JP2007197564A - Urethane compound obtained by addition of unsaturated group-containing isocyanate compound, photocurable composition containing the same and its cured material - Google Patents
Urethane compound obtained by addition of unsaturated group-containing isocyanate compound, photocurable composition containing the same and its cured material Download PDFInfo
- Publication number
- JP2007197564A JP2007197564A JP2006017789A JP2006017789A JP2007197564A JP 2007197564 A JP2007197564 A JP 2007197564A JP 2006017789 A JP2006017789 A JP 2006017789A JP 2006017789 A JP2006017789 A JP 2006017789A JP 2007197564 A JP2007197564 A JP 2007197564A
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- Prior art keywords
- group
- meth
- methyl
- acrylate
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- Prior art date
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- -1 Urethane compound Chemical class 0.000 title claims abstract description 89
- 239000000203 mixture Substances 0.000 title claims abstract description 24
- 239000012948 isocyanate Substances 0.000 title claims abstract description 16
- 239000000463 material Substances 0.000 title claims abstract description 13
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 43
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 24
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 21
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 16
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 16
- 239000004417 polycarbonate Substances 0.000 claims abstract description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 11
- 125000002947 alkylene group Chemical group 0.000 claims description 26
- 125000003158 alcohol group Chemical group 0.000 claims description 23
- 125000004432 carbon atom Chemical group C* 0.000 claims description 19
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 10
- 239000003505 polymerization initiator Substances 0.000 claims description 9
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 8
- PGMMMHFNKZSYEP-UHFFFAOYSA-N 1,20-Eicosanediol Chemical compound OCCCCCCCCCCCCCCCCCCCCO PGMMMHFNKZSYEP-UHFFFAOYSA-N 0.000 claims description 8
- UNVGBIALRHLALK-UHFFFAOYSA-N 1,5-Hexanediol Chemical compound CC(O)CCCCO UNVGBIALRHLALK-UHFFFAOYSA-N 0.000 claims description 8
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims description 8
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 8
- XSMIOONHPKRREI-UHFFFAOYSA-N undecane-1,11-diol Chemical compound OCCCCCCCCCCCO XSMIOONHPKRREI-UHFFFAOYSA-N 0.000 claims description 8
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 claims description 6
- SDQROPCSKIYYAV-UHFFFAOYSA-N 2-methyloctane-1,8-diol Chemical compound OCC(C)CCCCCCO SDQROPCSKIYYAV-UHFFFAOYSA-N 0.000 claims description 6
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 claims description 6
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 6
- GHLKSLMMWAKNBM-UHFFFAOYSA-N dodecane-1,12-diol Chemical compound OCCCCCCCCCCCCO GHLKSLMMWAKNBM-UHFFFAOYSA-N 0.000 claims description 6
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 claims description 4
- JVZZUPJFERSVRN-UHFFFAOYSA-N 2-methyl-2-propylpropane-1,3-diol Chemical compound CCCC(C)(CO)CO JVZZUPJFERSVRN-UHFFFAOYSA-N 0.000 claims description 4
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims description 4
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 claims description 4
- 150000002009 diols Chemical class 0.000 claims description 4
- XVEOUOTUJBYHNL-UHFFFAOYSA-N heptane-2,4-diol Chemical compound CCCC(O)CC(C)O XVEOUOTUJBYHNL-UHFFFAOYSA-N 0.000 claims description 4
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 4
- XRVCFZPJAHWYTB-UHFFFAOYSA-N prenderol Chemical compound CCC(CC)(CO)CO XRVCFZPJAHWYTB-UHFFFAOYSA-N 0.000 claims description 4
- 229950006800 prenderol Drugs 0.000 claims description 4
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 claims description 4
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 claims description 3
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 3
- SXCBDZAEHILGLM-UHFFFAOYSA-N heptane-1,7-diol Chemical compound OCCCCCCCO SXCBDZAEHILGLM-UHFFFAOYSA-N 0.000 claims description 3
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 claims description 3
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 3
- AJKXDPSHWRTFOZ-UHFFFAOYSA-N 2-ethylhexane-1,6-diol Chemical compound CCC(CO)CCCCO AJKXDPSHWRTFOZ-UHFFFAOYSA-N 0.000 claims description 2
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 abstract description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 81
- 239000000178 monomer Substances 0.000 description 23
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 230000003287 optical effect Effects 0.000 description 11
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 10
- 238000001723 curing Methods 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 229940035437 1,3-propanediol Drugs 0.000 description 2
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 2
- JCTXKRPTIMZBJT-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)C(C)(C)CO JCTXKRPTIMZBJT-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 2
- 125000003438 dodecyl 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])C([H])([H])C([H])([H])* 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 239000013307 optical fiber Substances 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- JNELGWHKGNBSMD-UHFFFAOYSA-N xanthone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3OC2=C1 JNELGWHKGNBSMD-UHFFFAOYSA-N 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- HIACAHMKXQESOV-UHFFFAOYSA-N 1,2-bis(prop-1-en-2-yl)benzene Chemical compound CC(=C)C1=CC=CC=C1C(C)=C HIACAHMKXQESOV-UHFFFAOYSA-N 0.000 description 1
- QVCUKHQDEZNNOC-UHFFFAOYSA-N 1,2-diazabicyclo[2.2.2]octane Chemical compound C1CC2CCN1NC2 QVCUKHQDEZNNOC-UHFFFAOYSA-N 0.000 description 1
- GJZFGDYLJLCGHT-UHFFFAOYSA-N 1,2-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=C(CC)C(CC)=CC=C3SC2=C1 GJZFGDYLJLCGHT-UHFFFAOYSA-N 0.000 description 1
- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- BOVQCIDBZXNFEJ-UHFFFAOYSA-N 1-chloro-3-ethenylbenzene Chemical compound ClC1=CC=CC(C=C)=C1 BOVQCIDBZXNFEJ-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- SDXHBDVTZNMBEW-UHFFFAOYSA-N 1-ethoxy-2-(2-hydroxyethoxy)ethanol Chemical compound CCOC(O)COCCO SDXHBDVTZNMBEW-UHFFFAOYSA-N 0.000 description 1
- ZMYIIHDQURVDRB-UHFFFAOYSA-N 1-phenylethenylbenzene Chemical group C=1C=CC=CC=1C(=C)C1=CC=CC=C1 ZMYIIHDQURVDRB-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- ISRGONDNXBCDBM-UHFFFAOYSA-N 2-chlorostyrene Chemical compound ClC1=CC=CC=C1C=C ISRGONDNXBCDBM-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- QPXVRLXJHPTCPW-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-(4-propan-2-ylphenyl)propan-1-one Chemical compound CC(C)C1=CC=C(C(=O)C(C)(C)O)C=C1 QPXVRLXJHPTCPW-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- QKTWWGYCVXCKOJ-UHFFFAOYSA-N 2-methoxy-1-(2-methoxyphenyl)-2-phenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1OC QKTWWGYCVXCKOJ-UHFFFAOYSA-N 0.000 description 1
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Images
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- Polyesters Or Polycarbonates (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
本発明は、ポリカーボネート両末端ジオール化合物に不飽和基を有するイソシアネート化合物を付加させてなる、分子量５００〜１００００のウレタン化合物、及びこれを含有した光硬化性組成物、ならびにその硬化物に関する。 The present invention relates to a urethane compound having a molecular weight of 500 to 10,000 obtained by adding an isocyanate compound having an unsaturated group to a polycarbonate both-end diol compound, a photocurable composition containing the urethane compound, and a cured product thereof.
