JP2007314490A - Method for producing material containing silicone monomer - Google Patents
Method for producing material containing silicone monomer Download PDFInfo
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- JP2007314490A JP2007314490A JP2006148507A JP2006148507A JP2007314490A JP 2007314490 A JP2007314490 A JP 2007314490A JP 2006148507 A JP2006148507 A JP 2006148507A JP 2006148507 A JP2006148507 A JP 2006148507A JP 2007314490 A JP2007314490 A JP 2007314490A
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- acid
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- acid residue
- silicone monomer
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- 239000000178 monomer Substances 0.000 title claims abstract description 66
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 58
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 title abstract description 24
- 239000011973 solid acid Substances 0.000 claims abstract description 38
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 32
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000004817 gas chromatography Methods 0.000 claims abstract description 21
- 238000005227 gel permeation chromatography Methods 0.000 claims abstract description 21
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 12
- 238000009833 condensation Methods 0.000 claims description 29
- 230000005494 condensation Effects 0.000 claims description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 26
- 125000004432 carbon atom Chemical group C* 0.000 claims description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 16
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 12
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 235000012239 silicon dioxide Nutrition 0.000 claims description 12
- 125000001424 substituent group Chemical group 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 125000005401 siloxanyl group Chemical group 0.000 claims description 8
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 claims description 6
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 6
- TXXHDPDFNKHHGW-UHFFFAOYSA-N muconic acid Chemical compound OC(=O)C=CC=CC(O)=O TXXHDPDFNKHHGW-UHFFFAOYSA-N 0.000 claims description 6
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 3
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 claims description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 3
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 claims description 3
- TXXHDPDFNKHHGW-CCAGOZQPSA-N Muconic acid Natural products OC(=O)\C=C/C=C\C(O)=O TXXHDPDFNKHHGW-CCAGOZQPSA-N 0.000 claims description 3
- 239000005642 Oleic acid Substances 0.000 claims description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 3
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 claims description 3
- 235000020661 alpha-linolenic acid Nutrition 0.000 claims description 3
- 229930016911 cinnamic acid Natural products 0.000 claims description 3
- 235000013985 cinnamic acid Nutrition 0.000 claims description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 3
- 229960004488 linolenic acid Drugs 0.000 claims description 3
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 claims description 3
- 125000005481 linolenic acid group Chemical group 0.000 claims description 3
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 claims description 3
- TXXHDPDFNKHHGW-ZPUQHVIOSA-N muconic acid group Chemical group C(\C=C\C=C\C(=O)O)(=O)O TXXHDPDFNKHHGW-ZPUQHVIOSA-N 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- 238000000752 ionisation method Methods 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 2
- 238000006467 substitution reaction Methods 0.000 claims 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 12
- -1 alkali metal methacrylate Chemical class 0.000 description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 229910000077 silane Inorganic materials 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 4
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 210000004087 cornea Anatomy 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 0 CCC(*1)C1(*)N(*)C(C)C Chemical compound CCC(*1)C1(*)N(*)C(C)C 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 210000005252 bulbus oculi Anatomy 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000006103 coloring component Substances 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 150000004677 hydrates Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012719 thermal polymerization Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- 235000019797 dipotassium phosphate Nutrition 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
本発明は、シリコーン単量体含有物の製造方法に関し、詳しくは、例えば、コンタクトレンズ、眼内レンズ、人工角膜等の眼用レンズの原料として特に好適に用いられるシリコーン単量体含有物の製造方法に関する。 The present invention relates to a method for producing a silicone monomer-containing material, and more specifically, production of a silicone monomer-containing material that is particularly suitably used as a raw material for ophthalmic lenses such as contact lenses, intraocular lenses, and artificial corneas. Regarding the method.
従来よりソフトコンタクトレンズ用モノマーとして、２−ヒドロキシエチルメタクリレート(ＨＥＭＡ)等の単量体が知られている。ＨＥＭＡを原料に用いて製造したソフトコンタクトレンズは、装用感は良いが、酸素透過性が低く、連続装用が困難といった問題がある。そこで、酸素透過性を向上させるための手段として、ケイ素基を有するモノマーを用いることが知られている。
該ケイ素基を有するモノマーとしては、例えば、式(３)又は(３')で表されるシリコーン単量体が知られている。式中Meはメチル基を示す。
Conventionally, monomers such as 2-hydroxyethyl methacrylate (HEMA) are known as monomers for soft contact lenses. Soft contact lenses manufactured using HEMA as a raw material have a good feeling of wear, but have a problem of low oxygen permeability and difficulty in continuous wear. Therefore, it is known to use a monomer having a silicon group as a means for improving oxygen permeability.
As the monomer having a silicon group, for example, a silicone monomer represented by the formula (3) or (3 ′) is known. In the formula, Me represents a methyl group.
しかし、このような製造方法では、反応過程で高極性物質及び着色成分、シロキサン縮合オリゴマー型架橋剤等の副生成物が生成するため、得られるシリコーン単量体含有物中のシリコーン単量体の純度は７５〜８０重量％程度までしか上がらない。例えば、このような純度のシリコーン単量体含有物を用いて製造したコンタクトレンズは、不純物によるレンズ物性への悪影響や、着色、装用感の悪化、眼球に対する悪影響といった問題があるため、不純物をできるだけ除去することが望まれている。
However, in such a production method, a by-product such as a highly polar substance, a coloring component, and a siloxane condensation oligomer type cross-linking agent is generated in the reaction process. The purity increases only to about 75 to 80% by weight. For example, a contact lens manufactured using a silicone monomer-containing material with such purity has problems such as adverse effects on the lens physical properties due to impurities, coloring, deterioration of wearing feeling, and adverse effects on the eyeball. It is desired to be removed.
そこで、特許文献２では、反応系にシリカゲル、アルミナ、ゼオライト、モレキュラーシーブ、活性炭等の多孔質粒子を加え、高極性物質と着色成分からなる不純物を除去する方法が報告されている。
しかし、この方法においても、副生成物であるシロキサン縮合オリゴマー型架橋剤が１０〜２０重量％残存する。該シロキサン縮合オリゴマー型架橋剤は、一分子内に複数の重合基を有するため、架橋成分として働き、これを含むシリコーン単量体含有物を用いて得られるポリマーは、硬くなる。このため、該ポリマーを、ソフトコンタクトレンズの原料に用いた場合には、装用感が劣り、長期間の装用によって眼球に傷がつき易いという問題がある。
そこで、これらの問題を解決する、シロキサン縮合オリゴマー型架橋剤の含量を簡単な操作で低減させることができるシリコーン単量体含有物の製造方法の開発が熱望されている。
However, even in this method, 10 to 20% by weight of a siloxane condensation oligomer type crosslinking agent as a by-product remains. Since the siloxane condensation oligomer type cross-linking agent has a plurality of polymer groups in one molecule, it functions as a cross-linking component, and a polymer obtained by using a silicone monomer-containing material containing the same becomes hard. For this reason, when the polymer is used as a raw material for soft contact lenses, there is a problem that the wearing feeling is inferior and the eyeball is easily damaged by long-term wearing.
Therefore, development of a method for producing a silicone monomer-containing material capable of reducing the content of the siloxane condensation oligomer type crosslinking agent to solve these problems by a simple operation is eagerly desired.
本発明の課題は、大量合成にも適応可能であり、シロキサン縮合オリゴマー型架橋剤の低減を簡便な工程により実施できる、シリコーン単量体の純度が高い、シリコーン単量体含有物の製造方法を提供することにある。 An object of the present invention is a method for producing a silicone monomer-containing material having high silicone monomer purity, which can be applied to large-scale synthesis and can reduce the siloxane condensation oligomer type crosslinking agent by a simple process. It is to provide.
