JP5453085B2 - Method for producing reaction product for producing plastic lens, method for producing plastic lens, and plastic lens - Google Patents
Method for producing reaction product for producing plastic lens, method for producing plastic lens, and plastic lens Download PDFInfo
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- JP5453085B2 JP5453085B2 JP2009512905A JP2009512905A JP5453085B2 JP 5453085 B2 JP5453085 B2 JP 5453085B2 JP 2009512905 A JP2009512905 A JP 2009512905A JP 2009512905 A JP2009512905 A JP 2009512905A JP 5453085 B2 JP5453085 B2 JP 5453085B2
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- Prior art keywords
- plastic lens
- producing
- reaction
- reaction product
- lens
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- 239000004033 plastic Substances 0.000 title claims description 142
- 239000007795 chemical reaction product Substances 0.000 title claims description 84
- 238000004519 manufacturing process Methods 0.000 title claims description 79
- 238000006243 chemical reaction Methods 0.000 claims description 100
- 150000001875 compounds Chemical class 0.000 claims description 46
- 229910052717 sulfur Inorganic materials 0.000 claims description 46
- 239000011593 sulfur Substances 0.000 claims description 44
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 43
- 239000002994 raw material Substances 0.000 claims description 42
- 239000000203 mixture Substances 0.000 claims description 39
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 31
- 239000001301 oxygen Substances 0.000 claims description 31
- 229910052760 oxygen Inorganic materials 0.000 claims description 31
- 229920006295 polythiol Polymers 0.000 claims description 23
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 238000004073 vulcanization Methods 0.000 description 52
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 239000007789 gas Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 238000003756 stirring Methods 0.000 description 12
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 8
- -1 phosphate ester Chemical class 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000004040 coloring Methods 0.000 description 6
- PKKGKUDPKRTKLJ-UHFFFAOYSA-L dichloro(dimethyl)stannane Chemical compound C[Sn](C)(Cl)Cl PKKGKUDPKRTKLJ-UHFFFAOYSA-L 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000004383 yellowing Methods 0.000 description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 5
- 238000007872 degassing Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000006082 mold release agent Substances 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 239000001294 propane Substances 0.000 description 5
- 238000009849 vacuum degassing Methods 0.000 description 5
- MLGITEWCALEOOJ-UHFFFAOYSA-N 2-(thiiran-2-ylmethylsulfanylmethyl)thiirane Chemical compound C1SC1CSCC1CS1 MLGITEWCALEOOJ-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- WKTYGZBVSZFPPF-UHFFFAOYSA-N 2,5-bis(2-methylthiiran-2-yl)-1,4-dithiane Chemical compound CC1(CS1)C1SCC(SC1)C1(C)CS1 WKTYGZBVSZFPPF-UHFFFAOYSA-N 0.000 description 3
- JRKRMWWBDZSDMT-UHFFFAOYSA-N 2-[(thiiran-2-ylmethyldisulfanyl)methyl]thiirane Chemical compound C1SC1CSSCC1CS1 JRKRMWWBDZSDMT-UHFFFAOYSA-N 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- LOZWAPSEEHRYPG-UHFFFAOYSA-N dithiane Natural products C1CSCCS1 LOZWAPSEEHRYPG-UHFFFAOYSA-N 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- PMRYVIKBURPHAH-UHFFFAOYSA-N methimazole Chemical compound CN1C=CNC1=S PMRYVIKBURPHAH-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000004434 sulfur atom Chemical group 0.000 description 3
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 3
- CXWGKAYMVASWDQ-UHFFFAOYSA-N 1,2-dithiane Chemical group C1CCSSC1 CXWGKAYMVASWDQ-UHFFFAOYSA-N 0.000 description 2
- MTZVWTOVHGKLOX-UHFFFAOYSA-N 2,2-bis(sulfanylmethyl)propane-1,3-dithiol Chemical compound SCC(CS)(CS)CS MTZVWTOVHGKLOX-UHFFFAOYSA-N 0.000 description 2
- CEUQYYYUSUCFKP-UHFFFAOYSA-N 2,3-bis(2-sulfanylethylsulfanyl)propane-1-thiol Chemical compound SCCSCC(CS)SCCS CEUQYYYUSUCFKP-UHFFFAOYSA-N 0.000 description 2
- MXZROAOUCUVNHX-UHFFFAOYSA-N 2-Aminopropanol Chemical compound CCC(N)O MXZROAOUCUVNHX-UHFFFAOYSA-N 0.000 description 2
- CSYORQWMUDZLND-UHFFFAOYSA-N 2-methyl-2-[(2-methylthiiran-2-yl)methyl]thiirane Chemical compound CC1(CS1)CC1(C)CS1 CSYORQWMUDZLND-UHFFFAOYSA-N 0.000 description 2
- YNXYMXGFVKQWAO-UHFFFAOYSA-N 2-methyl-2-[2-(2-methylthiiran-2-yl)ethyl]thiirane Chemical compound CC1(CS1)CCC1(C)CS1 YNXYMXGFVKQWAO-UHFFFAOYSA-N 0.000 description 2
- XQNSEXCYPXLFPH-UHFFFAOYSA-N 2-methyl-2-[3-(2-methylthiiran-2-yl)propyl]thiirane Chemical compound CC1(CS1)CCCC1(C)CS1 XQNSEXCYPXLFPH-UHFFFAOYSA-N 0.000 description 2
- OTGSZJOAKZWKHH-UHFFFAOYSA-N 2-methyl-2-[4-(2-methylthiiran-2-yl)cyclohexyl]thiirane Chemical compound CC1(CS1)C1CCC(CC1)C1(C)CS1 OTGSZJOAKZWKHH-UHFFFAOYSA-N 0.000 description 2
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- RGDDNZPCGLMOMQ-UHFFFAOYSA-N [2-(sulfanylmethyl)-1,4-dithian-2-yl]methanethiol Chemical compound SCC1(CS)CSCCS1 RGDDNZPCGLMOMQ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- INBDPOJZYZJUDA-UHFFFAOYSA-N methanedithiol Chemical compound SCS INBDPOJZYZJUDA-UHFFFAOYSA-N 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001226 reprecipitation Methods 0.000 description 2
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 2
- NNJRPZZMNBNRFJ-UHFFFAOYSA-N (3-ethoxy-3-oxo-2-phenylpropyl)azanium;chloride Chemical compound Cl.CCOC(=O)C(CN)C1=CC=CC=C1 NNJRPZZMNBNRFJ-UHFFFAOYSA-N 0.000 description 1
- DHBXNPKRAUYBTH-UHFFFAOYSA-N 1,1-ethanedithiol Chemical compound CC(S)S DHBXNPKRAUYBTH-UHFFFAOYSA-N 0.000 description 1
- OPNUROKCUBTKLF-UHFFFAOYSA-N 1,2-bis(2-methylphenyl)guanidine Chemical compound CC1=CC=CC=C1N\C(N)=N\C1=CC=CC=C1C OPNUROKCUBTKLF-UHFFFAOYSA-N 0.000 description 1
- BIGYLAKFCGVRAN-UHFFFAOYSA-N 1,3,4-thiadiazolidine-2,5-dithione Chemical compound S=C1NNC(=S)S1 BIGYLAKFCGVRAN-UHFFFAOYSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- OXFSTTJBVAAALW-UHFFFAOYSA-N 1,3-dihydroimidazole-2-thione Chemical compound SC1=NC=CN1 OXFSTTJBVAAALW-UHFFFAOYSA-N 0.000 description 1
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- JFLJVRLBIZHFSU-UHFFFAOYSA-N 1,4-dithiane-2,5-dithiol Chemical compound SC1CSC(S)CS1 JFLJVRLBIZHFSU-UHFFFAOYSA-N 0.000 description 1
- SRZXCOWFGPICGA-UHFFFAOYSA-N 1,6-Hexanedithiol Chemical compound SCCCCCCS SRZXCOWFGPICGA-UHFFFAOYSA-N 0.000 description 1
- FTMOZBNCMQDACZ-UHFFFAOYSA-N 1-(2-sulfanylethylsulfanyl)propane-1,3-dithiol Chemical compound SCCSC(S)CCS FTMOZBNCMQDACZ-UHFFFAOYSA-N 0.000 description 1
- NPEIGRBGMUJNFE-UHFFFAOYSA-N 1-aminohexan-1-ol Chemical compound CCCCCC(N)O NPEIGRBGMUJNFE-UHFFFAOYSA-N 0.000 description 1
- WGAOZGUUHIBABN-UHFFFAOYSA-N 1-aminopentan-1-ol Chemical compound CCCCC(N)O WGAOZGUUHIBABN-UHFFFAOYSA-N 0.000 description 1
- KKKDZZRICRFGSD-UHFFFAOYSA-N 1-benzylimidazole Chemical compound C1=CN=CN1CC1=CC=CC=C1 KKKDZZRICRFGSD-UHFFFAOYSA-N 0.000 description 1
- NPFLRDFQLIRHMC-UHFFFAOYSA-N 1-butylimidazole;1h-imidazole Chemical class C1=CNC=N1.CCCCN1C=CN=C1 NPFLRDFQLIRHMC-UHFFFAOYSA-N 0.000 description 1
- IWDFHWZHHOSSGR-UHFFFAOYSA-N 1-ethylimidazole Chemical compound CCN1C=CN=C1 IWDFHWZHHOSSGR-UHFFFAOYSA-N 0.000 description 1
- JEARXBADBBQFGS-UHFFFAOYSA-N 1-methoxypropane-1,2-dithiol Chemical compound COC(S)C(C)S JEARXBADBBQFGS-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- DLLOHKQWGFKFLO-UHFFFAOYSA-N 1-methylcyclohexane-1,2-dithiol Chemical compound CC1(S)CCCCC1S DLLOHKQWGFKFLO-UHFFFAOYSA-N 0.000 description 1
- SEULWJSKCVACTH-UHFFFAOYSA-N 1-phenylimidazole Chemical compound C1=NC=CN1C1=CC=CC=C1 SEULWJSKCVACTH-UHFFFAOYSA-N 0.000 description 1
- IMQFZQVZKBIPCQ-UHFFFAOYSA-N 2,2-bis(3-sulfanylpropanoyloxymethyl)butyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(CC)(COC(=O)CCS)COC(=O)CCS IMQFZQVZKBIPCQ-UHFFFAOYSA-N 0.000 description 1
- SGLYOTGYKDFSSC-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-dithiol Chemical compound SCC(C)(C)CS SGLYOTGYKDFSSC-UHFFFAOYSA-N 0.000 description 1
- FQZMBPXSKSSKCP-UHFFFAOYSA-N 2,3-bis(sulfanyl)propyl 2-sulfanylacetate Chemical compound SCC(S)COC(=O)CS FQZMBPXSKSSKCP-UHFFFAOYSA-N 0.000 description 1
- WXDDGAZCUPULGL-UHFFFAOYSA-N 2,3-bis(sulfanylmethylsulfanyl)propylsulfanylmethanethiol Chemical compound SCSCC(SCS)CSCS WXDDGAZCUPULGL-UHFFFAOYSA-N 0.000 description 1
- LOIPCSUANZPEME-UHFFFAOYSA-N 2,5-bis(2-propylsulfanylthiiran-2-yl)-1,4-dithiane Chemical compound C1SC(C2(SC2)SCCC)CSC1C1(SCCC)CS1 LOIPCSUANZPEME-UHFFFAOYSA-N 0.000 description 1
- SDMYZIQYGCCLHR-UHFFFAOYSA-N 2,5-bis(thiiran-2-ylmethylsulfanylmethyl)-1,4-dithiane Chemical compound C1SC1CSCC(SC1)CSC1CSCC1CS1 SDMYZIQYGCCLHR-UHFFFAOYSA-N 0.000 description 1
- PSYGHMBJXWRQFD-UHFFFAOYSA-N 2-(2-sulfanylacetyl)oxyethyl 2-sulfanylacetate Chemical compound SCC(=O)OCCOC(=O)CS PSYGHMBJXWRQFD-UHFFFAOYSA-N 0.000 description 1
- CNDCQWGRLNGNNO-UHFFFAOYSA-N 2-(2-sulfanylethoxy)ethanethiol Chemical compound SCCOCCS CNDCQWGRLNGNNO-UHFFFAOYSA-N 0.000 description 1
- SPAAESPYCDSRIW-UHFFFAOYSA-N 2-(2-sulfanylethyldisulfanyl)ethanethiol Chemical compound SCCSSCCS SPAAESPYCDSRIW-UHFFFAOYSA-N 0.000 description 1
- KSJBMDCFYZKAFH-UHFFFAOYSA-N 2-(2-sulfanylethylsulfanyl)ethanethiol Chemical compound SCCSCCS KSJBMDCFYZKAFH-UHFFFAOYSA-N 0.000 description 1
- RDNOXVONDLWZCI-UHFFFAOYSA-N 2-(2-sulfanylethylsulfanylmethylsulfanyl)ethanethiol Chemical compound SCCSCSCCS RDNOXVONDLWZCI-UHFFFAOYSA-N 0.000 description 1
- HAQZWTGSNCDKTK-UHFFFAOYSA-N 2-(3-sulfanylpropanoyloxy)ethyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCCOC(=O)CCS HAQZWTGSNCDKTK-UHFFFAOYSA-N 0.000 description 1
