilic siloxanyl macromers were synthesized by reaction of trifluoropropyl group-substituted siloxane units with a content ratio of about 3.9 mol% and 6.4 mol%, respectively, and 2-isocyanatoethyl methacrylate.
上記親水性シロキサニルマクロマー４８重量部、Ｎ−ビニルピロリドン２３重量部、Ｎ−ビニル−フォルムアミド１１重量部、ヒドロキシブチルメタアクリレート１１重量部、イソボルニルメタアクリレート６．８重量部、トリアリルイソシアヌレート０．７重量部のモノマー混合物に重合開始剤として２，２’-アゾビス（２，４-ジメチルバレロニトリル）０．１重量部を添加し、これをＰＴＴ樹脂（サンデルタ株式会社製 サンビスロンＴＭ Ａ０１２０ 吸水率０．０４％）の成型直後のキャスト重合用鋳型（水接触角７５度）に注入し、８０℃で1時間加熱して重合した。重合直後の鋳型は、手で容易に剥離可能で、ポリマーシートも鋳型から容易に剥離できた。試料片を燐酸バッファーのコンタクトレンズ保存液で膨潤して含水ポリマーシートを得た。得られた含水ポリマーシートの物性を評価した結果、含水率は４８％、水接触角２４度、水濡れ性はランク３で優れていた。 48 parts by weight of the above hydrophilic siloxanyl macromer, 23 parts by weight of N-vinylpyrrolidone, 11 parts by weight of N-vinylformamide, 11 parts by weight of hydroxybutyl methacrylate, 6.8 parts by weight of isobornyl methacrylate, triallyl 0.1 part by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added as a polymerization initiator to a monomer mixture of 0.7 part by weight of isocyanurate, and this was added to PTT resin (Sunbislon ™ manufactured by Sun Delta Co., Ltd.). A0120 (water absorption rate 0.04%) was cast into a cast polymerization mold (water contact angle 75 degrees) immediately after molding and polymerized by heating at 80 ° C. for 1 hour. The mold immediately after polymerization was easily peelable by hand, and the polymer sheet was also easily peeled from the mold. The sample piece was swollen with a phosphate buffer contact lens preservation solution to obtain a water-containing polymer sheet. As a result of evaluating the physical properties of the obtained water-containing polymer sheet, the water content was 48%, the water contact angle was 24 degrees, and the water wettability was excellent in rank 3.
分子側鎖に重合度７のメチル基末端のポリエチレングリコール基、トリフロロプロピル基を有する平均分子量約１００００の両末端ヒドロキシエトキシプロピル基を有するポリジメチルシロキサン（シロキサン骨格において、ポリエチレングリコール基置換シロキサン単位、トリフロロプロピル基置換シロキサン単位の含有比率がそれぞれ約３．９モル％、６．４モル％）と、２−イソシアナトエチルメタアクリレートとの反応により親水性シロキサニルマクロマーを合成した。 Polydimethylsiloxane having both molecular end chain hydroxyethylenepropyl groups having an average molecular weight of about 10,000 having a polyethylene glycol group having a polymerization degree of 7 in the molecular side chain and a trifluoropropyl group (in the siloxane skeleton, a polyethylene glycol group-substituted siloxane unit, Hydrophilic siloxanyl macromers were synthesized by reaction of trifluoropropyl group-substituted siloxane units with a content ratio of about 3.9 mol% and 6.4 mol%, respectively, and 2-isocyanatoethyl methacrylate.