ポリカーボネートを主骨格とする樹脂硬化物は、耐衝撃性などの機械的特性や光透過性などの光学的特性にも優れた樹脂であり、光学式情報記録媒体に用いられる光学式ディスクなどの幅広い分野で利用されている、しかし一方では、アルカリや溶剤で劣化するといった耐薬品性に乏しいことや、高温高湿の過酷な環境下では、加水分解を起こし、やはり劣化を伴うといった問題点がある。また、メディアの大容量化に伴い、より低波長のレーザーを用いての記録を行うために、一層の光透過性の向上が望まれる。 Cured resin with polycarbonate as the main skeleton is a resin with excellent mechanical properties such as impact resistance and optical properties such as light transmission, and is widely used for optical discs used in optical information recording media. It is used in the field, but on the other hand, there are problems such as poor chemical resistance such as deterioration with alkalis and solvents, and hydrolysis under the harsh environment of high temperature and high humidity, which also involves deterioration. . In addition, as the capacity of media increases, in order to perform recording using a laser having a lower wavelength, further improvement in light transmittance is desired.
例えば、特開昭６１−１４２５４５号公報（特許文献１）及び特開平６−８９４６２号公報（特許文献２）にはウレタンアクリレートを主成分とする紫外線硬化性樹脂接着剤が示されているが、この接着剤は光硬化性、硬化により得られる硬化物の耐熱性、耐湿性や接着性の点で十分に満足する性能が得られていない。特開平１０−２８７７１８号公報（特許文献３）ではこれらを改善するために、硬化性樹脂の組成に、分子内に不飽和二重結合を少なくとも一つ有する有機リン酸エステルを加えることを提案している。しかしながら、リンを含んだ構造であるために、環境への負荷が懸念される。 For example, Japanese Patent Application Laid-Open No. 61-142545 (Patent Document 1) and Japanese Patent Application Laid-Open No. 6-89462 (Patent Document 2) show an ultraviolet curable resin adhesive mainly composed of urethane acrylate. This adhesive does not have sufficient performance in terms of photocurability and the heat resistance, moisture resistance and adhesion of a cured product obtained by curing. JP-A-10-287718 (Patent Document 3) proposes to add an organic phosphate ester having at least one unsaturated double bond in the molecule to the composition of the curable resin in order to improve these problems. ing. However, since the structure contains phosphorus, there is a concern about the burden on the environment.
また、特開昭６４−２４８１７号公報（特許文献４）では、紫外線または電子線の照射によって、塗料、接着剤、粘着剤等に利用できる樹脂組成物として、メチルオクタンジオール／ノナンジオールのポリカーボネートをポリウレタン骨格に有するウレタン変性アクリレート樹脂組成物を報告しているが、ウレタン変性アクリレートを用いた場合、得られた樹脂組成物は、硬化性が充分ではなかった。一方で、特開平１０−９５８２２号公報（特許文献５）では、ポリカーボネートにジイソシアネートとヒドロキシル基を有する多官能アクリレートを用いこの問題を解決しようとしている。しかし、多官能アクリレートモノマーを用いているため、硬化収縮性が増してしまう恐れがある。 Further, in Japanese Patent Application Laid-Open No. 64-24817 (Patent Document 4), a polycarbonate of methyloctanediol / nonanediol is used as a resin composition that can be used for paints, adhesives, pressure-sensitive adhesives, etc. by irradiation with ultraviolet rays or electron beams. Although a urethane-modified acrylate resin composition having a polyurethane skeleton has been reported, when a urethane-modified acrylate is used, the resulting resin composition has not been sufficiently hardened. On the other hand, Japanese Patent Application Laid-Open No. 10-95822 (Patent Document 5) attempts to solve this problem by using a polyfunctional acrylate having a diisocyanate and a hydroxyl group for polycarbonate. However, since a polyfunctional acrylate monomer is used, there is a risk that curing shrinkage may increase.
特開平６−１６７３２号公報（特許文献６）では、紫外線硬化性樹脂を用いてレンズを製作する検討がなされている。具体的には、レンズ形状の付いた金型と透明樹脂基板との間に紫外線硬化性組成物を流し込み、該組成物を硬化させることで短時間でレンズを製造することができる。しかしながら、反りやレンズのゆがみが発生するという点において、性能的に不十分であった。特開２００３−４８９４２号公報（特許文献７）においても、レンズシートに耐熱性を付与する目的では、多官能（メタ）アクリレートモノマーを多用することにより硬化物中の架橋密度を上げる手法を提案しているが、硬化物の軟化点が増大させることができる、すなわち、耐熱性が改善される効果を有する反面、硬化時の反りが増加するという欠点があった。これに関して特開２００５−１７０９６１号公報（特許文献８）においては、特定の構造を有する（メタ）アクリレート化合物を用いることにより、上記問題の解決を提案している。しかし、これを光学材料として用いるのに十分な透明性を与えるにはいたっていない。 Japanese Patent Laid-Open No. 6-16732 (Patent Document 6) discusses manufacturing a lens using an ultraviolet curable resin. Specifically, a lens can be produced in a short time by pouring an ultraviolet curable composition between a lens-shaped mold and a transparent resin substrate and curing the composition. However, in terms of warping and distortion of the lens, performance was insufficient. Japanese Patent Application Laid-Open No. 2003-48942 (Patent Document 7) also proposes a technique for increasing the crosslink density in a cured product by using a polyfunctional (meth) acrylate monomer for the purpose of imparting heat resistance to a lens sheet. However, the softening point of the cured product can be increased, that is, it has an effect of improving the heat resistance, but there is a drawback that the warp during curing increases. In this regard, Japanese Patent Laid-Open No. 2005-170961 (Patent Document 8) proposes a solution to the above problem by using a (meth) acrylate compound having a specific structure. However, it does not provide sufficient transparency for use as an optical material.
一方、反応性のエチレン性不飽和基を含有したイソシアネート化合物が付加したウレタン結合をもつモノマー、オリゴマーあるいはポリマーは、コーティング材料、ＵＶ硬化塗料及び熱硬化塗料、成形材料、接着剤、インキ、レジスト、光学材料、光造形材料、印刷版材料、歯科材料、ポリマー電池材料、及びポリマーの原料などの広範な分野で使用されている。 On the other hand, a monomer, oligomer or polymer having a urethane bond to which an isocyanate compound containing a reactive ethylenically unsaturated group is added is a coating material, UV curable paint and thermosetting paint, molding material, adhesive, ink, resist, It is used in a wide range of fields such as optical materials, stereolithography materials, printing plate materials, dental materials, polymer battery materials, and polymer raw materials.
例えば、光学材料の用途としては、光学レンズ、フィルム、ＣＲＴ用ガラスなどの光反射防止膜用材料や、光ファイバーのクラッド材用材料や、あるいは光ファイバー、光学レンズ等のための光学接着剤などを挙げることができる。さらに、各種ディスプレイ等のガラス基材、あるいはプラスチック基材の表面を保護するために使用されるハードコート材料として、特開平９−２９６１５２号公報（特許文献９）には、ビスフェノール型アクリレートにジイソシアネートを付加させて得られる多官能ウレタンアクリレートが開示され、特開平１０−２８７７１８号公報（特許文献１０）には、ポリエステルポリオールまたはポリカーボネートポリオールと、ポリイソシアネートと、水酸基含有（メタ）アクリレートと、を反応させて得られるウレタンアクリレート化合物からなる硬化性組成物が開示されている。 For example, applications of optical materials include optical anti-reflection film materials such as optical lenses, films, and CRT glass, optical fiber cladding materials, and optical adhesives for optical fibers and optical lenses. be able to. Furthermore, as a hard coat material used for protecting the surface of glass substrates or plastic substrates for various displays, JP-A-9-296152 (Patent Document 9) discloses a diisocyanate in a bisphenol type acrylate. A polyfunctional urethane acrylate obtained by addition is disclosed. JP-A-10-287718 (Patent Document 10) reacts a polyester polyol or polycarbonate polyol, a polyisocyanate, and a hydroxyl group-containing (meth) acrylate. A curable composition comprising a urethane acrylate compound obtained in this manner is disclosed.
