WO2014084360A1 - Method for producing plastic lens - Google Patents
Method for producing plastic lens Download PDFInfo
- Publication number
- WO2014084360A1 WO2014084360A1 PCT/JP2013/082203 JP2013082203W WO2014084360A1 WO 2014084360 A1 WO2014084360 A1 WO 2014084360A1 JP 2013082203 W JP2013082203 W JP 2013082203W WO 2014084360 A1 WO2014084360 A1 WO 2014084360A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- monomer
- polyisocyanate
- plastic lens
- melting point
- room temperature
- Prior art date
Links
- 239000004033 plastic Substances 0.000 title claims abstract description 48
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 39
- 239000000178 monomer Substances 0.000 claims abstract description 175
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 84
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 84
- 238000002844 melting Methods 0.000 claims abstract description 44
- 230000008018 melting Effects 0.000 claims abstract description 44
- 239000000203 mixture Substances 0.000 claims abstract description 32
- 239000007787 solid Substances 0.000 claims abstract description 25
- 229920006295 polythiol Polymers 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims description 33
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 25
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 239000012948 isocyanate Substances 0.000 claims 1
- 150000002513 isocyanates Chemical class 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 18
- 239000007858 starting material Substances 0.000 abstract 2
- 229910019142 PO4 Inorganic materials 0.000 description 15
- 239000002253 acid Substances 0.000 description 15
- 239000007788 liquid Substances 0.000 description 15
- 239000010452 phosphate Substances 0.000 description 15
- 241000239290 Araneae Species 0.000 description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 14
- 239000000654 additive Substances 0.000 description 10
- 230000000996 additive effect Effects 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 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 6
- -1 lysine ester Chemical class 0.000 description 6
- 239000002685 polymerization catalyst Substances 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 125000006226 butoxyethyl group Chemical group 0.000 description 4
- PKKGKUDPKRTKLJ-UHFFFAOYSA-L dichloro(dimethyl)stannane Chemical compound C[Sn](C)(Cl)Cl PKKGKUDPKRTKLJ-UHFFFAOYSA-L 0.000 description 4
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- 235000002597 Solanum melongena Nutrition 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000006082 mold release agent Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- COYTVZAYDAIHDK-UHFFFAOYSA-N [5-(sulfanylmethyl)-1,4-dithian-2-yl]methanethiol Chemical compound SCC1CSC(CS)CS1 COYTVZAYDAIHDK-UHFFFAOYSA-N 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 150000008366 benzophenones Chemical class 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 150000001565 benzotriazoles Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- YPQKTLPPOXNDMC-UHFFFAOYSA-N isocyanic acid;methylcyclohexane Chemical compound N=C=O.CC1CCCCC1 YPQKTLPPOXNDMC-UHFFFAOYSA-N 0.000 description 2
- UMRZSTCPUPJPOJ-UHFFFAOYSA-N norbornane Chemical compound C1CC2CCC1C2 UMRZSTCPUPJPOJ-UHFFFAOYSA-N 0.000 description 2
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 2
- GAJQCIFYLSXSEZ-UHFFFAOYSA-N tridecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCOP(O)(O)=O GAJQCIFYLSXSEZ-UHFFFAOYSA-N 0.000 description 2
- SXJSETSRWNDWPP-UHFFFAOYSA-N (2-hydroxy-4-phenylmethoxyphenyl)-phenylmethanone Chemical compound C=1C=C(C(=O)C=2C=CC=CC=2)C(O)=CC=1OCC1=CC=CC=C1 SXJSETSRWNDWPP-UHFFFAOYSA-N 0.000 description 1
- ARVUDIQYNJVQIW-UHFFFAOYSA-N (4-dodecoxy-2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC(OCCCCCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 ARVUDIQYNJVQIW-UHFFFAOYSA-N 0.000 description 1
- DHBXNPKRAUYBTH-UHFFFAOYSA-N 1,1-ethanedithiol Chemical compound CC(S)S DHBXNPKRAUYBTH-UHFFFAOYSA-N 0.000 description 1
- LFTMJBWNOFFSRW-UHFFFAOYSA-N 1,2-Butanedithiol Chemical compound CCC(S)CS LFTMJBWNOFFSRW-UHFFFAOYSA-N 0.000 description 1
- JRNVQLOKVMWBFR-UHFFFAOYSA-N 1,2-benzenedithiol Chemical compound SC1=CC=CC=C1S JRNVQLOKVMWBFR-UHFFFAOYSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- PIDUEESSWOVGNT-UHFFFAOYSA-N 1,2-diethyl-3,4-diisocyanatobenzene Chemical compound CCC1=CC=C(N=C=O)C(N=C=O)=C1CC PIDUEESSWOVGNT-UHFFFAOYSA-N 0.000 description 1
- MMJDYWRDMVPQPF-UHFFFAOYSA-N 1,2-diisocyanato-3,4-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=C(N=C=O)C(N=C=O)=C1C(C)C MMJDYWRDMVPQPF-UHFFFAOYSA-N 0.000 description 1
- QOKSGFNBBSSNAL-UHFFFAOYSA-N 1,2-diisocyanato-3,4-dimethylbenzene Chemical compound CC1=CC=C(N=C=O)C(N=C=O)=C1C QOKSGFNBBSSNAL-UHFFFAOYSA-N 0.000 description 1
- HMDXXHVBUMKDQL-UHFFFAOYSA-N 1,2-diisocyanato-3-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC(N=C=O)=C1N=C=O HMDXXHVBUMKDQL-UHFFFAOYSA-N 0.000 description 1
- OEAKMLDCNATGIH-UHFFFAOYSA-N 1,2-dimethylcyclohexa-3,5-diene-1,2-dithiol Chemical group SC1(C(C=CC=C1)(C)S)C OEAKMLDCNATGIH-UHFFFAOYSA-N 0.000 description 1
- XIQLNXQBMLWSLV-UHFFFAOYSA-N 1,2-dimethylcyclohexa-3,5-diene-1,3-dithiol Chemical group SC1(C(C(=CC=C1)S)C)C XIQLNXQBMLWSLV-UHFFFAOYSA-N 0.000 description 1
- VYMPLPIFKRHAAC-UHFFFAOYSA-N 1,2-ethanedithiol Chemical compound SCCS VYMPLPIFKRHAAC-UHFFFAOYSA-N 0.000 description 1
- YGKHJWTVMIMEPQ-UHFFFAOYSA-N 1,2-propanedithiol Chemical compound CC(S)CS YGKHJWTVMIMEPQ-UHFFFAOYSA-N 0.000 description 1
- XMEPRJBZFCWFKN-UHFFFAOYSA-N 1,3-Butanedithiol Chemical compound CC(S)CCS XMEPRJBZFCWFKN-UHFFFAOYSA-N 0.000 description 1
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 1
- XSCLFFBWRKTMTE-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCCC(CN=C=O)C1 XSCLFFBWRKTMTE-UHFFFAOYSA-N 0.000 description 1
- CZTCQAYHNHNTAP-UHFFFAOYSA-N 1,3-dithiane-4,5-dithiol Chemical compound SC1SCSCC1S CZTCQAYHNHNTAP-UHFFFAOYSA-N 0.000 description 1
- SHIZKKCREJRNQH-UHFFFAOYSA-N 1,3-dithiolane-2,2-dithiol Chemical compound SC1(S)SCCS1 SHIZKKCREJRNQH-UHFFFAOYSA-N 0.000 description 1
- OHLKMGYGBHFODF-UHFFFAOYSA-N 1,4-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=C(CN=C=O)C=C1 OHLKMGYGBHFODF-UHFFFAOYSA-N 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-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
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 description 1
- AXIWPQKLPMINAT-UHFFFAOYSA-N 1-ethyl-2,3-diisocyanatobenzene Chemical compound CCC1=CC=CC(N=C=O)=C1N=C=O AXIWPQKLPMINAT-UHFFFAOYSA-N 0.000 description 1
- MEZZCSHVIGVWFI-UHFFFAOYSA-N 2,2'-Dihydroxy-4-methoxybenzophenone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1O MEZZCSHVIGVWFI-UHFFFAOYSA-N 0.000 description 1
- TWWSEEHCVDRRRI-UHFFFAOYSA-N 2,3-Butanedithiol Chemical compound CC(S)C(C)S TWWSEEHCVDRRRI-UHFFFAOYSA-N 0.000 description 1
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 1
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 1
- JRRSZPBVIHXNBS-UHFFFAOYSA-N 2-(2H-benzotriazol-4-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)c1ccc(O)c(c1)-c1cccc2[nH]nnc12 JRRSZPBVIHXNBS-UHFFFAOYSA-N 0.000 description 1
- LHPPDQUVECZQSW-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-ditert-butylphenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=CC=CC3=N2)=C1O LHPPDQUVECZQSW-UHFFFAOYSA-N 0.000 description 1
- WXHVQMGINBSVAY-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 WXHVQMGINBSVAY-UHFFFAOYSA-N 0.000 description 1
- ITLDHFORLZTRJI-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-5-octoxyphenol Chemical compound OC1=CC(OCCCCCCCC)=CC=C1N1N=C2C=CC=CC2=N1 ITLDHFORLZTRJI-UHFFFAOYSA-N 0.000 description 1
- HJHZRZFONUPQAA-UHFFFAOYSA-N 2-isocyanato-1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=C(N=C=O)C(C)=C1 HJHZRZFONUPQAA-UHFFFAOYSA-N 0.000 description 1
- IAUYDCXDXJTGTB-UHFFFAOYSA-N 3,4-dimethylcyclohexa-1,5-diene-1,4-dithiol Chemical group CC1C=C(S)C=CC1(C)S IAUYDCXDXJTGTB-UHFFFAOYSA-N 0.000 description 1
- JRANNTKZJNTXAU-UHFFFAOYSA-N CC1=C(C)C(C)=CC=C1.N=C=O.N=C=O.N=C=O Chemical compound CC1=C(C)C(C)=CC=C1.N=C=O.N=C=O.N=C=O JRANNTKZJNTXAU-UHFFFAOYSA-N 0.000 description 1
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- LRNAHSCPGKWOIY-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=CC=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=CC=C1 LRNAHSCPGKWOIY-UHFFFAOYSA-N 0.000 description 1
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical compound CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- YHSYZOUUNYOPKT-UHFFFAOYSA-N [5-(sulfanylmethyl)-1,3-dithiolan-4-yl]methanethiol Chemical compound SCC1SCSC1CS YHSYZOUUNYOPKT-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- ZWOASCVFHSYHOB-UHFFFAOYSA-N benzene-1,3-dithiol Chemical compound SC1=CC=CC(S)=C1 ZWOASCVFHSYHOB-UHFFFAOYSA-N 0.000 description 1
- WYLQRHZSKIDFEP-UHFFFAOYSA-N benzene-1,4-dithiol Chemical compound SC1=CC=C(S)C=C1 WYLQRHZSKIDFEP-UHFFFAOYSA-N 0.000 description 1
- OCWYEMOEOGEQAN-UHFFFAOYSA-N bumetrizole Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O OCWYEMOEOGEQAN-UHFFFAOYSA-N 0.000 description 1
- FJTUUPVRIANHEX-UHFFFAOYSA-N butan-1-ol;phosphoric acid Chemical compound CCCCO.OP(O)(O)=O FJTUUPVRIANHEX-UHFFFAOYSA-N 0.000 description 1
- UNQHMFJVBBWADE-UHFFFAOYSA-N butane-1,1-dithiol Chemical compound CCCC(S)S UNQHMFJVBBWADE-UHFFFAOYSA-N 0.000 description 1
- SMTOKHQOVJRXLK-UHFFFAOYSA-N butane-1,4-dithiol Chemical compound SCCCCS SMTOKHQOVJRXLK-UHFFFAOYSA-N 0.000 description 1
- HLCGVCZVBXKAMT-UHFFFAOYSA-N butane-2,2-dithiol Chemical compound CCC(C)(S)S HLCGVCZVBXKAMT-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- KWTSZCJMWHGPOS-UHFFFAOYSA-M chloro(trimethyl)stannane Chemical compound C[Sn](C)(C)Cl KWTSZCJMWHGPOS-UHFFFAOYSA-M 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- ARUKYTASOALXFG-UHFFFAOYSA-N cycloheptylcycloheptane Chemical compound C1CCCCCC1C1CCCCCC1 ARUKYTASOALXFG-UHFFFAOYSA-N 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- NZZIMKJIVMHWJC-UHFFFAOYSA-N dibenzoylmethane Chemical compound C=1C=CC=CC=1C(=O)CC(=O)C1=CC=CC=C1 NZZIMKJIVMHWJC-UHFFFAOYSA-N 0.000 description 1
- RJGHQTVXGKYATR-UHFFFAOYSA-L dibutyl(dichloro)stannane Chemical compound CCCC[Sn](Cl)(Cl)CCCC RJGHQTVXGKYATR-UHFFFAOYSA-L 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- DOHQOGRRQASQAR-UHFFFAOYSA-L dimethyltin(2+);dibromide Chemical compound C[Sn](C)(Br)Br DOHQOGRRQASQAR-UHFFFAOYSA-L 0.000 description 1
- FRXGWNKDEMTFPL-UHFFFAOYSA-N dioctadecyl hydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCCCOP(O)(=O)OCCCCCCCCCCCCCCCCCC FRXGWNKDEMTFPL-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- QPPQHRDVPBTVEV-UHFFFAOYSA-N isopropyl dihydrogen phosphate Chemical compound CC(C)OP(O)(O)=O QPPQHRDVPBTVEV-UHFFFAOYSA-N 0.000 description 1
- INBDPOJZYZJUDA-UHFFFAOYSA-N methanedithiol Chemical compound SCS INBDPOJZYZJUDA-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UHGIMQLJWRAPLT-UHFFFAOYSA-N octadecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCCCOP(O)(O)=O UHGIMQLJWRAPLT-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- NCNISYUOWMIOPI-UHFFFAOYSA-N propane-1,1-dithiol Chemical compound CCC(S)S NCNISYUOWMIOPI-UHFFFAOYSA-N 0.000 description 1
- ZJLMKPKYJBQJNH-UHFFFAOYSA-N propane-1,3-dithiol Chemical compound SCCCS ZJLMKPKYJBQJNH-UHFFFAOYSA-N 0.000 description 1
- HMPSOEYFMTWOFC-UHFFFAOYSA-N propane-2,2-dithiol Chemical compound CC(C)(S)S HMPSOEYFMTWOFC-UHFFFAOYSA-N 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- CXVGEDCSTKKODG-UHFFFAOYSA-N sulisobenzone Chemical compound C1=C(S(O)(=O)=O)C(OC)=CC(O)=C1C(=O)C1=CC=CC=C1 CXVGEDCSTKKODG-UHFFFAOYSA-N 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- DFNPRTKVCGZMMC-UHFFFAOYSA-M tributyl(fluoro)stannane Chemical compound CCCC[Sn](F)(CCCC)CCCC DFNPRTKVCGZMMC-UHFFFAOYSA-M 0.000 description 1
- YFRLQYJXUZRYDN-UHFFFAOYSA-K trichloro(methyl)stannane Chemical compound C[Sn](Cl)(Cl)Cl YFRLQYJXUZRYDN-UHFFFAOYSA-K 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3876—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing mercapto groups
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- 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
Definitions
- the present invention relates to a method for producing a plastic lens having excellent transparency and productivity.