上記親水性シロキサニルマクロマー４９重量部、Ｎ−ビニルピロリドン２２重量部、Ｎ−ビニル−フォルムアミド１１重量部、ヒドロキシブチルメタアクリレート１１重量部、イソボルニルメタアクリレート６．７重量部、トリアリルイソシアヌレート０．７重量部のモノマー混合物にエトキシエタノール３０重量部を加え、これに重合開始剤として２，２’-アゾビス（２，４-ジメチルバレロニトリル）０．１重量部を添加し重合モノマー混合液を調合した。ＰＴＴ樹脂（サンデルタ株式会社製 サンビスロンＴＭ Ａ０１２０ 吸水率０．０４％）製の室温（２５℃、３５％ＲＨ）で保管した鋳型（使用前の水接触角６８度）に重合モノマー混合液を注入し、８０℃で1時間加熱して重合した。重合直後の鋳型は、手で剥離が可能で、ポリマーシートも鋳型から剥離できた。試料片を燐酸バッファーのコンタクトレンズ保存液で膨潤して含水ポリマーシートを得た。得られた含水ポリマーシートの物性を評価した結果、含水率は４１％、水接触角５８度、水濡れ性はランク３で優れていた。また、含水ポリマーシートを、１２１℃で６０分間オートクレーブ滅菌処理した後に測定した水接触角は５９度、水濡れ性はランク３で処理前と同じであった。 49 parts by weight of the above hydrophilic siloxanyl macromer, 22 parts by weight of N-vinylpyrrolidone, 11 parts by weight of N-vinyl-formamide, 11 parts by weight of hydroxybutyl methacrylate, 6.7 parts by weight of isobornyl methacrylate, triallyl 30 parts by weight of ethoxyethanol is added to a monomer mixture of 0.7 parts by weight of isocyanurate, and 0.1 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) is added as a polymerization initiator to the monomer mixture. A mixed solution was prepared. The polymerization monomer mixture was poured into a mold (water contact angle 68 degrees before use) stored at room temperature (25 ° C, 35% RH) made of PTT resin (San Delta Co., Ltd., Sunbislon TM A0120 water absorption 0.04%). And polymerized by heating at 80 ° C. for 1 hour. The mold immediately after polymerization could be peeled by hand, and the polymer sheet could also be peeled from the mold. The sample piece was swollen with a phosphate buffer contact lens preservation solution to obtain a water-containing polymer sheet. As a result of evaluating the physical properties of the obtained water-containing polymer sheet, the water content was 41%, the water contact angle was 58 degrees, and the water wettability was excellent at rank 3. Moreover, the water contact angle measured after autoclaving the water-containing polymer sheet at 121 ° C. for 60 minutes was 59 degrees, and the water wettability was rank 3 and the same as before the treatment.
（比較例１）
実施例１で合成した親水性シロキサニルマクロマー６０重量部、Ｎ、Ｎ−ジメチルアクリルアミド３０重量部、トリフロロエチルメタアクリレート９重量部、エチレングリコールジメタアクリレート１重量部のモノマー混合物に重合開始剤として２，２’-アゾビス（２，４-ジメチルバレロニトリル）０．１重量部を加えエチレンビニルアルコール共重合物（日本合成化学製、ソアライトＳ、吸水率０．６％）製のキャスト重合用鋳型（ポリエチレン袋中で保管したもので、使用前の水接触角６７度）に注入し、８０℃で1時間加熱して重合した。重合後鋳型は物理的に剥離が出来ず、９０℃熱水中に浸漬したのち、ようやく鋳型および試料片を剥離した。試料片を燐酸バッファーのコンタクトレンズ保存液で膨潤して含水ポリマーシートを得た。実施例１と同様にして物性を評価した結果、含水率は２５％、Ｄｋ値は１５５で、水濡れ性はランク３で、タンパク質及び脂質の付着性はそれぞれ１５μｇ／ｃｍ平方、４４μｇ／ｃｍ平方であった。また、引っ張り弾性率は１．３×１０７ｄｙｎｅ／ｃｍ２であった。
(Comparative Example 1)
A polymerization initiator was added to a monomer mixture of 60 parts by weight of hydrophilic siloxanyl macromer synthesized in Example 1, 30 parts by weight of N, N-dimethylacrylamide, 9 parts by weight of trifluoroethyl methacrylate, and 1 part by weight of ethylene glycol dimethacrylate. For cast polymerization of ethylene vinyl alcohol copolymer (Nippon GOHSEI, Soarlite S, water absorption 0.6%) with 0.1 part by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) added as The solution was poured into a mold (stored in a polyethylene bag, water contact angle before use of 67 degrees) and polymerized by heating at 80 ° C. for 1 hour. After the polymerization, the mold could not be physically peeled off, and after being immersed in hot water at 90 ° C., the mold and the sample piece were finally peeled off. The sample piece was swollen with a phosphate buffer contact lens preservation solution to obtain a water-containing polymer sheet. As a result of evaluating physical properties in the same manner as in Example 1, the water content was 25%, the Dk value was 155, the water wettability was rank 3, and the adhesion of proteins and lipids was 15 μg / cm 2 and 44 μg / cm 2 respectively. Met. Moreover, the tensile elastic modulus was 1.3 × 10 7 dyne / cm 2 .