- UREAOTFLSRRYKQ-UHFFFAOYSA-N 2-(sulfanylmethylsulfanyl)ethylsulfanylmethanethiol Chemical compound SCSCCSCS UREAOTFLSRRYKQ-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- LOSJLAVLYJUGJO-UHFFFAOYSA-N 2-[1,3-bis(sulfanyl)propan-2-ylsulfanyl]propane-1,3-dithiol Chemical compound SCC(CS)SC(CS)CS LOSJLAVLYJUGJO-UHFFFAOYSA-N 0.000 description 1
- QTEWPHJCEXIMRJ-UHFFFAOYSA-N 2-[2,3-bis(2-sulfanylethylsulfanyl)propylsulfanyl]ethanethiol Chemical compound SCCSCC(SCCS)CSCCS QTEWPHJCEXIMRJ-UHFFFAOYSA-N 0.000 description 1
- ISGHUYCZFWLBRU-UHFFFAOYSA-N 2-[2-(2-sulfanylacetyl)oxyethoxy]ethyl 2-sulfanylacetate Chemical compound SCC(=O)OCCOCCOC(=O)CS ISGHUYCZFWLBRU-UHFFFAOYSA-N 0.000 description 1
- ZQLHFUHXRDOCBC-UHFFFAOYSA-N 2-[2-(3-sulfanylpropanoyloxy)ethoxy]ethyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCCOCCOC(=O)CCS ZQLHFUHXRDOCBC-UHFFFAOYSA-N 0.000 description 1
- DAUUORKACOSESW-UHFFFAOYSA-N 2-[2-[2-(2-sulfanylethylsulfanyl)ethylsulfanyl]ethylsulfanylmethyl]propane-1,2,3-trithiol Chemical compound SCCSCCSCCSCC(S)(CS)CS DAUUORKACOSESW-UHFFFAOYSA-N 0.000 description 1
- KIVDBXVDNQFFFL-UHFFFAOYSA-N 2-[3-(2-sulfanylethylsulfanyl)-2,2-bis(2-sulfanylethylsulfanylmethyl)propyl]sulfanylethanethiol Chemical compound SCCSCC(CSCCS)(CSCCS)CSCCS KIVDBXVDNQFFFL-UHFFFAOYSA-N 0.000 description 1
- XYHKMRNYSMEEDT-UHFFFAOYSA-N 2-[3-(2-sulfanylethylsulfanyl)propylsulfanyl]ethanethiol Chemical compound SCCSCCCSCCS XYHKMRNYSMEEDT-UHFFFAOYSA-N 0.000 description 1
- JCBPETKZIGVZRE-UHFFFAOYSA-N 2-aminobutan-1-ol Chemical compound CCC(N)CO JCBPETKZIGVZRE-UHFFFAOYSA-N 0.000 description 1
- NAPDOWNULRULLI-UHFFFAOYSA-N 2-benzyl-1h-imidazole Chemical compound C=1C=CC=CC=1CC1=NC=CN1 NAPDOWNULRULLI-UHFFFAOYSA-N 0.000 description 1
- SLLDUURXGMDOCY-UHFFFAOYSA-N 2-butyl-1h-imidazole Chemical compound CCCCC1=NC=CN1 SLLDUURXGMDOCY-UHFFFAOYSA-N 0.000 description 1
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 description 1
- LPUUPYOHXHWKAR-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol 3,3,3-tris(sulfanyl)propanoic acid Chemical compound SC(CC(=O)O)(S)S.C(O)C(CC)(CO)CO LPUUPYOHXHWKAR-UHFFFAOYSA-N 0.000 description 1
- NTYQWXQLHWROSQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;2,2,2-tris(sulfanyl)acetic acid Chemical compound OC(=O)C(S)(S)S.CCC(CO)(CO)CO NTYQWXQLHWROSQ-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- ZCCUIXLWYNCODM-UHFFFAOYSA-N 2-methyl-2-(2-methylthiiran-2-yl)oxythiirane Chemical compound CC1(CS1)OC1(C)CS1 ZCCUIXLWYNCODM-UHFFFAOYSA-N 0.000 description 1
- MWBLSTZUZOANHW-UHFFFAOYSA-N 2-methyl-2-[4-(2-methylthiiran-2-yl)phenyl]thiirane Chemical compound CC1(CS1)C1=CC=C(C=C1)C1(C)CS1 MWBLSTZUZOANHW-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- KOCAIQHVJFBWHC-UHFFFAOYSA-N 3,4-dimethoxybutane-1,2-dithiol Chemical compound COCC(OC)C(S)CS KOCAIQHVJFBWHC-UHFFFAOYSA-N 0.000 description 1
- XBNYMYZLSBMANG-UHFFFAOYSA-N 3-(sulfanylmethylsulfanyl)propylsulfanylmethanethiol Chemical compound SCSCCCSCS XBNYMYZLSBMANG-UHFFFAOYSA-N 0.000 description 1
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- KLGUKVGNYAOWNX-UHFFFAOYSA-N 3-[3-(3-sulfanylpropylsulfanyl)-2,2-bis(3-sulfanylpropylsulfanylmethyl)propyl]sulfanylpropane-1-thiol Chemical compound SCCCSCC(CSCCCS)(CSCCCS)CSCCCS KLGUKVGNYAOWNX-UHFFFAOYSA-N 0.000 description 1
- WNCVPVXTNBBVHH-UHFFFAOYSA-N 3-[3-(3-sulfanylpropylsulfanyl)propylsulfanyl]propane-1-thiol Chemical compound SCCCSCCCSCCCS WNCVPVXTNBBVHH-UHFFFAOYSA-N 0.000 description 1
- BUZICZZQJDLXJN-UHFFFAOYSA-N 3-azaniumyl-4-hydroxybutanoate Chemical compound OCC(N)CC(O)=O BUZICZZQJDLXJN-UHFFFAOYSA-N 0.000 description 1
- QDNHFLDYNJTWKV-UHFFFAOYSA-N 3-methoxypropane-1,2-dithiol Chemical compound COCC(S)CS QDNHFLDYNJTWKV-UHFFFAOYSA-N 0.000 description 1
- RXXCIBALSKQCAE-UHFFFAOYSA-N 3-methylbutoxymethylbenzene Chemical compound CC(C)CCOCC1=CC=CC=C1 RXXCIBALSKQCAE-UHFFFAOYSA-N 0.000 description 1
- YOTBOYFKPMRBAG-UHFFFAOYSA-N 5-butyl-1h-imidazole Chemical compound CCCCC1=CNC=N1 YOTBOYFKPMRBAG-UHFFFAOYSA-N 0.000 description 1
- NJQHZENQKNIRSY-UHFFFAOYSA-N 5-ethyl-1h-imidazole Chemical compound CCC1=CNC=N1 NJQHZENQKNIRSY-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- PWGOWIIEVDAYTC-UHFFFAOYSA-N ICR-170 Chemical compound Cl.Cl.C1=C(OC)C=C2C(NCCCN(CCCl)CC)=C(C=CC(Cl)=C3)C3=NC2=C1 PWGOWIIEVDAYTC-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- OPBBHYMSLROTGW-UHFFFAOYSA-N SCCCSCCCS.SCCSCCS Chemical compound SCCCSCCCS.SCCSCCS OPBBHYMSLROTGW-UHFFFAOYSA-N 0.000 description 1
- RXSXNCRSBAYNJH-UHFFFAOYSA-N SCCSSCCS.SCSSCS Chemical compound SCCSSCCS.SCSSCS RXSXNCRSBAYNJH-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical group [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- HRSPMOZFFLQNSB-UHFFFAOYSA-N [1-(sulfanylmethyl)cyclohexyl]methanethiol Chemical compound SCC1(CS)CCCCC1 HRSPMOZFFLQNSB-UHFFFAOYSA-N 0.000 description 1
- RUDUCNPHDIMQCY-UHFFFAOYSA-N [3-(2-sulfanylacetyl)oxy-2,2-bis[(2-sulfanylacetyl)oxymethyl]propyl] 2-sulfanylacetate Chemical compound SCC(=O)OCC(COC(=O)CS)(COC(=O)CS)COC(=O)CS RUDUCNPHDIMQCY-UHFFFAOYSA-N 0.000 description 1
- JOBBTVPTPXRUBP-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS JOBBTVPTPXRUBP-UHFFFAOYSA-N 0.000 description 1
- VLDJWLWRDVWISM-UHFFFAOYSA-N [3-(sulfanylmethylsulfanyl)-2,2-bis(sulfanylmethylsulfanylmethyl)propyl]sulfanylmethanethiol Chemical compound SCSCC(CSCS)(CSCS)CSCS VLDJWLWRDVWISM-UHFFFAOYSA-N 0.000 description 1
- VLCCKNLIFIJYOQ-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] 2,2,3,3-tetrakis(sulfanyl)propanoate Chemical compound OCC(CO)(CO)COC(=O)C(S)(S)C(S)S VLCCKNLIFIJYOQ-UHFFFAOYSA-N 0.000 description 1
- COYTVZAYDAIHDK-UHFFFAOYSA-N [5-(sulfanylmethyl)-1,4-dithian-2-yl]methanethiol Chemical compound SCC1CSC(CS)CS1 COYTVZAYDAIHDK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- 239000001055 blue pigment Substances 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 235000010338 boric acid Nutrition 0.000 description 1
- 125000005619 boric acid group Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- VSARMWHOISBCGR-UHFFFAOYSA-N cyclohexane-1,1-dithiol Chemical compound SC1(S)CCCCC1 VSARMWHOISBCGR-UHFFFAOYSA-N 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- WQABCVAJNWAXTE-UHFFFAOYSA-N dimercaprol Chemical compound OCC(S)CS WQABCVAJNWAXTE-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- RVVRZLSZZKMJCB-UHFFFAOYSA-N heptane-1,7-dithiol Chemical compound SCCCCCCCS RVVRZLSZZKMJCB-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Chemical class 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000005496 phosphonium group Chemical group 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- NCNISYUOWMIOPI-UHFFFAOYSA-N propane-1,1-dithiol Chemical compound CCC(S)S NCNISYUOWMIOPI-UHFFFAOYSA-N 0.000 description 1
- UWHMFGKZAYHMDJ-UHFFFAOYSA-N propane-1,2,3-trithiol Chemical compound SCC(S)CS UWHMFGKZAYHMDJ-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000001044 red dye Substances 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 230000003763 resistance to breakage Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 125000005624 silicic acid group Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- WTSBJMAOQNCZBF-UHFFFAOYSA-N sulfanylmethylsulfanylmethanethiol Chemical compound SCSCS WTSBJMAOQNCZBF-UHFFFAOYSA-N 0.000 description 1
- QNITWMBGUWZSSI-UHFFFAOYSA-N sulfanylmethylsulfanylmethylsulfanylmethanethiol Chemical compound SCSCSCS QNITWMBGUWZSSI-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium group Chemical group [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- IBWGNZVCJVLSHB-UHFFFAOYSA-M tetrabutylphosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CCCC IBWGNZVCJVLSHB-UHFFFAOYSA-M 0.000 description 1
- CCIYPTIBRAUPLQ-UHFFFAOYSA-M tetrabutylphosphanium;iodide Chemical compound [I-].CCCC[P+](CCCC)(CCCC)CCCC CCIYPTIBRAUPLQ-UHFFFAOYSA-M 0.000 description 1
- LIXPXSXEKKHIRR-UHFFFAOYSA-M tetraethylphosphanium;bromide Chemical compound [Br-].CC[P+](CC)(CC)CC LIXPXSXEKKHIRR-UHFFFAOYSA-M 0.000 description 1
- FBOJNMRAZJRCNS-UHFFFAOYSA-M tetraethylphosphanium;chloride Chemical compound [Cl-].CC[P+](CC)(CC)CC FBOJNMRAZJRCNS-UHFFFAOYSA-M 0.000 description 1
- ZTXFOCMYRCGSMU-UHFFFAOYSA-M tetramethylphosphanium;bromide Chemical compound [Br-].C[P+](C)(C)C ZTXFOCMYRCGSMU-UHFFFAOYSA-M 0.000 description 1
- NJFUXFRJVIXVSG-UHFFFAOYSA-M tetramethylphosphanium;chloride Chemical compound [Cl-].C[P+](C)(C)C NJFUXFRJVIXVSG-UHFFFAOYSA-M 0.000 description 1
- 229960002178 thiamazole Drugs 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 150000003553 thiiranes Chemical class 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- TWXMZYPORGXIFB-UHFFFAOYSA-N thiophene-3,4-dithiol Chemical compound SC1=CSC=C1S TWXMZYPORGXIFB-UHFFFAOYSA-N 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/06—Polythioethers from cyclic thioethers
- C08G75/08—Polythioethers from cyclic thioethers from thiiranes
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/041—Lenses
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B3/00—Simple or compound lenses
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Optics & Photonics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Physics & Mathematics (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Eyeglasses (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は、高屈折率及び高アッベ数を有するプラスチックレンズ、特に眼鏡用プラスチックレンズの製造に好適に用いられるプラスチックレンズ製造用反応生成物の製造方法、該プラスチックレンズ製造用反応生成物を主成分とするレンズ原料組成物を用いたプラスチックレンズの製造方法及び該製造方法により得られるプラスチックレンズに関するものである。 The present invention relates to a method for producing a reaction product for producing a plastic lens suitably used for producing a plastic lens having a high refractive index and a high Abbe number, particularly a plastic lens for spectacles, and the reaction product for producing the plastic lens as a main component. And a plastic lens obtained by the manufacturing method.