- Raw material monomers such as polythiol monomers and polyisocyanate monomers used in the production of plastic lenses are often liquid at room temperature of about 25 ° C. Therefore, in most cases, if the liquid raw material monomers are mixed as they are to prepare a mixture for polymerization, they can be uniformly mixed without supplying heat from the outside.
- the raw material monomer that is solid at room temperature is easy to handle in work, it is usually heated by a method such as a hot water bath, and once melted into a liquid and then mixed with other raw material monomers (for example, , See Patent Document 1).
- a method such as a hot water bath
- the present invention has been made in view of the above-described circumstances. Even when a polyisocyanate monomer that is solid at room temperature is used as a raw material monomer, the plastic lens has excellent transparency and productivity, and can be mass-produced. It is an object to provide a manufacturing method.
- the present inventors have found that the above-mentioned problems can be solved by dissolving a polyisocyanate monomer that is solid at room temperature under a specific temperature in the specific monomer, and completed. That is, the present invention is as follows.
- a method for producing a plastic lens for polymerizing a mixture containing a polyisocyanate monomer (A) having a melting point of room temperature or higher and a monomer (B) having a melting point of less than room temperature In the step of preparing the mixture, the solid polyisocyanate monomer (A) and the monomer (B) are mixed to dissolve the polyisocyanate monomer (A), and the mixture is mixed with the polyisocyanate monomer (A).
- a method for producing a plastic lens which is performed at a temperature lower than the melting point of the monomer (B) and higher than the melting point of the monomer (B).
- the production method of the present invention even when a polyisocyanate monomer that is solid at room temperature is used as a raw material monomer, it is possible to mass-produce plastic lenses having excellent transparency free from turbidity and spiders. Furthermore, according to the production method of the present invention, when a polyisocyanate monomer that is solid at room temperature is used, it is not necessary to melt in advance, so that plastic lenses can be produced with high productivity.
- the polyisocyanate monomer (A) having a melting point of room temperature or higher (sometimes referred to as polyisocyanate monomer (A)) and the melting point being lower than room temperature
- a method for producing a plastic lens for polymerizing a mixture containing monomer (B) (sometimes referred to as monomer (B)), which is characterized by the step of preparing the mixture to be subjected to the polymerization.
- the present invention dissolves the polyisocyanate monomer (A) by mixing the solid-state polyisocyanate monomer (A) and the monomer (B), It is characterized by being carried out at a temperature lower than the melting point of the polyisocyanate monomer (A) and higher than the melting point of the monomer (B).
- the production method of the present invention utilizes the property that the polyisocyanate monomer (A) in the solid state dissolves in the liquid monomer (B) without applying heat from the outside. Therefore, when preparing the mixture containing the polyisocyanate monomer (A) and the monomer (B), the polyisocyanate monomer (A) in the solid state can be mixed with the monomer (B) at the above mixing temperature. The polyisocyanate monomer (A) can be uniformly dissolved.
- the mixing temperature is in the range of a temperature lower than the melting point of the polyisocyanate monomer (A) and a temperature at which the monomer (B) exists in a liquid state, that is, a temperature higher than the melting point of the monomer (B).
- the mixing temperature is a temperature at which the polyisocyanate monomer (A) in the solid state is mixed with the monomer (B) and the polyisocyanate monomer (A) is uniformly dissolved.
- the upper limit of the mixing temperature when two or more polyisocyanate monomers (A) are used is a temperature lower than the lowest temperature among the melting points of the plurality of polyisocyanate monomers (A).
- the minimum of the mixing temperature in the case of using 2 or more types of monomers (B) is a temperature higher than the highest temperature among melting
- the mixing temperature is preferably a temperature within the above range that can avoid the progress of an undesired polymerization reaction that may occur until uniform dissolution of the polyisocyanate monomer (A) is achieved. ) And the like, and so on.
- the specific mixing temperature is preferably room temperature, and more specifically 20 to 30 ° C. It is preferably 20 to 27 ° C.
- the mixing order of the raw material monomers is not limited, including the case of using any additive described later.
- the polyisocyanate monomer (A) is mixed with the solid polyisocyanate monomer (A) and the monomer (B). It is preferable to prepare a mixture by mixing the polythiol monomer after dissolving.
- An additive can be added simultaneously when mixing with a polyisocyanate monomer (A) and a monomer (B). Also, before mixing with the polyisocyanate monomer (A) and the monomer (B), an additive can be added to the monomer (B) and dissolved in advance. If the additive does not show good solubility, it can be added. It may be dissolved while warm. For example, when the additive is added to the monomer (B) and heated to dissolve the additive, the monomer (B) and the monomer (B) are adjusted after adjusting the temperature to be lower than the melting point of the polyisocyanate monomer (A). What is necessary is just to mix the said polyisocyanate monomer (A) in what mixed and dissolved the additive.
- a raw material monomer containing at least a polyisocyanate monomer and a polythiol monomer is used.
- the raw material monomer includes a polyisocyanate monomer (A) having a melting point of room temperature or higher and a monomer having a melting point of less than room temperature (B ) Is included.
- the polyisocyanate monomer (A) has a melting point equal to or higher than room temperature, and has a property of being dissolved by mixing with the monomer (B) that is liquid at room temperature as described above.
- the polyisocyanate monomer (A) is used in a solid state. By using it in a solid state without melting, the polyisocyanate monomer (A) can be mixed with the monomer (B) without deterioration of properties due to heat. There can be no excellent transparency.
- the polyisocyanate monomer (A) having the above properties is preferably an aromatic polyisocyanate from the viewpoint of availability.
- an aromatic polyisocyanate having the above properties there is, for example, 4,4′-diphenylmethane diisocyanate (MDI) (melting point: 37 ° C .: from International Chemical Safety Card).
- MDI 4,4′-diphenylmethane diisocyanate
- it is a polyisocyanate monomer which has said property, not only MDI but the effect of this invention can be exhibited.
- MDI is prone to deterioration of properties due to heat, such as impurities such as dimers and oligomers.
- the plastic lens is turbid and spoiled.
- the deterioration of the lens quality becomes significant. For this reason, it is not preferable to use a large amount of MDI for production after it has been melted at one end or stored for a certain period of time. Therefore, when MDI is used as the polyisocyanate monomer (A) in the production method of the present invention that does not go through a melting step by heat, the effects of the present invention can be remarkably exhibited. Particularly suitable as the monomer (A).
- the shape of the polyisocyanate monomer (A) is preferably, for example, in the form of flakes, granules, and powders from the viewpoint of uniformly dissolving in the monomer (B) in a short time. Further, the size is not particularly limited, and may be appropriately adjusted from the scale and workability in mass production.
- a monomer (B) is a monomer used when melt
- the monomer (B) any monomer conventionally employed as a raw material monomer for plastic lenses can be used as long as it has a melting point of less than room temperature and dissolves the polyisocyanate monomer (A).
- the monomer (B) include polyisocyanate monomers and polythiol monomers having a melting point of less than room temperature.
- the monomer (B) is preferably a polyisocyanate monomer having a melting point of less than room temperature.
- polyisocyanate monomer having a melting point of less than room temperature examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylxylylene diisocyanate, ethylphenylene diisocyanate, dimethylphenylene diisocyanate, diethylphenylene diisocyanate, isopropylphenylene diisocyanate, diisopropylphenylene diisocyanate, trimethylbenzene triisocyanate, benzene triisocyanate, 1,6-hexamethylene Diisocyanate, lysine ester triisocyanate, mesitylene triisocyanate, 1,3,6-hexamethyl Rentriisocyanate, isophor
- 1,6-hexamethylene diisocyanate, isophorone diisocyanate, and 1,3-bis (isocyanatomethyl) cyclohexane are preferable from the viewpoint of yellowing resistance and alteration resistance.
- the said polyisocyanate monomer may be used independently and may use 2 or more types together.
- polyisocyanate compounds exemplified above can also be used as raw material monomers other than the monomer (B), and preferred polyisocyanate compounds are the same as described above.
- Examples of the polythiol monomer having a melting point of less than room temperature include dimercaptomethane, 1,1-dimercaptoethane, 1,2-dimercaptoethane, 1,1-dimercaptopropane, 1,2-dimercaptopropane, 1,3-dimercaptopropane, 2,2-dimercaptopropane, 1,1-dimercaptobutane, 1,2-dimercaptobutane, 1,3-dimercaptobutane, 1,4-dimercaptobutane, 2, 2-dimercaptobutane, 2,3-dimercaptobutane, 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-dimercaptoxylene, 1,3- Dimercaptoxylene, 1,4-dimercaptoxylene, 2,5-bismercaptomethyl-1,4-dithiane, 4,5-bis
- 2,5-bismercaptomethyl-1,4-dithiane and pentaerythritol tetrakis (mercaptoacetate) are preferable from the viewpoints of operability and resistance to alteration.
- the said polythiol monomer may be used independently and may use 2 or more types together.
- the raw material monomer other than the monomer (B) the polythiol compounds exemplified above can be used, and preferred polythiol compounds are the same as above.
- the blending ratio of various raw material monomers may be within the range usually employed in the plastic lens production field.
- the molar ratio of NCO groups / SH groups is 0.5 to 2.0 from the viewpoint of allowing the polymerization reaction to proceed without leaving unreacted groups.
- the blending ratio is preferable, and more preferably 0.95 to 1.05.
- additives in addition to the said raw material monomer, various additives can be contained in the above-mentioned mixture in the range which does not impair the objective of this invention.
- a well-known polymerization catalyst, a ultraviolet absorber, a mold release agent etc. can be used.
- an organic tin compound is preferable, for example, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dimethyltin dichloride, monomethyltin trichloride, trimethyltin chloride, tributyltin chloride, tributyltin fluoride, Dimethyltin dibromide or the like can be used.
- the said polymerization catalyst may be used independently and may use 2 or more types together.
- benzophenone compounds for example, benzophenone compounds, benzotriazole compounds, dibenzoylmethane, 4-tert-butyl-4′-methoxybenzoylmethane and the like can be used.
- benzophenone compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octoxybenzophenone, Examples include 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, and 2,2′-dihydroxy-4-methoxybenzophenone.
- benzotriazole compounds examples include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chloro.
- the said ultraviolet absorber may be used independently and may use 2 or more types together.
- a phosphoric acid monoester compound As a mold release agent, a phosphoric acid monoester compound, a phosphoric acid diester compound, etc. can be used, for example.
- the phosphoric acid monoester compound include isopropyl acid phosphate, butyl acid phosphate, octyl acid phosphate, nonyl acid phosphate, decyl acid phosphate, isodecyl acid phosphate, tridecyl acid phosphate, stearyl acid phosphate , Propylphenyl acid phosphate and butylphenyl acid phosphate.
- Examples of the phosphoric acid diester compound include diisopropyl acid phosphate, dibutyl acid phosphate, dioctyl acid phosphate, diisodecyl acid phosphate, bis (tridecyl acid phosphate), distearyl acid phosphate, dipropyl phenyl acid phosphate, Examples include dibutylphenyl acid phosphate and butoxyethyl acid phosphate.
- the said mold release agent may be used independently and may use 2 or more types together.
- the conditions for the polymerization reaction of the mixture containing the raw material monomer described above vary depending on the composition of the mixture and the lens molding die, and cannot be generally limited, but are about 0.5 to 72 hours at a polymerization reaction temperature of 30 to 150 ° C. .
- the production method of the present invention can produce a plastic lens without causing thermal degradation of the raw material monomer, and thus can provide a plastic lens having excellent transparency.
- the plastic lens manufactured according to the present invention include spectacle lenses, camera lenses, projector lenses, telescope lenses, and magnifier lenses.
- Example 1 Take out 22.88 g of MDI (melting point: 37 ° C.) as a solid from an oil can containing 4,4′-diphenylmethane diisocyanate (MDI) 20 kg stored refrigerated at 5 ° C. and put it into flakes into a 500 ml eggplant flask. I put it in. Subsequently, 25.09 g of 1,6-hexamethylene diisocyanate (HDI) (melting point -67 ° C.) was taken out from an 18 kg oil can stored at room temperature and placed in the flask.
- MDI 4,4′-diphenylmethane diisocyanate
- Example 2 23.09 g of MDI (melting point: 37 ° C.) as a solid was taken out from an oil can containing 20 kg of MDI stored refrigerated at 5 ° C. and put into a 500 ml eggplant flask in the form of flakes. Subsequently, 11.66 g of HDI (melting point -67 ° C.) was taken out from an 18 kg oil can stored at room temperature and placed in the flask. Further, 15.38 g of isophorone diisocyanate (IPDI) (melting point ⁇ 60 ° C.) was taken out from an 18 kg oil can stored at room temperature and charged into the flask.
- IPDI isophorone diisocyanate
- Example 3 23.55 g of MDI (melting point: 37 ° C.) was taken out from a petroleum can containing 20 kg of MDI stored refrigerated at 5 ° C. as a solid and put into a 500 ml eggplant flask. Subsequently, 11.87 g of HDI (melting point: ⁇ 67 ° C.) was taken out from an 18 kg oil can stored at room temperature and placed in the flask. Further, 13.71 g of 1,3-bis (isocyanatemethyl) cyclohexane (hydrogenated XDI) (melting point ⁇ 50 ° C.) was taken out from an 18 kg oil can stored at room temperature and placed in the flask.
- MDI melting point: 37 ° C.