（比較例２）
実施例１で合成した親水性シロキサニルマクロマー７０重量部、Ｎ−ビニルピロリドン１５重量部、Ｎ−ビニル−Ｎ−メチルアセトアミド５重量部、トリフロロエチルメタアクリレート９重量部、エチレングリコールジメタアクリレート１重量部のモノマー混合物に重合開始剤として２，２’-アゾビス（２，４-ジメチルバレロニトリル）０．１重量部を加えエチレンビニルアルコール共重合物（日本合成化学製、ソアライトＳ、吸水率０．６％）を射出成型して室内で保管したキャスト重合用鋳型（水接触角６７度）に注入し、８０℃で1時間加熱して重合した。重合後鋳型は物理的に剥離が出来ず、９０℃熱水中に浸漬したのち、ようやく鋳型および試料片を剥離した。試料片を膨潤して含水ポリマーシートを得た。実施例１と同様にして物性を評価した結果、含水率は２５％、Ｄｋ値は１９０で、水濡れ性はランク３、タンパク質及び脂質の付着性はそれぞれ１５μｇ／ｃｍ平方、６μｇ／ｃｍ平方であった。また、引っ張り弾性率は１．０×１０７ｄｙｎｅ／ｃｍ２であった。
(Comparative Example 2)
70 parts by weight of hydrophilic siloxanyl macromer synthesized in Example 1, 15 parts by weight of N-vinylpyrrolidone, 5 parts by weight of N-vinyl-N-methylacetamide, 9 parts by weight of trifluoroethyl methacrylate, ethylene glycol dimethacrylate 0.1 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator is added to 1 part by weight of the monomer mixture, and an ethylene vinyl alcohol copolymer (manufactured by Nippon Gosei Kagaku, Sorelite S, water absorption rate) 0.6%) was injected and cast into a cast polymerization mold (water contact angle of 67 degrees) stored indoors, and polymerized by heating at 80 ° C. for 1 hour. After the polymerization, the mold could not be physically peeled off, and after being immersed in hot water at 90 ° C., the mold and the sample piece were finally peeled off. The sample piece was swollen to obtain a water-containing polymer sheet. As a result of evaluating physical properties in the same manner as in Example 1, the water content was 25%, the Dk value was 190, the water wettability was rank 3, and the adhesion of proteins and lipids was 15 μg / cm 2 and 6 μg / cm 2 respectively. there were. The tensile elastic modulus was 1.0 × 10 7 dyne / cm 2 .
（比較例３）
実施例１で合成した親水性シロキサニルマクロマー７０重量部、Ｎ−ビニルピロリドン１５重量部、Ｎ−ビニル−Ｎ−メチルアセトアミド５重量部、トリフロロエチルメタアクリレート９重量部、エチレングリコールジメタアクリレート１重量部のモノマー混合物に重合開始剤として２，２’-アゾビス（２，４-ジメチルバレロニトリル）０．１重量部を加えポリエチレンテレフタレート（三菱レイヨン製、ダイヤナイト、吸水率０．１６％）製のキャスト重合用鋳型（室内で保管したもので、使用前の水接触角７５度）に注入し、８０℃で1時間加熱して重合した。重合後鋳型は手で剥離が可能で鋳型および試料片を剥離した。試料片を膨潤して含水ポリマーシートを得た。実施例１と同様にして物性を評価した結果、含水率は２５％、Ｄｋ値は１９０であったが、水濡れ性はランク２と劣るものであった。タンパク質及び脂質の付着性はそれぞれ１５μｇ／ｃｍ平方、６μｇ／ｃｍ平方であった。また、引っ張り弾性率は１．０×１０７ｄｙｎｅ／ｃｍ２であった。
(Comparative Example 3)
70 parts by weight of hydrophilic siloxanyl macromer synthesized in Example 1, 15 parts by weight of N-vinylpyrrolidone, 5 parts by weight of N-vinyl-N-methylacetamide, 9 parts by weight of trifluoroethyl methacrylate, ethylene glycol dimethacrylate 0.1 part by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator is added to 1 part by weight of the monomer mixture, and polyethylene terephthalate (manufactured by Mitsubishi Rayon, Dianite, water absorption 0.16%) The polymer was cast into a cast polymerization mold (stored indoors, with a water contact angle of 75 degrees before use) and polymerized by heating at 80 ° C. for 1 hour. After polymerization, the mold was peelable by hand, and the mold and sample piece were peeled off. The sample piece was swollen to obtain a water-containing polymer sheet. As a result of evaluating physical properties in the same manner as in Example 1, the water content was 25% and the Dk value was 190, but the water wettability was inferior to rank 2. The adhesion of protein and lipid was 15 μg / cm 2 and 6 μg / cm 2 respectively. The tensile elastic modulus was 1.0 × 10 7 dyne / cm 2 .