近年、プラスチックレンズは、無機ガラスレンズと比較して、軽量で割れにくい上、染色が容易であるなどの特性を有することから、ファッション性が重視される眼鏡レンズなどに広く普及している。しかしながら、一般的なレンズ用プラスチックは、ガラスよりも屈折率が小さい。したがって、プラスチックレンズは、ガラスレンズに比べ、マイナスレンズではコバ厚が厚くなり、プラスレンズでは中心厚が厚くなるのを免れないという欠点を有している。そのため、屈折率がより高いプラスチックレンズ材料の開発が進められてきた。屈折率を高くする方法としては、これまで、例えば芳香環を導入する方法、フッ素原子以外のハロゲン原子を導入する方法、硫黄原子を導入する方法などが、数多く提案されている。
例えば特許文献１及び２には、エピチオ化合物等の含硫黄化合物と、硫黄原子及び／又はセレン原子との混合物を含有してなる光学材料用組成物を重合硬化させることにより、屈折率１．７１以上のプラスチックレンズを得る方法が開示されている。
しかしながら、特許文献１又は２に記載の方法では、屈折率が特に高く、透明性に優れ、高いアッベ数が維持された色収差に優れる、高品質の眼鏡用レンズを製造することが難しい。すなわち、より高屈折率のプラスチックレンズを得るために、特許文献１又は２に記載の方法で材料を調製すると、製造されたレンズに無機化合物が析出しやすくなる。この傾向は、屈折率が１．７５以上の高屈率レンズにおいて特に顕著である。無機化合物が析出しているレンズは、透明性が低下したりアッベ数が低くなったり、黄味着色を帯びてしまう。
また、特許文献３では、硫黄と、エピチオ化合物のプレポリマー（プラスチックレンズ用反応生成物）を作製し、該プレポリマーをフィルターで濾過して得られた硫黄含有プレポリマーを用いたプラスチックレンズの製造方法が提案されているが、屈折率が１．７５以上のレンズは得られていない。In recent years, plastic lenses are widely used in spectacle lenses and the like where fashionability is important because they have characteristics such as light weight, resistance to breakage, and easy dyeing compared to inorganic glass lenses. However, a general lens plastic has a refractive index smaller than that of glass. Therefore, the plastic lens has a drawback that the edge thickness is increased with the minus lens and the center thickness is increased with the plus lens compared to the glass lens. Therefore, development of a plastic lens material having a higher refractive index has been advanced. As a method for increasing the refractive index, many methods have been proposed so far, for example, a method of introducing an aromatic ring, a method of introducing a halogen atom other than a fluorine atom, and a method of introducing a sulfur atom.
For example, Patent Documents 1 and 2 disclose that a refractive index of 1.71 is obtained by polymerizing and curing a composition for an optical material containing a mixture of a sulfur-containing compound such as an epithio compound and a sulfur atom and / or a selenium atom. A method for obtaining the above plastic lens is disclosed.
However, with the method described in Patent Document 1 or 2, it is difficult to produce a high-quality spectacle lens having a particularly high refractive index, excellent transparency, and excellent chromatic aberration while maintaining a high Abbe number. That is, when a material is prepared by the method described in Patent Document 1 or 2 in order to obtain a plastic lens having a higher refractive index, an inorganic compound tends to precipitate on the manufactured lens. This tendency is particularly remarkable in a high refractive index lens having a refractive index of 1.75 or more. A lens on which an inorganic compound is deposited has low transparency, a low Abbe number, or yellowish coloring.
Moreover, in patent document 3, manufacture of the plastic lens using the sulfur containing prepolymer obtained by producing the prepolymer (reaction product for plastic lenses) of sulfur and an epithio compound, and filtering this prepolymer with a filter. Although a method has been proposed, a lens having a refractive index of 1.75 or more has not been obtained.
本発明は、高屈折率などの所望の特性を有するプラスチックレンズが製造可能なプラスチックレンズ製造用反応生成物の製造方法を提供することを目的とする。さらに、本発明は、高屈折率でありながら、優れた透明性と黄味着色の少ない高アッベ数が実現された高品質なプラスチックレンズの製造方法、及び該製造方法により得られる高品質なプラスチックレンズを提供することを目的とする。 An object of this invention is to provide the manufacturing method of the reaction product for plastic lens manufacture which can manufacture the plastic lens which has desired characteristics, such as high refractive index. Furthermore, the present invention relates to a method for producing a high-quality plastic lens in which a high Abbe number with a high refractive index and excellent transparency and little yellowing is realized, and a high-quality plastic obtained by the production method The object is to provide a lens.
本発明者らが鋭意研究を重ねた結果、エピチオ基を有する化合物（以下、「エピチオ化合物」と称することがある。）と硫黄との加硫反応を特定の条件下で行って得られるプラスチックレンズ製造用反応生成物を用いることにより、高屈折率などの所望の特性を有するプラスチックレンズが得られることがわかった。
すなわち、加硫促進剤や触媒を過剰に加えることなく、上記加硫反応を短時間で終了させることにより得られるプラスチックレンズ製造用反応生成物を原料に用いることにより、高アッベ数で黄味着色が抑制され、透明性に優れる高屈折率プラスチックレンズを得ることに初めて成功し、新規なプラスチックレンズ製造用反応生成物の製造方法を見出したのである。
また、本発明者らは、上記プラスチックレンズ製造用反応生成物の製造方法を見出したことによって、曇りの発生や硫黄の再析出が抑制された新規なプラスチックレンズを製造する方法をも見出した。
本発明はかかる知見に基づいて完成したものである。As a result of extensive studies by the present inventors, a plastic lens obtained by performing a vulcanization reaction between a compound having an epithio group (hereinafter sometimes referred to as “epithio compound”) and sulfur under specific conditions. It was found that a plastic lens having desired characteristics such as a high refractive index can be obtained by using the reaction product for production.
That is, by using as a raw material a reaction product for plastic lens production obtained by completing the above vulcanization reaction in a short time without adding an excessive amount of a vulcanization accelerator or catalyst, it is colored yellow at a high Abbe number. For the first time, it has succeeded in obtaining a high-refractive-index plastic lens excellent in transparency, and has found a novel method for producing a reaction product for producing a plastic lens.
In addition, the present inventors have also found a method for producing a novel plastic lens in which generation of fogging and reprecipitation of sulfur are suppressed by finding a method for producing the reaction product for producing the plastic lens.
The present invention has been completed based on such findings.
すなわち、本発明は、以下のプラスチックレンズ製造用反応生成物の製造方法、プラスチックレンズの製造方法及びプラスチックレンズを提供するものである。
１． エピチオ基を有する化合物の少なくとも１種と硫黄を含む原料組成物を投入した反応容器内の酸素分圧を１０００Ｐａ以下とし、該反応容器を密閉した状態で反応させることを特徴とする、３０℃における粘度が１００〜１０００ｍＰａ・ｓであるプラスチックレンズ製造用反応生成物の製造方法。
２． 反応容器内の酸素分圧を、該反応容器を減圧することによって調整する上記１記載のプラスチックレンズ製造用反応生成物の製造方法。
３． 硫黄の含有量が、レンズ原料組成物の全量を基準として１０〜２５質量％の範囲である上記１又は２記載のプラスチックレンズ製造用反応生成物の製造方法。
４． ポリチオール化合物を、原料組成物と共に反応容器に投入する上記１〜３のいずれかに記載のプラスチックレンズ製造用反応生成物の製造方法。That is, this invention provides the manufacturing method of the following reaction product for plastic lens manufacture, the manufacturing method of a plastic lens, and a plastic lens.
1. The oxygen partial pressure in a reaction vessel charged with a raw material composition containing at least one compound having an epithio group and sulfur is 1000 Pa or less, and the reaction is carried out in a sealed state at 30 ° C. The manufacturing method of the reaction product for plastic lens manufacture whose viscosity is 100-1000 mPa * s.
2. 2. The method for producing a reaction product for producing a plastic lens as described in 1 above, wherein the partial pressure of oxygen in the reaction vessel is adjusted by depressurizing the reaction vessel.
3. 3. The method for producing a reaction product for producing a plastic lens as described in 1 or 2 above, wherein the sulfur content is in the range of 10 to 25% by mass based on the total amount of the lens raw material composition.
4). 4. The method for producing a reaction product for producing a plastic lens according to any one of 1 to 3, wherein the polythiol compound is charged into a reaction vessel together with the raw material composition.
５． エピチオ基を有する化合物の少なくとも１種と硫黄を含む原料組成物を投入した反応容器内の酸素分圧を１０００Ｐａ以下とし、該反応容器を密閉した状態で反応させて３０℃における粘度が１００〜１０００ｍＰａ・ｓであるプラスチックレンズ製造用反応生成物を製造し、その後、該反応生成物とポリチオール化合物とを重合させることを特徴とするプラスチックレンズの製造方法。
６． 重合に用いるポリチオール化合物の少なくとも一部を、原料組成物と共に反応容器に投入する上記５記載のプラスチックレンズの製造方法。
７． 反応容器内の酸素分圧を、該反応容器を減圧することによって調整する上記５又は６記載のプラスチックレンズの製造方法。
８． 硫黄の含有量が、レンズ原料組成物の全量を基準として１０〜２５質量％の範囲である上記５〜７のいずれかに記載のプラスチックレンズの製造方法。
９． 上記５〜８のいずれかに記載の製造方法により得られるプラスチックレンズ。5. An oxygen partial pressure in a reaction vessel charged with a raw material composition containing at least one compound having an epithio group and sulfur is set to 1000 Pa or less, and the reaction is carried out in a sealed state so that the viscosity at 30 ° C. is 100 to 1000 mPa. A method for producing a plastic lens, comprising producing a reaction product for producing a plastic lens, which is s, and then polymerizing the reaction product and a polythiol compound.
6). 6. The method for producing a plastic lens as described in 5 above, wherein at least a part of the polythiol compound used for polymerization is charged into a reaction vessel together with the raw material composition.
7). 7. The method for producing a plastic lens as described in 5 or 6 above, wherein the partial pressure of oxygen in the reaction vessel is adjusted by reducing the pressure of the reaction vessel.
8). The method for producing a plastic lens according to any one of 5 to 7 above, wherein the sulfur content is in the range of 10 to 25% by mass based on the total amount of the lens raw material composition.
9. The plastic lens obtained by the manufacturing method in any one of said 5-8.
本発明のプラスチックレンズ製造用反応生成物の製造方法によれば、比較的低温、かつ短時間で加硫反応を促進させることができる。このため、プラスチックレンズ製造用反応生成物の黄味着色や透明度の低下が抑制される。また、加硫促進剤が過剰に添加されないので、加硫反応の制御が容易である。
また、プラスチックレンズ製造用反応生成物の３０℃における粘度を１００〜１０００ｍＰａ・ｓに設定することにより、注入作業が行いやすく、しかも、反応生成物中の硫黄が適度に消費されて硫黄の析出が抑制される。According to the method for producing a reaction product for producing a plastic lens of the present invention, the vulcanization reaction can be promoted at a relatively low temperature and in a short time. For this reason, the yellowish coloring of the reaction product for plastic lens manufacture and the fall of transparency are suppressed. Further, since the vulcanization accelerator is not added excessively, it is easy to control the vulcanization reaction.
In addition, by setting the viscosity of the reaction product for plastic lens production at 30 ° C. to 100 to 1000 mPa · s, the injection work can be easily performed, and the sulfur in the reaction product is moderately consumed and the sulfur is precipitated. It is suppressed.
また、本発明のプラスチックレンズの製造方法によれば、上記プラスチック製造用反応生成物とポリチオール化合物との重合により、耐光性が改善された透明性に優れる高屈折率かつ高アッベ数のプラスチックレンズを得ることができる。 Further, according to the method for producing a plastic lens of the present invention, a plastic lens having a high refractive index and a high Abbe number excellent in transparency and improved in light resistance can be obtained by polymerization of the reaction product for plastic production and a polythiol compound. Can be obtained.
本発明のプラスチックレンズ製造用反応生成物の製造方法は、エピチオ化合物の少なくとも１種と硫黄を含む原料組成物を投入した反応容器内の酸素分圧を１０００Ｐａ以下とし、該反応容器を密閉した状態で反応させる製造方法である。この製造方法により、３０℃における粘度が１００〜１０００ｍＰａ・ｓであるプラスチックレンズ製造用反応生成物を得ることができる。 In the method for producing a reaction product for producing a plastic lens of the present invention, the oxygen partial pressure in a reaction vessel charged with a raw material composition containing at least one epithio compound and sulfur is 1000 Pa or less, and the reaction vessel is sealed. It is the manufacturing method made to react by. By this production method, a reaction product for producing a plastic lens having a viscosity of 100 to 1000 mPa · s at 30 ° C. can be obtained.