本発明によれば、エポキシシランと不飽和カルボン酸とを反応させる工程(a)と、得られた反応物を固体酸により処理する工程(b)とを含む、ゲル浸透クロマトグラフィーを用いて測定したときの式(Ａ)で算出されるシロキサン縮合オリゴマー型架橋剤の含有度(Ｑ１)が８％以下で、且つガスクロマトグラフィーを用いて測定したときの式(Ｂ)で算出されるシリコーン単量体の含有度(Ｑ２)が８５％以上であるシリコーン単量体含有物の製造方法が提供される。
(Ｑ１)＝[Ｐ１／(Ｐ２−Ｐ３)]×１００(％)・・・（Ａ）
(式(Ａ)において、Ｐ１はゲル浸透クロマトグラフィーを用いて測定したとき示差屈折率計で検出されるシロキサン縮合オリゴマー型架橋剤に由来するピークの総面積、Ｐ２はゲル浸透クロマトグラフィーを用いて測定したとき示差屈折率計で検出される全ピークの総面積、Ｐ３はゲル浸透クロマトグラフィーを用いて測定したとき示差屈折率計で検出される溶媒ピークの面積をそれぞれ示す。)
(Ｑ２)＝[Ｐ４／(Ｐ５−Ｐ６)]×[１−(Ｑ１／１００)]×１００(％)・・・（Ｂ）
(式(Ｂ)において、Ｑ１は式(Ａ)で算出されるシロキサン縮合オリゴマー型架橋剤の含有度、Ｐ４はガスクロマトグラフィーを用いて測定したとき水素炎イオン化法(ＦＩＤ)で検出されるシリコーン単量体に由来するピークの総面積、Ｐ５はガスクロマトグラフィーを用いて測定したときＦＩＤで検出される全ピークの総面積、Ｐ６はガスクロマトグラフィーを用いて測定したときＦＩＤで検出される溶媒ピークの面積をそれぞれ示す。)
According to the present invention, measurement using gel permeation chromatography comprising the step (a) of reacting an epoxysilane with an unsaturated carboxylic acid and the step (b) of treating the resulting reaction product with a solid acid. The content (Q1) of the siloxane condensation oligomer type cross-linking agent calculated by the formula (A) is 8% or less, and the silicone single unit calculated by the formula (B) when measured by gas chromatography is used. There is provided a method for producing a silicone monomer-containing material having a content (Q2) of a monomer of 85% or more.
(Q1) = [P1 / (P2-P3)] × 100 (%) (A)
(In Formula (A), P1 is the total area of peaks derived from the siloxane condensation oligomer type cross-linking agent detected by a differential refractometer when measured using gel permeation chromatography, and P2 is obtained using gel permeation chromatography. (The total area of all peaks detected by the differential refractometer when measured, and P3 indicates the area of the solvent peak detected by the differential refractometer when measured using gel permeation chromatography.)
(Q2) = [P4 / (P5-P6)] × [1- (Q1 / 100)] × 100 (%) (B)
(In the formula (B), Q1 is the content of the siloxane condensation oligomer type cross-linking agent calculated by the formula (A), and P4 is a silicone detected by the flame ionization method (FID) when measured using gas chromatography. Total area of peaks derived from monomers, P5 is the total area of all peaks detected by FID when measured using gas chromatography, and P6 is a solvent detected by FID when measured using gas chromatography (The area of each peak is shown.)
本発明の製造方法は、特に、エポキシシランと不飽和カルボン酸との反応物を、アルミナと二酸化ケイ素との水和物からなる固体酸等の固体酸により処理するという簡便の工程を採用するので、大量合成にも適応可能であり、シロキサン縮合オリゴマー型架橋剤等の副生成物が低減され、シリコーン単量体の純度が高い、シリコーン単量体含有物を容易に得ることができる。従って、得られるシリコーン単量体含有物を含む重合性組成物を重合したポリマーは、コンタクトレンズ、眼内レンズ、人工角膜等の眼用レンズの原料として特に好適である。 The production method of the present invention particularly adopts a simple process of treating a reaction product of an epoxy silane and an unsaturated carboxylic acid with a solid acid such as a solid acid composed of a hydrate of alumina and silicon dioxide. It is also applicable to large-scale synthesis, and by-products such as siloxane condensation oligomer type cross-linking agents are reduced, and a silicone monomer-containing product with high silicone monomer purity can be easily obtained. Therefore, a polymer obtained by polymerizing a polymerizable composition containing a silicone monomer-containing material is particularly suitable as a raw material for ophthalmic lenses such as contact lenses, intraocular lenses, and artificial corneas.
以下、本発明を更に詳細に説明する。
本発明の製造方法は、エポキシシランと不飽和カルボン酸とを反応させる工程(a)を含む。
工程(a)に用いるエポキシシランとしては、式(１)で表されるエポキシシランが挙げられる。
Hereinafter, the present invention will be described in more detail.
The production method of the present invention includes a step (a) of reacting an epoxy silane with an unsaturated carboxylic acid.
As an epoxy silane used for a process (a), the epoxy silane represented by Formula (1) is mentioned.
Ａ1のシロキサニル基としては、式(４)で表される基が挙げられる。
式(４)において、Ｒ4〜Ｒ14はそれぞれが互いに独立に水素原子、炭素数１〜２０のアルキル基又は炭素数６〜２０のアリール基を表す。ｄは０〜２０の整数を表し、ａ、ｂ及びｃはそれぞれ互いに独立に０〜１０の整数を表す。ただし、a＋b＋c＝０の場合を除く。
Ｒ4〜Ｒ14における、炭素数１〜２０のアルキル基としては、例えば、メチル基、エチル基、イソプロピル基が挙げられ、炭素数６〜２０のアリール基としては、例えば、フェニル基が挙げられる。中でも、入手のし易さの理由からはメチル基であることが好ましい。
式(４)における、ｄは、入手のし易さの理由からは０であることが好ましい。ａ、ｂ及びｃは、入手のし易さの理由からは、ａ＝ｂ＝１、ｃ＝０であることが好ましい。
In the formula (4), R 4 to R 14 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. d represents an integer of 0 to 20, and a, b and c each independently represent an integer of 0 to 10. However, the case where a + b + c = 0 is excluded.
Examples of the alkyl group having 1 to 20 carbon atoms in R 4 to R 14 include a methyl group, an ethyl group, and an isopropyl group. Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group. . Among these, a methyl group is preferable for the reason of availability.
In formula (4), d is preferably 0 for reasons of availability. a, b and c are preferably a = b = 1 and c = 0 from the viewpoint of easy availability.
式(１)のＲ1〜Ｒ3において、炭素数１〜２０の置換基としては、例えば、メチル基、エチル基、イソプロピル基が挙げられる。一方、炭素数１〜２０の２価の置換基としては、例えば、−ＣＨ2−Ｏ−ＣＨ2−、−ＣＨ2−Ｏ−(ＣＨ2)3−が挙げられ、原料の入手のし易さの理由からは−ＣＨ2−Ｏ−(ＣＨ2)3−であることが好ましい。Ｒ1〜Ｒ3は、入手のし易さの理由からは水素原子であることが最も好ましい。
式(１)で表されるエポキシシランとしては、例えば、入手のし易さの理由からメチルジ(トリメチルシロキシ)シリルプロピルグリシドールが好ましく挙げられる。
In R 1 to R 3 of the formula (1), examples of the substituent having 1 to 20 carbon atoms include a methyl group, an ethyl group, and an isopropyl group. On the other hand, examples of the divalent substituent having 1 to 20 carbon atoms include —CH 2 —O—CH 2 — and —CH 2 —O— (CH 2 ) 3 —. For this reason, —CH 2 —O— (CH 2 ) 3 — is preferable. R 1 to R 3 are most preferably a hydrogen atom for reasons of availability.