（比較例４）
実施例１に記載のモノマー混合物をポリプロピレン（株式会社チッソ製、ホモポリマー、吸水率０．０１％未満）製のレンズ形状にしたキャスト重合用鋳型（室内で保管したもので、使用前の水接触角１０５度）に注入し、８０℃で1時間加熱して重合した。重合後鋳型は手で剥離が可能で鋳型および試料片を剥離した。膨潤してソフトコンタクトレンズを得た。
(Comparative Example 4)
Cast polymerization mold (stored indoors) in the shape of a lens made of polypropylene (made by Chisso Corporation, homopolymer, water absorption of less than 0.01%) from the monomer mixture described in Example 1; water contact before use Was injected at an angle of 105 degrees) and polymerized by heating at 80 ° C. for 1 hour. After polymerization, the mold was peelable by hand, and the mold and sample piece were peeled off. A soft contact lens was obtained by swelling.
実施例１と同様にして物性を評価した結果、含水率は３０％、Ｄｋ値は１６５で、タンパク質及び脂質の付着性はそれぞれ１８μｇ／ｃｍ平方、１０３μｇ／ｃｍ平方と多かった。水濡れ性は保存液浸漬レンズではランク１であり、該レンズ表面の水を拭き取ってから試験するとランク０で乾燥により表面の水濡れ性が大幅に低下した。また、引っ張り弾性率は１．２×１０７ｄｙｎｅ／ｃｍ２であった。 As a result of evaluating physical properties in the same manner as in Example 1, the water content was 30%, the Dk value was 165, and the adhesion of proteins and lipids was as high as 18 μg / cm 2 and 103 μg / cm 2, respectively. The wettability of the storage solution immersion lens was rank 1, and when the test was conducted after wiping off the water on the lens surface, the wettability of the surface was greatly reduced by drying at rank 0. Moreover, the tensile elastic modulus was 1.2 × 10 7 dyne / cm 2 .
（比較例５）
実施例１で合成した親水性シロキサニルマクロマー８５重量部、Ｎ−ビニルピロリドン１０重量部、Ｎ、Ｎ−ジメチルアクリルアミド５重量部、トリフロロエチルメタアクリレート５重量部、エチレングリコールジメタアクリレート１重量部のモノマー混合物に重合開始剤として２，２’-アゾビス（２，４-ジメチルバレロニトリル）０．１重量部を加えポリプロピレン製（比較例４に同じ）のレンズ形状にしたキャスト重合用鋳型に注入し、８０℃で1時間加熱して重合し、膨潤してソフトコンタクトレンズを得た。
(Comparative Example 5)
85 parts by weight of hydrophilic siloxanyl macromer synthesized in Example 1, 10 parts by weight of N-vinylpyrrolidone, 5 parts by weight of N, N-dimethylacrylamide, 5 parts by weight of trifluoroethyl methacrylate, 1 part by weight of ethylene glycol dimethacrylate As a polymerization initiator, 0.1 part by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added to the monomer mixture as a polymerization initiator to form a cast polymerization template having a lens shape made of polypropylene (same as Comparative Example 4). The mixture was injected, heated at 80 ° C. for 1 hour to polymerize, and swollen to obtain a soft contact lens.
実施例１と同様にして物性を評価した結果、含水率は１２％、Ｄｋ値は２５６で、タンパク質及び脂質の付着性はそれぞれ１５μｇ／ｃｍ平方、１０４μｇ／ｃｍ平方と多かった。水濡れ性は保存液浸漬レンズではランク１であり、該レンズ表面の水を拭き取ってから試験するとランク０で乾燥により表面の水濡れ性が大幅に低下した。また、引っ張り弾性率は０．９×１０７ｄｙｎｅ／ｃｍ２であった。 As a result of evaluating the physical properties in the same manner as in Example 1, the water content was 12%, the Dk value was 256, and the adhesion of proteins and lipids was as high as 15 μg / cm 2 and 104 μg / cm 2, respectively. The wettability of the storage solution immersion lens was rank 1, and when the test was conducted after wiping off the water on the lens surface, the wettability of the surface was significantly reduced by drying at rank 0. Moreover, the tensile elastic modulus was 0.9 × 10 7 dyne / cm 2 .