本発明の目的は、それらのエチレン性不飽和基含有イソシアネート化合物をポリカーボネートジオール化合物に付加させることにより耐薬品性に優れ、高い透過性を与え、低硬化収縮性を与える光硬化型樹脂組成物を提供することにある。 It is an object of the present invention to provide a photocurable resin composition that is excellent in chemical resistance, imparts high permeability, and imparts low curing shrinkage by adding those ethylenically unsaturated group-containing isocyanate compounds to a polycarbonate diol compound. It is to provide.
本発明者は、分子量が１００〜９０００のポリカーボネートジオールの両末端ヒドロキシル基を、反応性の不飽和結合を分子内に含むイソシアネート化合物で封鎖することによって、ウレタン化合物を得た。また、該化合物と光硬化剤を併用することによりその硬化性樹脂組成物を得た。さらにそれを硬化させることにより、硬化物を得た。 The inventor obtained a urethane compound by blocking both terminal hydroxyl groups of a polycarbonate diol having a molecular weight of 100 to 9000 with an isocyanate compound containing a reactive unsaturated bond in the molecule. Moreover, the curable resin composition was obtained by using this compound and a photocuring agent together. Further, it was cured to obtain a cured product.
また、本発明は以下の事項からなる。
［１］分子の両末端にヒドロキシル基を有するポリカーボネートジオールに、分子内に１つ以上の（メタ）アクリル基を有するイソシアネート化合物を付加させて得られる、下記一般式（１）
で示されるウレタン化合物。
［２］分子量が５００〜１００００である前記［１］に記載のウレタン化合物。
［３］一般式（２）
で示される前記［１］または［２］に記載のウレタン化合物。
［４］一般式（３）
で示される前記［１］または［２］に記載のウレタン化合物。
［５］一般式（４）
で示される前記［１］または［２］に記載のウレタン化合物。
［６］一般式（１）のＲ1が、一種類以上の２−メチル−１，３−プロパンジオール、１，３−ブタンジオール、２，４−ヘプタンジオール、２，２−ジエチル−１，３−プロパンジオール、２−メチル−２−プロピル−１，３−プロパンジオール、２−エチル−１，３−ヘキサンジオール、２−メチル−２，４−ペンタンジオール、２，２，４−トリメチル−１，３−ペンタンジオール、２−ブチル−２−エチル−１，３−プロパンジオール等のアルキレン基がトリメチレン基である脂肪族２価アルコール残基；１，４−ブタンジオール等のアルキレン基がテトラメチレン基である脂肪族２価アルコール残基；１，５−ペンタンジオール、３−メチル−１，５−ペンタンジオール、１，５−ヘキサンジオール等のアルキレン基がペンタメチレン基である脂肪族２価アルコール残基；１，６−ヘキサンジオール、２−エチル−１，６−ヘキサンジオール等のアルキレン基がヘキサメチレン基である脂肪族２価アルコール残基；１，７−ヘプタンジオール等のアルキレン基がヘプタメチレン基である脂肪族２価アルコール残基；１，８−オクタンジオール、２−メチル−１，８−オクタンジオールのアルキレン基がオクタメチレン基である脂肪族２価アルコール残基；１，９−ノナンジオール、１，１０−デカンジオール、１，１１−ウンデカンジオール、１，１２−ドデカンジオール、１，２０−エイコサンジオール、１，４−シクロヘキサンジメタノールの各残基である前記［１］〜［５］のいずれかに記載のウレタン化合物。
［７］前記［１］〜［６］のいずれかに記載のウレタン化合物と、重合開始剤とを含有することを特徴とする硬化性組成物。
［８］前記［１］〜［７］に記載される硬化性組成物によって得られた硬化物。
Moreover, this invention consists of the following matters.
[1] The following general formula (1) obtained by adding an isocyanate compound having one or more (meth) acryl groups in a molecule to a polycarbonate diol having hydroxyl groups at both ends of the molecule
Urethane compound represented by
[2] The urethane compound according to [1], which has a molecular weight of 500 to 10,000.
[3] General formula (2)
The urethane compound according to [1] or [2], which is represented by:
[4] General formula (3)
The urethane compound according to [1] or [2], which is represented by:
[5] General formula (4)
The urethane compound according to [1] or [2], which is represented by:
[6] R 1 in the general formula (1) is one or more kinds of 2-methyl-1,3-propanediol, 1,3-butanediol, 2,4-heptanediol, 2,2-diethyl-1, 3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl- An aliphatic dihydric alcohol residue in which an alkylene group such as 1,3-pentanediol and 2-butyl-2-ethyl-1,3-propanediol is a trimethylene group; an alkylene group such as 1,4-butanediol is tetra An aliphatic dihydric alcohol residue which is a methylene group; an alkylene group such as 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,5-hexanediol is pentamethyl An aliphatic dihydric alcohol residue that is an aliphatic group; an aliphatic dihydric alcohol residue in which an alkylene group such as 1,6-hexanediol or 2-ethyl-1,6-hexanediol is a hexamethylene group; 1,7 An aliphatic dihydric alcohol residue in which an alkylene group such as heptanediol is a heptamethylene group; aliphatic 2 in which an alkylene group of 1,8-octanediol or 2-methyl-1,8-octanediol is an octamethylene group 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,20-eicosanediol, 1,4-cyclohexanedimethanol The urethane compound according to any one of [1] to [5], which is a residue.
[7] A curable composition comprising the urethane compound according to any one of [1] to [6] and a polymerization initiator.
[8] A cured product obtained by the curable composition described in [1] to [7].
本発明によれば、非晶性のポリカーボネート構造による高い透過性を有し、ウレタン樹脂の特長である柔らかさも有している。またこの硬化物は低い硬化収縮性により、（メタ）アクリル樹脂でありながら、基盤への高い密着強度を示す硬化物を提供することが可能である。 According to this invention, it has the high permeability | transmittance by an amorphous polycarbonate structure, and also has the softness which is the characteristic of a urethane resin. In addition, this cured product can provide a cured product exhibiting high adhesion strength to the substrate while being a (meth) acrylic resin due to low curing shrinkage.
以下、本発明における実施形態について詳細に説明する。
本発明に使用されるウレタン化合物は、一般式（１）
The urethane compound used in the present invention has the general formula (1)
上記一般式（１）中、Ｒ1は炭素数が１〜２０、好ましくは１〜１０である直鎖、分岐または環状構造を含む飽和脂肪族基を一種類以上含んだ構造であり、具体的には、２−メチル−１，３−プロパンジオール、１，３−ブタンジオール、２，４−ヘプタンジオール、２，２−ジエチル−１，３−プロパンジオール、２−メチル−２−プロピル−１，３−プロパンジオール、２−エチル−１，３−ヘキサンジオール、２−メチル−２，４−ペンタンジオール、２，２，４−トリメチル−１，３−ペンタンジオール、２−ブチル−２−エチル−１，３−プロパンジオール等のアルキレン基がトリメチレン基である脂肪族２価アルコール残基；１，４−ブタンジオール等のアルキレン基がテトラメチレン基である脂肪族２価アルコール残基；１，５−ペンタンジオール、３−メチル−１，５−ペンタンジオール、１，５−ヘキサンジオール等のアルキレン基がペンタメチレン基である脂肪族２価アルコール残基；１，６−ヘキサンジオール、２−エチル−１，６−ヘキサンジオール等のアルキレン基がヘキサメチレン基である脂肪族２価アルコール残基；１，７−ヘプタンジオール等のアルキレン基がヘプタメチレン基である脂肪族２価アルコール残基；１，８−オクタンジオール、２−メチル−１，８−オクタンジオールのアルキレン基がオクタメチレン基である脂肪族２価アルコール残基；１，９−ノナンジオール、１，１０−デカンジオール、１，１１−ウンデカンジオール、１，１２−ドデカンジオール、１，２０−エイコサンジオール、１，４−シクロヘキサンジメタノール等の各残基である。その中でも、３−メチル−１，５−ペンタンジオール、１，６−ヘキサンジオール、１，４−シクロヘキサンジメタノール、２−メチル−１，８−オクタンジオール、及び１，９−ノナンジオールの各残基が特に好ましい。 In the general formula (1), R 1 has a structure containing one or more saturated aliphatic groups containing a linear, branched or cyclic structure having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. 2-methyl-1,3-propanediol, 1,3-butanediol, 2,4-heptanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-2-propyl-1 , 3-propanediol, 2-ethyl-1,3-hexanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-butyl-2-ethyl An aliphatic dihydric alcohol residue in which an alkylene group such as 1,3-propanediol is a trimethylene group; an aliphatic dihydric alcohol residue in which an alkylene group such as 1,4-butanediol is a tetramethylene group; An aliphatic dihydric alcohol residue in which an alkylene group such as pentanediol, 3-methyl-1,5-pentanediol, 1,5-hexanediol or the like is a pentamethylene group; 1,6-hexanediol, 2-ethyl- An aliphatic dihydric alcohol residue in which an alkylene group such as 1,6-hexanediol is a hexamethylene group; an aliphatic dihydric alcohol residue in which an alkylene group such as 1,7-heptanediol is a heptamethylene group; Aliphatic dihydric alcohol residues in which the alkylene group of 8-octanediol and 2-methyl-1,8-octanediol is an octamethylene group; 1,9-nonanediol, 1,10-decanediol, 1,11- Undecanediol, 1,12-dodecanediol, 1,20-eicosanediol, 1,4-cyclohexanedimethanol, etc. Each residue. Among these, each residue of 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 2-methyl-1,8-octanediol, and 1,9-nonanediol The group is particularly preferred.