- Example 1 A 20 kg MDI oil can stored refrigerated at 5 ° C. was melted in a constant temperature oven at 70 ° C. for 30 hours. A plastic lens was produced in the same procedure as in Example 1 except that 22.88 g of melted MDI was taken out and used. As long as the obtained plastic lens was observed indoors, no spider was observed, but when it was visually confirmed under a fluorescent lamp in a dark room, spiders were generated.
- Example 2 A 20 kg MDI oil can stored refrigerated at 5 ° C. was melted in a constant temperature oven at 70 ° C. for 30 hours. A plastic lens was produced in the same manner as in Example 2 except that 23.09 g of melted MDI was taken out and used. As long as the obtained plastic lens was observed indoors, no spider was observed, but when it was visually confirmed under a fluorescent lamp in a dark room, spiders were generated.
- Example 3 A 20 kg MDI oil can stored refrigerated at 5 ° C. was melted in a constant temperature oven at 70 ° C. for 30 hours. A plastic lens was produced in the same procedure as in Example 3 except that 23.55 g of melted MDI was taken out and used. As long as the obtained plastic lens was observed indoors, no spider was observed, but when it was visually confirmed under a fluorescent lamp in a dark room, spiders were generated.
- a polyisocyanate monomer that is solid at room temperature can be used in a solid state without being previously melted, and as a result, a plastic lens having excellent transparency can be produced.
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Abstract
Provided is a method for producing a plastic lens, which achieves excellent productivity and excellent transparency of a plastic lens produced thereby even in cases where a polyisocyanate monomer that is in a solid state at room temperature is used as a starting material monomer, and which enables mass production of the plastic lens.
A method for producing a plastic lens, wherein a mixture that contains (A) a polyisocyanate monomer having a melting point that is not less than room temperature and (B) a monomer having a melting point that is less than room temperature among the starting material monomers that include at least a polyisocyanate monomer and a polythiol monomer is polymerized. This method for producing a plastic lens is characterized in that: the polyisocyanate monomer (A) is dissolved by mixing the polyisocyanate monomer (A) in a solid state with the monomer (B) in the above-mentioned step for preparing the mixture; and the mixing is carried out at a temperature that is lower than the melting point of the polyisocyanate monomer (A) but higher than the melting point of the monomer (B).
Description
本発明は、透明性及び生産性に優れたプラスチックレンズを製造する方法に関する。
The present invention relates to a method for producing a plastic lens having excellent transparency and productivity.
プラスチックレンズの製造に用いられるポリチオールモノマーやポリイソシアネートモノマーなどの原料モノマーは、２５℃程度の室温において液体のものが多い。そのためほとんどの場合、この液体の各種原料モノマーをそのまま混合して重合に供する混合物を調合すれば、外部から熱を供給せずとも均一に混合させることができる。
一方で、室温において固体の原料モノマーは作業上の取り扱い易さから、湯煎などの方法で加熱をし、一端液体に溶融してから他の原料モノマーと混合することが通常行われている（例えば、特許文献１参照）。
また、プラスチックレンズを量産するには、工業的生産性の観点から一度に数百ｋｇ～数トン以上の固体の原料モノマーを液体に溶融する必要があり、場合によってはこの液体に溶融したものを、数日～一週間程度液体のまま保管したものが原料モノマーとして用いられる。 Raw material monomers such as polythiol monomers and polyisocyanate monomers used in the production of plastic lenses are often liquid at room temperature of about 25 ° C. Therefore, in most cases, if the liquid raw material monomers are mixed as they are to prepare a mixture for polymerization, they can be uniformly mixed without supplying heat from the outside.
On the other hand, since the raw material monomer that is solid at room temperature is easy to handle in work, it is usually heated by a method such as a hot water bath, and once melted into a liquid and then mixed with other raw material monomers (for example, , See Patent Document 1).
In addition, in order to mass-produce plastic lenses, it is necessary to melt several hundred kg to several tons or more of solid raw material monomers into a liquid from the viewpoint of industrial productivity. Those stored in liquid form for several days to one week are used as raw material monomers.
一方で、室温において固体の原料モノマーは作業上の取り扱い易さから、湯煎などの方法で加熱をし、一端液体に溶融してから他の原料モノマーと混合することが通常行われている（例えば、特許文献１参照）。
また、プラスチックレンズを量産するには、工業的生産性の観点から一度に数百ｋｇ～数トン以上の固体の原料モノマーを液体に溶融する必要があり、場合によってはこの液体に溶融したものを、数日～一週間程度液体のまま保管したものが原料モノマーとして用いられる。 Raw material monomers such as polythiol monomers and polyisocyanate monomers used in the production of plastic lenses are often liquid at room temperature of about 25 ° C. Therefore, in most cases, if the liquid raw material monomers are mixed as they are to prepare a mixture for polymerization, they can be uniformly mixed without supplying heat from the outside.
On the other hand, since the raw material monomer that is solid at room temperature is easy to handle in work, it is usually heated by a method such as a hot water bath, and once melted into a liquid and then mixed with other raw material monomers (for example, , See Patent Document 1).
In addition, in order to mass-produce plastic lenses, it is necessary to melt several hundred kg to several tons or more of solid raw material monomers into a liquid from the viewpoint of industrial productivity. Those stored in liquid form for several days to one week are used as raw material monomers.
プラスチックレンズを量産するうえで、上記のように大量の原料モノマーを液体にするには長時間熱にさらす必要があり、その間に、熱によってモノマーが反応してオリゴマーなどの不純物が生じたり、あるいは着色したりなどして性状が劣化してしまうといった問題が生じることがある。また、加熱して溶融した時点ではモノマーの性状の劣化がほとんどない場合であっても、一端加熱溶融させたモノマーを液体で一定期間保管すると、その性状が劣化するといった問題が生じることがある。また、溶融した原料モノマーを液体ではなく固体にしてから保管し、次回使用する際に再度液体にしたとしても、該原料モノマーには熱履歴が残ってしまい性状の劣化を回避することができない。また、大量の原料モノマーをその都度加熱溶融することは効率が悪く、工業的に現実的ではない。
In mass production of plastic lenses, as described above, in order to make a large amount of raw material monomer into a liquid, it is necessary to expose it to heat for a long time. During that time, the monomer reacts with the heat to generate impurities such as oligomers, or There may be a problem that the properties deteriorate due to coloring. Further, even when there is almost no deterioration of the properties of the monomer when heated and melted, there may be a problem that if the monomer once heated and melted is stored in a liquid for a certain period, its properties deteriorate. Further, even if the melted raw material monomer is stored in a solid state instead of a liquid, and is made liquid again at the next use, a thermal history remains in the raw material monomer, and deterioration of properties cannot be avoided. Moreover, it is inefficient and industrially impractical to heat and melt a large amount of raw material monomers each time.
上述のとおり、プラスチックレンズの原料モノマーとして用いられる、ポリイソシアネートモノマー及びポリチオールモノマーは室温において液体のものが多い。しかしながら、室温で固体であるポリイソシアネート化合物、特に４，４’－ジフェニルメタンジイソシアネートを上記のように量産する際の原料として熱により一端液体に溶融してから用いた場合、得られるプラスチックレンズには濁りやクモリなどが生じ、良好な透明性を得ることができなかった。また、作業時間やエネルギーを浪費するため、生産効率の観点からしても大量の原料を熱により一端液体に溶融してから用いることに問題があった。
As described above, many polyisocyanate monomers and polythiol monomers used as raw material monomers for plastic lenses are liquid at room temperature. However, when a polyisocyanate compound that is solid at room temperature, particularly 4,4′-diphenylmethane diisocyanate, is used as a raw material for mass production as described above after being melted into a liquid by heat, the resulting plastic lens becomes cloudy. And spiders were generated, and good transparency could not be obtained. In addition, since work time and energy are wasted, there is a problem in using a large amount of raw material after being melted into a liquid by heat from the viewpoint of production efficiency.
本発明は上述した事情に鑑みなされたもので、室温において固体であるポリイソシアネートモノマーを原料モノマーとして用いても、プラスチックレンズの透明性及び生産性に優れ、さらに量産することができる、プラスチックレンズの製造方法を提供することを課題とする。
The present invention has been made in view of the above-described circumstances. Even when a polyisocyanate monomer that is solid at room temperature is used as a raw material monomer, the plastic lens has excellent transparency and productivity, and can be mass-produced. It is an object to provide a manufacturing method.
本発明者らは、鋭意検討を進めた結果、特定の温度の下、室温において固体であるポリイソシアネートモノマーを、特定のモノマーに溶解させることにより上記課題を解決し得ることを見出し、本発明を完成した。
すなわち、本発明は下記のとおりである。 As a result of diligent investigations, the present inventors have found that the above-mentioned problems can be solved by dissolving a polyisocyanate monomer that is solid at room temperature under a specific temperature in the specific monomer, and completed.
That is, the present invention is as follows.
すなわち、本発明は下記のとおりである。 As a result of diligent investigations, the present inventors have found that the above-mentioned problems can be solved by dissolving a polyisocyanate monomer that is solid at room temperature under a specific temperature in the specific monomer, and completed.
That is, the present invention is as follows.
１． 少なくともポリイソシアネートモノマー及びポリチオールモノマーを含む原料モノマーのうち、融点が室温以上であるポリイソシアネートモノマー（Ａ）及び融点が室温未満であるモノマー（Ｂ）を含む混合物を重合するプラスチックレンズの製造方法であって、
上記混合物を調製する工程において、固体状態のポリイソシアネートモノマー（Ａ）とモノマー（Ｂ）とを混合して上記ポリイソシアネートモノマー（Ａ）を溶解し、また上記混合を、上記ポリイソシアネートモノマー（Ａ）の融点より低くかつ上記モノマー（Ｂ）の融点よりも高い温度で行うことを特徴とするプラスチックレンズの製造方法。
２． 前記ポリイソシアネートモノマー（Ａ）が、芳香族ポリイソシアネートである、前記１に記載のプラスチックレンズの製造方法。
３． 前記ポリイソシアネートモノマー（Ａ）が、４，４’－ジフェニルメタンジイソシアネートである、前記１又は２に記載のプラスチックレンズの製造方法。
４． 前記モノマー（Ｂ）が、融点が室温未満のポリイソシアネートモノマーである、前記１～３のいずれかに記載のプラスチックレンズの製造方法。
５． 固体状態のポリイソシアネートモノマー（Ａ）とモノマー（Ｂ）とを混合して上記ポリイソシアネートモノマー（Ａ）を溶解した後、ポリチオールモノマーを混合して混合物を調製する、前記１～４のいずれかに記載のプラスチックレンズの製造方法。 1. Among the raw material monomers containing at least a polyisocyanate monomer and a polythiol monomer, a method for producing a plastic lens for polymerizing a mixture containing a polyisocyanate monomer (A) having a melting point of room temperature or higher and a monomer (B) having a melting point of less than room temperature. And
In the step of preparing the mixture, the solid polyisocyanate monomer (A) and the monomer (B) are mixed to dissolve the polyisocyanate monomer (A), and the mixture is mixed with the polyisocyanate monomer (A). A method for producing a plastic lens, which is performed at a temperature lower than the melting point of the monomer (B) and higher than the melting point of the monomer (B).
2. 2. The method for producing a plastic lens as described in 1 above, wherein the polyisocyanate monomer (A) is an aromatic polyisocyanate.
3. 3. The method for producing a plastic lens as described in 1 or 2 above, wherein the polyisocyanate monomer (A) is 4,4′-diphenylmethane diisocyanate.
4). 4. The method for producing a plastic lens according to any one of 1 to 3, wherein the monomer (B) is a polyisocyanate monomer having a melting point of less than room temperature.
5. Any of the above 1 to 4, wherein the solid polyisocyanate monomer (A) and the monomer (B) are mixed to dissolve the polyisocyanate monomer (A), and then the polythiol monomer is mixed to prepare a mixture. The manufacturing method of the plastic lens of description.
上記混合物を調製する工程において、固体状態のポリイソシアネートモノマー（Ａ）とモノマー（Ｂ）とを混合して上記ポリイソシアネートモノマー（Ａ）を溶解し、また上記混合を、上記ポリイソシアネートモノマー（Ａ）の融点より低くかつ上記モノマー（Ｂ）の融点よりも高い温度で行うことを特徴とするプラスチックレンズの製造方法。
２． 前記ポリイソシアネートモノマー（Ａ）が、芳香族ポリイソシアネートである、前記１に記載のプラスチックレンズの製造方法。
３． 前記ポリイソシアネートモノマー（Ａ）が、４，４’－ジフェニルメタンジイソシアネートである、前記１又は２に記載のプラスチックレンズの製造方法。
４． 前記モノマー（Ｂ）が、融点が室温未満のポリイソシアネートモノマーである、前記１～３のいずれかに記載のプラスチックレンズの製造方法。
５． 固体状態のポリイソシアネートモノマー（Ａ）とモノマー（Ｂ）とを混合して上記ポリイソシアネートモノマー（Ａ）を溶解した後、ポリチオールモノマーを混合して混合物を調製する、前記１～４のいずれかに記載のプラスチックレンズの製造方法。 1. Among the raw material monomers containing at least a polyisocyanate monomer and a polythiol monomer, a method for producing a plastic lens for polymerizing a mixture containing a polyisocyanate monomer (A) having a melting point of room temperature or higher and a monomer (B) having a melting point of less than room temperature. And
In the step of preparing the mixture, the solid polyisocyanate monomer (A) and the monomer (B) are mixed to dissolve the polyisocyanate monomer (A), and the mixture is mixed with the polyisocyanate monomer (A). A method for producing a plastic lens, which is performed at a temperature lower than the melting point of the monomer (B) and higher than the melting point of the monomer (B).
2. 2. The method for producing a plastic lens as described in 1 above, wherein the polyisocyanate monomer (A) is an aromatic polyisocyanate.
3. 3. The method for producing a plastic lens as described in 1 or 2 above, wherein the polyisocyanate monomer (A) is 4,4′-diphenylmethane diisocyanate.
4). 4. The method for producing a plastic lens according to any one of 1 to 3, wherein the monomer (B) is a polyisocyanate monomer having a melting point of less than room temperature.
5. Any of the above 1 to 4, wherein the solid polyisocyanate monomer (A) and the monomer (B) are mixed to dissolve the polyisocyanate monomer (A), and then the polythiol monomer is mixed to prepare a mixture. The manufacturing method of the plastic lens of description.