（比較例６）
実施例１に記載のモノマー混合物を親水性改質ポリプロピレン（株式会社チッソ製ホモポリマーに住友精化製吸水樹脂アクアコークＴＷを１０％ブレンドした樹脂、吸水率０．０３％）で射出成型して室内で保管したキャスト重合用鋳型（水接触角９５度）に注入し、８０℃で1時間加熱して重合し、膨潤して含水ポリマーシートを得た。
(Comparative Example 6)
The monomer mixture described in Example 1 was injection-molded with hydrophilic modified polypropylene (a resin obtained by blending 10% of Sumitomo Seika's water-absorbing resin Aqua Coke TW with a homopolymer manufactured by Chisso Corporation, water absorption rate 0.03%). It was poured into a cast polymerization mold (water contact angle 95 °) stored indoors, polymerized by heating at 80 ° C. for 1 hour, and swollen to obtain a water-containing polymer sheet.
実施例１と同様にして物性を評価した結果、含水率は３０％、Ｄｋ値は１６５で、タンパク質及び脂質の付着性はそれぞれ１８μｇ／ｃｍ平方、１０３μｇ／ｃｍ平方と多かった。水濡れ性は保存液浸漬シートではランク２であり、該シート表面の水を拭き取ってから試験するとランク０で乾燥により表面の水濡れ性が大幅に低下した。また、引っ張り弾性率は１．２×１０７ｄｙｎｅ／ｃｍ２であった。 As a result of evaluating the physical properties in the same manner as in Example 1, the water content was 30%, the Dk value was 165, and the adhesion of proteins and lipids was as high as 18 μg / cm 2 and 103 μg / cm 2, respectively. The wettability of the storage solution-immersed sheet was rank 2, and when tested after wiping off the water on the surface of the sheet, the wettability of the surface was significantly reduced by drying at rank 0. Moreover, the tensile elastic modulus was 1.2 × 10 7 dyne / cm 2 .
（比較例７）
樹脂鋳型としてポリエチレンテレフタレート（三菱レイヨン製、ダイヤナイト、吸水率０．１６％）製のキャスト重合用鋳型（水接触角７５度）、親水性改質ポリプロピレン（株式会社チッソ製ホモポリマーに住友精化製吸水樹脂アクアコークＴＷを１０％ブレンドした樹脂、吸水率０．０３％）製のキャスト重合用鋳型（水接触角９５度）を使用した他は実施例３と同様の方法で含水ポリマーシートを作成した。得られた含水ポリマーシートの物性を評価した結果、含水率はそれぞれ４１％および４１％、水接触角はそれぞれ８４度および１１５度で、水濡れ性はランク１およびランク０と劣るものであった。また、得られた含水ポリマーシートを、１２１℃で６０分間オートクレーブ滅菌処理した後の水接触角はそれぞれ８７度、１２０度と処理前よりも大きくなり水濡れ性が低下していた。
(Comparative Example 7)
As a resin mold, cast polymerization mold (water contact angle 75 degrees) made of polyethylene terephthalate (Mitsubishi Rayon, Dianite, water absorption 0.16%), hydrophilic modified polypropylene (Hitopolymer made by Chisso Corporation) A water-containing polymer sheet was prepared in the same manner as in Example 3 except that a cast polymerization mold (water contact angle 95 °) made of 10% water-absorbing resin Aqua Coke TW resin, water absorption rate 0.03%) was used. Created. As a result of evaluating the physical properties of the obtained water-containing polymer sheet, the water content was 41% and 41%, the water contact angle was 84 degrees and 115 degrees, respectively, and the water wettability was inferior to rank 1 and rank 0. . Further, the water contact angles after the obtained water-containing polymer sheet was autoclaved at 121 ° C. for 60 minutes were 87 degrees and 120 degrees, respectively, which were larger than before the treatment, and the water wettability was reduced.