Ｒ2は炭素数が１〜１０である直鎖、分岐または環状構造を含む飽和脂肪族基または芳香環を含んだ構造であり、分岐または環状構造を含む飽和脂肪族基または芳香環を表わすときのＲ2の具体例としては、
Ｒ3は水素原子またはメチル基である。また、ｎは１〜５０の整数であり、ｍは１〜３の整数である。
R 2 is a structure containing a saturated aliphatic group or aromatic ring containing a linear, branched or cyclic structure having 1 to 10 carbon atoms, and when R 2 represents a saturated aliphatic group or aromatic ring containing a branched or cyclic structure As a specific example of R 2 of
R 3 is a hydrogen atom or a methyl group. Moreover, n is an integer of 1-50, m is an integer of 1-3.
さらに、本発明で使用されるウレタン化合物は下記の一般式（５）
一般式（５）の化合物は、二個のヒドロキシル基を有するポリカーボネートジオール化合物であるが、その両末端にヒドロキシル基を有することが好ましい。分子量は１００〜９０００が好ましく、１０００〜４０００であることがより好ましい。Ｒ1は炭素数が１〜２０、好ましくは１〜１０である直鎖、分岐または環状構造を含む飽和脂肪族基を一種類以上含んだ構造であり、具体的には、２−メチル−１，３−プロパンジオール、１，３−ブタンジオール、２，４−ヘプタンジオール、２，２−ジエチル−１，３−プロパンジオール、２−メチル−２−プロピル−１，３−プロパンジオール、２−エチル−１，３−ヘキサンジオール、２−メチル−２，４−ペンタンジオール、２，２，４−トリメチル−１，３−ペンタンジオール、２−ブチル−２−エチル−１，３−プロパンジオール等のアルキレン基がトリメチレン基である脂肪族２価アルコール残基；１，４−ブタンジオール等のアルキレン基がテトラメチレン基である脂肪族２価アルコール残基；１，５−ペンタンジオール、３−メチル−１，５−ペンタンジオール、１，５−ヘキサンジオール等のアルキレン基がペンタメチレン基である脂肪族２価アルコール残基；１，６−ヘキサンジオール、２−エチル−１，６−ヘキサンジオール等のアルキレン基がヘキサメチレン基である脂肪族２価アルコール残基；１，７−ヘプタンジオール等のアルキレン基がヘプタメチレン基である脂肪族２価アルコール残基；１，８−オクタンジオール、２−メチル−１，８−オクタンジオールのアルキレン基がオクタメチレン基である脂肪族２価アルコール残基；１，９−ノナンジオール、１，１０−デカンジオール、１，１１−ウンデカンジオール、１，１２−ドデカンジオール、１，２０−エイコサンジオール、１，４−シクロヘキサンジメタノール等の各残基が挙げられる。その中でも、３−メチル−１，５−ペンタンジオール、１，６−ヘキサンジオール、１，４−シクロヘキサンジメタノール、２−メチル−１，８−オクタンジオール、及び１，９−ノナンジオールの各残基が特に好ましい。また、ｎは１から５０の整数で、ｍは１から３の整数である。 The compound of the general formula (5) is a polycarbonate diol compound having two hydroxyl groups, but preferably has hydroxyl groups at both ends. The molecular weight is preferably from 100 to 9000, and more preferably from 1000 to 4000. R 1 is a structure containing one or more saturated aliphatic groups containing a straight chain, branched or cyclic structure having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Specifically, 2-methyl-1 , 3-propanediol, 1,3-butanediol, 2,4-heptanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2- Ethyl-1,3-hexanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, etc. An aliphatic dihydric alcohol residue whose alkylene group is a trimethylene group; an aliphatic dihydric alcohol residue whose alkylene group is a tetramethylene group such as 1,4-butanediol; 1,5-pentanediol An aliphatic dihydric alcohol residue in which an alkylene group such as 3-methyl-1,5-pentanediol and 1,5-hexanediol is a pentamethylene group; 1,6-hexanediol, 2-ethyl-1,6- Aliphatic dihydric alcohol residue in which an alkylene group such as hexanediol is a hexamethylene group; Aliphatic dihydric alcohol residue in which an alkylene group such as 1,7-heptanediol is a heptamethylene group; 1,8-octanediol An aliphatic dihydric alcohol residue in which the alkylene group of 2-methyl-1,8-octanediol is an octamethylene group; 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, , 12-dodecanediol, 1,20-eicosanediol, 1,4-cyclohexanedimethanol and the like. . Among these, each residue of 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 2-methyl-1,8-octanediol, and 1,9-nonanediol The group is particularly preferred. N is an integer from 1 to 50, and m is an integer from 1 to 3.
一般式（６）の化合物は、１つ以上のイソシアネート基と１つ以上の反応性不飽和二重結合を有する化合物であり、Ｒ2は、炭素数が１から１０である直鎖、分岐または環状構造を含む飽和脂肪族基か芳香環を含んだ構造であり、分岐または環状構造を含む飽和脂肪族基または芳香環を表わすときのＲ2の具体例としては、
Ｒ3は水素原子またはメチル基である。また、この成分には１％以下の重合禁止剤が含まれていても良いものとし、レベリング剤、充填剤、顔料、その他改質剤を加えても良いものとする。
The compound of the general formula (6) is a compound having one or more isocyanate groups and one or more reactive unsaturated double bonds, and R 2 is a linear, branched or branched group having 1 to 10 carbon atoms. Specific examples of R 2 when a saturated aliphatic group containing a cyclic structure or a structure containing an aromatic ring and representing a saturated aliphatic group or aromatic ring containing a branched or cyclic structure are as follows:
R 3 is a hydrogen atom or a methyl group. Further, this component may contain 1% or less of a polymerization inhibitor, and a leveling agent, a filler, a pigment, and other modifiers may be added.