本発明の製造方法によれば、室温において固体であるポリイソシアネートモノマーを原料モノマーとして用いても、濁りやクモリのない優れた透明性を有したプラスチックレンズを量産することができる。
さらに本発明の製造方法によれば、室温において固体であるポリイソシアネートモノマーを用いるに際し、予め溶融する必要がないため、プラスチックレンズの製造を生産性よく行うことができる。 According to the production method of the present invention, even when a polyisocyanate monomer that is solid at room temperature is used as a raw material monomer, it is possible to mass-produce plastic lenses having excellent transparency free from turbidity and spiders.
Furthermore, according to the production method of the present invention, when a polyisocyanate monomer that is solid at room temperature is used, it is not necessary to melt in advance, so that plastic lenses can be produced with high productivity.
さらに本発明の製造方法によれば、室温において固体であるポリイソシアネートモノマーを用いるに際し、予め溶融する必要がないため、プラスチックレンズの製造を生産性よく行うことができる。 According to the production method of the present invention, even when a polyisocyanate monomer that is solid at room temperature is used as a raw material monomer, it is possible to mass-produce plastic lenses having excellent transparency free from turbidity and spiders.
Furthermore, according to the production method of the present invention, when a polyisocyanate monomer that is solid at room temperature is used, it is not necessary to melt in advance, so that plastic lenses can be produced with high productivity.
（混合物の調製）
本発明は、少なくともポリイソシアネートモノマー及びポリチオールモノマーを含む原料モノマーのうち、融点が室温以上であるポリイソシアネートモノマー（Ａ）（ポリイソシアネートモノマー（Ａ）と称すことがある）及び融点が室温未満であるモノマー（Ｂ）（モノマー（Ｂ）と称すことがある）を含む混合物を重合するプラスチックレンズの製造方法であって、上記重合に供する混合物を調製する工程に特徴を有するものである。
すなわち本発明は、上記混合物を調製する工程において、固体状態のポリイソシアネートモノマー（Ａ）とモノマー（Ｂ）とを混合することで上記ポリイソシアネートモノマー（Ａ）を溶解し、また上記混合を、上記ポリイソシアネートモノマー（Ａ）の融点より低くかつ上記モノマー（Ｂ）の融点よりも高い温度で行うことを特徴とする。 (Preparation of mixture)
In the present invention, among the raw material monomers including at least a polyisocyanate monomer and a polythiol monomer, the polyisocyanate monomer (A) having a melting point of room temperature or higher (sometimes referred to as polyisocyanate monomer (A)) and the melting point being lower than room temperature A method for producing a plastic lens for polymerizing a mixture containing monomer (B) (sometimes referred to as monomer (B)), which is characterized by the step of preparing the mixture to be subjected to the polymerization.
That is, in the step of preparing the mixture, the present invention dissolves the polyisocyanate monomer (A) by mixing the solid-state polyisocyanate monomer (A) and the monomer (B), It is characterized by being carried out at a temperature lower than the melting point of the polyisocyanate monomer (A) and higher than the melting point of the monomer (B).
本発明は、少なくともポリイソシアネートモノマー及びポリチオールモノマーを含む原料モノマーのうち、融点が室温以上であるポリイソシアネートモノマー（Ａ）（ポリイソシアネートモノマー（Ａ）と称すことがある）及び融点が室温未満であるモノマー（Ｂ）（モノマー（Ｂ）と称すことがある）を含む混合物を重合するプラスチックレンズの製造方法であって、上記重合に供する混合物を調製する工程に特徴を有するものである。
すなわち本発明は、上記混合物を調製する工程において、固体状態のポリイソシアネートモノマー（Ａ）とモノマー（Ｂ）とを混合することで上記ポリイソシアネートモノマー（Ａ）を溶解し、また上記混合を、上記ポリイソシアネートモノマー（Ａ）の融点より低くかつ上記モノマー（Ｂ）の融点よりも高い温度で行うことを特徴とする。 (Preparation of mixture)
In the present invention, among the raw material monomers including at least a polyisocyanate monomer and a polythiol monomer, the polyisocyanate monomer (A) having a melting point of room temperature or higher (sometimes referred to as polyisocyanate monomer (A)) and the melting point being lower than room temperature A method for producing a plastic lens for polymerizing a mixture containing monomer (B) (sometimes referred to as monomer (B)), which is characterized by the step of preparing the mixture to be subjected to the polymerization.
That is, in the step of preparing the mixture, the present invention dissolves the polyisocyanate monomer (A) by mixing the solid-state polyisocyanate monomer (A) and the monomer (B), It is characterized by being carried out at a temperature lower than the melting point of the polyisocyanate monomer (A) and higher than the melting point of the monomer (B).
本発明の製造方法は、外部から熱を加えなくても、固体状態のポリイソシアネートモノマー（Ａ）が、液体のモノマー（Ｂ）に溶解する性質を利用するものである。そのため、ポリイソシアネートモノマー（Ａ）とモノマー（Ｂ）とを含む混合物を調製する際、上記混合温度であれば、固体状態のままのポリイソシアネートモノマー（Ａ）をモノマー（Ｂ）と混合しても、ポリイソシアネートモノマー（Ａ）を均一に溶解させることができる。
The production method of the present invention utilizes the property that the polyisocyanate monomer (A) in the solid state dissolves in the liquid monomer (B) without applying heat from the outside. Therefore, when preparing the mixture containing the polyisocyanate monomer (A) and the monomer (B), the polyisocyanate monomer (A) in the solid state can be mixed with the monomer (B) at the above mixing temperature. The polyisocyanate monomer (A) can be uniformly dissolved.
上記混合温度は、ポリイソシアネートモノマー（Ａ）の融点より低い温度、かつモノマー（Ｂ）が液体で存在する温度、すなわちモノマー（Ｂ）の融点よりも高い温度の範囲内である。なお、上記混合温度とは、固体状態のポリイソシアネートモノマー（Ａ）をモノマー（Ｂ）と混合して、ポリイソシアネートモノマー（Ａ）を均一に溶解させる際の温度である。
ポリイソシアネートモノマー（Ａ）を２種以上用いる場合の混合温度の上限は、複数のポリイソシアネートモノマー（Ａ）の融点のうち、最も低い温度よりも低い温度である。また、モノマー（Ｂ）を２種以上用いる場合の混合温度の下限は、複数のモノマー（Ｂ）の融点のうち、最も高い温度よりも高い温度である。 The mixing temperature is in the range of a temperature lower than the melting point of the polyisocyanate monomer (A) and a temperature at which the monomer (B) exists in a liquid state, that is, a temperature higher than the melting point of the monomer (B). The mixing temperature is a temperature at which the polyisocyanate monomer (A) in the solid state is mixed with the monomer (B) and the polyisocyanate monomer (A) is uniformly dissolved.
The upper limit of the mixing temperature when two or more polyisocyanate monomers (A) are used is a temperature lower than the lowest temperature among the melting points of the plurality of polyisocyanate monomers (A). Moreover, the minimum of the mixing temperature in the case of using 2 or more types of monomers (B) is a temperature higher than the highest temperature among melting | fusing point of a some monomer (B).
ポリイソシアネートモノマー（Ａ）を２種以上用いる場合の混合温度の上限は、複数のポリイソシアネートモノマー（Ａ）の融点のうち、最も低い温度よりも低い温度である。また、モノマー（Ｂ）を２種以上用いる場合の混合温度の下限は、複数のモノマー（Ｂ）の融点のうち、最も高い温度よりも高い温度である。 The mixing temperature is in the range of a temperature lower than the melting point of the polyisocyanate monomer (A) and a temperature at which the monomer (B) exists in a liquid state, that is, a temperature higher than the melting point of the monomer (B). The mixing temperature is a temperature at which the polyisocyanate monomer (A) in the solid state is mixed with the monomer (B) and the polyisocyanate monomer (A) is uniformly dissolved.
The upper limit of the mixing temperature when two or more polyisocyanate monomers (A) are used is a temperature lower than the lowest temperature among the melting points of the plurality of polyisocyanate monomers (A). Moreover, the minimum of the mixing temperature in the case of using 2 or more types of monomers (B) is a temperature higher than the highest temperature among melting | fusing point of a some monomer (B).
また、ポリイソシアネートモノマー（Ａ）の融点よりも高い温度で混合を行うと、原料モノマーの活性が上がり、その結果増粘が早くなるため生産がしにくくなる。すなわち、ポリイソシアネートモノマー（Ａ）の融点よりも低い温度で混合物を調合することによって、原料モノマーのポットライフが延び、生産を安定化させることができる。
また、混合温度は上記範囲内において、ポリイソシアネートモノマー（Ａ）の均一な溶解が達成されるまでの間に起こりうる望まない重合反応の進行を回避できる温度であることが好ましく、さらにモノマー（Ｂ）との溶解性などを考慮し適宜決定すればよい。
例えば、ポリイソシアネートモノマー（Ａ）として４，４’－ジフェニルメタンジイソシアネート（ＭＤＩ）を使用した場合、具体的な混合温度としては室温であることが好ましく、さらにより具体的には２０～３０℃であることが好ましく、２０～２７℃であることがより好ましい。 Moreover, when mixing is performed at a temperature higher than the melting point of the polyisocyanate monomer (A), the activity of the raw material monomer is increased, and as a result, the viscosity is increased and production is difficult. That is, by preparing the mixture at a temperature lower than the melting point of the polyisocyanate monomer (A), the pot life of the raw material monomer can be extended and the production can be stabilized.
Further, the mixing temperature is preferably a temperature within the above range that can avoid the progress of an undesired polymerization reaction that may occur until uniform dissolution of the polyisocyanate monomer (A) is achieved. ) And the like, and so on.
For example, when 4,4′-diphenylmethane diisocyanate (MDI) is used as the polyisocyanate monomer (A), the specific mixing temperature is preferably room temperature, and more specifically 20 to 30 ° C. It is preferably 20 to 27 ° C.
また、混合温度は上記範囲内において、ポリイソシアネートモノマー（Ａ）の均一な溶解が達成されるまでの間に起こりうる望まない重合反応の進行を回避できる温度であることが好ましく、さらにモノマー（Ｂ）との溶解性などを考慮し適宜決定すればよい。
例えば、ポリイソシアネートモノマー（Ａ）として４，４’－ジフェニルメタンジイソシアネート（ＭＤＩ）を使用した場合、具体的な混合温度としては室温であることが好ましく、さらにより具体的には２０～３０℃であることが好ましく、２０～２７℃であることがより好ましい。 Moreover, when mixing is performed at a temperature higher than the melting point of the polyisocyanate monomer (A), the activity of the raw material monomer is increased, and as a result, the viscosity is increased and production is difficult. That is, by preparing the mixture at a temperature lower than the melting point of the polyisocyanate monomer (A), the pot life of the raw material monomer can be extended and the production can be stabilized.
Further, the mixing temperature is preferably a temperature within the above range that can avoid the progress of an undesired polymerization reaction that may occur until uniform dissolution of the polyisocyanate monomer (A) is achieved. ) And the like, and so on.
For example, when 4,4′-diphenylmethane diisocyanate (MDI) is used as the polyisocyanate monomer (A), the specific mixing temperature is preferably room temperature, and more specifically 20 to 30 ° C. It is preferably 20 to 27 ° C.
原料モノマーの混合順序は、後述する任意の添加剤を使用する場合を含め、制限されることはない。特に、ポリイソシアネートモノマー（Ａ）とポリチオールモノマーとの望まない重合反応の進行を回避する観点から、固体状態のポリイソシアネートモノマー（Ａ）とモノマー（Ｂ）とを混合して上記ポリイソシアネートモノマー（Ａ）を溶解した後、ポリチオールモノマーを混合して混合物を調製することが好ましい。
The mixing order of the raw material monomers is not limited, including the case of using any additive described later. In particular, from the viewpoint of avoiding an undesirable polymerization reaction between the polyisocyanate monomer (A) and the polythiol monomer, the polyisocyanate monomer (A) is mixed with the solid polyisocyanate monomer (A) and the monomer (B). It is preferable to prepare a mixture by mixing the polythiol monomer after dissolving.
添加剤は、ポリイソシアネートモノマー（Ａ）とモノマー（Ｂ）と混合する際に、同時に添加することができる。
また、ポリイソシアネートモノマー（Ａ）とモノマー（Ｂ）と混合する前に、添加剤をモノマー（Ｂ）に添加して予め溶解させることもでき、添加剤が良好な溶解性を示さない場合は加温しながら溶解させてもよい。例えば、添加剤をモノマー（Ｂ）に添加し加温して該添加剤を溶解した場合は、ポリイソシアネートモノマー（Ａ）の融点より低い温度となるように調整してから、モノマー（Ｂ）と添加剤とを混合溶解させたものに上記ポリイソシアネートモノマー（Ａ）を混合すればよい。 An additive can be added simultaneously when mixing with a polyisocyanate monomer (A) and a monomer (B).
Also, before mixing with the polyisocyanate monomer (A) and the monomer (B), an additive can be added to the monomer (B) and dissolved in advance. If the additive does not show good solubility, it can be added. It may be dissolved while warm. For example, when the additive is added to the monomer (B) and heated to dissolve the additive, the monomer (B) and the monomer (B) are adjusted after adjusting the temperature to be lower than the melting point of the polyisocyanate monomer (A). What is necessary is just to mix the said polyisocyanate monomer (A) in what mixed and dissolved the additive.
また、ポリイソシアネートモノマー（Ａ）とモノマー（Ｂ）と混合する前に、添加剤をモノマー（Ｂ）に添加して予め溶解させることもでき、添加剤が良好な溶解性を示さない場合は加温しながら溶解させてもよい。例えば、添加剤をモノマー（Ｂ）に添加し加温して該添加剤を溶解した場合は、ポリイソシアネートモノマー（Ａ）の融点より低い温度となるように調整してから、モノマー（Ｂ）と添加剤とを混合溶解させたものに上記ポリイソシアネートモノマー（Ａ）を混合すればよい。 An additive can be added simultaneously when mixing with a polyisocyanate monomer (A) and a monomer (B).
Also, before mixing with the polyisocyanate monomer (A) and the monomer (B), an additive can be added to the monomer (B) and dissolved in advance. If the additive does not show good solubility, it can be added. It may be dissolved while warm. For example, when the additive is added to the monomer (B) and heated to dissolve the additive, the monomer (B) and the monomer (B) are adjusted after adjusting the temperature to be lower than the melting point of the polyisocyanate monomer (A). What is necessary is just to mix the said polyisocyanate monomer (A) in what mixed and dissolved the additive.