（比較例８）
樹脂鋳型としてポリエチレンテレフタレート（三菱レイヨン製、ダイヤナイト、吸水率０．１６％）製のキャスト重合用鋳型（水接触角７５度）、親水性改質ポリプロピレン（株式会社チッソ製ホモポリマーに住友精化製吸水樹脂アクアコークＴＷを１０％ブレンドした樹脂、吸水率０．０３％）製のキャスト重合用鋳型（水接触角９５度）を使用した他は実施例４と同様の方法で含水ポリマーシートを作成した。得られた含水ポリマーシートの物性を評価した結果、含水率、水接触角および水濡れ性は、それぞれ、ポリエチレンテレフタレートでは４８％、４５度およびランク２、改質ポリプロピレンでは４８％、１１４度およびランク０で、実施例４と比較して水濡れ性に劣るものであった。
(Comparative Example 8)
As a resin mold, cast polymerization mold (water contact angle 75 degrees) made of polyethylene terephthalate (Mitsubishi Rayon, Dianite, water absorption 0.16%), hydrophilic modified polypropylene (Hitopolymer made by Chisso Corporation) A water-containing polymer sheet was prepared in the same manner as in Example 4 except that a cast polymerization mold (water contact angle 95 degrees) made of a water-absorbing resin Aqua Coke TW 10% blended resin, water absorption 0.03%) was used. Created. As a result of evaluating the physical properties of the obtained water-containing polymer sheet, the water content, water contact angle and water wettability were 48%, 45 ° and rank 2 for polyethylene terephthalate, and 48%, 114 ° and rank for modified polypropylene, respectively. 0, which was inferior in water wettability as compared with Example 4.
（比較例９）
実施例１で合成した親水性シロキサニルマクロマー７０重量部、Ｎ−ビニルピロリドン１５重量部、Ｎ−ビニル−Ｎ−メチルアセトアミド５重量部、トリフロロエチルメタアクリレート９重量部、エチレングリコールジメタアクリレート１重量部のモノマー混合物に重合開始剤として２，２’-アゾビス（２，４-ジメチルバレロニトリル）０．１重量部を加えエチレンビニルアルコール共重合物（クラレ製、エバールＥＰＥ１０５Ａ、吸水率０．３％）製のキャスト重合用鋳型（水接触角７３度）に注入し、８０℃で1時間加熱して重合した。重合後鋳型は物理的に剥離が出来ず、９０℃熱水中に浸漬したのち、ようやく鋳型および試料片を剥離した。試料片を膨潤して含水ポリマーシートを得た。実施例１と同様にして物性を評価した結果、含水率は２４％、Ｄｋ値は１８５で、水濡れ性はランク３、タンパク質及び脂質の付着性はそれぞれ１４μｇ／ｃｍ平方、５μｇ／ｃｍ平方であった。また、引っ張り弾性率は０．９×１０７ｄｙｎｅ／ｃｍ２であった。
(Comparative Example 9)
70 parts by weight of hydrophilic siloxanyl macromer synthesized in Example 1, 15 parts by weight of N-vinylpyrrolidone, 5 parts by weight of N-vinyl-N-methylacetamide, 9 parts by weight of trifluoroethyl methacrylate, ethylene glycol dimethacrylate 0.1 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator was added to 1 part by weight of the monomer mixture, and an ethylene vinyl alcohol copolymer (Kuraray, Eval EPE105A, water absorption of 0. 3%) and was cast into a cast polymerization mold (water contact angle 73 °) and heated at 80 ° C. for 1 hour for polymerization. After the polymerization, the mold could not be physically peeled off, and after being immersed in hot water at 90 ° C., the mold and the sample piece were finally peeled off. The sample piece was swollen to obtain a water-containing polymer sheet. As a result of evaluating the physical properties in the same manner as in Example 1, the water content was 24%, the Dk value was 185, the water wettability was rank 3, and the adhesion of proteins and lipids was 14 μg / cm 2 and 5 μg / cm 2 respectively. there were. Moreover, the tensile elastic modulus was 0.9 × 10 7 dyne / cm 2 .