重合禁止剤としては、例えば、ハイドロキノン、ハイドロキノンモノメチルエーテル、ベンゾキノン、ｐ−ｔ−ブチルカテコール、２，６−ジ−ｔ−ブチル−４−メチルフェノール等が挙げられる。レベリング剤としては、例えば、ポリエーテル変性ジメチルポリシロキサン共重合物、ポリエステル変性ジメチルポリシロキサン共重合物、ポリエーテル変性メチルアルキルポリシロキサン共重合物、アラルキル変性メチルアルキルポリシロキサン共重合物、ポリエーテル変性メチルアルキルポリシロキサン共重合物等が挙げられる。充填剤又は顔料としては、炭酸カルシウム、タルク、マイカ、クレー、シリカパウダー、コロイダルシリカ、硫酸バリウム、水酸化アルミニウム、ステアリン酸亜鉛、亜鉛華、ベンガラ、アゾ顔料等が挙げられる。その他の改質剤としては、ポリオレフィン系樹脂、塩素化変性ポリオレフィン系樹脂、不飽和ポリエステル樹脂、ビニルエステル樹脂、ビニルウレタン樹脂、ビニルエステルウレタン樹脂、ポリイソシアネート、ポリエポキシド、エポキシ末端ポリオキサゾリドン、アクリル樹脂類、アルキド樹脂類、尿素樹脂類、メラミン樹脂類、ポリジエン系エラストマー、飽和ポリエステル類、飽和ポリエーテル類、ニトロセルロース、セルロースアセテートブチレート等のセルロース誘導体、アマニ油、桐油、大豆油、ヒマシ油、エポキシ化油等の油脂類等の天然及び合成高分子物質が挙げられる。 Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, benzoquinone, pt-butylcatechol, 2,6-di-t-butyl-4-methylphenol, and the like. Examples of leveling agents include polyether-modified dimethylpolysiloxane copolymer, polyester-modified dimethylpolysiloxane copolymer, polyether-modified methylalkylpolysiloxane copolymer, aralkyl-modified methylalkylpolysiloxane copolymer, and polyether-modified. Examples thereof include methylalkylpolysiloxane copolymer. Examples of the filler or pigment include calcium carbonate, talc, mica, clay, silica powder, colloidal silica, barium sulfate, aluminum hydroxide, zinc stearate, zinc white, bengara, and azo pigment. Other modifiers include polyolefin resins, chlorinated modified polyolefin resins, unsaturated polyester resins, vinyl ester resins, vinyl urethane resins, vinyl ester urethane resins, polyisocyanates, polyepoxides, epoxy-terminated polyoxazolidones, acrylic resins , Alkyd resins, urea resins, melamine resins, polydiene elastomers, saturated polyesters, saturated polyethers, cellulose derivatives such as nitrocellulose, cellulose acetate butyrate, flaxseed oil, tung oil, soybean oil, castor oil, epoxy And natural and synthetic polymer substances such as oils and fats such as chemical oils.
エチレン性不飽和基含有イソシアネート化合物と、ヒドロキシル基を含有する化合物とを反応させる際には、ウレタン化触媒を使用することが好ましい。ウレタン化触媒を使用することにより、著しく反応を速めることができる。ウレタン化触媒の具体例としては、ジブチル錫ジラウレート、ナフテン酸銅、ナフテン酸コバルト、ナフテン酸亜鉛、トリエチルアミン、１，４−ジアザビシクロ［２．２．２］オクタン、２，６，７−トリメチル−１，４−ジアザビシクロ［２．２．２］オクタンなどが挙げられる。 When reacting an ethylenically unsaturated group-containing isocyanate compound with a compound containing a hydroxyl group, it is preferable to use a urethanization catalyst. By using the urethanization catalyst, the reaction can be remarkably accelerated. Specific examples of the urethanization catalyst include dibutyltin dilaurate, copper naphthenate, cobalt naphthenate, zinc naphthenate, triethylamine, 1,4-diazabicyclo [2.2.2] octane, 2,6,7-trimethyl-1. , 4-diazabicyclo [2.2.2] octane.
これらのウレタン化触媒は１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。ウレタン化触媒の添加量は、イソシアネート化合物を１００質量部に対して０．０１〜５質量部が好ましく、より好ましくは０．１〜１質量部である。添加量が０．０１質量部未満では反応性が著しく低下する場合がある。一方、添加量が５質量部を超えると反応時に副反応が起きる可能性がある。 These urethanization catalysts may be used individually by 1 type, and may be used in combination of 2 or more type. 0.01-5 mass parts is preferable with respect to 100 mass parts of isocyanate compounds, and, as for the addition amount of a urethanization catalyst, More preferably, it is 0.1-1 mass part. If the addition amount is less than 0.01 parts by mass, the reactivity may be significantly reduced. On the other hand, when the addition amount exceeds 5 parts by mass, a side reaction may occur during the reaction.
一般式（６）のエチレン性不飽和基含有イソシアネート化合物と、ヒドロキシル基を含有する化合物（５）とを反応させる際における反応温度は、好ましくは−１０〜１００℃、より好ましくは０〜８０℃である。 The reaction temperature when the ethylenically unsaturated group-containing isocyanate compound of the general formula (6) is reacted with the hydroxyl group-containing compound (5) is preferably −10 to 100 ° C., more preferably 0 to 80 ° C. It is.
本発明ウレタン化合物として好ましくは、一般式（２）
本発明の硬化組成物は、一般式（１）で示されるウレタン化合物すなわち反応性モノマーと、重合開始剤とを含有する。重合開始剤としては光重合開始剤が使用でき、紫外線あるいは可視光線などの活性エネルギー線を照射することで、反応性モノマーの重合反応を起こし硬化物を得ることができる。このような光重合開始剤の具体例としては、１−ヒドロキシシクロヘキシルフェニルケトン、２，２'−ジメトキシ−２−フェニルアセトフェノン、キサントン、フルオレン、フルオレノン、ベンズアルデヒド、アントラキノン、トリフェニルアミン、カルバゾール、３−メチルアセトフェノン、４−クロロベンゾフェノン、４，４'−ジメトキシベンゾフェノン、４，４'−ジアミノベンゾフェノン、ミヒラーケトン、ベンゾイルプロピルエーテル、ベンゾインエチルエーテル、ベンジルジメチルケタール、１−（４−イソプロピルフェニル）−２−ヒドロキシ−２−メチルプロパン−１−オン、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、チオキサントン、ジエチルチオキサントン、２−イソプロピルチオキサントン、２−クロロチオキサントン、２−メチル−１−［４−（メチルチオ）フェニル］−２−モルフォリノプロパン−１−オン、２，４，６−トリメチルベンゾイルジフェニルフォスフィンオキサイド、２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）ブタン−１−オン、１−［４−（２−ヒドロキシエトキシ）−フェニル］−２−ヒドロキシ−２−メチルプロパン−１−オンなどが挙げられる。 The cured composition of the present invention contains a urethane compound represented by the general formula (1), that is, a reactive monomer, and a polymerization initiator. As the polymerization initiator, a photopolymerization initiator can be used. By irradiating active energy rays such as ultraviolet rays or visible rays, a polymerization reaction of the reactive monomer is caused to obtain a cured product. Specific examples of such a photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2,2′-dimethoxy-2-phenylacetophenone, xanthone, fluorene, fluorenone, benzaldehyde, anthraquinone, triphenylamine, carbazole, 3- Methyl acetophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-diaminobenzophenone, Michler's ketone, benzoylpropyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy 2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, -Chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-benzyl-2-dimethylamino Examples include -1- (4-morpholinophenyl) butan-1-one and 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methylpropan-1-one.
これらの中でも、２，４，６−トリメチルベンゾイルジフェニルフォスフィンオキサイド、１−ヒドロキシシクロヘキシルフェニルケトンが好ましい。上記の光重合開始剤は、１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Among these, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 1-hydroxycyclohexyl phenyl ketone are preferable. Said photoinitiator may be used individually by 1 type, and may be used in combination of 2 or more type.