本発明において、「プラスチックレンズ製造用反応生成物」とは、エピチオ化合物と硫黄の加硫反応が適度進行して粘性の増した流動体をいう。プラスチックレンズ製造用反応生成物には、加硫反応に実質的に関与しない他の原料成分や溶媒などが混入しているものも含まれる。
例えば、上記原料組成物と共に、加硫に関与しないポリチオール化合物を反応容器に投入して反応を行った場合のポリチオール化合物を含む反応生成物も、ここで言う「プラスチックレンズ製造用反応生成物」に含まれる。In the present invention, the “reaction product for producing a plastic lens” refers to a fluid having an increased viscosity due to a moderate progress of a vulcanization reaction between an epithio compound and sulfur. The reaction product for producing a plastic lens includes a product mixed with other raw material components and a solvent that are not substantially involved in the vulcanization reaction.
For example, together with the raw material composition, a reaction product containing a polythiol compound when a reaction is carried out by introducing a polythiol compound not involved in vulcanization into a reaction vessel is also referred to as a “plastic lens manufacturing reaction product” here. included.
上記原料組成物は、エピチオ化合物中に硫黄を混合し、溶解させたものである。高屈折率のプラスチックレンズを得るためには、プラスチックレンズ製造用反応生成物中の硫黄濃度が高いこと、すなわち上記原料組成物中の硫黄濃度が高いことが好ましい。このため、エピチオ化合物への硫黄の溶解は、エピチオ化合物を８０℃以下の温度で、好ましくは６０〜８０℃の温度で加熱し、攪拌しながら行うことが好ましい。
また、原料組成物の状態を安定化させて加硫反応を再現性良く行なうために、硫黄溶解時または溶解後に１０〜２０００Ｐａの圧力範囲で５〜６０分間の減圧脱泡を行なうのが好ましい。加硫促進剤は、硫黄を溶解し、減圧脱泡した後に、温調下で適量を添加する。The raw material composition is prepared by mixing and dissolving sulfur in an epithio compound. In order to obtain a plastic lens having a high refractive index, it is preferable that the sulfur concentration in the reaction product for producing a plastic lens is high, that is, the sulfur concentration in the raw material composition is high. For this reason, it is preferable to melt | dissolve sulfur to an epithio compound, heating an epithio compound at the temperature of 80 degrees C or less, Preferably it is the temperature of 60-80 degreeC, and stirring.
Moreover, in order to stabilize the state of the raw material composition and perform the vulcanization reaction with good reproducibility, it is preferable to perform degassing under reduced pressure for 5 to 60 minutes in the pressure range of 10 to 2000 Pa during or after dissolution of sulfur. The vulcanization accelerator is dissolved in sulfur, degassed under reduced pressure, and then added in an appropriate amount under temperature control.
加硫促進剤としては、２−メルカプト−Ｎ−メチルイミダゾール、Ｎ−メチルイミダゾール，２−メチルイミダゾール、４−メチルイミダゾール、Ｎ−エチルイミダゾール、２−エチルイミダゾール、４−エチルイミダゾール、Ｎ−ブチルイミダゾール、２−ブチルイミダゾール、４−ブチルイミダゾール、Ｎ−フェニルイミダゾール、２−フェニルイミダゾール、Ｎ−ベンジルイミダゾール、２−ベンジルイミダゾール、２−メルカプトイミダゾール、２−メルカプトベンゾイミダゾール等のイミダゾール系、テトラメチルチウラムジスルフィド、テトラメチルチウラムモノスルフィド等のチウラム系、ジフェニルグアニジン、ジ−ｏ−トリルグアニジン等のグアニジン系などが挙げられる。これらの好ましい添加量は、上記原料組成物の全量を基準にして０．００１〜０．１質量％の範囲である。 As vulcanization accelerators, 2-mercapto-N-methylimidazole, N-methylimidazole, 2-methylimidazole, 4-methylimidazole, N-ethylimidazole, 2-ethylimidazole, 4-ethylimidazole, N-butylimidazole Imidazole series such as 2-butylimidazole, 4-butylimidazole, N-phenylimidazole, 2-phenylimidazole, N-benzylimidazole, 2-benzylimidazole, 2-mercaptoimidazole, 2-mercaptobenzimidazole, tetramethylthiuram disulfide And thiurams such as tetramethylthiuram monosulfide, and guanidines such as diphenylguanidine and di-o-tolylguanidine. These preferable addition amounts are in the range of 0.001 to 0.1% by mass based on the total amount of the raw material composition.
本発明のプラスチックレンズ製造用反応生成物の製造において、加硫反応における反応容器内の酸素分圧は１０００Ｐａ以下に調整する。
反応容器内の酸素分圧を調整する方法は、特に限定されない。例えば、反応容器内の空気を排気したり、反応容器内の空気を不活性ガスで置換したりすることにより、反応容器内の酸素分圧を１０００Ｐａ以下とすることができる。具体的には、加硫促進剤投入後に減圧脱泡操作を行って、そのまま反応容器内の減圧状態を保つことにより、反応容器内の酸素分圧を低下させることができる。なお、ここでの酸素分圧とは、反応容器内圧力と反応容器内の気体の常圧相当時の酸素濃度の積として定義される。
反応容器内の空気を不活性ガスで置換する場合、不活性ガスとしては、例えば、ヘリウム、ネオン、アルゴン等の希ガスや窒素を用いることができる。これらの中で、安価で入手が容易である点から窒素が好ましい。しかし、窒素には、不純物として、加硫反応を阻害する要素になり得る酸素が含まれやすいので、純度９９％以上の窒素を用いるのがより好ましい。In the production of the reaction product for producing a plastic lens of the present invention, the oxygen partial pressure in the reaction vessel in the vulcanization reaction is adjusted to 1000 Pa or less.
The method for adjusting the oxygen partial pressure in the reaction vessel is not particularly limited. For example, the oxygen partial pressure in the reaction vessel can be reduced to 1000 Pa or less by exhausting the air in the reaction vessel or replacing the air in the reaction vessel with an inert gas. Specifically, the partial pressure of oxygen in the reaction vessel can be reduced by performing a vacuum degassing operation after adding the vulcanization accelerator and maintaining the reduced pressure state in the reaction vessel as it is. Here, the oxygen partial pressure is defined as the product of the pressure in the reaction vessel and the oxygen concentration at the time corresponding to the normal pressure of the gas in the reaction vessel.
When the air in the reaction vessel is replaced with an inert gas, for example, a rare gas such as helium, neon, or argon, or nitrogen can be used as the inert gas. Among these, nitrogen is preferable because it is inexpensive and easily available. However, since nitrogen easily contains oxygen that can be an element inhibiting the vulcanization reaction as an impurity, it is more preferable to use nitrogen having a purity of 99% or more.
一方、大気下で加硫反応させた場合、あるいは減圧操作によって生成ガスを排気しながら加硫反応させた場合、同じ粘度のプラスチックレンズ製造用反応生成物を得るための反応時間は極端に長くなり、その結果、該反応生成物を用いて得られたレンズの黄味着色が大きくなってしまう。同じ反応時間で同等の粘度を得るためには、加硫促進剤をより多く投入したり、反応温度を高くしたりする必要があるが、レンズの着色防止の観点から好ましくない。さらにこのような条件では、加硫反応の進行とともに反応速度が加速度的に速くなってしまう等の不都合があり、反応の制御もより困難なものとなる。 On the other hand, when the vulcanization reaction is performed in the atmosphere, or when the vulcanization reaction is performed while exhausting the product gas by depressurization, the reaction time for obtaining a reaction product for producing a plastic lens having the same viscosity becomes extremely long. As a result, the yellow coloration of the lens obtained using the reaction product becomes large. In order to obtain the same viscosity at the same reaction time, it is necessary to add more vulcanization accelerators or increase the reaction temperature, but this is not preferable from the viewpoint of preventing coloring of the lens. Furthermore, under such conditions, there are inconveniences such as the reaction speed increasing at an accelerated rate as the vulcanization reaction proceeds, and the control of the reaction becomes more difficult.
酸素分圧を所定圧力に調整した後、反応容器を密閉した状態で攪拌しながら適度な温度を保って加硫反応を進行させる。加硫反応では、酸素は実質的に生成されない。加硫反応中の反応容器内の酸素分圧は、事前に調整した値が維持される。したがって、加硫反応が進行しているときの反応容器内は、酸素分圧１０００Ｐａ以下の状態が維持される。
また、反応容器が密閉されると、反応で生成した硫黄分を含むガス（例えば、硫化水素）が外部に流出することが抑制される。この硫黄分を含むガスは、反応容器内での加硫反応に効率的に利用されるので、反応容器に投入したほとんどの硫黄成分を、加硫反応で消費することができる。さらに、加硫反応で発生したガスは、硫黄による加硫反応を穏やかに促進する効果を有していると考えられる。加硫反応で発生したガスを排出しないことにより、過剰の加硫促進剤や触媒を使用しなくても、加硫反応が短時間で終了する。
また、過剰の加硫促進剤や触媒を使用しないので、反応が急激に進行しない。このため、加硫反応の制御が容易である。したがって、次工程の注入に適した増粘領域で再現性よく正確に反応を停止させることが可能となり、常に均等なプラスチックレンズ用反応性生物を得ることができる。After adjusting the oxygen partial pressure to a predetermined pressure, the vulcanization reaction is allowed to proceed while maintaining an appropriate temperature while stirring with the reaction vessel sealed. In the vulcanization reaction, oxygen is not substantially generated. The oxygen partial pressure in the reaction vessel during the vulcanization reaction is maintained at a value adjusted in advance. Therefore, the state of the oxygen partial pressure of 1000 Pa or less is maintained in the reaction vessel when the vulcanization reaction is in progress.
Moreover, when the reaction vessel is sealed, it is possible to suppress a gas (for example, hydrogen sulfide) containing sulfur generated by the reaction from flowing out. Since the gas containing this sulfur content is efficiently used for the vulcanization reaction in the reaction vessel, most of the sulfur component charged into the reaction vessel can be consumed in the vulcanization reaction. Furthermore, the gas generated by the vulcanization reaction is considered to have an effect of gently accelerating the vulcanization reaction with sulfur. By not discharging the gas generated in the vulcanization reaction, the vulcanization reaction can be completed in a short time without using an excessive vulcanization accelerator or catalyst.
In addition, since no excessive vulcanization accelerator or catalyst is used, the reaction does not proceed rapidly. For this reason, control of a vulcanization reaction is easy. Accordingly, the reaction can be accurately stopped with high reproducibility in a thickening region suitable for the injection in the next step, and a uniform reactive organism for a plastic lens can always be obtained.
本発明のプラスチックレンズ製造用反応生成物を用いて得られるレンズの黄味着色を防ぐ観点から、加硫反応は、できるだけ低温、且つ短時間で終えることが好ましい。加硫反応は、好ましくは３０〜８０℃の温度範囲で、より好ましくは４０〜６５℃の温度範囲で攪拌しながら行うことが好ましい。反応時間は、好ましくは１〜５時間、より好ましくは２〜５時間である。
本発明のプラスチックレンズ製造用反応生成物の製造方法においては、このような比較的低温の温度範囲でも加硫反応は十分に進行する。このため、該反応生成物を用いて製造されたプラスチックレンズにおける曇りの発生や硫黄の再析出が抑制される。
本発明のプラスチックレンズ製造用反応生成物の製造方法によれば、加硫反応の制御が容易で、しかも穏やかな条件の低温、短時間で反応を終えることができるため、得られたプラスチックレンズ製造用反応生成物を用いることにより、黄味着色の少ないプラスチックレンズを効率的に製造することができる。From the viewpoint of preventing yellowing of the lens obtained using the reaction product for producing a plastic lens of the present invention, the vulcanization reaction is preferably completed in as low a temperature as possible and in a short time. The vulcanization reaction is preferably carried out with stirring in a temperature range of 30 to 80 ° C, more preferably in a temperature range of 40 to 65 ° C. The reaction time is preferably 1 to 5 hours, more preferably 2 to 5 hours.
In the method for producing a reaction product for producing a plastic lens of the present invention, the vulcanization reaction proceeds sufficiently even in such a relatively low temperature range. For this reason, generation | occurrence | production of the haze and reprecipitation of sulfur in the plastic lens manufactured using this reaction product are suppressed.
According to the method for producing a reaction product for producing a plastic lens of the present invention, the vulcanization reaction can be easily controlled, and the reaction can be completed in a low temperature and in a short time under mild conditions. By using the reaction product for use, a plastic lens with little yellowing can be efficiently produced.
高屈折率レンズを得るための硫黄の好ましい添加量は、レンズ原料組成物の全量を基準として、１０〜２５質量％程度である。硫黄の添加量がレンズ原料組成物の全量を基準として１０質量％未満であると、得られるプラスチックレンズの屈折率が不十分となり、２５質量％を超えると硫黄の溶解状態が不安定となって、得られるプラスチックレンズに曇りが発生したり、硫黄の再析出が起こる場合がある。
また、得られるプラスチックレンズの着色を少なくするという観点から、上記硫黄としては、沸点１２０℃以下の不純物を除去し、かつ純度が９８質量％以上のものが好ましく用いられる。沸点１２０℃以下の不純物の除去方法としては、特に限定されないが、例えば硫黄を常圧又は減圧加熱して不純物を除去する方法、硫黄を昇華させて再結晶化させる方法、及び硫黄を加熱溶解させて再結晶化させる方法などが挙げられる。The preferable addition amount of sulfur for obtaining a high refractive index lens is about 10 to 25% by mass based on the total amount of the lens raw material composition. If the amount of sulfur added is less than 10% by mass based on the total amount of the lens raw material composition, the refractive index of the obtained plastic lens becomes insufficient, and if it exceeds 25% by mass, the dissolved state of sulfur becomes unstable. In some cases, the resulting plastic lens may be fogged or sulfur may be reprecipitated.