（比較例１０）
実施例１で合成した親水性シロキサニルマクロマー７０重量部、Ｎ−ビニルピロリドン１５重量部、Ｎ−ビニル−Ｎ−メチルアセトアミド５重量部、トリフロロエチルメタアクリレート９重量部、エチレングリコールジメタアクリレート１重量部のモノマー混合物に重合開始剤として２，２’-アゾビス（２，４-ジメチルバレロニトリル）０．１重量部を加えエチレンビニルアルコール共重合物（日本合成化学製、ソアライトＭ、吸水率０．６％）製のキャスト重合用鋳型（水接触角５９度）に注入し、８０℃で1時間加熱して重合した。重合後鋳型は物理的に剥離が出来ず、９０℃熱水中に浸漬したのち８０％エタノール溶液に２４時間浸漬して、ようやく鋳型および試料片を剥離した。試料片をレンズ保存液で膨潤して含水ポリマーシートを得た。実施例１と同様にして物性を評価した結果、含水率は２５％、Ｄｋ値は１８７で、水濡れ性はランク３、タンパク質及び脂質の付着性はそれぞれ１６μｇ／ｃｍ平方、７μｇ／ｃｍ平方であった。また、引っ張り弾性率は０．９×１０７ｄｙｎｅ／ｃｍ２であった。
(Comparative Example 10)
70 parts by weight of hydrophilic siloxanyl macromer synthesized in Example 1, 15 parts by weight of N-vinylpyrrolidone, 5 parts by weight of N-vinyl-N-methylacetamide, 9 parts by weight of trifluoroethyl methacrylate, ethylene glycol dimethacrylate 0.1 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator is added to 1 part by weight of the monomer mixture, and an ethylene vinyl alcohol copolymer (manufactured by Nippon Gosei Kagaku, Sorelite M, water absorption rate) 0.6%) cast polymerization mold (water contact angle 59 °) and heated at 80 ° C. for 1 hour for polymerization. After the polymerization, the mold could not be physically peeled off, and after being immersed in hot water at 90 ° C., it was immersed in an 80% ethanol solution for 24 hours to finally peel off the mold and the sample piece. The sample piece was swollen with a lens preservation solution to obtain a water-containing polymer sheet. As a result of evaluating the physical properties in the same manner as in Example 1, the water content was 25%, the Dk value was 187, the water wettability was rank 3, and the adhesion of proteins and lipids was 16 μg / cm 2 and 7 μg / cm 2 respectively. there were. Moreover, the tensile elastic modulus was 0.9 × 10 7 dyne / cm 2 .
（比較例１１）
実施例１で合成した親水性シロキサニルマクロマー７０重量部、Ｎ−ビニルピロリドン１５重量部、Ｎ−ビニル−Ｎ−メチルアセトアミド５重量部、トリフロロエチルメタアクリレート９重量部、エチレングリコールジメタアクリレート１重量部のモノマー混合物に重合開始剤として２，２’-アゾビス（２，４-ジメチルバレロニトリル）０．１重量部を加え熱可塑性ポリビニルアルコール（クラレ製、エクセバールＣＰ−７０００、吸水率８％以上）を射出成型し密閉容器で保管したキャスト重合用鋳型（水接触角５８度）に注入し、８０℃で1時間加熱して重合した。重合後鋳型は物理的に剥離が出来ず、９０℃熱水中に浸漬して、ようやく試料片を剥離した。試料片を膨潤して含水ポリマーシートを得た。実施例１と同様にして物性を評価した結果、含水率は２４％、Ｄｋ値は１８５で、水濡れ性はランク３、タンパク質及び脂質の付着性はそれぞれ１４μｇ／ｃｍ平方、５μｇ／ｃｍ平方であった。また、引っ張り弾性率は０．９×１０７ｄｙｎｅ／ｃｍ２であった。
(Comparative Example 11)
70 parts by weight of hydrophilic siloxanyl macromer synthesized in Example 1, 15 parts by weight of N-vinylpyrrolidone, 5 parts by weight of N-vinyl-N-methylacetamide, 9 parts by weight of trifluoroethyl methacrylate, ethylene glycol dimethacrylate 0.1 part by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator is added to 1 part by weight of the monomer mixture, and thermoplastic polyvinyl alcohol (manufactured by Kuraray, EXEVAL CP-7000, water absorption 8%) The above was injected into a cast polymerization mold (water contact angle 58 °) which was injection molded and stored in a sealed container, and heated at 80 ° C. for 1 hour for polymerization. After polymerization, the mold could not be physically peeled off, and was immersed in hot water at 90 ° C. to finally peel off the sample piece. The sample piece was swollen to obtain a water-containing polymer sheet. As a result of evaluating the physical properties in the same manner as in Example 1, the water content was 24%, the Dk value was 185, the water wettability was rank 3, and the adhesion of proteins and lipids was 14 μg / cm 2 and 5 μg / cm 2 respectively. there were. The tensile elastic modulus was 0.9 × 10 7 dyne / cm 2 .