また、熱により反応性モノマーの重合反応を起こし、硬化物を得ることもできる。すなわち、熱重合開始剤を反応性モノマーに添加することで、熱硬化性組成物とすることができる。このような熱重合開始剤としては、ジアシルパーオキサイド類、ケトンパーオキサイド類、ハイドロパーオキサイド類、ジアルキルパーオキサイド類、パーオキシエステル類、アゾ系化合物、過硫酸塩などが挙げられる。これらは１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。 In addition, a cured product can be obtained by causing a polymerization reaction of the reactive monomer by heat. That is, it can be set as a thermosetting composition by adding a thermopolymerization initiator to a reactive monomer. Examples of such thermal polymerization initiators include diacyl peroxides, ketone peroxides, hydroperoxides, dialkyl peroxides, peroxyesters, azo compounds, and persulfates. These may be used alone or in combination of two or more.
重合開始剤の使用量は、反応性モノマー１００質量部に対して好ましくは０．１〜２０質量部、より好ましくは０．５〜１０質量部である。重合開始剤の使用量が０．１質量部未満となると、反応性モノマーの重合速度が遅くなる場合がある。また、酸素等による重合阻害を受け易くなる場合がある。一方、重合開始剤の使用量が２０質量部を超えると、逆に重合反応が抑制され、得られる硬化膜の強度、密着強度、耐熱性が低下する場合がある。さらに、着色の原因となる。 The amount of the polymerization initiator used is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the reactive monomer. When the usage-amount of a polymerization initiator will be less than 0.1 mass part, the polymerization rate of a reactive monomer may become slow. Moreover, it may become easy to receive the polymerization inhibition by oxygen etc. On the other hand, when the usage-amount of a polymerization initiator exceeds 20 mass parts, a polymerization reaction may be suppressed conversely and the intensity | strength of the obtained cured film, adhesive strength, and heat resistance may fall. Furthermore, it causes coloring.
本発明の硬化性組成物は、本発明一般式（１）の反応性モノマー以外の反応性モノマーを含有していてもよい。このような反応性モノマーを含有させることにより、組成物の粘度調整ができるとともに、得られる硬化物の特性、例えば、反応性、硬度、弾性、密着性などの機械的特性、透明性などの光学的特性を調整できる。 The curable composition of this invention may contain reactive monomers other than the reactive monomer of this invention general formula (1). By containing such a reactive monomer, the viscosity of the composition can be adjusted, and the properties of the resulting cured product, for example, mechanical properties such as reactivity, hardness, elasticity and adhesion, optical properties such as transparency, etc. Can be adjusted.
このような反応性モノマーの具体例としては、スチレン、α−メチルスチレン、ｏ−メチルスチレン、ｍ−メチルスチレン、ｐ−メチルスチレン、ｐ−ｔｅｒｔ−ブチルスチレン、ジイソプロペニルベンゼン、ｏ−クロロスチレン、ｍ−クロロスチレン、ｐ−クロロスチレン、１，１−ジフェニルエチレン、ｐ−メトキシスチレン、Ｎ，Ｎ−ジメチル−ｐ−アミノスチレン、Ｎ，Ｎ−ジエチル−ｐ−アミノスチレン、エチレン性不飽和ピリジン、エチレン性不飽和イミダゾールなどのエチレン性不飽和芳香族化合物；（メタ）アクリル酸、クロトン酸、マレイン酸、フマル酸、イタコン酸などのカルボキシル基含有化合物；メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔｅｒｔ−ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、アミル（メタ）アクリレート、イソアミル（メタ）アクリレート、ヘキシル（メタ）アクリレート、ヘプチル（メタ）アクリレート、オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ノニル（メタ）アクリレート、デシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ウンデシル（メタ）アクリレート、ドデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソステアリル（メタ）アクリレートなどのアルキル（メタ）アクリレート類；トリフルオロエチル（メタ）アクリレート、テトラフルオロプロピル（メタ）アクリレート、ヘキサフルオロイソプロピル（メタ）アクリレート、オクタフルオロペンチル（メタ）アクリレート、ヘプタデカフルオロデシル（メタ）アクリレートなどのフルオロアルキル（メタ）アクリレート類；ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、ヒドロキシブチル（メタ）アクリレートなどのヒドロキシアルキル（メタ）アクリレート類；フェノキシエチル（メタ）アクリレート、２−ヒドロキシ−３−フェノキシプロピル（メタ）アクリレートなどのフェノキシアルキル（メタ）アクリレート類；メトキシエチル（メタ）アクリレート、エトキシエチル（メタ）アクリレート、プロポキシエチル（メタ）アクリレート、ブトキシエチル（メタ）アクリレート、メトキシブチル（メタ）アクリレートなどのアルコキシアルキル（メタ）アクリレート類；ポリエチレングリコールモノ（メタ）アクリレート、エトキシジエチレングリコール（メタ）アクリレート、メトキシポリエチレングリコール（メタ）アクリレート、フェノキシポリエチレングリコール（メタ）アクリレート、ノニルフェノキシポリエチレングリコール（メタ）アクリレートなどのポリエチレングリコール（メタ）アクリレート類；ポリプロピレングリコールモノ（メタ）アクリレート、メトキシポリプロピレングリコール（メタ）アクリレート、エトキシポリプロピレングリコール（メタ）アクリレート、ノニルフェノキシポリプロピレングリコール（メタ）アクリレートなどのポリプロピレングリコール（メタ）アクリレート類；シクロヘキシル（メタ）アクリレート、４−ブチルシクロヘキシル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンタジエニル（メタ）アクリレート、ボルニル（メタ）アクリレート、イソボルニル（メタ）アクリレート、トリシクロデカニル（メタ）アクリレートなどのシクロアルキル（メタ）アクリレート類；ベンジル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、ジプロピレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、１，３−プロパンジオールジ（メタ）アクリレート、１，４−ブタンジオールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、ヒドロキシピバリン酸エステルネオペンチルグリコールジ（メタ）アクリレート、ビスフェノールＡジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、トリメチロールプロパントリオキシエチル（メタ）アクリレート、トリス（２−ヒドロキシエチル）イソシアヌレートトリ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレートなどが挙げられる。これらの反応性モノマーは１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Specific examples of such reactive monomers include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-tert-butylstyrene, diisopropenylbenzene, and o-chlorostyrene. , M-chlorostyrene, p-chlorostyrene, 1,1-diphenylethylene, p-methoxystyrene, N, N-dimethyl-p-aminostyrene, N, N-diethyl-p-aminostyrene, ethylenically unsaturated pyridine Ethylenically unsaturated aromatic compounds such as ethylenically unsaturated imidazole; carboxyl group-containing compounds such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid; methyl (meth) acrylate, ethyl (meth) Acrylate, propyl (meth) acrylate, isopropyl (meth) Acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) Acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) Alkyl (meth) acrylates such as acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate; trifluoroethyl Fluoroalkyl (meth) acrylates such as (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoroisopropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate; hydroxyethyl ( Hydroxyalkyl (meth) acrylates such as meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate; phenoxyalkyl such as phenoxyethyl (meth) acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate (Meth) acrylates; methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, propoxyethyl (meth) acrylate, Alkoxyalkyl (meth) acrylates such as xylethyl (meth) acrylate and methoxybutyl (meth) acrylate; polyethylene glycol mono (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meta ) Acrylate, polyethylene glycol (meth) acrylates such as nonylphenoxypolyethylene glycol (meth) acrylate; polypropylene glycol mono (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol ( Polypropylene such as (meth) acrylate Glycol (meth) acrylates: cyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, bornyl Cycloalkyl (meth) acrylates such as (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate; benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ethylene glycol di (meth) acrylate , Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) ) Acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, hydroxypivalate ester neopentyl glycol di (meth) acrylate, bisphenol A di (meth) acrylate, trimethylolpropane tri ( (Meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri ( Data) acrylate, dipentaerythritol hexa (meth) acrylate. These reactive monomers may be used individually by 1 type, and may be used in combination of 2 or more type.