Further, from the viewpoint of reducing the coloration of the obtained plastic lens, as the sulfur, those having impurities with a boiling point of 120 ° C. or less and having a purity of 98% by mass or more are preferably used. A method for removing impurities having a boiling point of 120 ° C. or lower is not particularly limited. For example, a method of removing impurities by heating sulfur at normal pressure or reduced pressure, a method of sublimating sulfur to recrystallize, and heating and dissolving sulfur. And recrystallization.
上記加硫反応の制御は、反応系の粘度や屈折率を適宜に測定、監視することによって行なわれる。なお、反応系における屈折率はｎｄである。反応の最適な停止点は、原料組成物におけるエピチオ化合物と硫黄の濃度、レンズ原料として使用するポリチオール化合物の種類と量によっても変化するため、一様に定めることはできないが、少なくとも最終的に得られるレンズに十分な透明性が得られるまでに加硫反応が進行した点である。
上記加硫反応により得られる本発明のプラスチックレンズ製造用反応生成物の粘度は、粘度と屈折率の関係から間接的に求めることができる。すなわち、上記加硫反応の複数の反応ポイントで反応生成物の屈折率を測定すると共に、その屈折率における粘度を測定し、屈折率と粘度との関係をあらかじめ求めておく。これにより、上記反応生成物の粘度は、該反応生成物の屈折率を測定することにより、上記関係に基づいて間接的に求めることができる。そして、最終的なレンズにおいて透明性が得られる範囲で、上記停止点となる屈折率を選択することにより、プラスチックレンズ製造用反応生成物の粘度を調整することができる。The vulcanization reaction is controlled by appropriately measuring and monitoring the viscosity and refractive index of the reaction system. The refractive index in the reaction system is nd. The optimal stopping point of the reaction varies depending on the concentration of epithio compound and sulfur in the raw material composition and the type and amount of the polythiol compound used as the lens raw material. The point is that the vulcanization reaction has progressed until sufficient transparency is obtained for the obtained lens.
The viscosity of the reaction product for producing a plastic lens of the present invention obtained by the vulcanization reaction can be indirectly determined from the relationship between the viscosity and the refractive index. That is, the refractive index of the reaction product is measured at a plurality of reaction points of the vulcanization reaction, the viscosity at the refractive index is measured, and the relationship between the refractive index and the viscosity is obtained in advance. Thereby, the viscosity of the reaction product can be obtained indirectly based on the above relationship by measuring the refractive index of the reaction product. And the viscosity of the reaction product for plastic lens manufacture can be adjusted by selecting the refractive index which becomes the said stop point in the range in which transparency is obtained in the final lens.
プラスチックレンズ製造用反応生成物を得るための加硫反応の停止点を、屈折率の測定によって決定する場合、例えば以下のように行うことができる。すなわち、エピチオ化合物と硫黄との加硫反応の過程でプラスチックレンズ製造用反応生成物の屈折率が段階的に異なるように、複数の反応ポイントで該反応生成物を抜き取る。そして、各反応生成物を室温近傍まで冷却しても硫黄が再析出せず、且つ、ポリチオール化合物等を加え、重合して得られる最終的なレンズにおいて透明性が得られるような条件のプラスチックレンズ製造用反応生成物の屈折率を停止点とすることができる。 When the stop point of the vulcanization reaction for obtaining the reaction product for producing the plastic lens is determined by measuring the refractive index, it can be performed, for example, as follows. That is, the reaction product is extracted at a plurality of reaction points so that the refractive index of the reaction product for plastic lens production varies stepwise in the course of the vulcanization reaction between the epithio compound and sulfur. Then, even if each reaction product is cooled to near room temperature, sulfur is not reprecipitated, and a plastic lens under such a condition that transparency is obtained in a final lens obtained by adding a polythiol compound or the like and polymerizing it. The refractive index of the production reaction product can be taken as a stopping point.
プラスチックレンズ製造用反応生成物の屈折率が停止点まで上昇した時点において、加温を終了し、速やかに室温近傍まで冷却させることが望ましい。その際に反応を十分に停止させるため、反応停止用助剤として酸性リン酸エステル類、ジメチルチンジクロライドなどを適量加えて停止させてもよい。停止点におけるプラスチックレンズ製造用反応生成物の３０℃における粘度は、１００〜１０００ｍＰａ・ｓの範囲であり、好ましくは２００〜８００ｍＰａ・ｓの範囲である。上記レンズ原料組成物の全量を基準として硫黄の添加量が１０質量％以上のときに粘度が１００ｍＰａ・ｓ未満であると、室温まで冷却したときに硫黄が再析出してしまうおそれがある。また、粘度が１０００ｍＰａ・ｓを超える領域では、粘度が急激に上昇する傾向が強くなって反応の制御が極めて難しくなり、さらに、後で加える他のレンズ原料との混合操作や鋳型への注入操作も困難になる。 When the refractive index of the reaction product for producing a plastic lens rises to the stopping point, it is desirable to end the heating and quickly cool it to near room temperature. In this case, in order to sufficiently stop the reaction, an appropriate amount of acidic phosphate ester, dimethyltin dichloride or the like may be added as an auxiliary for stopping the reaction. The viscosity at 30 ° C. of the reaction product for producing a plastic lens at the stopping point is in the range of 100 to 1000 mPa · s, and preferably in the range of 200 to 800 mPa · s. If the viscosity is less than 100 mPa · s when the addition amount of sulfur is 10% by mass or more based on the total amount of the lens raw material composition, sulfur may be re-precipitated when cooled to room temperature. In addition, in the region where the viscosity exceeds 1000 mPa · s, the tendency of the viscosity to increase sharply becomes strong, and the control of the reaction becomes extremely difficult. Further, the mixing operation with other lens materials to be added later or the injection operation into the mold Also becomes difficult.
本発明において、エピチオ化合物はエピスルフィド系のモノマーとも言い、このモノマーの具体例としては、１，３−及び１，４−ビス（β−エピチオプロピルチオ）シクロヘキサン、１，３−及び１，４−ビス（β−エピチオプロピルチオメチル）シクロヘキサン、ビス〔４−（β−エピチオプロピルチオ）シクロヘキシル〕メタン、２，２−ビス〔４−（β−エピチオプロピルチオ）シクロヘキシル〕プロパン、ビス〔４−（β−エピチオプロピルチオ）シクロヘキシル〕スルフィド、１，３−及び１，４−ビス（β−エピチオプロピル）シクロヘキサン等の脂環族骨格を有するエピスルフィド化合物；１，３−及び１，４−ビス（β−エピチオプロピルチオ）ベンゼン、１，３−及び１，４−ビス（β−エピチオプロピルチオメチル）ベンゼン、ビス〔４−（β−エピチオプロピルチオ）フェニル〕メタン、２，２−ビス〔４−（β−エピチオプロピルチオ）フェニル〕プロパン、ビス〔４−（β−エピチオプロピルチオ）フェニル〕スルフィド、ビス〔４−（β−エピチオプロピルチオ）フェニル〕スルフィド、４，４−ビス（β−エピチオプロピルチオ）ビフェニル、１，３−及び１，４−ビス（β−エピチオプロピル）ベンゼン等の芳香族骨格を有するエピスルフィド化合物；２，５−ビス（β−エピチオプロピルチオメチル）−１，４−ジチアン、２，５−ビス（β−エピチオプロピルチオエチルチオメチル）−１，４−ジチアン、２，５−ビス（β−エピチオプロピルチオエチル）−１，４−ジチアン、２，３、５−トリ（β−エピチオプロピルチオエチル）−１，４−ジチアン、２，５−ビス（β−エピチオプロピル）−１，４−ジチアン等のジチアン環骨格を有するエピスルフィド化合物；２−（２−β−エピチオプロピルチオエチルチオ）−１，３−ビス（β−エピチオプロピルチオ）プロパン、１，２−ビス〔（２−β−エピチオプロピルチオエチル）チオ〕−３−（β−エピチオプロピルチオ）プロパン、テトラキス（β−エピチオプロピルチオメチル）メタン、１，１，１−トリス（β−エピチオプロピルチオメチル）プロパン、ビス（β−エピチオプロピル）スルフィド、ビス（β−エピチオプロピル）ジスルフィド、ビス（β−エピチオプロピル）エーテル、ビス（β−エピチオプロピル）メタン、１，２−ビス（β−エピチオプロピル）エタン、１，３−ビス（β−エピチオプロピル）プロパン等の脂肪族骨格を有するエピスルフィド化合物などが挙げられる。 In the present invention, the epithio compound is also referred to as an episulfide monomer, and specific examples of this monomer include 1,3- and 1,4-bis (β-epithiopropylthio) cyclohexane, 1,3- and 1,4. -Bis (β-epithiopropylthiomethyl) cyclohexane, bis [4- (β-epithiopropylthio) cyclohexyl] methane, 2,2-bis [4- (β-epithiopropylthio) cyclohexyl] propane, bis [4- (β-epithiopropylthio) cyclohexyl] sulfide, episulfide compounds having an alicyclic skeleton such as 1,3- and 1,4-bis (β-epithiopropyl) cyclohexane; 1,3- and 1 , 4-Bis (β-epithiopropylthio) benzene, 1,3- and 1,4-bis (β-epithiopropylthiomethyl) benzene , Bis [4- (β-epithiopropylthio) phenyl] methane, 2,2-bis [4- (β-epithiopropylthio) phenyl] propane, bis [4- (β-epithiopropylthio) Phenyl] sulfide, bis [4- (β-epithiopropylthio) phenyl] sulfide, 4,4-bis (β-epithiopropylthio) biphenyl, 1,3- and 1,4-bis (β-epithio) Episulfide compounds having an aromatic skeleton such as propyl) benzene; 2,5-bis (β-epithiopropylthiomethyl) -1,4-dithiane, 2,5-bis (β-epithiopropylthioethylthiomethyl) -1,4-dithiane, 2,5-bis (β-epithiopropylthioethyl) -1,4-dithiane, 2,3,5-tri (β-epithiopropylthioethyl) -1,4-dithia , Episulfide compounds having a dithian ring skeleton such as 2,5-bis (β-epithiopropyl) -1,4-dithiane; 2- (2-β-epithiopropylthioethylthio) -1,3-bis ( β-epithiopropylthio) propane, 1,2-bis [(2-β-epithiopropylthioethyl) thio] -3- (β-epithiopropylthio) propane, tetrakis (β-epithiopropylthiomethyl) ) Methane, 1,1,1-tris (β-epithiopropylthiomethyl) propane, bis (β-epithiopropyl) sulfide, bis (β-epithiopropyl) disulfide, bis (β-epithiopropyl) ether Aliphatic bones such as bis (β-epithiopropyl) methane, 1,2-bis (β-epithiopropyl) ethane, 1,3-bis (β-epithiopropyl) propane Such as episulfide compound having the like.
これらの中でも、好ましいエピチオ化合物としては、ビス（β−エピチオプロピル）スルフィド、ビス（β−エピチオプロピル）ジスルフィド、ビス（β−エピチオプロピル）エーテル、ビス（β−エピチオプロピル）メタン、１，２−ビス（β−エピチオプロピル）エタン、１，３−ビス（β−エピチオプロピル）プロパン、２，５−ビス（β−エピチオプロピル）−１，４−ジチアン、１，３−及び１，４−ビス（β−エピチオプロピル）シクロヘキサン、１，３−及び１，４−ビス（β−エピチオプロピル）ベンゼン、ビス〔４−（β−エピチオプロピルチオ）フェニル〕スルフィド、ビス〔４−（β−エピチオプロピルチオ）シクロヘキシル〕スルフィドが挙げられ、高屈折率レンズ用途として、特に好ましいエピチオ化合物としては、ビス（β−エピチオプロピル）スルフィド、ビス（β−エピチオプロピル）ジスルフィド、２，５−ビス（β−エピチオプロピル）−１，４−ジチアンが挙げられる。なお、これらのエピチオ化合物は、単独で用いても２種以上を混合して用いてもよい。 Among these, preferred epithio compounds include bis (β-epithiopropyl) sulfide, bis (β-epithiopropyl) disulfide, bis (β-epithiopropyl) ether, bis (β-epithiopropyl) methane, 1,2-bis (β-epithiopropyl) ethane, 1,3-bis (β-epithiopropyl) propane, 2,5-bis (β-epithiopropyl) -1,4-dithiane, 1,3 -And 1,4-bis (β-epithiopropyl) cyclohexane, 1,3- and 1,4-bis (β-epithiopropyl) benzene, bis [4- (β-epithiopropylthio) phenyl] sulfide Bis [4- (β-epithiopropylthio) cyclohexyl] sulfide, and as a particularly preferred epithio compound for high refractive index lens use, bis (Β-epithiopropyl) sulfide, bis (β-epithiopropyl) disulfide, 2,5-bis (β-epithiopropyl) -1,4-dithiane. In addition, these epithio compounds may be used independently or may be used in mixture of 2 or more types.