（原料モノマー）
本発明の製造方法では、少なくともポリイソシアネートモノマー及びポリチオールモノマーを含む原料モノマーが用いられ、上記原料モノマーには、融点が室温以上であるポリイソシアネートモノマー（Ａ）及び融点が室温未満であるモノマー（Ｂ）が含まれる。 (Raw material monomer)
In the production method of the present invention, a raw material monomer containing at least a polyisocyanate monomer and a polythiol monomer is used. The raw material monomer includes a polyisocyanate monomer (A) having a melting point of room temperature or higher and a monomer having a melting point of less than room temperature (B ) Is included.
本発明の製造方法では、少なくともポリイソシアネートモノマー及びポリチオールモノマーを含む原料モノマーが用いられ、上記原料モノマーには、融点が室温以上であるポリイソシアネートモノマー（Ａ）及び融点が室温未満であるモノマー（Ｂ）が含まれる。 (Raw material monomer)
In the production method of the present invention, a raw material monomer containing at least a polyisocyanate monomer and a polythiol monomer is used. The raw material monomer includes a polyisocyanate monomer (A) having a melting point of room temperature or higher and a monomer having a melting point of less than room temperature (B ) Is included.
〈ポリイソシアネートモノマー（Ａ）〉
ポリイソシアネートモノマー（Ａ）は、室温以上の融点を有するものであり、また上述したとおり室温で液体であるモノマー（Ｂ）と混合することにより溶解する性質を有するものである。
また、本発明の製造方法においてポリイソシアネートモノマー（Ａ）は固体の状態で用いられる。あえて融解せずに固体の状態で用いることにより、熱による性状の劣化がないままポリイソシアネートモノマー（Ａ）をモノマー（Ｂ）と混合することができ、これによって得られるプラスチックレンズは濁りやクモリのない優れた透明性を有ものとすることがきる。 <Polyisocyanate monomer (A)>
The polyisocyanate monomer (A) has a melting point equal to or higher than room temperature, and has a property of being dissolved by mixing with the monomer (B) that is liquid at room temperature as described above.
In the production method of the present invention, the polyisocyanate monomer (A) is used in a solid state. By using it in a solid state without melting, the polyisocyanate monomer (A) can be mixed with the monomer (B) without deterioration of properties due to heat. There can be no excellent transparency.
ポリイソシアネートモノマー（Ａ）は、室温以上の融点を有するものであり、また上述したとおり室温で液体であるモノマー（Ｂ）と混合することにより溶解する性質を有するものである。
また、本発明の製造方法においてポリイソシアネートモノマー（Ａ）は固体の状態で用いられる。あえて融解せずに固体の状態で用いることにより、熱による性状の劣化がないままポリイソシアネートモノマー（Ａ）をモノマー（Ｂ）と混合することができ、これによって得られるプラスチックレンズは濁りやクモリのない優れた透明性を有ものとすることがきる。 <Polyisocyanate monomer (A)>
The polyisocyanate monomer (A) has a melting point equal to or higher than room temperature, and has a property of being dissolved by mixing with the monomer (B) that is liquid at room temperature as described above.
In the production method of the present invention, the polyisocyanate monomer (A) is used in a solid state. By using it in a solid state without melting, the polyisocyanate monomer (A) can be mixed with the monomer (B) without deterioration of properties due to heat. There can be no excellent transparency.
上記性質を有するポリイソシアネートモノマー（Ａ）としては、入手し易さなどの点から、芳香族ポリイソシアネートであることが好ましい。
上記性質を有する芳香族ポリイソシアネートとしては、例えば、４，４’－ジフェニルメタンジイソシアネート（ＭＤＩ）（融点３７℃：国際化学物質安全性カードより）がある。また、上記の性質を有するポリイソシアネートモノマーであれば、ＭＤＩに限らず本発明の効果を発揮することができる。 The polyisocyanate monomer (A) having the above properties is preferably an aromatic polyisocyanate from the viewpoint of availability.
As an aromatic polyisocyanate having the above properties, there is, for example, 4,4′-diphenylmethane diisocyanate (MDI) (melting point: 37 ° C .: from International Chemical Safety Card). Moreover, if it is a polyisocyanate monomer which has said property, not only MDI but the effect of this invention can be exhibited.
上記性質を有する芳香族ポリイソシアネートとしては、例えば、４，４’－ジフェニルメタンジイソシアネート（ＭＤＩ）（融点３７℃：国際化学物質安全性カードより）がある。また、上記の性質を有するポリイソシアネートモノマーであれば、ＭＤＩに限らず本発明の効果を発揮することができる。 The polyisocyanate monomer (A) having the above properties is preferably an aromatic polyisocyanate from the viewpoint of availability.
As an aromatic polyisocyanate having the above properties, there is, for example, 4,4′-diphenylmethane diisocyanate (MDI) (melting point: 37 ° C .: from International Chemical Safety Card). Moreover, if it is a polyisocyanate monomer which has said property, not only MDI but the effect of this invention can be exhibited.
ＭＤＩは、ダイマーやオリゴマーなどの不純物が生じるなどの熱による性状の劣化が起きやすく、このように劣化したＭＤＩをそのまま原料として用いるとプラスチックレンズに濁りやクモリが生じるなどして、製造されたプラスチックレンズの品質の低下が著しくなる。そのため、大量のＭＤＩを熱により一端融解してから、あるいは、一端融解したものを一定期間保管してから生産に用いることは好ましくなかった。そこで、熱による溶融工程を経ない本発明の製造方法において、ポリイソシアネートモノマー（Ａ）としてＭＤＩを用いた場合、本発明の効果を顕著に発揮することができることから、本発明においてＭＤＩはポリイソシアネートモノマー（Ａ）として特に好適である。
MDI is prone to deterioration of properties due to heat, such as impurities such as dimers and oligomers. When such deteriorated MDI is used as a raw material as it is, the plastic lens is turbid and spoiled. The deterioration of the lens quality becomes significant. For this reason, it is not preferable to use a large amount of MDI for production after it has been melted at one end or stored for a certain period of time. Therefore, when MDI is used as the polyisocyanate monomer (A) in the production method of the present invention that does not go through a melting step by heat, the effects of the present invention can be remarkably exhibited. Particularly suitable as the monomer (A).
ポリイソシアネートモノマー（Ａ）の形状は、短時間でモノマー（Ｂ）に均一に溶解させる観点から、例えばフレーク状、顆粒状及び粉末状などであることが好ましい。また、そのサイズは、特に限定されず量産する際のスケールや作業性から適宜調整すればよい。
The shape of the polyisocyanate monomer (A) is preferably, for example, in the form of flakes, granules, and powders from the viewpoint of uniformly dissolving in the monomer (B) in a short time. Further, the size is not particularly limited, and may be appropriately adjusted from the scale and workability in mass production.
〈モノマー（Ｂ）〉
モノマー（Ｂ）は、上記ポリイソシアネートモノマー（Ａ）を溶解する際に用いられるモノマーである。モノマー（Ｂ）としては、融点が室温未満であり、ポリイソシアネートモノマー（Ａ）を溶解するものであれば、プラスチックレンズの原料モノマーとして従来採用されているモノマーを用いることができる。
モノマー（Ｂ）として、例えば、融点が室温未満である、ポリイソシアネートモノマー及びポリチオールモノマーなどが挙げられる。これらの中でも、ポリイソシアネートモノマー（Ａ）が良好な溶解性を示す観点から、モノマー（Ｂ）は融点が室温未満のポリイソシアネートモノマーであることが好ましい。 <Monomer (B)>
A monomer (B) is a monomer used when melt | dissolving the said polyisocyanate monomer (A). As the monomer (B), any monomer conventionally employed as a raw material monomer for plastic lenses can be used as long as it has a melting point of less than room temperature and dissolves the polyisocyanate monomer (A).
Examples of the monomer (B) include polyisocyanate monomers and polythiol monomers having a melting point of less than room temperature. Among these, from the viewpoint that the polyisocyanate monomer (A) exhibits good solubility, the monomer (B) is preferably a polyisocyanate monomer having a melting point of less than room temperature.
モノマー（Ｂ）は、上記ポリイソシアネートモノマー（Ａ）を溶解する際に用いられるモノマーである。モノマー（Ｂ）としては、融点が室温未満であり、ポリイソシアネートモノマー（Ａ）を溶解するものであれば、プラスチックレンズの原料モノマーとして従来採用されているモノマーを用いることができる。
モノマー（Ｂ）として、例えば、融点が室温未満である、ポリイソシアネートモノマー及びポリチオールモノマーなどが挙げられる。これらの中でも、ポリイソシアネートモノマー（Ａ）が良好な溶解性を示す観点から、モノマー（Ｂ）は融点が室温未満のポリイソシアネートモノマーであることが好ましい。 <Monomer (B)>
A monomer (B) is a monomer used when melt | dissolving the said polyisocyanate monomer (A). As the monomer (B), any monomer conventionally employed as a raw material monomer for plastic lenses can be used as long as it has a melting point of less than room temperature and dissolves the polyisocyanate monomer (A).
Examples of the monomer (B) include polyisocyanate monomers and polythiol monomers having a melting point of less than room temperature. Among these, from the viewpoint that the polyisocyanate monomer (A) exhibits good solubility, the monomer (B) is preferably a polyisocyanate monomer having a melting point of less than room temperature.
上記融点が室温未満であるポリイソシアネートモノマーとしては、例えば、２，４－トリレンジイソシアネート、２，６－トリレンジイソシアネート、ｏ－キシリレンジイソシアネート、ｍ－キシリレンジイソシアネート、ｐ－キシリレンジイソシアネート、α，α，α’，α’－テトラメチルキシリレンジイソシアネート、エチルフェニレンジイソシアネート、ジメチルフェニレンジイソシアネート、ジエチルフェニレンジイソシアネート、イソプロピルフェニレンジイソシアネート、ジイソプロピルフェニレンジイソシアネート、トリメチルベンゼントリイソシアネート、ベンゼントリイソシアネート、１，６－ヘキサメチレンジイソシアネート、リジンエステルトリイソシアネート、メシチレントリイソシアネート、１，３，６－ヘキサメチレントリイソシアネート、イソホロンジイソシアネート、ジシクロヘキシルメタン４，４’－ジイソシアネート、１，３－シクロヘキサンジイソシアネート、１，４－シクロヘキサンジイソシアネート、１，２－ビス（イソシアネートメチル）シクロヘキサン、１，３－ビス（イソシアネートメチル）シクロヘキサン、１，４－ビス（イソシアネートメチル）シクロヘキサン、２，５－ビス（イソシアネートメチル）ビシクロ［２，２，１］－ヘプタン、２，６－ビス（イソシアネートメチル）ビシクロ［２，２，１］－ヘプタン、１，３，５－トリス（イソシアネートメチル）シクロヘキサン、ビシクロヘプタントリイソシアネートなどが挙げられる。
これらの中でも耐黄変性や耐変質性の観点から、１，６－ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、１，３－ビス（イソシアネートメチル）シクロヘキサンが好ましい。
上記ポリイソシアネートモノマーは、単独で用いてもよく、２種以上を併用してもよい。 Examples of the polyisocyanate monomer having a melting point of less than room temperature include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, α , Α, α ', α'-tetramethylxylylene diisocyanate, ethylphenylene diisocyanate, dimethylphenylene diisocyanate, diethylphenylene diisocyanate, isopropylphenylene diisocyanate, diisopropylphenylene diisocyanate, trimethylbenzene triisocyanate, benzene triisocyanate, 1,6-hexamethylene Diisocyanate, lysine ester triisocyanate, mesitylene triisocyanate, 1,3,6-hexamethyl Rentriisocyanate, isophorone diisocyanate, dicyclohexylmethane 4,4'-diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, 1,2-bis (isocyanate methyl) cyclohexane, 1,3-bis (isocyanate methyl) Cyclohexane, 1,4-bis (isocyanatemethyl) cyclohexane, 2,5-bis (isocyanatemethyl) bicyclo [2,2,1] -heptane, 2,6-bis (isocyanatemethyl) bicyclo [2,2,1] -Heptane, 1,3,5-tris (isocyanatemethyl) cyclohexane, bicycloheptane triisocyanate and the like.
Among these, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, and 1,3-bis (isocyanatomethyl) cyclohexane are preferable from the viewpoint of yellowing resistance and alteration resistance.
The said polyisocyanate monomer may be used independently and may use 2 or more types together.
これらの中でも耐黄変性や耐変質性の観点から、１，６－ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、１，３－ビス（イソシアネートメチル）シクロヘキサンが好ましい。
上記ポリイソシアネートモノマーは、単独で用いてもよく、２種以上を併用してもよい。 Examples of the polyisocyanate monomer having a melting point of less than room temperature include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, α , Α, α ', α'-tetramethylxylylene diisocyanate, ethylphenylene diisocyanate, dimethylphenylene diisocyanate, diethylphenylene diisocyanate, isopropylphenylene diisocyanate, diisopropylphenylene diisocyanate, trimethylbenzene triisocyanate, benzene triisocyanate, 1,6-hexamethylene Diisocyanate, lysine ester triisocyanate, mesitylene triisocyanate, 1,3,6-hexamethyl Rentriisocyanate, isophorone diisocyanate, dicyclohexylmethane 4,4'-diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, 1,2-bis (isocyanate methyl) cyclohexane, 1,3-bis (isocyanate methyl) Cyclohexane, 1,4-bis (isocyanatemethyl) cyclohexane, 2,5-bis (isocyanatemethyl) bicyclo [2,2,1] -heptane, 2,6-bis (isocyanatemethyl) bicyclo [2,2,1] -Heptane, 1,3,5-tris (isocyanatemethyl) cyclohexane, bicycloheptane triisocyanate and the like.
Among these, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, and 1,3-bis (isocyanatomethyl) cyclohexane are preferable from the viewpoint of yellowing resistance and alteration resistance.
The said polyisocyanate monomer may be used independently and may use 2 or more types together.
また、モノマー（Ｂ）以外の原料モノマーとしても、上記に例示したポリイソシアネート化合物を使用することができ、好ましいポリイソシアネート化合物についても上記と同様である。
Moreover, the polyisocyanate compounds exemplified above can also be used as raw material monomers other than the monomer (B), and preferred polyisocyanate compounds are the same as described above.