As the epoxy silane represented by the formula (1), for example, methyldi (trimethylsiloxy) silylpropyl glycidol is preferable because of its availability.
工程(a)に用いる不飽和カルボン酸としては、不飽和脂肪族カルボン酸が好ましく、例えば、(メタ)アクリル酸、イタコン酸、フマル酸、マレイン酸、メサコン酸、オレイン酸、リノレン酸、ムコン酸、ケイ皮酸又はスチレンカルボン酸が挙げられ、なかでも、(メタ)アクリル酸、イタコン酸、メサコン酸、オレイン酸、リノレン酸、ムコン酸、ケイ皮酸又はスチレンカルボン酸が好ましく、原料の相溶性の理由からは(メタ)アクリル酸が最も好ましく挙げられる。 The unsaturated carboxylic acid used in the step (a) is preferably an unsaturated aliphatic carboxylic acid, for example, (meth) acrylic acid, itaconic acid, fumaric acid, maleic acid, mesaconic acid, oleic acid, linolenic acid, muconic acid. , Cinnamic acid or styrene carboxylic acid, among which (meth) acrylic acid, itaconic acid, mesaconic acid, oleic acid, linolenic acid, muconic acid, cinnamic acid or styrene carboxylic acid are preferred, and compatibility of raw materials For this reason, (meth) acrylic acid is most preferred.
工程(a)において、上記エポキシシランと不飽和カルボン酸との反応は、公知の方法で行なうことができ、反応条件も適宜選択することができる。例えば、反応温度は、通常７０〜１５０℃から選択でき、反応時間は、通常１５〜４８時間から選択できる。
工程(a)において得られる反応物は、シリコーン単量体と、シロキサン縮合オリゴマー型架橋剤等の副生成物との混合物である。
In the step (a), the reaction between the epoxy silane and the unsaturated carboxylic acid can be performed by a known method, and the reaction conditions can be appropriately selected. For example, the reaction temperature can usually be selected from 70 to 150 ° C., and the reaction time can be usually selected from 15 to 48 hours.
The reaction product obtained in step (a) is a mixture of a silicone monomer and a by-product such as a siloxane condensation oligomer type cross-linking agent.
前記シリコーン単量体としては、式(５)及び／又は式(５')で表されるシリコーン単量体が挙げられる。
式(５)及び式(５')において、Ａ1はシロキサニル基を示し、Ｘは炭素数１〜２０の２価の置換基を表す。Ｒ1〜Ｒ3はそれぞれ独立に、水素原子又は炭素数１〜２０の置換基を表す。これら各基は、上記式(１)のＡ1、Ｘ及びＲ1〜Ｒ3と同一である。
Ｙは、(メタ)アクリル酸残基、イタコン酸残基、フマル酸残基、マレイン酸残基、メサコン酸残基、オレイン酸残基、リノレン酸残基、ムコン酸残基、ケイ皮酸残基又はスチレンカルボン酸残基を示す。得られる単量体の相溶性の理由からはＹが(メタ)アクリル酸残基であることが好ましい。
式(５)又は式(５')で表されるシリコーン単量体の具体例としては、原料の入手のし易さ、単量体の相溶性の理由からは式(３)又は(３')で示されるシリコーン単量体が挙げられる。式中Meはメチル基を示す。
In Formula (5) and Formula (5 ′), A 1 represents a siloxanyl group, and X represents a divalent substituent having 1 to 20 carbon atoms. R < 1 > -R < 3 > represents a hydrogen atom or a C1-C20 substituent each independently. These groups are the same as A 1 , X and R 1 to R 3 in the above formula (1).
Y is (meth) acrylic acid residue, itaconic acid residue, fumaric acid residue, maleic acid residue, mesaconic acid residue, oleic acid residue, linolenic acid residue, muconic acid residue, cinnamic acid residue Group or styrene carboxylic acid residue. Y is preferably a (meth) acrylic acid residue for reasons of compatibility of the resulting monomer.
Specific examples of the silicone monomer represented by formula (5) or formula (5 ′) include formula (3) or (3 ′) from the viewpoint of easy availability of raw materials and monomer compatibility. ) Is a silicone monomer. In the formula, Me represents a methyl group.
前記副生成物であるシロキサン縮合オリゴマー型架橋剤としては、式(２)で表されるシロキサン縮合オリゴマー型架橋剤が挙げられる。
式(２)中、Ａ2及びＡ3はシロキサニル基を表し、Ｒ1〜Ｒ3はそれぞれ独立に水素原子又は炭素数１〜２０の置換基を表す。ｎは２〜１０の整数を表す。Ｘは置換されていてもよい炭素数１〜２０の２価の置換基を表す。Ｙは（メタ）アクリル酸残基、イタコン酸残基、フマル酸残基、マレイン酸残基、メサコン酸残基、オレイン酸残基、リノレン酸残基、ムコン酸残基、ケイ皮酸残基又はスチレンカルボン酸残基を示す。
式(２)のＲ1〜Ｒ3において、炭素数１〜２０の置換基としては、例えば、メチル基、エチル基、イソプロピル基が挙げられる。一方、炭素数１〜２０の２価の置換基としては、例えば、−ＣＨ2−Ｏ−ＣＨ2−、−ＣＨ2−Ｏ−(ＣＨ2)3−が挙げられ、原料の入手のし易さの理由からは−ＣＨ2−Ｏ−(ＣＨ2)3−であることが好ましい。Ｒ1〜Ｒ3は、入手のし易さの理由からは水素原子であることが最も好ましい。Ｙは、相溶性の理由から(メタ)アクリル酸残基であることが好ましい。
In Formula (2), A 2 and A 3 represent a siloxanyl group, and R 1 to R 3 each independently represent a hydrogen atom or a substituent having 1 to 20 carbon atoms. n represents an integer of 2 to 10. X represents an optionally substituted divalent substituent having 1 to 20 carbon atoms. Y is a (meth) acrylic acid residue, itaconic acid residue, fumaric acid residue, maleic acid residue, mesaconic acid residue, oleic acid residue, linolenic acid residue, muconic acid residue, cinnamic acid residue Or a styrenecarboxylic acid residue is shown.
In R 1 to R 3 of the formula (2), examples of the substituent having 1 to 20 carbon atoms include a methyl group, an ethyl group, and an isopropyl group. On the other hand, examples of the divalent substituent having 1 to 20 carbon atoms include —CH 2 —O—CH 2 — and —CH 2 —O— (CH 2 ) 3 —. For this reason, —CH 2 —O— (CH 2 ) 3 — is preferable. R 1 to R 3 are most preferably a hydrogen atom for reasons of availability. Y is preferably a (meth) acrylic acid residue for compatibility reasons.