本発明の硬化性組成物は、本発明の一般式（１）の反応性モノマーと重合開始剤とを、室温または加熱条件下で、ミキサー、ボールミル、３本ロールなどの混合機により混合するか、あるいは、反応性モノマーや溶剤などを希釈剤として添加して溶解することによって、配合及び調整することができる。ここで希釈剤として用いられる反応性モノマーの具体例としては、上述した反応性モノマーなどを挙げることができる。溶剤の具体例としては、酢酸エチル、酢酸ブチル、酢酸イソプロピルなどのエステル類；アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノンなどのケトン類；テトラヒドロフラン、ジオキサンなどの環状エーテル類；Ｎ，Ｎ−ジメチルホルムアミドなどのアミド類；トルエンなどの芳香族炭化水素類、塩化メチレンなどのハロゲン化炭化水素などが挙げられる。 In the curable composition of the present invention, the reactive monomer of the general formula (1) of the present invention and the polymerization initiator are mixed by a mixer such as a mixer, a ball mill, or a three roll at room temperature or under heating conditions. Alternatively, it can be blended and adjusted by adding a reactive monomer or solvent as a diluent and dissolving it. Here, specific examples of the reactive monomer used as the diluent include the reactive monomers described above. Specific examples of the solvent include esters such as ethyl acetate, butyl acetate and isopropyl acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; cyclic ethers such as tetrahydrofuran and dioxane; N, N-dimethylformamide and the like Amides; aromatic hydrocarbons such as toluene; halogenated hydrocarbons such as methylene chloride.
本発明の硬化性組成物は、例えば、基材上に硬化性組成物を塗布し、塗膜を形成した後、放射線を照射することによって、あるいは加熱することによって硬化させることができる。硬化のために、放射線の照射と加熱との両方を行ってもよい。 The curable composition of the present invention can be cured, for example, by applying a curable composition on a substrate and forming a coating film, and then irradiating with radiation or heating. You may perform both irradiation of a radiation and a heating for hardening.
塗膜の厚さは、評価用としては１〜２００μｍが好ましいが、用途により適宜に設定される。塗布方法としては、例えば、ダイコーター、スピンコーター、スプレーコーター、カーテンコーター、ロールコーターなどによる塗布、スクリーン印刷などによる塗布、ディッピングなどによる塗布が挙げられる。 The thickness of the coating film is preferably 1 to 200 μm for evaluation, but is appropriately set depending on the application. Examples of the coating method include coating by a die coater, spin coater, spray coater, curtain coater, roll coater, etc., coating by screen printing, and coating by dipping.
硬化のために使用される放射線としては、電子線、または紫外から赤外の波長範囲の光が好ましい。例えば、紫外線であれば超高圧水銀光源またはメタルハライド光源、可視光線であればメタルハライド光源またはハロゲン光源、赤外線であればハロゲン光源が使用できるが、この他にもレーザー、ＬＥＤなどの光源が使用できる。放射線の照射量は、光源の種類、塗膜の膜厚などに応じて適宜に設定される。 The radiation used for curing is preferably an electron beam or light in the ultraviolet to infrared wavelength range. For example, an ultra-high pressure mercury light source or a metal halide light source can be used for ultraviolet rays, a metal halide light source or a halogen light source can be used for visible rays, and a halogen light source can be used for infrared rays, but other light sources such as lasers and LEDs can be used. The radiation dose is appropriately set according to the type of light source, the film thickness of the coating film, and the like.
以下、実施例及び比較例により本発明をさらに詳細に説明するが、本発明はこれらの記載により何らの限定を受けるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention does not receive any limitation by these description.
実施例１〜２１、比較例１，２：
（１）本発明反応性モノマー（ウレタン化合物）の調製
表１のポリカーボネート両末端ジオール化合物、あるいは［５，２，１，０］−トリシクロデカンと、表２の分子内に不飽和結合を有するイソシアネート化合物より表３の反応性モノマーを得た。
Examples 1-21, Comparative Examples 1 and 2:
(1) Preparation of Reactive Monomer (Urethane Compound) of the Present Invention The polycarbonate both-end diol compound of Table 1 or [5,2,1,0] -tricyclodecane and the unsaturated bond in the molecule of Table 2 The reactive monomer shown in Table 3 was obtained from the isocyanate compound.
（２）硬化性組成物の調製及び評価サンプル作成
反応性モノマー（表３に記載）に対して、光重合開始剤として１−ヒドロキシシクロヘキシルフェニルケトン（チバスペシャルティケミカルズ（株）製、Irgacure184）を用いて、表４に記載される配合量を、ジクロロメタン（純正化学（株）製）２０ｇに室温で撹拌混合し、均一に溶解させて硬化性組成物溶液を得た（実施例１〜２２、比較例１，２）。さらに、これらの硬化性組成物溶液をガラス基板（大きさ５０ｍｍ×５０ｍｍ）に、乾燥膜厚が約２００μｍとなるように塗布し、実施例１〜２１、比較例１，２の評価サンプルを得た。
(2) Preparation of curable composition and preparation of evaluation sample For reactive monomer (described in Table 3), 1-hydroxycyclohexyl phenyl ketone (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) was used as a photopolymerization initiator. Then, the compounding amounts shown in Table 4 were stirred and mixed at room temperature with 20 g of dichloromethane (manufactured by Junsei Chemical Co., Ltd.) and uniformly dissolved to obtain curable composition solutions (Examples 1 to 22, comparison) Examples 1, 2). Furthermore, these curable composition solutions were applied to a glass substrate (size 50 mm × 50 mm) so that the dry film thickness was about 200 μm, and evaluation samples of Examples 1 to 21 and Comparative Examples 1 and 2 were obtained. It was.
（３）硬化性組成物の評価
＜透過率＞
（２）で作成した実施例１〜２１、比較例１，２の評価サンプルを超高圧水銀ランプを組み込んだ露光装置で３ｊ／ｃｍ2露光した。その硬化した各サンプルについて、分光光度計（日本分光製、ＵＶ３１００）を用いて、５５０ｎｍの透過率を測定した。その結果を表５に示した。
(3) Evaluation of curable composition <Transmissivity>
The evaluation samples of Examples 1 to 21 and Comparative Examples 1 and 2 prepared in (2) were exposed at 3 j / cm 2 with an exposure apparatus incorporating an ultrahigh pressure mercury lamp. About each cured sample, the transmittance | permeability of 550 nm was measured using the spectrophotometer (the JASCO make, UV3100). The results are shown in Table 5.
＜硬化収縮性＞
（２）で作成した実施例１〜２１、比較例１，２の評価サンプルを超高圧水銀ランプを組み込んだ露光装置で１．５ｊ／ｃｍ2露光した。その硬化した各サンプルについて、接触式膜厚計で硬化前後の膜厚を測定し硬化収縮率を求めた。その結果を表５に示した。
<Curing shrinkage>
The evaluation samples of Examples 1 to 21 and Comparative Examples 1 and 2 prepared in (2) were exposed to 1.5 j / cm 2 with an exposure apparatus incorporating an ultrahigh pressure mercury lamp. For each cured sample, the film thickness before and after curing was measured with a contact-type film thickness meter to determine the curing shrinkage. The results are shown in Table 5.