ポリチオ−ル化合物は高い屈折率と高いアッベ数を維持しながら実用的な耐光性を付与するために加えられる。ポリチオール化合物の使用量は、上記プラスチックレンズ製造用反応生成物とポリチオール化合物を含むレンズ原料組成物の全量を基準として、好ましくは３〜３０質量％、より好ましくは５〜２０質量％である。ポリチオール化合物の使用量が３質量％未満であると耐光性の改善が不十分となり、３０質量％を超えると目標とする１．７５以上の屈折率が得られなくなる。
なお、プラスチックレンズ製造用反応生成物と混合するポリチオール化合物は、少なくともその一部を、プラスチックレンズ製造用反応生成物を得るための原料組成物にあらかじめ加えておくこともできる。これによりプラスチックレンズ製造用反応生成物中への硫黄の溶解量を増やすことができるため、より高い屈折率を有するプラスチックレンズを得ることができる。Polythiol compounds are added to provide practical light resistance while maintaining a high refractive index and a high Abbe number. The amount of the polythiol compound used is preferably 3 to 30% by mass, more preferably 5 to 20% by mass, based on the total amount of the lens raw material composition containing the reaction product for producing a plastic lens and the polythiol compound. When the amount of the polythiol compound used is less than 3% by mass, the light resistance is not sufficiently improved, and when it exceeds 30% by mass, the target refractive index of 1.75 or more cannot be obtained.
In addition, at least a part of the polythiol compound to be mixed with the reaction product for producing a plastic lens can be added in advance to a raw material composition for obtaining a reaction product for producing a plastic lens. As a result, the amount of sulfur dissolved in the reaction product for producing a plastic lens can be increased, so that a plastic lens having a higher refractive index can be obtained.
本発明で用いるポリチオ−ル化合物としては、例えば、メタンジチオール、エタンジチオール、プロパンジチオール、１，６−ヘキサンジチオール、１，２，３−トリメルカプトプロパン、テトラキス（メルカプトメチル）メタン、シクロヘキサンジチオール、２，２−ジメチルプロパン−１，３−ジチオール、３，４−ジメトキシブタン−１，２−ジチオール、２−メチルシクロヘキサン−２，３−ジチオール、ビス（メルカプトメチル）シクロヘキサン、２，３−ジメルカプト−１−プロパノール（２−メルカプトアセテート）、２，３−ジメルカプト−１−プロパノール（３−メルカプトアセテート）、ジエチレングリコールビス（２−メルカプトアセテート）、ジエチレングリコールビス（３−メルカプトプロピオネート）、１，２−ジメルカプトプロピルメチルエーテル、２，３−ジメルカプトプロピルメチルエーテル、２，２−ビス（メルカプトメチル）−１，３−プロパンジチオール、ビス（２−メルカプトエチル）エーテル、エチレングリコールビス（２−メルカプトアセテート）、エチレングリコールビス（３−メルカプトプロピオネート）、トリメチロールプロパントリス（２−メルカプトアセテート）、トリメチロールプロパントリス（３−メルカプトプロピオネート）、ペンタエリスリトールテトラキス（２−メルカプトアセテート）、ペンタエリスリトールテトラキス（３−メルカプトプロピオネート）、１，２−ビス（２−メルカプトエチルチオ）−３−メルカプトプロパン、ビス（メルカプトメチル）スルフィド、ビス（メルカプトエチル）スルフィド、ビス（メルカプトプロピル）スルフィド、ビス（メルカプトメチルチオ）メタン、ビス（２−メルカプトエチルチオ）メタン、ビス（３−メルカプトプロピル）メタン、１，２−ビス（メルカプトメチルチオ）エタン、１，２−（２−メルカプトエチルチオ）エタン、１，２−（３−メルカプトプロピル）エタン、１，３−ビス（メルカプトメチルチオ）プロパン、１，３−ビス（２−メルカプトエチルチオ）プロパン、１，３−ビス（３−メルカプトプロピルチオ）プロパン、１，２−ビス（２−メルカプトエチルチオ）−３−メルカプトプロパン、２−メルカプトエチルチオ−１，３−プロパンジチオール、１，２，３−トリス（メルカプトメチルチオ）プロパン、１，２，３−トリス（２−メルカプトエチルチオ）プロパン、１，２，３−トリス（３−メルカプトプロピルチオ）プロパン、テトラキス（メルカプトメチルチオメチル）メタン、テトラキス（２−メルカプトエチルチオメチル）メタン、テトラキス（３−メルカプトプロピルチオメチル）メタン、ビス（メルカプトメチル）ジスルフィド、ビス（メルカプトエチル）ジスルフィド、ビス（メルカプトメチル）−３，６，９−トリチア−１，１１−ウンデカンジチオール、ビス（１，３−ジメルカプト−２−プロピル）スルフィド、３，４−チオフェンジチオール、テトラヒドロチオフェン−２，５−ジメルカプトメチル、２，５−ジメルカプト−１，３，４−チアジアゾール、２，５−ジメルカプト−１，４−ジチアン、２，５−ビス（メルカプトメチル）−１，４−ジチアン、２，５−ビス（メルカプトエチル）−１，４−ジチアン等のメルカプト基以外に硫黄原子を含有するもしくは含有しない化合物等が挙げられる。 Examples of the polythiol compound used in the present invention include methanedithiol, ethanedithiol, propanedithiol, 1,6-hexanedithiol, 1,2,3-trimercaptopropane, tetrakis (mercaptomethyl) methane, cyclohexanedithiol, 2 , 2-dimethylpropane-1,3-dithiol, 3,4-dimethoxybutane-1,2-dithiol, 2-methylcyclohexane-2,3-dithiol, bis (mercaptomethyl) cyclohexane, 2,3-dimercapto-1 -Propanol (2-mercaptoacetate), 2,3-dimercapto-1-propanol (3-mercaptoacetate), diethylene glycol bis (2-mercaptoacetate), diethylene glycol bis (3-mercaptopropionate), 1,2 Dimercaptopropyl methyl ether, 2,3-dimercaptopropyl methyl ether, 2,2-bis (mercaptomethyl) -1,3-propanedithiol, bis (2-mercaptoethyl) ether, ethylene glycol bis (2-mercaptoacetate) ), Ethylene glycol bis (3-mercaptopropionate), trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol Tetrakis (3-mercaptopropionate), 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane, bis (mercaptomethyl) sulfide, bis (mercaptoethyl) sulfur Bis (mercaptopropyl) sulfide, bis (mercaptomethylthio) methane, bis (2-mercaptoethylthio) methane, bis (3-mercaptopropyl) methane, 1,2-bis (mercaptomethylthio) ethane, 1,2- (2-mercaptoethylthio) ethane, 1,2- (3-mercaptopropyl) ethane, 1,3-bis (mercaptomethylthio) propane, 1,3-bis (2-mercaptoethylthio) propane, 1,3- Bis (3-mercaptopropylthio) propane, 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane, 2-mercaptoethylthio-1,3-propanedithiol, 1,2,3-tris (mercapto Methylthio) propane, 1,2,3-tris (2-mercaptoethylthio) propane, 1, 2,3-tris (3-mercaptopropylthio) propane, tetrakis (mercaptomethylthiomethyl) methane, tetrakis (2-mercaptoethylthiomethyl) methane, tetrakis (3-mercaptopropylthiomethyl) methane, bis (mercaptomethyl) disulfide Bis (mercaptoethyl) disulfide, bis (mercaptomethyl) -3,6,9-trithia-1,11-undecanedithiol, bis (1,3-dimercapto-2-propyl) sulfide, 3,4-thiophenedithiol, Tetrahydrothiophene-2,5-dimercaptomethyl, 2,5-dimercapto-1,3,4-thiadiazole, 2,5-dimercapto-1,4-dithiane, 2,5-bis (mercaptomethyl) -1,4 Dithiane, 2,5-bis (mercapto Chill) -1,4-containing sulfur atoms in addition to mercapto groups such as dithiane or not containing compounds, and the like.
これらの化合物の中で、好ましいポリチオ−ル化合物としては、ビス（メルカプトメチル）−１，４−ジチアン、ビス（メルカプトエチル）スルフィド、ビス（メルカプトエチル）ジスルフィド、１，２−ビス（メルカプトエチル）チオ−３−メルカプトプロパン、ペンタエリスリトールテトラキスメルカプトアセテート、ペンタエリスリトールテトラキスメルカプトプロピオネート、トリメチロールプロパントリスメルカプトアセテート、トリメチロールプロパントリスメルカプトプロピオネート及びトリメルカプトプロパンが挙げられる。なお、これらのポリチオール化合物は単独で用いても、２種以上を混合して用いてもよい。
本発明において、上記プラスチックレンズ製造用反応生成物とポリチオール化合物を含むレンズ原料組成物には、所望により、紫外線吸収剤、赤外線吸収剤、光安定剤、内部離型剤、酸化防止剤、染料、フォトクロ染料、顔料及び帯電防止剤等の公知の各種添加剤を加えてもよい。Among these compounds, preferred polythiol compounds include bis (mercaptomethyl) -1,4-dithiane, bis (mercaptoethyl) sulfide, bis (mercaptoethyl) disulfide, and 1,2-bis (mercaptoethyl). Examples include thio-3-mercaptopropane, pentaerythritol tetrakismercaptoacetate, pentaerythritol tetrakismercaptopropionate, trimethylolpropane trismercaptoacetate, trimethylolpropane trismercaptopropionate and trimercaptopropane. In addition, these polythiol compounds may be used independently or may be used in mixture of 2 or more types.
In the present invention, the lens raw material composition containing the reaction product for producing a plastic lens and a polythiol compound may optionally include an ultraviolet absorber, an infrared absorber, a light stabilizer, an internal mold release agent, an antioxidant, a dye, Various known additives such as photochromic dyes, pigments and antistatic agents may be added.
また、上記プラスチックレンズ製造用反応生成物とポリチオール化合物との反応に際して、反応を促進するために触媒を添加してもよい。その触媒としては、アミン類、フォスフィン類、第４級アンモニウム塩類、第４級ホスホニウム塩類、第３級スルホニウム塩類、第２級ヨードニウム塩類、鉱酸類、ルイス酸類、有機酸類、ケイ酸類及び四フッ化ホウ酸類等を挙げることができる。これらの中でも好ましい触媒の例として、アミノエタノール、１−アミノプロパノール、２−アミノプロパノール、アミノブタノール、アミノペンタノール、アミノヘキサノール等のアミン類、テトラメチルホスホニウムクロライド、テトラメチルホスホニウムブロマイド、テトラエチルホスホニウムクロライド、テトラエチルホスホニウムブロマイド、テトラ−ｎ−ブチルホスホニウムクロライド、テトラ−ｎ−ブチルホスホニウムブロマイド、テトラ−ｎ−ブチルホスホニウムヨーダイド、テトラ−ｎ−ヘキシルホスホニウムブロマイド、テトラ−ｎ−オクチルホスホニウムブロマイド等の第４級ホスホニウム塩類などを挙げることができる。また、使用される触媒は、使用するモノマーの種類に応じて選択し、使用量も調整する必要があるが、一般的にはレンズ原料組成物の全量を基準として０．００１〜０．１質量％が好ましい範囲である。 In addition, a catalyst may be added in order to accelerate the reaction when the reaction product for producing the plastic lens is reacted with the polythiol compound. The catalysts include amines, phosphine, quaternary ammonium salts, quaternary phosphonium salts, tertiary sulfonium salts, secondary iodonium salts, mineral acids, Lewis acids, organic acids, silicic acids and tetrafluoride. Examples thereof include boric acids. Examples of preferred catalysts among these include amines such as aminoethanol, 1-aminopropanol, 2-aminopropanol, aminobutanol, aminopentanol, aminohexanol, tetramethylphosphonium chloride, tetramethylphosphonium bromide, tetraethylphosphonium chloride, Quaternary phosphonium such as tetraethylphosphonium bromide, tetra-n-butylphosphonium chloride, tetra-n-butylphosphonium bromide, tetra-n-butylphosphonium iodide, tetra-n-hexylphosphonium bromide, tetra-n-octylphosphonium bromide Examples thereof include salts. The catalyst to be used is selected according to the type of monomer to be used, and the amount used needs to be adjusted, but generally 0.001 to 0.1 mass based on the total amount of the lens raw material composition. % Is a preferred range.
また、各レンズ原料、添加剤の混合前、混合時あるいは混合後に、減圧下に脱ガス操作を行うことが、後の注型重合硬化中の気泡発生を防止する点から好ましい。この脱ガス操作における減圧度は、好ましくは１０〜５０００Ｐａ程度であり、より好ましくは１００〜２０００Ｐａの範囲である。本発明のプラスチックレンズ製造用反応生成物を含むレンズ原料組成物、あるいはプラスチックレンズ製造用反応生成物及びポリチオール化合物を０．２〜２０μｍ程度の孔径を有するフィルターで濾過し精製することは、本発明のプラスチックレンズの品質をさらに高める上から好ましい。
プラスチックレンズを得るためのレンズ原料組成物をガラスや金属製の型に注入後、電気炉等による重合硬化を行うことにより、プラスチックレンズを得ることができる。硬化温度は５〜１２０℃程度、硬化時間は、通常１〜７２時間程度である。また、硬化終了後、本発明のプラスチックレンズの歪を除くために、硬化物を５０〜１５０℃の温度で１０分〜５時間程度アニール処理を行うことが好ましい。Further, it is preferable to perform a degassing operation under reduced pressure before, during or after mixing the lens raw materials and additives from the viewpoint of preventing the generation of bubbles during the subsequent cast polymerization curing. The degree of reduced pressure in this degassing operation is preferably about 10 to 5000 Pa, more preferably in the range of 100 to 2000 Pa. Filtering and purifying the lens raw material composition containing the reaction product for producing a plastic lens of the present invention, or the reaction product for producing a plastic lens and the polythiol compound with a filter having a pore diameter of about 0.2 to 20 μm is the present invention. From the viewpoint of further improving the quality of the plastic lens.