式(２)において、Ａ2のシロキサニル基としては、例えば、式(６)で表される基が挙げられる。
式(２)において、Ａ3のシロキサニル基としては、例えば、式(７)で表される基が挙げられる。
式(２)で表されるシロキサン縮合オリゴマー型架橋剤としては、原料の入手のし易さの理由から式(８)で示される架橋剤が挙げられる。
本発明の製造方法では、工程(a)で得られた反応物を固体酸により処理する工程(b)を含む。
工程(b)に用いる固体酸とは、その表面が酸性を示す固体で、表面積を増やす観点からは細粒状、微粉状のものが好ましい。
該固体酸としては、例えば、アルミナと二酸化ケイ素との水和物、酸化マグネシウムと二酸化ケイ素との水和物が挙げられる。酸強度が高く、シロキサン縮合オリゴマー型架橋剤の吸着量が増加する理由からは、アルミナと二酸化ケイ素の水和物からなる固体酸であるのが好ましい。
The production method of the present invention includes a step (b) in which the reaction product obtained in the step (a) is treated with a solid acid.
The solid acid used in the step (b) is a solid whose surface is acidic, and is preferably in the form of fine particles or fine powder from the viewpoint of increasing the surface area.
Examples of the solid acid include hydrates of alumina and silicon dioxide, and hydrates of magnesium oxide and silicon dioxide. For the reason that the acid strength is high and the adsorption amount of the siloxane condensation oligomer type cross-linking agent is increased, a solid acid composed of a hydrate of alumina and silicon dioxide is preferable.
アルミナと二酸化ケイ素との水和物構造を有する固体酸の成分の組成は、固体酸１００重量部に対して、通常アルミナが１〜４０重量部、二酸化ケイ素が４０〜９０重量部、水が１〜３０重量部であり、好ましくはアルミナが２〜３０重量部、二酸化ケイ素が４５〜８０重量部、水が２〜２５重量部であり、最も好ましくはアルミナが５〜２０重量部、二酸化ケイ素が５０〜７０重量部、水が５〜２０重量部である。
このようなアルミナと二酸化ケイ素との水和物からなる固体酸は、細粒状、粉末状等の形状のものが良く、市販品としては、商品名「キョーワード７００」(協和化学工業株式会社製）、商品名「トミタＡＤ７００」(富田製薬株式会社製)等が挙げられる。
The composition of the solid acid component having a hydrate structure of alumina and silicon dioxide is usually 1 to 40 parts by weight of alumina, 40 to 90 parts by weight of silicon dioxide, and 1 of water to 100 parts by weight of the solid acid. To 30 parts by weight, preferably 2 to 30 parts by weight of alumina, 45 to 80 parts by weight of silicon dioxide, and 2 to 25 parts by weight of water, most preferably 5 to 20 parts by weight of alumina and silicon dioxide. 50 to 70 parts by weight and 5 to 20 parts by weight of water.
The solid acid composed of a hydrate of alumina and silicon dioxide is preferably in the form of fine particles, powders, etc., and as a commercial product, the trade name “KYOWARD 700” (manufactured by Kyowa Chemical Industry Co., Ltd.) ) And trade name “Tomita AD700” (manufactured by Tomita Pharmaceutical Co., Ltd.).
工程(b)において、固体酸による処理は、工程(a)で得られた反応物と固体酸とを接触させ、固体酸に、反応物中のシロキサン縮合オリゴマー型架橋剤を吸着させ、反応物中の該架橋剤を減少させ、反応物中のシリコーン単量体の純度を向上させる処理である。
処理形態としては、例えば、反応系に固体酸を加える方法、反応終了後に固体酸を加えて処理する方法が挙げられる。固体酸からの金属塩の溶出を抑制する理由からは反応後に加えるのがよい。反応終了後に処理する方法においてはバッチ式あるいは流通式により処理を行う方法が挙げられる。
ここでいうバッチ式とは、例えば、シリコーン単量体含有物あるいはシリコーン単量体含有物の溶液に、固体酸を添加処理した後、固体酸を濾別する処理方法である。また、流通式とは、例えば、固体酸を筒状の容器に充填した後、シリコーン単量体あるいはシリコーン単量体溶液を流通させる処理方法である。
In the step (b), the treatment with the solid acid is performed by bringing the reaction product obtained in the step (a) into contact with the solid acid, and adsorbing the siloxane condensation oligomer type cross-linking agent in the reaction product to the solid acid. This is a treatment for reducing the amount of the crosslinking agent therein and improving the purity of the silicone monomer in the reaction product.
Examples of the treatment form include a method of adding a solid acid to the reaction system and a method of adding a solid acid after the reaction is completed. For the reason of suppressing the elution of the metal salt from the solid acid, it should be added after the reaction. In the method of processing after completion of the reaction, a method of performing the processing by a batch method or a flow method can be mentioned.
The batch type referred to here is, for example, a treatment method in which a solid acid is added to a silicone monomer-containing material or a silicone monomer-containing solution, and then the solid acid is filtered off. The flow type is a treatment method in which, for example, a silicone monomer or a silicone monomer solution is circulated after filling a cylindrical container with a solid acid.
工程(b)において、固体酸の使用量は、工程(a)で得られる反応物１００重量部に対して、通常０．０１〜１０００重量部、好ましくは０．１〜５００重量部、最も好ましくは５〜２００重量部である。固体酸の使用量が、前記０．０１重量部未満の場合、シロキサン縮合オリゴマー型架橋剤に対する十分な吸着能が得られない恐れがある。また、固体酸の使用量が、前記１０００重量部を超える場合は、収率が低下し、シリコーン単量体も除去される恐れがある。 In step (b), the amount of solid acid used is usually 0.01 to 1000 parts by weight, preferably 0.1 to 500 parts by weight, most preferably 100 parts by weight of the reaction product obtained in step (a). Is 5 to 200 parts by weight. When the amount of the solid acid used is less than 0.01 parts by weight, there is a possibility that sufficient adsorption ability for the siloxane condensation oligomer type crosslinking agent cannot be obtained. Moreover, when the usage-amount of a solid acid exceeds 1000 weight part, a yield falls and there exists a possibility that a silicone monomer may also be removed.
前記固体酸による処理の温度は、特に限定されないが、−５０℃〜２５０℃が好ましく、−１０℃〜２００℃がより好ましく、−５℃〜１５０℃が最も好ましい。処理を行う際の温度が２５０℃を超える場合、シリコーン単量体の分解や重合といった安定性に問題が生じる恐れがある。一方、−５０℃未満の場合、固体酸による吸着効率が低下する恐れがある。
前記固体酸による処理の時間は、通常３０分〜７日間、好ましくは１時間〜３日間、より好ましくは１時間〜１日である。処理時間が７日間を超える場合、シロキサン縮合オリゴマー型架橋剤の固体酸への吸着量に変化がなくなるため非経済的である。一方、処理時間が、３０分未満の場合、精製不十分や再現性が得られない恐れがある。
The temperature of the treatment with the solid acid is not particularly limited, but is preferably −50 ° C. to 250 ° C., more preferably −10 ° C. to 200 ° C., and most preferably −5 ° C. to 150 ° C. When the temperature at the time of processing exceeds 250 ° C., there is a risk of problems in stability such as decomposition and polymerization of the silicone monomer. On the other hand, when the temperature is lower than −50 ° C., the adsorption efficiency by the solid acid may be lowered.
The treatment time with the solid acid is usually 30 minutes to 7 days, preferably 1 hour to 3 days, more preferably 1 hour to 1 day. When the treatment time exceeds 7 days, the amount of adsorption of the siloxane condensation oligomer type crosslinking agent on the solid acid is not changed, which is uneconomical. On the other hand, when the treatment time is less than 30 minutes, there is a possibility that insufficient purification or reproducibility cannot be obtained.