上記融点が室温未満であるポリチオールモノマーとしては、例えば、ジメルカプトメタン、１，１－ジメルカプトエタン、１，２－ジメルカプトエタン、１，１－ジメルカプトプロパン、１，２－ジメルカプトプロパン、１，３－ジメルカプトプロパン、２，２－ジメルカプトプロパン、１，１－ジメルカプトブタン、１，２－ジメルカプトブタン、１，３－ジメルカプトブタン、１，４－ジメルカプトブタン、２，２－ジメルカプトブタン、２，３－ジメルカプトブタン、１，２－ジメルカプトベンゼン、１，３－ジメルカプトベンゼン、１，４－ジメルカプトベンゼン、１，２－ジメルカプトキシレン、１，３－ジメルカプトキシレン、１，４－ジメルカプトキシレン、２，５－ビスメルカプトメチル－１，４－ジチアン、４，５－ビスメルカプトメチル－１，３－ジチアン、２，５－ジメルカプト－１，４－ジチアン、４，５－ジメルカプト－１，３－ジチアン、４，５－ビスメルカプトメチル－１，３－ジチオラン、４，５－ジメルカプト－１，３－ジチオラン、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）などが挙げられる。
これらの中でも操作性や耐変質性の観点から、２，５－ビスメルカプトメチル－１，４－ジチアン、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）が好ましい。
上記ポリチオールモノマーは、単独で用いてもよく、２種以上を併用してもよい。 Examples of the polythiol monomer having a melting point of less than room temperature include dimercaptomethane, 1,1-dimercaptoethane, 1,2-dimercaptoethane, 1,1-dimercaptopropane, 1,2-dimercaptopropane, 1,3-dimercaptopropane, 2,2-dimercaptopropane, 1,1-dimercaptobutane, 1,2-dimercaptobutane, 1,3-dimercaptobutane, 1,4-dimercaptobutane, 2, 2-dimercaptobutane, 2,3-dimercaptobutane, 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-dimercaptoxylene, 1,3- Dimercaptoxylene, 1,4-dimercaptoxylene, 2,5-bismercaptomethyl-1,4-dithiane, 4,5-bis Lucaptomethyl-1,3-dithiane, 2,5-dimercapto-1,4-dithiane, 4,5-dimercapto-1,3-dithiane, 4,5-bismercaptomethyl-1,3-dithiolane, 4,5- Examples include dimercapto-1,3-dithiolane, pentaerythritol tetrakis (mercaptoacetate), and the like.
Among these, 2,5-bismercaptomethyl-1,4-dithiane and pentaerythritol tetrakis (mercaptoacetate) are preferable from the viewpoints of operability and resistance to alteration.
The said polythiol monomer may be used independently and may use 2 or more types together.
これらの中でも操作性や耐変質性の観点から、２，５－ビスメルカプトメチル－１，４－ジチアン、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）が好ましい。
上記ポリチオールモノマーは、単独で用いてもよく、２種以上を併用してもよい。 Examples of the polythiol monomer having a melting point of less than room temperature include dimercaptomethane, 1,1-dimercaptoethane, 1,2-dimercaptoethane, 1,1-dimercaptopropane, 1,2-dimercaptopropane, 1,3-dimercaptopropane, 2,2-dimercaptopropane, 1,1-dimercaptobutane, 1,2-dimercaptobutane, 1,3-dimercaptobutane, 1,4-dimercaptobutane, 2, 2-dimercaptobutane, 2,3-dimercaptobutane, 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-dimercaptoxylene, 1,3- Dimercaptoxylene, 1,4-dimercaptoxylene, 2,5-bismercaptomethyl-1,4-dithiane, 4,5-bis Lucaptomethyl-1,3-dithiane, 2,5-dimercapto-1,4-dithiane, 4,5-dimercapto-1,3-dithiane, 4,5-bismercaptomethyl-1,3-dithiolane, 4,5- Examples include dimercapto-1,3-dithiolane, pentaerythritol tetrakis (mercaptoacetate), and the like.
Among these, 2,5-bismercaptomethyl-1,4-dithiane and pentaerythritol tetrakis (mercaptoacetate) are preferable from the viewpoints of operability and resistance to alteration.
The said polythiol monomer may be used independently and may use 2 or more types together.
また、モノマー（Ｂ）以外の原料モノマーとしても、上記に例示したポリチオール化合物を使用することができ、好ましいポリチオール化合物についても上記と同様である。
Also, as the raw material monomer other than the monomer (B), the polythiol compounds exemplified above can be used, and preferred polythiol compounds are the same as above.
本発明の製造方法において各種原料モノマーの配合割合は、プラスチックレンズ製造分野で通常採用されている範囲内であればよい。例えば、原料モノマーとして上記のポリイソシアネートモノマー及びポリチオールモノマーを用いる場合、未反応基を残さずに重合反応を進行させる観点から、ＮＣＯ基／ＳＨ基のモル比が０．５～２．０となる配合割合が好ましく、より好ましくは０．９５～１．０５である。
In the production method of the present invention, the blending ratio of various raw material monomers may be within the range usually employed in the plastic lens production field. For example, when the above polyisocyanate monomer and polythiol monomer are used as raw material monomers, the molar ratio of NCO groups / SH groups is 0.5 to 2.0 from the viewpoint of allowing the polymerization reaction to proceed without leaving unreacted groups. The blending ratio is preferable, and more preferably 0.95 to 1.05.
（添加剤）
また、本発明の製造方法において、前記原料モノマーの他に、本発明の目的を損ねない範囲において、各種添加剤を上述の混合物に含有させることができる。添加剤としては特に制限はなく公知の重合触媒、紫外線吸収剤、離型剤などを使用することができる。 (Additive)
Moreover, in the manufacturing method of this invention, in addition to the said raw material monomer, various additives can be contained in the above-mentioned mixture in the range which does not impair the objective of this invention. There is no restriction | limiting in particular as an additive, A well-known polymerization catalyst, a ultraviolet absorber, a mold release agent etc. can be used.
また、本発明の製造方法において、前記原料モノマーの他に、本発明の目的を損ねない範囲において、各種添加剤を上述の混合物に含有させることができる。添加剤としては特に制限はなく公知の重合触媒、紫外線吸収剤、離型剤などを使用することができる。 (Additive)
Moreover, in the manufacturing method of this invention, in addition to the said raw material monomer, various additives can be contained in the above-mentioned mixture in the range which does not impair the objective of this invention. There is no restriction | limiting in particular as an additive, A well-known polymerization catalyst, a ultraviolet absorber, a mold release agent etc. can be used.
重合触媒としては、有機錫化合物が好ましく、例えば、ジブチル錫ジアセテ－ト、ジブチル錫ジラウレ－ト、ジブチル錫ジクロライド、ジメチル錫ジクロライド、モノメチル錫トリクロライド、トリメチル錫クロライド、トリブチル錫クロライド、トリブチル錫フロライド、ジメチル錫ジブロマイドなどを用いることができる。
上記重合触媒は、単独で用いてもよく、２種以上を併用してもよい。 As the polymerization catalyst, an organic tin compound is preferable, for example, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dimethyltin dichloride, monomethyltin trichloride, trimethyltin chloride, tributyltin chloride, tributyltin fluoride, Dimethyltin dibromide or the like can be used.
The said polymerization catalyst may be used independently and may use 2 or more types together.
上記重合触媒は、単独で用いてもよく、２種以上を併用してもよい。 As the polymerization catalyst, an organic tin compound is preferable, for example, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dimethyltin dichloride, monomethyltin trichloride, trimethyltin chloride, tributyltin chloride, tributyltin fluoride, Dimethyltin dibromide or the like can be used.
The said polymerization catalyst may be used independently and may use 2 or more types together.
紫外線吸収剤としては、例えば、ベンゾフェノン系化合物、ベンゾトリアゾール系化合物、ジベンゾイルメタン、４－ｔｅｒｔ－ブチル－４’－メトキシベンゾイルメタンなどを用いることができる。
上記ベンゾフェノン系化合物としては、２，４－ジヒドロキシベンゾフェノン、２－ヒドロキシ－４－メトキシベンゾフェノン、２－ヒドロキシ－４－メトキシベンゾフェノン－５－スルホニックアシッド、２－ヒドロキシ－４－ｎ－オクトキシベンゾフェノン、２－ヒドロキシ－４－ｎ－ドデシルオキシベンゾフェノン、２－ヒドロキシ－４－ベンジルオキシベンゾフェノン及び２，２’－ジヒドロキシ－４－メトキシベンゾフェノンなどが挙げられる。 As the ultraviolet absorber, for example, benzophenone compounds, benzotriazole compounds, dibenzoylmethane, 4-tert-butyl-4′-methoxybenzoylmethane and the like can be used.
Examples of the benzophenone compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octoxybenzophenone, Examples include 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, and 2,2′-dihydroxy-4-methoxybenzophenone.
上記ベンゾフェノン系化合物としては、２，４－ジヒドロキシベンゾフェノン、２－ヒドロキシ－４－メトキシベンゾフェノン、２－ヒドロキシ－４－メトキシベンゾフェノン－５－スルホニックアシッド、２－ヒドロキシ－４－ｎ－オクトキシベンゾフェノン、２－ヒドロキシ－４－ｎ－ドデシルオキシベンゾフェノン、２－ヒドロキシ－４－ベンジルオキシベンゾフェノン及び２，２’－ジヒドロキシ－４－メトキシベンゾフェノンなどが挙げられる。 As the ultraviolet absorber, for example, benzophenone compounds, benzotriazole compounds, dibenzoylmethane, 4-tert-butyl-4′-methoxybenzoylmethane and the like can be used.
Examples of the benzophenone compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octoxybenzophenone, Examples include 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, and 2,2′-dihydroxy-4-methoxybenzophenone.
上記ベンゾトリアゾール系化合物としては、２－（２’－ヒドロキシ－５’－メチルフェニル）ベンゾトリアゾール、２－（２’－ヒドロキシ－３’，５’－ジ－ｔ－ブチルフェニル）－５－クロロベンゾトリアゾール、２－（２’－ヒドロキシ－３’－ｔ－ブチル－５’－メチルフェニル）－５－クロロベンゾトリアゾール、２－（２’－ヒドロキシ－３’，５’－ジ－ｔ－アミルフェニル）ベンゾトリアゾール、２－（２’－ヒドロキシ－３’，５’－ジ－ｔ－ブチルフェニル）ベンゾトリアゾール、２－（２’－ヒドロキシ－５’－ｔ－ブチルフェニル）ベンゾトリアゾール、２－（２’－ヒドロキシ－５’－ｔ－オクチルフェニル）ベンゾトリアゾール及び２－（２－ヒドロキシ－４－オクチルオキシフェニル）ベンゾトリアゾールなどが挙げられる。
上記紫外線吸収剤は、単独で用いてもよく、２種以上を併用してもよい。 Examples of the benzotriazole compounds include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chloro. Benzotriazole, 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-amyl) Phenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- And (2′-hydroxy-5′-t-octylphenyl) benzotriazole and 2- (2-hydroxy-4-octyloxyphenyl) benzotriazole.
The said ultraviolet absorber may be used independently and may use 2 or more types together.
上記紫外線吸収剤は、単独で用いてもよく、２種以上を併用してもよい。 Examples of the benzotriazole compounds include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chloro. Benzotriazole, 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-amyl) Phenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- And (2′-hydroxy-5′-t-octylphenyl) benzotriazole and 2- (2-hydroxy-4-octyloxyphenyl) benzotriazole.
The said ultraviolet absorber may be used independently and may use 2 or more types together.
離型剤としては、例えば、リン酸モノエステル化合物、リン酸ジエステル化合物などを用いることができる。
上記リン酸モノエステル化合物としては、イソプロピルアシッドフォスフェート、ブチルアシッドフォスフェート、オクチルアシッドフォスフェート、ノニルアシッドフォスフェート、デシルアシッドフォスフェート、イソデシルアシッドフォスフェート、トリデシルアシッドフォスフェート、ステアリルアシッドフォスフェート、プロピルフェニルアシッドフォスフェート及びブチルフェニルアシッドフォスフェートなどが挙げられる。
上記リン酸ジエステル化合物としては、ジイソプロピルアシッドフォスフェート、ジブチルアシッドフォスフェート、ジオクチルアシッドフォスフェート、ジイソデシルアシッドフォスフェート、ビス（トリデシルアシッドフォスフェート）、ジステアリルアシッドフォスフェート、ジプロピルフェニルアシッドフォスフェート、ジブチルフェニルアシッドフォスフェート及びブトキシエチルアシッドフォスフェートなどが挙げられる。
上記離型剤は、単独で用いてもよく、２種以上を併用してもよい。 As a mold release agent, a phosphoric acid monoester compound, a phosphoric acid diester compound, etc. can be used, for example.
Examples of the phosphoric acid monoester compound include isopropyl acid phosphate, butyl acid phosphate, octyl acid phosphate, nonyl acid phosphate, decyl acid phosphate, isodecyl acid phosphate, tridecyl acid phosphate, stearyl acid phosphate , Propylphenyl acid phosphate and butylphenyl acid phosphate.
Examples of the phosphoric acid diester compound include diisopropyl acid phosphate, dibutyl acid phosphate, dioctyl acid phosphate, diisodecyl acid phosphate, bis (tridecyl acid phosphate), distearyl acid phosphate, dipropyl phenyl acid phosphate, Examples include dibutylphenyl acid phosphate and butoxyethyl acid phosphate.
The said mold release agent may be used independently and may use 2 or more types together.
上記リン酸モノエステル化合物としては、イソプロピルアシッドフォスフェート、ブチルアシッドフォスフェート、オクチルアシッドフォスフェート、ノニルアシッドフォスフェート、デシルアシッドフォスフェート、イソデシルアシッドフォスフェート、トリデシルアシッドフォスフェート、ステアリルアシッドフォスフェート、プロピルフェニルアシッドフォスフェート及びブチルフェニルアシッドフォスフェートなどが挙げられる。
上記リン酸ジエステル化合物としては、ジイソプロピルアシッドフォスフェート、ジブチルアシッドフォスフェート、ジオクチルアシッドフォスフェート、ジイソデシルアシッドフォスフェート、ビス（トリデシルアシッドフォスフェート）、ジステアリルアシッドフォスフェート、ジプロピルフェニルアシッドフォスフェート、ジブチルフェニルアシッドフォスフェート及びブトキシエチルアシッドフォスフェートなどが挙げられる。
上記離型剤は、単独で用いてもよく、２種以上を併用してもよい。 As a mold release agent, a phosphoric acid monoester compound, a phosphoric acid diester compound, etc. can be used, for example.