A plastic lens can be obtained by injecting a lens raw material composition for obtaining a plastic lens into a glass or metal mold, followed by polymerization and curing in an electric furnace or the like. The curing temperature is about 5 to 120 ° C., and the curing time is usually about 1 to 72 hours. In addition, after the curing is completed, it is preferable to anneal the cured product at a temperature of 50 to 150 ° C. for about 10 minutes to 5 hours in order to remove the distortion of the plastic lens of the present invention.
本発明のプラスチックレンズの製造方法により得られたプラスチックレンズが重合後に型から剥がれにくい場合は、公知の外部離型剤を使用して型から剥がすか、あるいは公知の内部離型剤をレンズ原料組成物に添加することにより、離型性を向上させることが好ましい。外部離型剤と内部離型剤の両方を使用してもよい。
また、本発明に係るレンズ原料組成物には、紫外線からレンズ及び／又は目を保護する目的で紫外線吸収剤を添加してもよい。また、赤外線から目を保護する目的で赤外線吸収剤を添加してもよい。これらの添加量は使用する添加剤の吸収能と最大吸収波長にもよるが、レンズ原料組成物の全量を基準として、通常０．０３〜３質量％程度である。またこれらの吸収剤を、プラスチックレンズに含浸させてもよい。さらに、レンズの美観を維持又は向上させる目的で、レンズ原料組成物に酸化防止剤を添加したり、微量の青系と赤系の染料又は微量の青系と赤系の顔料を添加したりすることによりブルーイングを行うこともできる。When the plastic lens obtained by the method for producing a plastic lens of the present invention is difficult to peel off from the mold after polymerization, it is peeled off from the mold using a known external mold release agent, or a known internal mold release agent is used as a lens raw material composition. It is preferable to improve releasability by adding to the product. Both external and internal mold release agents may be used.
Moreover, you may add a ultraviolet absorber to the lens raw material composition which concerns on this invention in order to protect a lens and / or eyes from an ultraviolet-ray. Moreover, you may add an infrared absorber in order to protect eyes from infrared rays. The amount of these additives is usually about 0.03 to 3% by mass, based on the total amount of the lens raw material composition, although it depends on the absorption capacity and the maximum absorption wavelength of the additive used. Moreover, you may impregnate a plastic lens with these absorbers. Furthermore, for the purpose of maintaining or improving the aesthetics of the lens, an antioxidant is added to the lens raw material composition, or a small amount of blue and red dyes or a small amount of blue and red pigments are added. Blueing can also be performed.
以下、実施例により本発明をさらに詳細に説明するが、本発明はこれらの実施例に限定されるものではない。なお、実施例及び比較例において、容器内酸素分圧は容器内圧力と容器内の気体をサンプリングして測定した酸素濃度の積として計算で求めた。また、得られたプラスチックレンズの物性評価は以下のようにして行った。
（１）屈折率（ｎｅ）とアッベ数
プラスチックレンズから測定用サンプル片を切り出し、カルニュー光学工業（株）製精密屈折率計ＫＰＲ−２００型を用いて２０℃で測定した。表１中、ｎｅは５４６．１ｎｍにおける屈折率。アッベ数νｅは（ｎｅ−１）／（ｎＦ−ｎＣ）の値である。また、ｎＣは６４３．９ｎｍ、ｎＦは４８０．０ｎｍでの屈折率である。
（２）黄色度（ＹＩ）
（株）日立製作所製の分光光度計Ｕ−４１００を用いて実質的に度数の付いていない同じ仕様の中心肉厚８．０ｍｍのレンズブランクスの分光測定を行ない、付属の演算プログラムにより黄色度（ＹＩ）を算出した。
（３）透明性
暗室にて黒色布を背景にして卓上蛍光灯下にプラスチックレンズの外観を目視で観察し、曇りの有無等を調べた。EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples. In Examples and Comparative Examples, the oxygen partial pressure in the container was obtained by calculation as the product of the oxygen pressure measured by sampling the gas in the container and the gas in the container. The physical properties of the obtained plastic lens were evaluated as follows.
(1) Refractive index (ne) and Abbe number A sample piece for measurement was cut out from a plastic lens and measured at 20 ° C. using a precision refractometer KPR-200 manufactured by Kalnew Optical Industry Co., Ltd. In Table 1, ne is the refractive index at 546.1 nm. The Abbe number νe is a value of (ne−1) / (nF−nC). NC is the refractive index at 643.9 nm, and nF is the refractive index at 480.0 nm.
(2) Yellowness (YI)
The spectrophotometer U-4100 manufactured by Hitachi, Ltd. is used to perform spectroscopic measurement of lens blanks with a center wall thickness of 8.0 mm, which have substantially no power, and the yellowness ( YI) was calculated.
(3) Transparency In the dark room, the appearance of the plastic lens was visually observed under a table fluorescent lamp against a black cloth as a background, and the presence or absence of cloudiness was examined.
実施例１
（ａ）プラスチックレンズ製造用反応生成物の製造
ジャケットを備えたステンレス製の攪拌機付き容器に、エピチオ化合物としてビス（β−エピチオプロピル）スルフィドを２３４７．５質量部、硫黄（和光純薬工業（株）製；硫黄華 純度９９質量％を瑪瑙乳鉢にて粉末化し、減圧乾燥装置（５５℃、１３３０Ｐａ）にて２４時間、加熱処理を行ったもの）を７１１質量部、ビス(メルカプトメチル)−１，４−ジチアン７５質量部、紫外線吸収剤（シプロ化成（株）製SEESORB707）を２２．５質量部加え、７０℃に加熱して攪拌溶解した。
次に容器内を６０℃に降温してそのまま温度を保ち、そこに加硫促進剤としてメチマゾール(２−メルカプト−Ｎ−メチルイミダゾール)を１．５質量部加えて密閉した。容器を真空ポンプに接続して攪拌しながら減圧脱泡を開始した。激しい発泡が始まり、容器内が２０００Ｐａに達してから１５分間そのまま脱泡操作を行なった。続いて容器を窒素ボンベに接続し、純度９９．９９％の窒素を導入して大気圧相当の圧力まで戻して密閉した。このときの容器内の気体をサンプリングして酸素濃度を測定したところ０．１％未満であった。従って、このときの酸素分圧は１０１．３Ｐａ未満となる。
さらに容器内を攪拌しながら温度を保ち、加硫促進剤を投入してから３時間５０分後、反応生成物の屈折率がｎｄ：１．６７１（６０℃）に達したところで反応停止剤としてジメチルチンジクロライド３．６質量部を投入し、直ちにジャケットに冷媒を通して内部の冷却を始めた。２０分で３０℃まで冷却し、粘度４００ｍＰａ・ｓ（３０℃）のプラスチックレンズ製造用反応生成物３１５７．５質量部を得た。なお、このときの粘度は温度を３０℃に保ったオーブン内でＣＢＣマテリアルズ(株)製のラボ用粘度計ＶＭ−１０Ａを用いて測定した。Example 1
(A) Production of reaction product for plastic lens production In a stainless steel vessel equipped with a jacket, 2347.5 parts by mass of bis (β-epithiopropyl) sulfide as an epithio compound, sulfur (Wako Pure Chemical Industries ( Manufactured by Co., Ltd .; sulfur flower 99% by mass in a mortar and powdered in a reduced pressure drying apparatus (55 ° C., 1330 Pa) for 24 hours) 711 parts by mass, bis (mercaptomethyl)- 75 parts by mass of 1,4-dithiane and 22.5 parts by mass of an ultraviolet absorber (SEESORB707 manufactured by Sipro Kasei Co., Ltd.) were added, heated to 70 ° C., and dissolved by stirring.
Next, the temperature in the container was lowered to 60 ° C. and the temperature was maintained as it was, and 1.5 parts by mass of methimazole (2-mercapto-N-methylimidazole) was added as a vulcanization accelerator and sealed. The container was connected to a vacuum pump and vacuum degassing was started while stirring. Severe foaming started, and after the inside of the container reached 2000 Pa, the defoaming operation was performed for 15 minutes. Subsequently, the container was connected to a nitrogen cylinder, nitrogen having a purity of 99.99% was introduced, the pressure was returned to a pressure corresponding to atmospheric pressure, and the container was sealed. When the gas in the container at this time was sampled and the oxygen concentration was measured, it was less than 0.1%. Therefore, the oxygen partial pressure at this time is less than 101.3 Pa.
Further, the temperature was maintained while stirring the container, and after 3 hours and 50 minutes from the introduction of the vulcanization accelerator, when the refractive index of the reaction product reached nd: 1.671 (60 ° C.), the reaction was stopped. 3.6 parts by mass of dimethyltin dichloride was added, and the inside of the jacket was immediately passed through the refrigerant to start cooling. It cooled to 30 degreeC in 20 minutes, and obtained 3157.5 mass parts of reaction products for plastic lens manufacture with a viscosity of 400 mPa * s (30 degreeC). The viscosity at this time was measured using a laboratory viscometer VM-10A manufactured by CBC Materials, Inc. in an oven maintained at a temperature of 30 ° C.
（ｂ）プラスチックレンズの製造
ポリチオール化合物としてビス(メルカプトメチル)−１，４−ジチアン７５質量部を秤量してフラスコに加え、内部離型剤として酸性リン酸エステル（城北化学工業（株）製JP-506H）を０．１２質量部、硬化触媒としてテトラブチルホスホニウムブロマイドを０．０９質量部、ブルーイング剤として、商品名：ダイヤレジン ブルーＧ(三菱化学（株）製)と、商品名：ダイヤレジン レッドＨＳ(三菱化学（株）製)とを、青：赤＝７：３の質量換算割合で配合し、レンズ原料組成物の全量を基準として２００質量ｐｐｂとなる量を加え、攪拌溶解させた。これを上記（ａ）で製造したプラスチックレンズ製造用反応生成物に加えてさらに攪拌した。ほぼ均一になったところで２０００Ｐａの減圧下で攪拌しながら１０分間脱気した。これを孔径１μｍのテフロン（登録商標）フィルターにてろ過し、ガラスモールドとガスケットからなる鋳型に注入して封止した。
この鋳型を２０℃から１００℃まで２２時間かけて緩やかに昇温し、１００℃で１時間保持して重合を行った。重合終了後、徐々に冷却し、プラスチックレンズを鋳型から取り出した。得られたレンズに生じている歪を軽減して度数を安定させるため、１０５℃で１時間加熱した後、室温まで徐冷するアニール処理を行い、プラスチックレンズを得た。
このようにして、得られたプラスチックレンズについて、上記（１）〜（３）の物性を測定し、評価した。結果を表１に示す。表１に示すように、得られたプラスチックレンズは屈折率ｎｅ：１．７５５、アッベ数νｅ：３０．３と優れた光学特性を有していた。また、ＹＩ：１．９２が示す通り黄味着色が少なく、曇りのない透明性に優れたレンズであった。(B) Manufacture of a plastic lens 75 parts by weight of bis (mercaptomethyl) -1,4-dithiane as a polythiol compound is weighed and added to a flask, and an acidic phosphate ester (Johoku Chemical Co., Ltd., JP) as an internal mold release agent. -506H) is 0.12 parts by mass, tetrabutylphosphonium bromide is 0.09 parts by mass as a curing catalyst, and as a bluing agent, trade name: Diaresin Blue G (manufactured by Mitsubishi Chemical Corporation) and trade name: Diamond Resin Red HS (manufactured by Mitsubishi Chemical Corporation) is blended in a mass conversion ratio of blue: red = 7: 3, and an amount of 200 mass ppb based on the total amount of the lens raw material composition is added and dissolved by stirring. It was. This was added to the reaction product for producing a plastic lens produced in the above (a) and further stirred. When it became almost uniform, it was deaerated for 10 minutes while stirring under a reduced pressure of 2000 Pa. This was filtered through a Teflon (registered trademark) filter having a pore diameter of 1 μm, and poured into a mold composed of a glass mold and a gasket and sealed.
The mold was gradually heated from 20 ° C. to 100 ° C. over 22 hours and held at 100 ° C. for 1 hour for polymerization. After completion of the polymerization, the mixture was gradually cooled, and the plastic lens was taken out from the mold. In order to reduce the distortion generated in the obtained lens and stabilize the frequency, the lens was heated at 105 ° C. for 1 hour, and then annealed to gradually cool to room temperature to obtain a plastic lens.
Thus, about the obtained plastic lens, the physical property of said (1)-(3) was measured and evaluated. The results are shown in Table 1. As shown in Table 1, the obtained plastic lens had excellent optical characteristics with a refractive index ne: 1.755 and an Abbe number νe: 30.3. Further, as indicated by YI: 1.92, it was a lens excellent in transparency with little yellowing and no haze.