工程(b)において、固体酸による処理を行う際に、処理中におけるシリコーン単量体の重合を防止するために公知の重合禁止剤を用いてもよい。該重合禁止剤としては、例えば、ハイドロキノン、ハイドロキノンモノメチルエーテル、２，６−ジ−t−ブチル−４−メチルフェノール、N−ニトロソフェニルヒドロキシルアミンアルミニウム、１，１−ジフェニル−２−ピドリルピクリジルが挙げられる。
重合禁止剤を用いる場合の添加量は、工程(a)で得られる反応物に対して、通常１〜１００００ｐｐｍ、好ましくは１０〜２０００ｐｐｍ、より好ましくは１００〜１０００ｐｐｍである。該添加量が、１００００ｐｐｍを超える場合、重合禁止剤の除去が煩雑化する恐れがある。一方、１ｐｐｍ未満の場合、固体酸による処理中に重合が起こる可能性がある。
In the step (b), when the treatment with the solid acid is performed, a known polymerization inhibitor may be used in order to prevent the polymerization of the silicone monomer during the treatment. Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, 2,6-di-t-butyl-4-methylphenol, N-nitrosophenylhydroxylamine aluminum, 1,1-diphenyl-2-pyridylpicridyl. Is mentioned.
The addition amount in the case of using a polymerization inhibitor is usually 1 to 10000 ppm, preferably 10 to 2000 ppm, more preferably 100 to 1000 ppm with respect to the reaction product obtained in step (a). When the added amount exceeds 10,000 ppm, the removal of the polymerization inhibitor may become complicated. On the other hand, if it is less than 1 ppm, polymerization may occur during the treatment with the solid acid.
工程(b)においては、最終的に固体酸等を濾別して、目的のシリコーン単量体含有物を得ることができるが、該濾別による収量の確保のために、得られるシリコーン単量体含有物を有機溶媒で希釈することができる。上記バッチ式あるいは流通式による処理形態において用いる有機溶媒としては、例えば、ベンゼン、トルエン、キシレン等の各種芳香族炭化水素；ヘキサン、ヘプタン、オクタン、デカン、石油エーテル、ケロシン、リグロインパラフィン等の各種脂肪族炭化水素；塩化メチレン、クロロホルム、ジクロロエタン、トリクロロエタン、トリクロロエチレン等のハロゲン系溶媒、又はこれらの２種以上の混合溶媒が好ましく用いられる。
工程(b)における処理の際に、水あるいは水混和性の有機溶媒単独で処理した場合には、固体酸からの金属塩の溶出、あるいは親水性副生成物が十分に取り除けない恐れがある。
In step (b), the solid acid or the like can be finally filtered off to obtain the desired silicone monomer-containing material. In order to secure the yield by the filtering, the obtained silicone monomer-containing material can be obtained. The product can be diluted with an organic solvent. Examples of the organic solvent used in the batch-type or flow-type treatment forms include various aromatic hydrocarbons such as benzene, toluene, and xylene; various fats such as hexane, heptane, octane, decane, petroleum ether, kerosene, and ligroin paraffin. Group hydrocarbons: halogen solvents such as methylene chloride, chloroform, dichloroethane, trichloroethane, trichloroethylene, or a mixed solvent of two or more of these are preferably used.
When the treatment in step (b) is carried out with water or a water-miscible organic solvent alone, elution of the metal salt from the solid acid or the hydrophilic by-product may not be sufficiently removed.
工程(b)において、上記有機溶媒を用いる場合の使用量としては、例えば、工程(a)で得られる反応物１００重量部に対して、通常０．０１〜１００００重量部、好ましくは０．５〜５０００重量部、より好ましくは１〜１０００重量部である。有機溶媒の使用量が、上記１００００重量部を超える場合、希釈により固体酸による吸着効率が著しく低下する恐れがある。 In the step (b), the amount used when the organic solvent is used is, for example, generally 0.01 to 10,000 parts by weight, preferably 0.5 to 100 parts by weight of the reaction product obtained in the step (a). -5000 parts by weight, more preferably 1-1000 parts by weight. When the amount of the organic solvent used exceeds 10000 parts by weight, the adsorption efficiency by the solid acid may be significantly reduced by dilution.
本発明の製造方法において得られるシリコーン単量体含有物は、ゲル浸透クロマトグラフィーを用いて測定したときの式(Ａ)で算出されるシロキサン縮合オリゴマー型架橋剤の含有度(Ｑ１)が８％以下、好ましくは３〜８％で、且つガスクロマトグラフィーを用いて測定したときの式(Ｂ)で算出されるシリコーン単量体の含有度(Ｑ２)が８５％以上、好ましくは８５〜９０％である。
(Ｑ１)＝[Ｐ１／(Ｐ２−Ｐ３)]×１００(％)・・・（Ａ）
式(Ａ)において、Ｐ１はゲル浸透クロマトグラフィーを用いて測定したとき示差屈折率計で検出されるシロキサン縮合オリゴマー型架橋剤に由来するピークの総面積、Ｐ２はゲル浸透クロマトグラフィーを用いて測定したとき示差屈折率計で検出される全ピークの総面積、Ｐ３はゲル浸透クロマトグラフィーを用いて測定したとき示差屈折率計で検出される溶媒ピークの面積をそれぞれ示す。
(Ｑ２)＝[Ｐ４／(Ｐ５−Ｐ６)]×[１−(Ｑ１／１００)]×１００(％)・・・（Ｂ）
式(Ｂ)において、Ｑ１は式(Ａ)で算出されるシロキサン縮合オリゴマー型架橋剤の含有度、Ｐ４はガスクロマトグラフィーを用いて測定したときＦＩＤで検出されるシリコーン単量体に由来するピークの総面積、Ｐ５はガスクロマトグラフィーを用いて測定したときＦＩＤで検出される全ピークの総面積、Ｐ６はガスクロマトグラフィーを用いて測定したときＦＩＤで検出される溶媒ピークの面積をそれぞれ示す。
The silicone monomer-containing material obtained in the production method of the present invention has a siloxane condensation oligomer type crosslinking agent content (Q1) calculated by the formula (A) of 8% as measured using gel permeation chromatography. Hereinafter, the content (Q2) of the silicone monomer calculated by the formula (B) when measured by gas chromatography is preferably 3 to 8%, and is 85% or more, preferably 85 to 90%. It is.
(Q1) = [P1 / (P2-P3)] × 100 (%) (A)
In formula (A), P1 is the total area of peaks derived from the siloxane condensation oligomer type crosslinker detected by a differential refractometer when measured using gel permeation chromatography, and P2 is measured using gel permeation chromatography. The total area of all peaks detected by the differential refractometer, P3 indicates the area of the solvent peak detected by the differential refractometer when measured using gel permeation chromatography.
(Q2) = [P4 / (P5-P6)] × [1- (Q1 / 100)] × 100 (%) (B)
In the formula (B), Q1 is the content of the siloxane condensation oligomer type crosslinking agent calculated by the formula (A), and P4 is a peak derived from the silicone monomer detected by FID when measured using gas chromatography , P5 represents the total area of all peaks detected by FID when measured using gas chromatography, and P6 represents the area of the solvent peak detected by FID when measured using gas chromatography.
ゲル浸透クロマトグラフィーを用いてシロキサン縮合オリゴマー型架橋剤の含有度(Ｑ１)を測定するときの条件は、例えば、東ソー社製の商品名「東ソービルドアップＧＰＣシステム」を用い、カラムとして、ポリマーラボラトリー社製のＰＬゲル ３μｍ 商品名「ＭＩＸ−Ｅ」を用いた場合、カラム温度４０℃、サンプル濃度０．２重量％、注入量７０μｌ、溶離液ＴＨＦ、流速は０．８ｍｌ／分で行うことができ、検出器としては示差屈折率計の使用が好ましい。 The conditions for measuring the content (Q1) of the siloxane condensation oligomer type crosslinking agent using gel permeation chromatography are, for example, the product name “Tosoh Build-Up GPC System” manufactured by Tosoh Corporation, and the polymer laboratory as a column. When using a PL gel 3 μm product name “MIX-E”, a column temperature of 40 ° C., a sample concentration of 0.2 wt%, an injection volume of 70 μl, an eluent THF, and a flow rate of 0.8 ml / min. It is possible to use a differential refractometer as the detector.