Examples of the phosphoric acid monoester compound include isopropyl acid phosphate, butyl acid phosphate, octyl acid phosphate, nonyl acid phosphate, decyl acid phosphate, isodecyl acid phosphate, tridecyl acid phosphate, stearyl acid phosphate , Propylphenyl acid phosphate and butylphenyl acid phosphate.
Examples of the phosphoric acid diester compound include diisopropyl acid phosphate, dibutyl acid phosphate, dioctyl acid phosphate, diisodecyl acid phosphate, bis (tridecyl acid phosphate), distearyl acid phosphate, dipropyl phenyl acid phosphate, Examples include dibutylphenyl acid phosphate and butoxyethyl acid phosphate.
The said mold release agent may be used independently and may use 2 or more types together.
（混合物の重合）
上述した原料モノマーを含む混合物の重合反応の条件は、混合物の組成やレンズ成形用型などによって条件が異なり一概に限定できないが、重合反応温度３０～１５０℃で０．５～７２時間程度である。 (Polymerization of mixture)
The conditions for the polymerization reaction of the mixture containing the raw material monomer described above vary depending on the composition of the mixture and the lens molding die, and cannot be generally limited, but are about 0.5 to 72 hours at a polymerization reaction temperature of 30 to 150 ° C. .
上述した原料モノマーを含む混合物の重合反応の条件は、混合物の組成やレンズ成形用型などによって条件が異なり一概に限定できないが、重合反応温度３０～１５０℃で０．５～７２時間程度である。 (Polymerization of mixture)
The conditions for the polymerization reaction of the mixture containing the raw material monomer described above vary depending on the composition of the mixture and the lens molding die, and cannot be generally limited, but are about 0.5 to 72 hours at a polymerization reaction temperature of 30 to 150 ° C. .
上述したように本発明の製造方法は、原料モノマーの熱劣化を生じさせずプラスチックレンズを製造することができるので、優れた透明性を有するプラスチックレンズを与えることができる。
このような本発明により製造されるプラスチックレンズとしては、例えば、眼鏡用レンズ、カメラレンズ、プロジェクターレンズ、望遠鏡レンズ、拡大鏡レンズなどが挙げられる。 As described above, the production method of the present invention can produce a plastic lens without causing thermal degradation of the raw material monomer, and thus can provide a plastic lens having excellent transparency.
Examples of the plastic lens manufactured according to the present invention include spectacle lenses, camera lenses, projector lenses, telescope lenses, and magnifier lenses.
このような本発明により製造されるプラスチックレンズとしては、例えば、眼鏡用レンズ、カメラレンズ、プロジェクターレンズ、望遠鏡レンズ、拡大鏡レンズなどが挙げられる。 As described above, the production method of the present invention can produce a plastic lens without causing thermal degradation of the raw material monomer, and thus can provide a plastic lens having excellent transparency.
Examples of the plastic lens manufactured according to the present invention include spectacle lenses, camera lenses, projector lenses, telescope lenses, and magnifier lenses.
実施例により本発明を説明するが、本発明はこれら実施例に制限されるものではない。
［実施例１］
５℃にて冷蔵保管している４，４’－ジフェニルメタンジイソシアネート（ＭＤＩ）２０ｋｇ入り石油缶から、ＭＤＩ（融点３７℃）を固体のまま２２．８８ｇを取り出し、フレーク状にして５００ｍｌのナスフラスコに投入した。続いて、室温にて保管している１８ｋｇ入り石油缶から１，６－ヘキサメチレンジイソシアネート（ＨＤＩ）（融点－６７℃）を液状のまま２５．０９ｇを取り出し、同フラスコに投入した。
上記フラスコに、さらに離型剤としてブトキシエチルアシッドホスフェートを０．２０ｇ、重合触媒としてジメチル錫ジクロライドを０．０６ｇ投入し、室温（２５℃）にて２０分間溶解を兼ねた攪拌混合を行い、ＭＤＩが完全に溶解したのを確認した。
次いで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）（ＰＥＴＭＡ）５２．０３ｇを同フラスコに投入後、１０℃に冷却しながら２０分間、２６７Ｐａ（２Ｔｏｒｒ）にて減圧攪拌を行ない、混合物を中心肉厚２．０ｍｍからなるレンズ成型用の型に注入した。
上記混合物を重合するために２４時間所定の温度プログラムにて加熱を行い、十分に硬化させたあと離型をし、プラスチックレンズを得た。
得られたプラスチックレンズを、暗室内蛍光灯下にてクモリの確認を目視で行ったところ、クモリはまったく見られず良好であった。 The present invention will be described with reference to examples, but the present invention is not limited to these examples.
[Example 1]
Take out 22.88 g of MDI (melting point: 37 ° C.) as a solid from an oil can containing 4,4′-diphenylmethane diisocyanate (MDI) 20 kg stored refrigerated at 5 ° C. and put it into flakes into a 500 ml eggplant flask. I put it in. Subsequently, 25.09 g of 1,6-hexamethylene diisocyanate (HDI) (melting point -67 ° C.) was taken out from an 18 kg oil can stored at room temperature and placed in the flask.
Further, 0.20 g of butoxyethyl acid phosphate as a release agent and 0.06 g of dimethyltin dichloride as a polymerization catalyst were added to the flask, and the mixture was stirred and mixed for 20 minutes at room temperature (25 ° C.). Was completely dissolved.
Next, 52.03 g of pentaerythritol tetrakis (mercaptoacetate) (PETMA) was charged into the same flask, and then the mixture was stirred at 267 Pa (2 Torr) for 20 minutes while cooling to 10 ° C. It was injected into a mold for forming a lens.
In order to polymerize the mixture, heating was carried out with a predetermined temperature program for 24 hours, and after sufficiently curing, the mold was released to obtain a plastic lens.
When the obtained plastic lens was visually checked for spiders under a fluorescent lamp in a dark room, it was good that no spiders were seen.
［実施例１］
５℃にて冷蔵保管している４，４’－ジフェニルメタンジイソシアネート（ＭＤＩ）２０ｋｇ入り石油缶から、ＭＤＩ（融点３７℃）を固体のまま２２．８８ｇを取り出し、フレーク状にして５００ｍｌのナスフラスコに投入した。続いて、室温にて保管している１８ｋｇ入り石油缶から１，６－ヘキサメチレンジイソシアネート（ＨＤＩ）（融点－６７℃）を液状のまま２５．０９ｇを取り出し、同フラスコに投入した。
上記フラスコに、さらに離型剤としてブトキシエチルアシッドホスフェートを０．２０ｇ、重合触媒としてジメチル錫ジクロライドを０．０６ｇ投入し、室温（２５℃）にて２０分間溶解を兼ねた攪拌混合を行い、ＭＤＩが完全に溶解したのを確認した。
次いで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）（ＰＥＴＭＡ）５２．０３ｇを同フラスコに投入後、１０℃に冷却しながら２０分間、２６７Ｐａ（２Ｔｏｒｒ）にて減圧攪拌を行ない、混合物を中心肉厚２．０ｍｍからなるレンズ成型用の型に注入した。
上記混合物を重合するために２４時間所定の温度プログラムにて加熱を行い、十分に硬化させたあと離型をし、プラスチックレンズを得た。
得られたプラスチックレンズを、暗室内蛍光灯下にてクモリの確認を目視で行ったところ、クモリはまったく見られず良好であった。 The present invention will be described with reference to examples, but the present invention is not limited to these examples.
[Example 1]
Take out 22.88 g of MDI (melting point: 37 ° C.) as a solid from an oil can containing 4,4′-diphenylmethane diisocyanate (MDI) 20 kg stored refrigerated at 5 ° C. and put it into flakes into a 500 ml eggplant flask. I put it in. Subsequently, 25.09 g of 1,6-hexamethylene diisocyanate (HDI) (melting point -67 ° C.) was taken out from an 18 kg oil can stored at room temperature and placed in the flask.
Further, 0.20 g of butoxyethyl acid phosphate as a release agent and 0.06 g of dimethyltin dichloride as a polymerization catalyst were added to the flask, and the mixture was stirred and mixed for 20 minutes at room temperature (25 ° C.). Was completely dissolved.
Next, 52.03 g of pentaerythritol tetrakis (mercaptoacetate) (PETMA) was charged into the same flask, and then the mixture was stirred at 267 Pa (2 Torr) for 20 minutes while cooling to 10 ° C. It was injected into a mold for forming a lens.
In order to polymerize the mixture, heating was carried out with a predetermined temperature program for 24 hours, and after sufficiently curing, the mold was released to obtain a plastic lens.
When the obtained plastic lens was visually checked for spiders under a fluorescent lamp in a dark room, it was good that no spiders were seen.
［実施例２］
５℃にて冷蔵保管しているＭＤＩ２０ｋｇ入り石油缶からＭＤＩ（融点３７℃）を固体のまま２３．０９ｇを取り出し、フレーク状にして５００ｍｌのナスフラスコに投入した。続いて、室温にて保管している１８ｋｇ入り石油缶からＨＤＩ（融点－６７℃）を液状のまま１１．６６ｇを取り出し、同フラスコに投入した。さらに室温にて保管している１８ｋｇ入り石油缶からイソホロンジイソシアネート（ＩＰＤＩ）（融点－６０℃）を液状のまま１５．３８ｇを取り出し、同フラスコに投入した。
上記フラスコに、さらに離型剤としてブトキシエチルアシッドホスフェートを０．２０ｇ、重合触媒としてジメチル錫ジクロライドを０．０６ｇ投入し、室温（２５℃）にて２０分間溶解を兼ねた攪拌混合を行い、ＭＤＩが完全に溶解したのを確認した。
次いでＰＥＴＭＡ４９．８９ｇを同フラスコに投入後、１０℃に冷却しながら２０分間、２６７Ｐａ（２Ｔｏｒｒ）にて減圧攪拌を行ない、混合物を中心肉厚２．０ｍｍからなるレンズ成型用の型に注入した。
上記混合物を重合するために２４時間所定の温度プログラムにて加熱を行い、十分に硬化させたあと離型をし、プラスチックレンズを得た。
得られたプラスチックレンズを、暗室内蛍光灯下にてクモリの確認を目視で行ったところ、クモリはまったく見られず良好であった。 [Example 2]
23.09 g of MDI (melting point: 37 ° C.) as a solid was taken out from an oil can containing 20 kg of MDI stored refrigerated at 5 ° C. and put into a 500 ml eggplant flask in the form of flakes. Subsequently, 11.66 g of HDI (melting point -67 ° C.) was taken out from an 18 kg oil can stored at room temperature and placed in the flask. Further, 15.38 g of isophorone diisocyanate (IPDI) (melting point−60 ° C.) was taken out from an 18 kg oil can stored at room temperature and charged into the flask.
Further, 0.20 g of butoxyethyl acid phosphate as a release agent and 0.06 g of dimethyltin dichloride as a polymerization catalyst were added to the flask, and the mixture was stirred and mixed for 20 minutes at room temperature (25 ° C.). Was completely dissolved.
Next, 49.89 g of PETMA was put into the same flask, and the mixture was stirred under reduced pressure at 267 Pa (2 Torr) for 20 minutes while cooling to 10 ° C., and the mixture was poured into a lens molding mold having a center thickness of 2.0 mm.
In order to polymerize the mixture, heating was carried out with a predetermined temperature program for 24 hours, and after sufficiently curing, the mold was released to obtain a plastic lens.
When the obtained plastic lens was visually checked for spiders under a fluorescent lamp in a dark room, it was good that no spiders were seen.
５℃にて冷蔵保管しているＭＤＩ２０ｋｇ入り石油缶からＭＤＩ（融点３７℃）を固体のまま２３．０９ｇを取り出し、フレーク状にして５００ｍｌのナスフラスコに投入した。続いて、室温にて保管している１８ｋｇ入り石油缶からＨＤＩ（融点－６７℃）を液状のまま１１．６６ｇを取り出し、同フラスコに投入した。さらに室温にて保管している１８ｋｇ入り石油缶からイソホロンジイソシアネート（ＩＰＤＩ）（融点－６０℃）を液状のまま１５．３８ｇを取り出し、同フラスコに投入した。
上記フラスコに、さらに離型剤としてブトキシエチルアシッドホスフェートを０．２０ｇ、重合触媒としてジメチル錫ジクロライドを０．０６ｇ投入し、室温（２５℃）にて２０分間溶解を兼ねた攪拌混合を行い、ＭＤＩが完全に溶解したのを確認した。
次いでＰＥＴＭＡ４９．８９ｇを同フラスコに投入後、１０℃に冷却しながら２０分間、２６７Ｐａ（２Ｔｏｒｒ）にて減圧攪拌を行ない、混合物を中心肉厚２．０ｍｍからなるレンズ成型用の型に注入した。
上記混合物を重合するために２４時間所定の温度プログラムにて加熱を行い、十分に硬化させたあと離型をし、プラスチックレンズを得た。
得られたプラスチックレンズを、暗室内蛍光灯下にてクモリの確認を目視で行ったところ、クモリはまったく見られず良好であった。 [Example 2]
23.09 g of MDI (melting point: 37 ° C.) as a solid was taken out from an oil can containing 20 kg of MDI stored refrigerated at 5 ° C. and put into a 500 ml eggplant flask in the form of flakes. Subsequently, 11.66 g of HDI (melting point -67 ° C.) was taken out from an 18 kg oil can stored at room temperature and placed in the flask. Further, 15.38 g of isophorone diisocyanate (IPDI) (melting point−60 ° C.) was taken out from an 18 kg oil can stored at room temperature and charged into the flask.
Further, 0.20 g of butoxyethyl acid phosphate as a release agent and 0.06 g of dimethyltin dichloride as a polymerization catalyst were added to the flask, and the mixture was stirred and mixed for 20 minutes at room temperature (25 ° C.). Was completely dissolved.
Next, 49.89 g of PETMA was put into the same flask, and the mixture was stirred under reduced pressure at 267 Pa (2 Torr) for 20 minutes while cooling to 10 ° C., and the mixture was poured into a lens molding mold having a center thickness of 2.0 mm.
In order to polymerize the mixture, heating was carried out with a predetermined temperature program for 24 hours, and after sufficiently curing, the mold was released to obtain a plastic lens.
When the obtained plastic lens was visually checked for spiders under a fluorescent lamp in a dark room, it was good that no spiders were seen.