実施例２
（ａ）プラスチックレンズ製造用反応生成物の製造
実施例１と同様の容器に各原料を投入して溶解し、加硫促進剤を投入して６０℃で減圧脱泡を行なうところまで実施例１とまったく同様の操作を行なった。脱泡を止めてから減圧状態のまま容器を密閉したときの酸素分圧は実施例１のときと同等以下であるはずであり、１０１．３Ｐａ未満と推定される。
実施例１のように、ここで窒素の導入を行なわず、減圧状態で攪拌しながら温度を保って反応を進行させた。屈折率の上昇挙動は実施例１とほとんど一致しており、加硫促進剤を投入してから３時間５０分後、反応生成物の屈折率がｎｄ：１．６７１（６０℃）に達したところで反応停止剤としてジメチルチンジクロライド３．６質量部を投入し、直ちに内部の冷却を始めた。２０分で３０℃まで冷却し、粘度４００ｍＰａ・ｓ（３０℃）のプラスチックレンズ製造用反応生成物を得た。
（ｂ）プラスチックレンズの製造
（ａ）で製造したプラスチックレンズ製造用反応生成物を用いて実施例１とまったく同様の操作を行い、プラスチックレンズを得た。このようにして、得られたプラスチックレンズについて、上記（１）〜（３）の物性を測定、評価し、表１に示した。ここで示したように、得られたプラスチックレンズは屈折率ｎｅ：１．７５５、アッベ数νｅ：３０．３と優れた光学特性を有していた。また、ＹＩ：１．９０が示す通り黄味着色が少なく、曇りのない透明性に優れたレンズであった。Example 2
(A) Production of reaction product for plastic lens production Example 1 up to the point where each raw material is charged and dissolved in the same container as in Example 1 and vulcanization accelerator is added and vacuum degassing is performed at 60 ° C. The same operation was performed. The oxygen partial pressure when the container is sealed in a reduced pressure state after degassing is stopped should be equal to or less than that in Example 1, and is estimated to be less than 101.3 Pa.
As in Example 1, the reaction was allowed to proceed while maintaining the temperature while stirring under reduced pressure without introducing nitrogen. The rising behavior of the refractive index is almost the same as in Example 1, and 3 hours and 50 minutes after the vulcanization accelerator was added, the refractive index of the reaction product reached nd: 1.671 (60 ° C.). By the way, 3.6 parts by mass of dimethyltin dichloride was added as a reaction terminator, and the inside was immediately cooled. It cooled to 30 degreeC in 20 minutes, and obtained the reaction product for plastic lens manufacture with a viscosity of 400 mPa * s (30 degreeC).
(B) Production of plastic lens Using the reaction product for producing a plastic lens produced in (a), the same operation as in Example 1 was performed to obtain a plastic lens. Thus, about the obtained plastic lens, the physical property of said (1)-(3) was measured and evaluated, and it showed in Table 1. As shown here, the obtained plastic lens had excellent optical characteristics with a refractive index ne: 1.755 and an Abbe number νe: 30.3. Further, as indicated by YI: 1.90, it was a lens with little yellowing and excellent transparency without cloudiness.
比較例１
（ａ）プラスチックレンズ製造用反応生成物の製造
実施例１と同様の容器に各原料を投入して溶解し、加硫促進剤を投入して６０℃で減圧脱泡を行なうところまで実施例１とまったく同様の操作を行なった。続いて容器を膜式窒素発生装置に接続し、窒素を導入して大気圧相当の圧力まで戻して密閉した。このときの容器内の気体をサンプリングして酸素濃度を測定したところ１．５％であった。従って、このときの酸素分圧は１５２０Ｐａとなる。なお、装置から供給される気体の酸素濃度を測定したところ１．５％であったので、用いた窒素の純度は９８．５％と推定される。
さらにこの状態で攪拌しながら温度を保って反応を進行させたところ、加硫促進剤を投入してから６時間２０分後、反応生成物の屈折率が実施例１と同様にｎｄ：１．６７１（６０℃）に達した。そこで、反応停止剤としてジメチルチンジクロライド３．６質量部を投入し、直ちに内部の冷却を始めた。２０分で３０℃まで冷却し、粘度４００ｍＰａ・ｓ（３０℃）のプラスチックレンズ製造用反応生成物を得た。
（ｂ）プラスチックレンズの製造
（ａ）で製造したプラスチックレンズ製造用反応生成物を用いて実施例１とまったく同様の操作を行い、プラスチックレンズを得た。このようにして、得られたプラスチックレンズについて、上記（１）〜（３）の物性を測定し、評価し、結果を表１に示す。表１に示すように、得られたプラスチックレンズは屈折率ｎｅ：１．７５５、アッベ数νｅ：３０．３と優れた光学特性を有していた。しかし、ＹＩ：４．４３が示す通り実施例１のレンズと比較して明らかに黄味着色が大きく、眼鏡用レンズとして好ましいものではなかった。Comparative Example 1
(A) Production of reaction product for plastic lens production Example 1 up to the point where each raw material is charged and dissolved in the same container as in Example 1 and vulcanization accelerator is added and vacuum degassing is performed at 60 ° C. The same operation was performed. Subsequently, the container was connected to a membrane nitrogen generator, and nitrogen was introduced to return to a pressure corresponding to atmospheric pressure and sealed. When the oxygen concentration was measured by sampling the gas in the container at this time, it was 1.5%. Therefore, the oxygen partial pressure at this time is 1520 Pa. Since the oxygen concentration of the gas supplied from the apparatus was measured and found to be 1.5%, the purity of the nitrogen used is estimated to be 98.5%.
Further, the reaction was allowed to proceed while maintaining the temperature while stirring in this state. As a result, after 6 hours and 20 minutes from the introduction of the vulcanization accelerator, the refractive index of the reaction product was nd: 1. 671 (60 ° C.) was reached. Therefore, 3.6 parts by mass of dimethyltin dichloride was added as a reaction terminator, and the internal cooling was immediately started. It cooled to 30 degreeC in 20 minutes, and obtained the reaction product for plastic lens manufacture with a viscosity of 400 mPa * s (30 degreeC).
(B) Production of plastic lens Using the reaction product for producing a plastic lens produced in (a), the same operation as in Example 1 was performed to obtain a plastic lens. Thus, about the obtained plastic lens, the physical property of said (1)-(3) was measured and evaluated, and a result is shown in Table 1. As shown in Table 1, the obtained plastic lens had excellent optical characteristics with a refractive index ne: 1.755 and an Abbe number νe: 30.3. However, as shown by YI: 4.43, the yellowish coloring was clearly larger than that of the lens of Example 1, which was not preferable as a spectacle lens.
比較例２
（ａ）プラスチックレンズ製造用反応生成物の製造
実施例１と容器に各原料を投入して溶解し、加硫促進剤を投入して６０℃で減圧脱泡を行なうところまで実施例１とまったく同様の操作を行なった。脱泡後、密閉状態を開放して容器内に空気を導入し、大気圧まで戻して密閉した。このときの容器内の気体をサンプリングして酸素濃度を測定したところ２０．８％であった。従って、このときの酸素分圧は２１０７０Ｐａとなる。
さらにこの状態で攪拌しながら温度を保って反応を進行させたところ、加硫促進剤を投入してから９時間３０分後、反応生成物の屈折率が実施例１と同様にｎｄ：１．６７１（６０℃）に達した。そこで、反応停止剤としてジメチルチンジクロライド３．６質量部を投入し、直ちに内部の冷却を始めた。２０分で３０℃まで冷却し、粘度４００ｍＰａ・ｓ（３０℃）のプラスチックレンズ製造用反応生成物を得た。
（ｂ）プラスチックレンズの製造
（ａ）で製造したプラスチックレンズ製造用反応生成物を用いて実施例１とまったく同様の操作を行い、プラスチックレンズを得た。このようにして、得られたプラスチックレンズについて、上記（１）〜（３）の物性を測定し、評価した。結果を表１に示す。表１に示すように、得られたプラスチックレンズは屈折率ｎｅ：１．７５５、アッベ数νｅ：３０．３と優れた光学特性を有していた。しかし、ＹＩ：７．２５が示す通り実施例１のレンズと比較して明らかに黄味着色が大きく、眼鏡用レンズとして好ましいものではなかった。Comparative Example 2
(A) Production of reaction product for plastic lens production Example 1 and Example 1 are exactly the same as in Example 1 until each raw material is charged and dissolved, and a vulcanization accelerator is added and vacuum degassing is performed at 60 ° C. The same operation was performed. After defoaming, the sealed state was opened, air was introduced into the container, and the container was returned to atmospheric pressure and sealed. When the oxygen concentration was measured by sampling the gas in the container at this time, it was 20.8%. Therefore, the oxygen partial pressure at this time is 21070 Pa.
Furthermore, when the reaction was allowed to proceed while maintaining the temperature while stirring in this state, 9 hours and 30 minutes after adding the vulcanization accelerator, the refractive index of the reaction product was nd: 1. 671 (60 ° C.) was reached. Therefore, 3.6 parts by mass of dimethyltin dichloride was added as a reaction terminator, and the internal cooling was immediately started. It cooled to 30 degreeC in 20 minutes, and obtained the reaction product for plastic lens manufacture with a viscosity of 400 mPa * s (30 degreeC).
(B) Production of plastic lens Using the reaction product for producing a plastic lens produced in (a), the same operation as in Example 1 was performed to obtain a plastic lens. Thus, about the obtained plastic lens, the physical property of said (1)-(3) was measured and evaluated. The results are shown in Table 1. As shown in Table 1, the obtained plastic lens had excellent optical characteristics with a refractive index ne: 1.755 and an Abbe number νe: 30.3. However, as shown by YI: 7.25, the yellowish coloring was clearly larger than that of the lens of Example 1, which was not preferable as a spectacle lens.
比較例３
（ａ）プラスチックレンズ製造用反応生成物の製造
容器に各原料を投入して溶解し、加硫促進剤を投入して６０℃で減圧脱泡を行なうところまで実施例１とまったく同様の操作を行なった。脱泡時の酸素分圧は実施例１のときと同等以下であるはずであり、１０１．３Ｐａ未満と推定される。
さらに、脱気しつつ脱泡状態を保ち、攪拌しながら反応を進行させたところ、加硫促進剤を投入してから８時間２０分後、反応生成物の屈折率が実施例１と同様にｎｄ：１．６７１（６０℃）に達した。そこで、反応停止剤としてジメチルチンジクロライド３．６質量部を投入し、直ちに内部の冷却を始めた。２０分で３０℃まで冷却し、粘度４００ｍＰａ・ｓ（３０℃）のプラスチックレンズ製造用反応生成物を得た。
（ｂ）プラスチックレンズの製造
（ａ）で製造したプラスチックレンズ製造用反応生成物を用いて実施例１とまったく同様の操作を行い、プラスチックレンズを得た。このようにして、得られたプラスチックレンズについて、上記（１）〜（３）の物性を測定し、評価した。結果を表１に示す。表１に示すように、得られたプラスチックレンズは屈折率ｎｅ：１．７５５、アッベ数νｅ：３０．３と優れた光学特性を有していたが、ＹＩ：６．０７が示す通り実施例１のレンズと比較して明らかに黄味着色が大きく、眼鏡用レンズとして好ましいものではなかった。Comparative Example 3
(A) Production of reaction product for plastic lens production Each raw material is charged into a container for dissolution, vulcanization accelerator is added, and degassing under reduced pressure at 60 ° C. is performed in exactly the same manner as in Example 1. I did it. The oxygen partial pressure at the time of defoaming should be equal to or less than that in Example 1, and is estimated to be less than 101.3 Pa.
Furthermore, the deaerated state was maintained while deaeration, and the reaction was allowed to proceed while stirring. As a result, the refractive index of the reaction product was the same as in Example 1 after 8 hours and 20 minutes from the introduction of the vulcanization accelerator. nd: 1.671 (60 ° C.) was reached. Therefore, 3.6 parts by mass of dimethyltin dichloride was added as a reaction terminator, and the internal cooling was immediately started. It cooled to 30 degreeC in 20 minutes, and obtained the reaction product for plastic lens manufacture with a viscosity of 400 mPa * s (30 degreeC).
(B) Production of plastic lens Using the reaction product for producing a plastic lens produced in (a), the same operation as in Example 1 was performed to obtain a plastic lens. Thus, about the obtained plastic lens, the physical property of said (1)-(3) was measured and evaluated. The results are shown in Table 1. As shown in Table 1, the obtained plastic lens had excellent optical properties such as a refractive index ne: 1.755 and an Abbe number νe: 30.3, but as shown by YI: 6.07 Compared with the lens No. 1, the yellowish coloring was clearly large, which was not preferable as a spectacle lens.
本発明の製造方法により得られたプラスチックレンズ製造用反応生成物を、レンズ原料組成物の主成分として用いることにより、屈折率１．７５以上の高屈折率領域において、高アッベ数が維持され、且つ黄味着色の少ないプラスチックレンズを効率的に製造することができる。また、得られたプラスチックレンズは、眼鏡用プラスチックレンズに好適である。 By using the reaction product for plastic lens production obtained by the production method of the present invention as the main component of the lens raw material composition, a high Abbe number is maintained in a high refractive index region having a refractive index of 1.75 or more, In addition, it is possible to efficiently produce a plastic lens with little yellowing. The obtained plastic lens is suitable for a plastic lens for spectacles.
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