ガスクロマトグラフィー分析を用いてシリコーン単量体の含有度(Ｑ２)を測定するときの条件は、例えば、ヒューレットパッカード社製の商品名「ＨＰ６８９０」、カラムとして、アジレント社製の商品名「ＨＰ−１」を用い、メチルシロキサン(０．５３μｍ×３０ｍ）、サンプル濃度１重量％アセトニトリル溶液、注入量２μｌ、昇温条件は２０℃／分の昇温速度で２０分間かけて８０℃から２５０℃まで昇温、スプリット比５：１、検出器ＦＩＤで行なうことが好ましい。 The conditions for measuring the content (Q2) of the silicone monomer using gas chromatography analysis are, for example, the product name “HP6890” manufactured by Hewlett-Packard Company, and the product name “HP- 1 ”, methylsiloxane (0.53 μm × 30 m), sample concentration 1 wt% acetonitrile solution, injection volume 2 μl, temperature rising condition from 80 ° C. to 250 ° C. over 20 minutes at a temperature rising rate of 20 ° C./min. It is preferable to carry out the temperature rise, split ratio 5: 1, and detector FID.
本発明の製造方法により得られたシリコーン単量体含有物を１０重量％以上含む重合性組成物を重合したポリマーは、例えば、コンタクトレンズ、眼内レンズ、人工角膜等の眼用レンズの原料として好意的に用いられる。
前記ポリマーの製造に用いる重合性組成物は、必要に応じて、例えば、メタクリル酸、アクリル酸、２−ヒドロキシエチルメタクリレート、Ｎ−ビニルピロリドン、Ｎ，Ｎ−ジメチルアクリルアミド、メチルメタクリレート、１，１，１−トリフルオロエチルメタクリレート、パーフルオロアルキルメタクリレート、シロキサニルメタクリレート、シロキサニルスチレン、エチレングリコールジメタクリレート、アリルメタクリレート、シリコンマクロマー又はこれらの２種以上の混合物等を含むことができる。
A polymer obtained by polymerizing a polymerizable composition containing 10% by weight or more of a silicone monomer-containing material obtained by the production method of the present invention is used as a raw material for ophthalmic lenses such as contact lenses, intraocular lenses, and artificial corneas. Used favorably.
The polymerizable composition used in the production of the polymer may be, for example, methacrylic acid, acrylic acid, 2-hydroxyethyl methacrylate, N-vinylpyrrolidone, N, N-dimethylacrylamide, methyl methacrylate, 1,1, 1-trifluoroethyl methacrylate, perfluoroalkyl methacrylate, siloxanyl methacrylate, siloxanyl styrene, ethylene glycol dimethacrylate, allyl methacrylate, silicon macromer or a mixture of two or more thereof may be included.
前記ポリマーを製造するための重合方法としては、例えば、熱重合、光重合が挙げられる。熱重合は、例えば、アゾ化合物或いは有機化酸化物存在下にオーブン中で、４０〜１５０℃で３０分〜２４時間重合させる方法により行うことができる。光重合は、例えば、光重合開始剤の存在下にＵＶランプ照射下で３０秒〜１時間重合させる方法により行うことができる。 Examples of the polymerization method for producing the polymer include thermal polymerization and photopolymerization. The thermal polymerization can be performed, for example, by a method of polymerizing in an oven in the presence of an azo compound or an organic oxide at 40 to 150 ° C. for 30 minutes to 24 hours. The photopolymerization can be performed, for example, by a method of polymerizing for 30 seconds to 1 hour under UV lamp irradiation in the presence of a photopolymerization initiator.
以下、実施例等を参照して、本発明を更に詳細に説明するが、本発明はこれらに限定されない。
尚、例中のシロキサン縮合オリゴマー型架橋剤の含有度(Ｑ１)、シリコーン単量体の含有度(Ｑ２)及び弾性率の測定、並びに透明性の評価は、以下の方法で行った。
ガスクロマトグラフィー(ＧＣ)分析による(Ｑ１)の測定
ヒューレットパッカード社製の商品名「ＨＰ６８９０」、カラムとして、アジレント社製の商品名「ＨＰ−１」を用い、メチルシロキサン(０．５３μｍ×３０ｍ）、サンプル濃度１重量％アセトニトリル溶液、注入量２μｌ、昇温条件は２０℃／分の昇温速度で２０分間かけて８０℃から２５０℃まで昇温し、スプリット比５：１分離して、検出器ＦＩＤにより検出を行った。この際の、式(３)及び／又は式(３')で表される成分の保持時間は約１６分である。尚、式(８)で表されるシロキサン縮合オリゴマー型架橋剤は、このＧＣ分析では計測不可能である。
Hereinafter, the present invention will be described in more detail with reference to examples and the like, but the present invention is not limited thereto.
In the examples, the content (Q1) of the siloxane condensation oligomer type cross-linking agent, the content (Q2) of the silicone monomer and the elastic modulus, and the evaluation of the transparency were evaluated by the following methods.
Measurement of (Q1) by Gas Chromatography (GC) Analysis Using a product name “HP6890” manufactured by Hewlett-Packard Co., and a product name “HP-1” manufactured by Agilent as a column, methylsiloxane (0.53 μm × 30 m) , Sample concentration 1 wt% acetonitrile solution, injection volume 2 μl, temperature increase condition is 20 ° C./min. Temperature increase rate from 80 ° C. to 250 ° C. over 20 minutes, split ratio 5: 1 separation, detection Detection was performed with a device FID. At this time, the retention time of the component represented by the formula (3) and / or the formula (3 ′) is about 16 minutes. In addition, the siloxane condensation oligomer type crosslinking agent represented by the formula (8) cannot be measured by this GC analysis.
ゲル浸透クロマトグラフィー(ＧＰＣ)分析による(Ｑ２)の測定
東ソー社製の商品名「東ソービルドアップＧＰＣシステム」を用い、カラムとして、ポリマーラボラトリー社製のＰＬゲル ３μｍ 商品名「ＭＩＸ−Ｅ」を用い、カラム温度４０℃、サンプル濃度０．２重量％、注入量７０μｌ、溶離液ＴＨＦ、流速は０．８ｍｌ／分で溶出し、示差屈折率計(ＲＩ)で検出を行った。この条件でＧＰＣ分析を行うと、式（３）及び／又は式(３')で表されるシリコーン単量体を含む、ＧＣ分析により確認される化合物が約１０分に重り１つのピークとして確認される。また、式(８)で表されるシロキサン縮合オリゴマー型架橋剤のピークが約８．５分〜９．５分に現れる。
Measurement of (Q2) by Gel Permeation Chromatography (GPC) Analysis Using “Tosoh Buildup GPC System” manufactured by Tosoh Corporation, and using PL Gel 3 μm manufactured by Polymer Laboratories as “Column” as the column “MIX-E” The column temperature was 40 ° C., the sample concentration was 0.2% by weight, the injection amount was 70 μl, the eluent THF, the flow rate was 0.8 ml / min, and detection was performed with a differential refractometer (RI). When GPC analysis is performed under these conditions, the compound confirmed by GC analysis including the silicone monomer represented by formula (3) and / or formula (3 ′) is weighted in about 10 minutes and confirmed as one peak. Is done. Moreover, the peak of the siloxane condensation oligomer type crosslinking agent represented by the formula (8) appears at about 8.5 minutes to 9.5 minutes.