実施製造例：ウレタンアクリレート（ＰＣＵＡ−２）の合成
撹拌装置、温度計、コンデンサーを備えた反応容器に、表１に記載のポリカーボネートジオール（ＰＣ−１）（宇部興産化学工業（株）製、商品名ＵＣ５０、平均分子量５００）を２ｇ（４．０ｍｍｏｌ）及び表２に記載の化合物１，３−ビスアクリロイルオキシ−２−メチルプロパン−２−イソシアネート（Ｍ−３）１．９６ｇ（８．２ｍｍｏｌ）を投入し、ジクロロメタンを１０ｍＬ加えた。その後、室温にて撹拌しながらジブチル錫ジラウレート０．０５２ｇを添加した。のち、赤外線吸収スペクトルでイソシアネート基の吸収スペクトル（２２８０ｃｍ-1）がほぼ消失したことを確認して反応を終了し、粘稠液体のウレタンアクリレート（ＰＣＵＡ−２）を得た。得られたウレタンアクリレートの平均分子量は約１０００であった。
Implementation Production Example: Synthesis of Urethane Acrylate (PCUA-2) Polycarbonate diol (PC-1) listed in Table 1 (commercially available from Ube Industries Chemical Co., Ltd.) in a reaction vessel equipped with a stirrer, a thermometer, and a condenser. 2 g (4.0 mmol) of name UC50, average molecular weight 500) and 1.96 g (8.2 mmol) of the compound 1,3-bisacryloyloxy-2-methylpropane-2-isocyanate (M-3) described in Table 2 And 10 mL of dichloromethane was added. Thereafter, 0.052 g of dibutyltin dilaurate was added while stirring at room temperature. After that, it was confirmed by the infrared absorption spectrum that the isocyanate group absorption spectrum (2280 cm −1 ) almost disappeared, and the reaction was terminated to obtain a viscous liquid urethane acrylate (PCUA-2). The average molecular weight of the obtained urethane acrylate was about 1000.
ＰＣＵＡ−２の1Ｈ−ＮＭＲチャートを図１に示す。1Ｈ−ＮＭＲはＢｒｕｋｅｒ社製ＡＭＸ４００を使用し、重クロロホルム中にて測定を行った。1Ｈ−ＮＭＲチャートの帰属を以下に示す。
1.31ｐｐｍ：１のメチル基由来の水素原子、
3.73 - 3.92ｐｐｍ：３のメチレン由来の水素原子、
4.17 - 4.28ｐｐｍ：２のメチレン由来の水素原子、
5.09ｐｐｍ：Ｈ4の水素原子、
5.75, 5.78ｐｐｍ：Ｈ2の水素原子、
5.98 - 6.05ｐｐｍ：Ｈ1の水素原子、
6.29, 6.33：Ｈ3の水素原子。
A 1 H-NMR chart of PCUA-2 is shown in FIG. 1 H-NMR was measured in deuterated chloroform using AMX400 manufactured by Bruker. The attribution of the 1 H-NMR chart is shown below.
1.31 ppm: a hydrogen atom derived from a methyl group,
3.73-3.92 ppm: 3 hydrogen atoms derived from methylene,
4.17-4.28 ppm: 2 hydrogen atoms derived from methylene,
5.09 ppm: H 4 hydrogen atom,
5.75, 5.78 ppm: H 2 hydrogen atom,
5.98-6.05 ppm: H 1 hydrogen atom,
6.29, 6.33: H 3 hydrogen atom.
比較製造例：ウレタンアクリレート（ＴＣＤＵＡ−２）の合成
撹拌装置、温度計、コンデンサーを備えた反応容器に、表１に記載の［５，２，１，０］−トリシクロデカン（東京化成工業（株）製）を２ｇ（１０．２ｍｍｏｌ）及び表２に記載の化合物１，３−ビスアクリロイルオキシ−２−メチルプロパン−２−イソシアネート（Ｍ−３）５．００ｇ（２０．９ｍｍｏｌ）を投入しジクロロメタンを１０ｍＬ加えた。その後、室温にて拡販しながらジブチル錫ジラウレート０．１３２ｇを添加した。のち、赤外線吸収スペクトルでイソシアネート基の吸収スペクトル（２２８０ｃｍ-1）がほぼ消失したことを確認して反応を終了し、粘稠液体のウレタンアクリレート（ＴＣＤＵＡ−２）を得た。
Comparative Production Example: Synthesis of Urethane Acrylate (TCDUA-2) [5,2,1,0] -Tricyclodecane (Tokyo Chemical Industry Co., Ltd.) described in Table 1 was added to a reaction vessel equipped with a stirrer, a thermometer, and a condenser. Co., Ltd.) 2 g (10.2 mmol) and the compound 1,3-bisacryloyloxy-2-methylpropane-2-isocyanate (M-3) listed in Table 2 was added in an amount of 5.00 g (20.9 mmol). 10 mL of dichloromethane was added. Thereafter, 0.132 g of dibutyltin dilaurate was added while expanding sales at room temperature. After that, it was confirmed that the absorption spectrum (2280 cm −1 ) of the isocyanate group almost disappeared in the infrared absorption spectrum, and the reaction was terminated to obtain a viscous liquid urethane acrylate (TCDUA-2).
以上の実施例から示されるように、これらの実施例から、分子内にエチレン性不飽和基を含有するイソシアネート化合物と、両末端にヒドロキシル基を有するポリカーボネートジオール化合物とを反応させて得られた反応性モノマー（ウレタン化合物）は、低い収縮性、透過性に優れており硬化性組成物に有用な反応性モノマーとして用いることができる。 As shown from the above examples, the reaction obtained by reacting an isocyanate compound containing an ethylenically unsaturated group in the molecule and a polycarbonate diol compound having hydroxyl groups at both ends from these examples. The polymerizable monomer (urethane compound) is excellent in low shrinkage and permeability and can be used as a reactive monomer useful for a curable composition.
Claims (8)
で示されるウレタン化合物。 The following general formula (1) obtained by adding an isocyanate compound having one or more (meth) acryl groups in a molecule to a polycarbonate diol having hydroxyl groups at both ends of the molecule.
Urethane compound represented by
で示される請求項１または２に記載のウレタン化合物。 General formula (2)
The urethane compound of Claim 1 or 2 shown by these.
で示される請求項１または２に記載のウレタン化合物。 General formula (3)
The urethane compound of Claim 1 or 2 shown by these.
で示される請求項１または２に記載のウレタン化合物。 General formula (4)
The urethane compound of Claim 1 or 2 shown by these.
Hardened | cured material obtained by the curable composition described in Claims 1-7.
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| JP2006291188A (en) * | 2005-03-15 | 2006-10-26 | Showa Denko Kk | (meth)acryloyl group-containing aromatic isocyanate compound and method for producing the same |
| JP2008201910A (en) * | 2007-02-20 | 2008-09-04 | Jsr Corp | Branched unsaturated polymer, radiosensitive resin composition and spacer for liquid crystal display element |
| CN105859586A (en) * | 2016-04-15 | 2016-08-17 | 江苏利田科技股份有限公司 | 2-functionality-degree makrolon urethane acrylate and preparation method and application thereof |
| CN105859997A (en) * | 2016-04-15 | 2016-08-17 | 江苏利田科技股份有限公司 | 3-functionality-degree polycaprolactone urethane acrylate and preparation method and application thereof |
| CN105860027A (en) * | 2016-04-15 | 2016-08-17 | 江苏利田科技股份有限公司 | 2-functionality-degree polyester-based urethane acrylate and preparation method and application thereof |
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| JP2008201910A (en) * | 2007-02-20 | 2008-09-04 | Jsr Corp | Branched unsaturated polymer, radiosensitive resin composition and spacer for liquid crystal display element |
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| CN105859586A (en) * | 2016-04-15 | 2016-08-17 | 江苏利田科技股份有限公司 | 2-functionality-degree makrolon urethane acrylate and preparation method and application thereof |
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| CN105860027A (en) * | 2016-04-15 | 2016-08-17 | 江苏利田科技股份有限公司 | 2-functionality-degree polyester-based urethane acrylate and preparation method and application thereof |
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| KR20200046153A (en) * | 2018-10-16 | 2020-05-07 | 주식회사 그래피 | Photocurable composition for 3D printer for the manufacture of transparent aligner |
| KR102111789B1 (en) | 2018-10-16 | 2020-05-18 | 주식회사 그래피 | Photocurable composition for 3D printer for the manufacture of transparent aligner |
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