［実施例３］
５℃にて冷蔵保管しているＭＤＩ２０ｋｇ入り石油缶からＭＤＩ（融点３７℃）を固体のまま２３．５５ｇを取り出し、フレーク状にして５００ｍｌのナスフラスコに投入した。続いて、室温にて保管している１８ｋｇ入り石油缶からＨＤＩ（融点－６７℃）を液状のまま１１．８７ｇを取り出し、同フラスコに投入した。さらに室温にて保管している１８ｋｇ入り石油缶から１，３－ビス（イソシアネートメチル）シクロヘキサン（水添ＸＤＩ）（融点－５０℃）を液状のまま１３．７１ｇを取り出し、同フラスコに投入した。
上記フラスコに、さらに離型剤としてブトキシエチルアシッドホスフェートを０．２０ｇ、重合触媒としてジメチル錫ジクロライドを０．０６ｇ投入し、室温（２５℃）にて２０分間溶解を兼ねた攪拌混合を行い、ＭＤＩが完全に溶解したのを確認した。
次いでＰＥＴＭＡ５０．８７ｇを同フラスコに投入後、１０℃に冷却しながら２０分間、２６７Ｐａ（２Ｔｏｒｒ）にて減圧攪拌を行ない、これを中心肉厚２．０ｍｍからなるレンズ成型用の型に注入した。
上記混合物を重合するために２４時間所定の温度プログラムにて加熱を行い、十分に硬化させたあと離型をし、プラスチックレンズを得た。
得られたプラスチックレンズを、暗室内蛍光灯下にてクモリの確認を目視で行ったところ、クモリはまったく見られず良好であった。 [Example 3]
23.55 g of MDI (melting point: 37 ° C.) was taken out from a petroleum can containing 20 kg of MDI stored refrigerated at 5 ° C. as a solid and put into a 500 ml eggplant flask. Subsequently, 11.87 g of HDI (melting point: −67 ° C.) was taken out from an 18 kg oil can stored at room temperature and placed in the flask. Further, 13.71 g of 1,3-bis (isocyanatemethyl) cyclohexane (hydrogenated XDI) (melting point −50 ° C.) was taken out from an 18 kg oil can stored at room temperature and placed in the flask.
Further, 0.20 g of butoxyethyl acid phosphate as a release agent and 0.06 g of dimethyltin dichloride as a polymerization catalyst were added to the flask, and the mixture was stirred and mixed for 20 minutes at room temperature (25 ° C.). Was completely dissolved.
Next, 50.87 g of PETMA was put into the same flask, stirred under reduced pressure at 267 Pa (2 Torr) for 20 minutes while cooling to 10 ° C., and poured into a lens molding die having a center thickness of 2.0 mm.
In order to polymerize the mixture, heating was carried out with a predetermined temperature program for 24 hours, and after sufficiently curing, the mold was released to obtain a plastic lens.
When the obtained plastic lens was visually checked for spiders under a fluorescent lamp in a dark room, it was good that no spiders were seen.
５℃にて冷蔵保管しているＭＤＩ２０ｋｇ入り石油缶からＭＤＩ（融点３７℃）を固体のまま２３．５５ｇを取り出し、フレーク状にして５００ｍｌのナスフラスコに投入した。続いて、室温にて保管している１８ｋｇ入り石油缶からＨＤＩ（融点－６７℃）を液状のまま１１．８７ｇを取り出し、同フラスコに投入した。さらに室温にて保管している１８ｋｇ入り石油缶から１，３－ビス（イソシアネートメチル）シクロヘキサン（水添ＸＤＩ）（融点－５０℃）を液状のまま１３．７１ｇを取り出し、同フラスコに投入した。
上記フラスコに、さらに離型剤としてブトキシエチルアシッドホスフェートを０．２０ｇ、重合触媒としてジメチル錫ジクロライドを０．０６ｇ投入し、室温（２５℃）にて２０分間溶解を兼ねた攪拌混合を行い、ＭＤＩが完全に溶解したのを確認した。
次いでＰＥＴＭＡ５０．８７ｇを同フラスコに投入後、１０℃に冷却しながら２０分間、２６７Ｐａ（２Ｔｏｒｒ）にて減圧攪拌を行ない、これを中心肉厚２．０ｍｍからなるレンズ成型用の型に注入した。
上記混合物を重合するために２４時間所定の温度プログラムにて加熱を行い、十分に硬化させたあと離型をし、プラスチックレンズを得た。
得られたプラスチックレンズを、暗室内蛍光灯下にてクモリの確認を目視で行ったところ、クモリはまったく見られず良好であった。 [Example 3]
23.55 g of MDI (melting point: 37 ° C.) was taken out from a petroleum can containing 20 kg of MDI stored refrigerated at 5 ° C. as a solid and put into a 500 ml eggplant flask. Subsequently, 11.87 g of HDI (melting point: −67 ° C.) was taken out from an 18 kg oil can stored at room temperature and placed in the flask. Further, 13.71 g of 1,3-bis (isocyanatemethyl) cyclohexane (hydrogenated XDI) (melting point −50 ° C.) was taken out from an 18 kg oil can stored at room temperature and placed in the flask.
Further, 0.20 g of butoxyethyl acid phosphate as a release agent and 0.06 g of dimethyltin dichloride as a polymerization catalyst were added to the flask, and the mixture was stirred and mixed for 20 minutes at room temperature (25 ° C.). Was completely dissolved.
Next, 50.87 g of PETMA was put into the same flask, stirred under reduced pressure at 267 Pa (2 Torr) for 20 minutes while cooling to 10 ° C., and poured into a lens molding die having a center thickness of 2.0 mm.
In order to polymerize the mixture, heating was carried out with a predetermined temperature program for 24 hours, and after sufficiently curing, the mold was released to obtain a plastic lens.
When the obtained plastic lens was visually checked for spiders under a fluorescent lamp in a dark room, it was good that no spiders were seen.
［比較例１］
５℃にて冷蔵保管しているＭＤＩ２０ｋｇ入り石油缶を、そのまま７０℃の恒温炉にて３０時間かけて融解させた。融解したＭＤＩ２２．８８ｇを取り出して使用した以外は、実施例１と同様の手順にてプラスチックレンズを作製した。
得られたプラスチックレンズを室内で観察するかぎりではクモリはみられなかったが、暗室内蛍光灯下にて確認を目視で行ったところ、クモリが発生していた。 [Comparative Example 1]
A 20 kg MDI oil can stored refrigerated at 5 ° C. was melted in a constant temperature oven at 70 ° C. for 30 hours. A plastic lens was produced in the same procedure as in Example 1 except that 22.88 g of melted MDI was taken out and used.
As long as the obtained plastic lens was observed indoors, no spider was observed, but when it was visually confirmed under a fluorescent lamp in a dark room, spiders were generated.
５℃にて冷蔵保管しているＭＤＩ２０ｋｇ入り石油缶を、そのまま７０℃の恒温炉にて３０時間かけて融解させた。融解したＭＤＩ２２．８８ｇを取り出して使用した以外は、実施例１と同様の手順にてプラスチックレンズを作製した。
得られたプラスチックレンズを室内で観察するかぎりではクモリはみられなかったが、暗室内蛍光灯下にて確認を目視で行ったところ、クモリが発生していた。 [Comparative Example 1]
A 20 kg MDI oil can stored refrigerated at 5 ° C. was melted in a constant temperature oven at 70 ° C. for 30 hours. A plastic lens was produced in the same procedure as in Example 1 except that 22.88 g of melted MDI was taken out and used.
As long as the obtained plastic lens was observed indoors, no spider was observed, but when it was visually confirmed under a fluorescent lamp in a dark room, spiders were generated.
［比較例２］
５℃にて冷蔵保管しているＭＤＩ２０ｋｇ入り石油缶を、そのまま７０℃の恒温炉にて３０時間かけて融解させた。融解したＭＤＩ２３．０９ｇを取り出して使用した以外は、実施例２と同様の手順にてプラスチックレンズを作製した。
得られたプラスチックレンズを室内で観察するかぎりではクモリはみられなかったが、暗室内蛍光灯下にて確認を目視で行ったところ、クモリが発生していた。 [Comparative Example 2]
A 20 kg MDI oil can stored refrigerated at 5 ° C. was melted in a constant temperature oven at 70 ° C. for 30 hours. A plastic lens was produced in the same manner as in Example 2 except that 23.09 g of melted MDI was taken out and used.
As long as the obtained plastic lens was observed indoors, no spider was observed, but when it was visually confirmed under a fluorescent lamp in a dark room, spiders were generated.
５℃にて冷蔵保管しているＭＤＩ２０ｋｇ入り石油缶を、そのまま７０℃の恒温炉にて３０時間かけて融解させた。融解したＭＤＩ２３．０９ｇを取り出して使用した以外は、実施例２と同様の手順にてプラスチックレンズを作製した。
得られたプラスチックレンズを室内で観察するかぎりではクモリはみられなかったが、暗室内蛍光灯下にて確認を目視で行ったところ、クモリが発生していた。 [Comparative Example 2]
A 20 kg MDI oil can stored refrigerated at 5 ° C. was melted in a constant temperature oven at 70 ° C. for 30 hours. A plastic lens was produced in the same manner as in Example 2 except that 23.09 g of melted MDI was taken out and used.
As long as the obtained plastic lens was observed indoors, no spider was observed, but when it was visually confirmed under a fluorescent lamp in a dark room, spiders were generated.
［比較例３］
５℃にて冷蔵保管しているＭＤＩ２０ｋｇ入り石油缶を、そのまま７０℃の恒温炉にて３０時間かけて融解させた。融解したＭＤＩ２３．５５ｇを取り出して使用した以外は、実施例３と同様の手順にてプラスチックレンズを作製した。
得られたプラスチックレンズを室内で観察するかぎりではクモリはみられなかったが、暗室内蛍光灯下にて確認を目視で行ったところ、クモリが発生していた。 [Comparative Example 3]
A 20 kg MDI oil can stored refrigerated at 5 ° C. was melted in a constant temperature oven at 70 ° C. for 30 hours. A plastic lens was produced in the same procedure as in Example 3 except that 23.55 g of melted MDI was taken out and used.
As long as the obtained plastic lens was observed indoors, no spider was observed, but when it was visually confirmed under a fluorescent lamp in a dark room, spiders were generated.
５℃にて冷蔵保管しているＭＤＩ２０ｋｇ入り石油缶を、そのまま７０℃の恒温炉にて３０時間かけて融解させた。融解したＭＤＩ２３．５５ｇを取り出して使用した以外は、実施例３と同様の手順にてプラスチックレンズを作製した。
得られたプラスチックレンズを室内で観察するかぎりではクモリはみられなかったが、暗室内蛍光灯下にて確認を目視で行ったところ、クモリが発生していた。 [Comparative Example 3]
A 20 kg MDI oil can stored refrigerated at 5 ° C. was melted in a constant temperature oven at 70 ° C. for 30 hours. A plastic lens was produced in the same procedure as in Example 3 except that 23.55 g of melted MDI was taken out and used.
As long as the obtained plastic lens was observed indoors, no spider was observed, but when it was visually confirmed under a fluorescent lamp in a dark room, spiders were generated.
本発明の製造方法によれば、室温において固体状であるポリイソシアネートモノマーを予め溶融することなく固体状態のまま使用し、その結果透明性に優れたプラスチックレンズを製造することができ、なおかつプラスチックレンズを生産性よく量産できることから、特に眼鏡などのプラスチックレンズの分野において極めて有用である。
According to the production method of the present invention, a polyisocyanate monomer that is solid at room temperature can be used in a solid state without being previously melted, and as a result, a plastic lens having excellent transparency can be produced. Can be mass-produced with high productivity, and is particularly useful in the field of plastic lenses such as eyeglasses.
Claims (5)
- 少なくともポリイソシアネートモノマー及びポリチオールモノマーを含む原料モノマーのうち、融点が室温以上であるポリイソシアネートモノマー（Ａ）及び融点が室温未満であるモノマー（Ｂ）を含む混合物を重合するプラスチックレンズの製造方法であって、
上記混合物を調製する工程において、固体状態のポリイソシアネートモノマー（Ａ）とモノマー（Ｂ）とを混合して上記ポリイソシアネートモノマー（Ａ）を溶解し、また上記混合を、上記ポリイソシアネートモノマー（Ａ）の融点より低くかつ上記モノマー（Ｂ）の融点よりも高い温度で行うことを特徴とするプラスチックレンズの製造方法。 Among the raw material monomers containing at least a polyisocyanate monomer and a polythiol monomer, a method for producing a plastic lens for polymerizing a mixture containing a polyisocyanate monomer (A) having a melting point of room temperature or higher and a monomer (B) having a melting point of less than room temperature. And
In the step of preparing the mixture, the solid polyisocyanate monomer (A) and the monomer (B) are mixed to dissolve the polyisocyanate monomer (A), and the mixture is mixed with the polyisocyanate monomer (A). A method for producing a plastic lens, which is performed at a temperature lower than the melting point of the monomer and higher than the melting point of the monomer (B). - 前記ポリイソシアネートモノマー（Ａ）が、芳香族ポリイソシアネートである、請求項１に記載のプラスチックレンズの製造方法。 The method for producing a plastic lens according to claim 1, wherein the polyisocyanate monomer (A) is an aromatic polyisocyanate.
- 前記ポリイソシアネートモノマー（Ａ）が、４，４’－ジフェニルメタンジイソシアネートである、請求項１又は２に記載のプラスチックレンズの製造方法。 The method for producing a plastic lens according to claim 1 or 2, wherein the polyisocyanate monomer (A) is 4,4'-diphenylmethane diisocyanate.
- 前記モノマー（Ｂ）が、融点が室温未満のポリイソシアネートモノマーである、請求項１～３のいずれかに記載のプラスチックレンズの製造方法。 The method for producing a plastic lens according to any one of claims 1 to 3, wherein the monomer (B) is a polyisocyanate monomer having a melting point of less than room temperature.
- 固体状態のポリイソシアネートモノマー（Ａ）とモノマー（Ｂ）とを混合して上記ポリイソシアネートモノマー（Ａ）を溶解した後、ポリチオールモノマーを混合して混合物を調製する、請求項１～４のいずれかに記載のプラスチックレンズの製造方法。 The solid isocyanate polyisocyanate (A) and the monomer (B) are mixed to dissolve the polyisocyanate monomer (A), and then the polythiol monomer is mixed to prepare a mixture. The manufacturing method of the plastic lens of description.
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