弾性率の測定
含水シートから長さ１５ｍｍ、幅２ｍｍの短冊２０枚を切り出し、引張試験機(山電株式会社製、商品名「レオナーＲｅ−３３０５」)を用いて、含水した短冊の弾性率を測定した。
透明性の評価
含水シートを目視により透明、不透明の判断を行った。
Measurement of elastic modulus Twenty strips with a length of 15 mm and a width of 2 mm were cut out from the water-containing sheet, and the elastic modulus of the water-containing strip was determined using a tensile tester (trade name “Leoner Re-3305” manufactured by Yamaden Co., Ltd.). It was measured.
Evaluation of transparency The water-containing sheet was visually judged to be transparent or opaque.
実施例１
１００ｍＬのナスフラスコに式(９)で表されるエポキシシラン１９．６ｍｇ(５８ｍｍｏｌ)、メタクリル酸１０ｇ(１１６ｍｍｏｌ)、メタクリル酸ナトリウム１．５ｇ(１４ｍｍｏｌ)、ｐ−メトキシフェノール１４ｍｇ(０．１２ｍｏｌ)を加え、空気雰囲気下で８５℃に加熱し磁気攪拌した。ＧＣ分析により式(９)で表されるエポキシシランの面積が０．３％以下になるのを確認した後、反応混合液を放冷し、室温とした。反応混合液にヘキサン１１０ｍＬを加えて希釈し、５％リン酸水素２カリウム水溶液３０ｍＬで７回、１％硫酸ナトリウム水溶液３０ｍＬで７回、有機層を洗浄・抽出した。有機層に硫酸ナトリウムを加えて乾燥し、減圧濃縮した。得られたシリコーン単量体含有粗生成物中のシロキサン縮合オリゴマー型架橋剤の含有度(Ｑ１)及びシリコーン単量体の含有度(Ｑ２)を測定し、シリコーン単量体の純度を確認した。この結果を表１の粗生成物の項に示す。
In a 100 mL eggplant flask, 19.6 mg (58 mmol) of epoxysilane represented by the formula (9), 10 g (116 mmol) of methacrylic acid, 1.5 g (14 mmol) of sodium methacrylate, and 14 mg (0.12 mol) of p-methoxyphenol were added. In addition, the mixture was heated to 85 ° C. in an air atmosphere and magnetically stirred. After confirming that the area of the epoxysilane represented by the formula (9) was 0.3% or less by GC analysis, the reaction mixture was allowed to cool to room temperature. The reaction mixture was diluted by adding 110 mL of hexane, and the organic layer was washed and extracted 7 times with 30 mL of 5% aqueous 2 potassium hydrogen phosphate solution and 7 times with 30 mL of 1% aqueous sodium sulfate solution. The organic layer was dried by adding sodium sulfate and concentrated under reduced pressure. The content (Q1) of the siloxane condensation oligomer type crosslinking agent and the content (Q2) of the silicone monomer in the obtained silicone monomer-containing crude product were measured to confirm the purity of the silicone monomer. The results are shown in the section of crude product in Table 1.
得られた粗生成物３ｇをトルエン１３ｍｌに溶解し、商品名「キョーワード７００」(協和化学工業社製：アルミナと二酸化ケイ素との水和物構造からなる固体酸)１．２ｇを加え、室温で１時間攪拌した。１時間後、ろ過して固体酸を除去し、シリコーン単量体含有物を得た。得られたシリコーン単量体含有物について上記ＧＣ及びＧＰＣ分析を行って(Ｑ１)及び(Ｑ２)を測定した。結果を表１に示す。 3 g of the obtained crude product was dissolved in 13 ml of toluene, 1.2 g of trade name “KYOWARD 700” (manufactured by Kyowa Chemical Industry Co., Ltd .: solid acid consisting of hydrate structure of alumina and silicon dioxide) was added, and room temperature was added. For 1 hour. After 1 hour, the solid acid was removed by filtration to obtain a silicone monomer-containing material. The obtained silicone monomer-containing material was subjected to the above GC and GPC analysis, and (Q1) and (Q2) were measured. The results are shown in Table 1.
比較例１〜６
実施例１において、商品名「キョーワード７００」(協和化学工業社製：アルミナと二酸化ケイ素との水和物構造からなる固体酸)の代わりに、活性炭(比較例１)、シリカゲル(和光純薬工業社製：商品名「ワコーシル C−３００」、球状、粒径４０〜８０μｍ)(比較例２)、合成ゼオライトA−３粉末(和光純薬工業社製の試薬)(比較例３)、活性白土(キシダ化学社製の試薬)(比較例４)、商品名「MP Alumina N-SuperＩ」(ＭＰＢ社製：中性アルミナ)(比較例５)又は商品名「ICN Alumina B-SuperＩ(ＭＰＢ社製：塩基性アルミナ)(比較例６)を用いて同様の処理を行い、シリコーン単量体含有物を得、同様にＧＣ及びＧＰＣ分析を行って(Ｑ１)及び(Ｑ２)を測定した。結果を表１に示す。
Comparative Examples 1-6
In Example 1, instead of trade name “KYOWARD 700” (manufactured by Kyowa Chemical Industry Co., Ltd .: solid acid having a hydrate structure of alumina and silicon dioxide), activated carbon (Comparative Example 1), silica gel (Wako Pure Chemical Industries, Ltd.) Manufactured by Kogyo Co., Ltd .: trade name “Wakosil C-300”, spherical, particle size 40-80 μm (Comparative Example 2), synthetic zeolite A-3 powder (Reagent manufactured by Wako Pure Chemical Industries, Ltd.) (Comparative Example 3), activity White clay (reagent manufactured by Kishida Chemical Co., Ltd.) (Comparative Example 4), trade name “MP Alumina N-SuperI” (manufactured by MPB: neutral alumina) (Comparative Example 5) or trade name “ICN Alumina B-SuperI (MPB Company) (Product: Basic Alumina) (Comparative Example 6) was subjected to the same treatment to obtain a silicone monomer-containing product, and GC and GPC analyzes were conducted in the same manner to measure (Q1) and (Q2). Is shown in Table 1.
実施例２、３及び比較例７
表２に示す組成の、実施例１で製造したシリコーン単量体含有物、３−トリス(トリメチルシリル)プロピル(メタ)アクリレート(ＴＲＩＳ)、２−ヒドロキシエチルメタクリレート(ＨＥＭＡ)、エチレングリコールジメタクリレート(ＥＤＭＡ)及びアゾビスイソブチロニトリル(ＡＩＢＮ)を混合溶解した。得られた溶液を、厚さ０．２ｍｍのテフロン（登録商標）シートをスペーサーとしてガラス板とポリエステルフィルムの間に挟みこんだセル内に流し込み、オーブン内の窒素置換を行った後、６５℃で３時間、８０℃で８時間加熱した。加熱終了後、硬化シートを型から取り出し大量のエチルアルコールに１２時間浸漬し、更に大量のイオン交換水に１２時間浸漬して含水シートを調製した。得られたシートから所定の形状のテストピースを作製し、弾性率の測定及び透明性の評価を行った。結果を表２に示す。
Examples 2 and 3 and Comparative Example 7
Silicone monomer-containing material prepared in Example 1 having the composition shown in Table 2, 3-tris (trimethylsilyl) propyl (meth) acrylate (TRIS), 2-hydroxyethyl methacrylate (HEMA), ethylene glycol dimethacrylate (EDMA) ) And azobisisobutyronitrile (AIBN) were mixed and dissolved. The obtained solution was poured into a cell sandwiched between a glass plate and a polyester film using a Teflon (registered trademark) sheet having a thickness of 0.2 mm as a spacer, and after substituting with nitrogen in the oven, at 65 ° C. Heated at 80 ° C. for 3 hours for 3 hours. After heating, the cured sheet was taken out of the mold and immersed in a large amount of ethyl alcohol for 12 hours, and further immersed in a large amount of ion-exchanged water for 12 hours to prepare a water-containing sheet. A test piece having a predetermined shape was produced from the obtained sheet, and the elastic modulus was measured and the transparency was evaluated. The results are shown in Table 2.