（発明の効果）
本発明は、製品の表面親水性が優れ、鋳型剥離性に優れた鋳型を提供し、表面の親水性が要求される医療機器、たとえば眼内レンズ、コンタクトレンズのキャスト重合用鋳型として製品の表面親水性、特に水濡れ性が優れかつ安定しており、鋳型からの製品の剥離性が優れ製造工程が簡便となるキャスト重合用の樹脂鋳型および該鋳型を用いる医療機器の製造方法を提供する。
(The invention's effect)
The present invention provides a mold having excellent surface hydrophilicity of the product and excellent mold releasability, and the surface of the product as a casting polymerization mold for medical devices such as intraocular lenses and contact lenses that require surface hydrophilicity. Provided are a resin mold for cast polymerization that has excellent hydrophilicity, particularly water wettability, is stable, has excellent product releasability from the mold, and facilitates the production process, and a method for producing a medical device using the mold.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013157320A1 (en) | 2012-04-18 | 2013-10-24 | Hoya株式会社 | Silicone hydrogel soft contact lens having wettable surface |
| US8845935B2 (en) | 2008-03-12 | 2014-09-30 | Novartis Ag | Method for cast molding contact lenses |
| JP2015211993A (en) * | 2014-05-02 | 2015-11-26 | 古河電気工業株式会社 | Polishing pad, polishing method using the polishing pad, and using method of the polishing pad |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0924523A (en) * | 1995-07-11 | 1997-01-28 | Ito Kogaku Kogyo Kk | Mold for molding plastic lens |
| JPH09183132A (en) * | 1995-09-29 | 1997-07-15 | Johnson & Johnson Vision Prod Inc | Mold for contact lens, mold material, and manufacture of contact lens |
| JPH1134178A (en) * | 1997-07-15 | 1999-02-09 | Canon Inc | Optical element, and method and apparatus for producing the same |
| JP2002006269A (en) * | 2000-06-22 | 2002-01-09 | Kuraray Co Ltd | Resin mold for manufacturing contact lens and method for manufacturing contact lens |
| JP2002137230A (en) * | 2000-11-06 | 2002-05-14 | Kuraray Co Ltd | Resin mold for manufacturing contact lens and method for manufacturing contact lens using the same |
| JP2002355830A (en) * | 2001-03-26 | 2002-12-10 | Novartis Ag | Mold and method for producing ophthalmic lens |
| JP2003311762A (en) * | 2002-04-19 | 2003-11-05 | Asahi Kasei Aimii Kk | Method for separating mold |
| JP2004085655A (en) * | 2002-08-23 | 2004-03-18 | Asahi Kasei Aimii Kk | Fouling resistant hydrous soft contact lens |
-
2005
- 2005-12-14 JP JP2005359893A patent/JP4824998B2/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0924523A (en) * | 1995-07-11 | 1997-01-28 | Ito Kogaku Kogyo Kk | Mold for molding plastic lens |
| JPH09183132A (en) * | 1995-09-29 | 1997-07-15 | Johnson & Johnson Vision Prod Inc | Mold for contact lens, mold material, and manufacture of contact lens |
| JPH1134178A (en) * | 1997-07-15 | 1999-02-09 | Canon Inc | Optical element, and method and apparatus for producing the same |
| JP2002006269A (en) * | 2000-06-22 | 2002-01-09 | Kuraray Co Ltd | Resin mold for manufacturing contact lens and method for manufacturing contact lens |
| JP2002137230A (en) * | 2000-11-06 | 2002-05-14 | Kuraray Co Ltd | Resin mold for manufacturing contact lens and method for manufacturing contact lens using the same |
| JP2002355830A (en) * | 2001-03-26 | 2002-12-10 | Novartis Ag | Mold and method for producing ophthalmic lens |
| JP2003311762A (en) * | 2002-04-19 | 2003-11-05 | Asahi Kasei Aimii Kk | Method for separating mold |
| JP2004085655A (en) * | 2002-08-23 | 2004-03-18 | Asahi Kasei Aimii Kk | Fouling resistant hydrous soft contact lens |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8845935B2 (en) | 2008-03-12 | 2014-09-30 | Novartis Ag | Method for cast molding contact lenses |
| WO2013157320A1 (en) | 2012-04-18 | 2013-10-24 | Hoya株式会社 | Silicone hydrogel soft contact lens having wettable surface |
| US10241234B2 (en) | 2012-04-18 | 2019-03-26 | Hoya Corporation | Silicone hydrogel soft contact lens having wettable surface |
| JP2015211993A (en) * | 2014-05-02 | 2015-11-26 | 古河電気工業株式会社 | Polishing pad, polishing method using the polishing pad, and using method of the polishing pad |
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| JP4824998B2 (en) | 2011-11-30 |
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