比較例８及び９
表２に示す組成の溶液を用いた以外は、実施例２と同様に含水シートを調製した。但し、比較例８ではシリコーン単量体含有物として、実施例１で製造したシリコーン単量体含有物の代わりに、比較例１で製造したシリコーン単量体含有物を用い、比較例９ではシリコーン単量体含有物を配合しなかった。得られたシートから所定の形状のテストピースを作製し、弾性率の測定及び透明性の評価を行った。結果を表２に示す。
尚、比較例８のシートの弾性率は１．５ＭＰａであったが、この弾性率では、例えば、このポリマーをソフトコンタクトレンズとして用いる場合、非常に硬いレンズとなり、装用した際の異物感や破損等が生じる問題がある。また、比較例９のシートの弾性率及び透明性は、実施例２及び３と同程度であったが、このポリマーは、シリコーン単量体が含まれていないので、ソフトコンタクトレンズとした際に酸素透過性が実施例２及び３のポリマーに比して著しく低下する。
Comparative Examples 8 and 9
A water-containing sheet was prepared in the same manner as in Example 2 except that the solution having the composition shown in Table 2 was used. However, in Comparative Example 8, the silicone monomer-containing material produced in Comparative Example 1 was used in place of the silicone monomer-containing material produced in Example 1 as the silicone monomer-containing material. No monomer-containing material was blended. A test piece having a predetermined shape was produced from the obtained sheet, and the elastic modulus was measured and the transparency was evaluated. The results are shown in Table 2.
In addition, although the elastic modulus of the sheet of Comparative Example 8 was 1.5 MPa, with this elastic modulus, for example, when this polymer is used as a soft contact lens, it becomes a very hard lens and feels foreign matter or breakage when worn. There is a problem that causes. Further, the elastic modulus and transparency of the sheet of Comparative Example 9 were similar to those of Examples 2 and 3, but since this polymer does not contain a silicone monomer, it was used as a soft contact lens. Oxygen permeability is significantly reduced compared to the polymers of Examples 2 and 3.
Claims (4)
ゲル浸透クロマトグラフィーを用いて測定したときの式(Ａ)で算出されるシロキサン縮合オリゴマー型架橋剤の含有度(Ｑ１)が８％以下で、且つガスクロマトグラフィーを用いて測定したときの式(Ｂ)で算出されるシリコーン単量体の含有度(Ｑ２)が８５％以上であるシリコーン単量体含有物の製造方法。
(Ｑ１)＝[Ｐ１／(Ｐ２−Ｐ３)]×１００(％)・・・（Ａ）
(式(Ａ)において、Ｐ１はゲル浸透クロマトグラフィーを用いて測定したとき示差屈折率計で検出されるシロキサン縮合オリゴマー型架橋剤に由来するピークの総面積、Ｐ２はゲル浸透クロマトグラフィーを用いて測定したとき示差屈折率計で検出される全ピークの総面積、Ｐ３はゲル浸透クロマトグラフィーを用いて測定したとき示差屈折率計で検出される溶媒ピークの面積をそれぞれ示す。)
(Ｑ２)＝[Ｐ４／(Ｐ５−Ｐ６)]×[１−(Ｑ１／１００)]×１００(％)・・・（Ｂ）
(式(Ｂ)において、Ｑ１は式(Ａ)で算出されるシロキサン縮合オリゴマー型架橋剤の含有度、Ｐ４はガスクロマトグラフィーを用いて測定したとき水素炎イオン化法(ＦＩＤ)で検出されるシリコーン単量体に由来するピークの総面積、Ｐ５はガスクロマトグラフィーを用いて測定したときＦＩＤで検出される全ピークの総面積、Ｐ６はガスクロマトグラフィーを用いて測定したときＦＩＤで検出される溶媒ピークの面積をそれぞれ示す。) A step (a) of reacting an epoxysilane with an unsaturated carboxylic acid, and a step (b) of treating the resulting reaction product with a solid acid.
The content (Q1) of the siloxane condensation oligomer type crosslinking agent calculated by the formula (A) when measured using gel permeation chromatography is 8% or less, and the formula when measured using gas chromatography ( A method for producing a silicone monomer-containing product, wherein the content (Q2) of the silicone monomer calculated in B) is 85% or more.
(Q1) = [P1 / (P2-P3)] × 100 (%) (A)
(In Formula (A), P1 is the total area of peaks derived from the siloxane condensation oligomer type cross-linking agent detected by a differential refractometer when measured using gel permeation chromatography, and P2 is obtained using gel permeation chromatography. (The total area of all peaks detected by the differential refractometer when measured, and P3 indicates the area of the solvent peak detected by the differential refractometer when measured using gel permeation chromatography.)
(Q2) = [P4 / (P5-P6)] × [1- (Q1 / 100)] × 100 (%) (B)
(In the formula (B), Q1 is the content of the siloxane condensation oligomer type cross-linking agent calculated by the formula (A), and P4 is a silicone detected by the flame ionization method (FID) when measured using gas chromatography. Total area of peaks derived from monomers, P5 is the total area of all peaks detected by FID when measured using gas chromatography, and P6 is a solvent detected by FID when measured using gas chromatography (The area of each peak is shown.)
不飽和カルボン酸が、(メタ)アクリル酸、イタコン酸、フマル酸、マレイン酸、メサコン酸、オレイン酸、リノレン酸、ムコン酸、ケイ皮酸又はスチレンカルボン酸である請求項１又は２記載の製造方法。 Epoxysilane is represented by the formula (1),
The production according to claim 1 or 2, wherein the unsaturated carboxylic acid is (meth) acrylic acid, itaconic acid, fumaric acid, maleic acid, mesaconic acid, oleic acid, linolenic acid, muconic acid, cinnamic acid or styrene carboxylic acid. Method.
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| WO2005005444A1 (en) * | 2003-06-30 | 2005-01-20 | Johnson & Johnson Vision Care, Inc. | Process for the production of bis(trimethylsilyloxy)silylalkylglycerol methacrylates |
| JP2005272459A (en) * | 2004-02-27 | 2005-10-06 | Toray Ind Inc | Silicone compound and its production method |
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| WO2005005444A1 (en) * | 2003-06-30 | 2005-01-20 | Johnson & Johnson Vision Care, Inc. | Process for the production of bis(trimethylsilyloxy)silylalkylglycerol methacrylates |
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| US8846843B2 (en) | 2009-09-02 | 2014-09-30 | Momentive Performance Materials Inc. | Silicone modified fatty acids, method of preparation and usage thereof |
| JP2016153390A (en) * | 2009-09-02 | 2016-08-25 | モメンティブ パフォーマンス マテリアルズ インコーポレイテッド | Silicone modified fatty acids, method of preparation and usage thereof |
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