WO2015049842A1 - 耐光性を有し、機械強度に優れるアクリル変性pb硬化性組成物 - Google Patents
耐光性を有し、機械強度に優れるアクリル変性pb硬化性組成物 Download PDFInfo
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- WO2015049842A1 WO2015049842A1 PCT/JP2014/004807 JP2014004807W WO2015049842A1 WO 2015049842 A1 WO2015049842 A1 WO 2015049842A1 JP 2014004807 W JP2014004807 W JP 2014004807W WO 2015049842 A1 WO2015049842 A1 WO 2015049842A1
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- WIPO (PCT)
- Prior art keywords
- formula
- group
- polybutadiene
- hydrogenated
- photocurable composition
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 85
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 61
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 61
- 229920000642 polymer Polymers 0.000 claims abstract description 28
- 239000000178 monomer Substances 0.000 claims abstract description 25
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 16
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims abstract description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 11
- 125000004406 C3-C8 cycloalkylene group Chemical group 0.000 claims abstract description 8
- 238000000016 photochemical curing Methods 0.000 claims abstract description 8
- 239000007870 radical polymerization initiator Substances 0.000 claims abstract description 8
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 57
- -1 isocyanate compound Chemical class 0.000 claims description 40
- 239000003999 initiator Substances 0.000 claims description 17
- 125000006832 (C1-C10) alkylene group Chemical group 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 claims description 7
- 239000003505 polymerization initiator Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000012948 isocyanate Substances 0.000 claims description 3
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- ODIARNBUHATISP-UHFFFAOYSA-N 2-hydroxy-1-[4-[[4-(2-hydroxy-2-methylpropyl)phenyl]methyl]phenyl]-2-methylpropan-1-one Chemical compound C1=CC(CC(C)(O)C)=CC=C1CC1=CC=C(C(=O)C(C)(C)O)C=C1 ODIARNBUHATISP-UHFFFAOYSA-N 0.000 claims 1
- 125000001424 substituent group Chemical group 0.000 abstract description 9
- 239000002131 composite material Chemical group 0.000 abstract 1
- 238000002845 discoloration Methods 0.000 abstract 1
- 238000005984 hydrogenation reaction Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 20
- 238000011156 evaluation Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 238000000034 method Methods 0.000 description 12
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 10
- 229910052753 mercury Inorganic materials 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 9
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- 238000002360 preparation method Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
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- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 6
- 239000000463 material Substances 0.000 description 6
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- SMNGQGWPUVVORF-UHFFFAOYSA-N 3,5-ditert-butyl-4-methylphenol Chemical compound CC1=C(C(C)(C)C)C=C(O)C=C1C(C)(C)C SMNGQGWPUVVORF-UHFFFAOYSA-N 0.000 description 5
- 238000001723 curing Methods 0.000 description 5
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- PCKZAVNWRLEHIP-UHFFFAOYSA-N 2-hydroxy-1-[4-[[4-(2-hydroxy-2-methylpropanoyl)phenyl]methyl]phenyl]-2-methylpropan-1-one Chemical compound C1=CC(C(=O)C(C)(O)C)=CC=C1CC1=CC=C(C(=O)C(C)(C)O)C=C1 PCKZAVNWRLEHIP-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 4
- 239000012965 benzophenone Substances 0.000 description 4
- 125000002993 cycloalkylene group Chemical group 0.000 description 4
- 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 4
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- 238000009864 tensile test Methods 0.000 description 4
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 3
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 3
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 3
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 3
- 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 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 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 3
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- 239000003112 inhibitor Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229940105570 ornex Drugs 0.000 description 3
- 229940059574 pentaerithrityl Drugs 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 238000001028 reflection method Methods 0.000 description 3
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 3
- 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 2
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical group NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 2
- 0 *C(C(O*OC(N*NC(O*)=O)=O)=O)=C Chemical compound *C(C(O*OC(N*NC(O*)=O)=O)=O)=C 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- UAQARUFKZPUPHY-UHFFFAOYSA-N 1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropan-2-ol Chemical compound CC(C)(O)CC1=CC=C(OCCO)C=C1 UAQARUFKZPUPHY-UHFFFAOYSA-N 0.000 description 2
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
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- 239000007983 Tris buffer Substances 0.000 description 2
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- 230000001588 bifunctional effect Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 2
- PESYEWKSBIWTAK-UHFFFAOYSA-N cyclopenta-1,3-diene;titanium(2+) Chemical compound [Ti+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 PESYEWKSBIWTAK-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
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- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
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- 150000005309 metal halides Chemical class 0.000 description 2
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 description 2
- GXELTROTKVKZBQ-UHFFFAOYSA-N n,n-dibenzylhydroxylamine Chemical compound C=1C=CC=CC=1CN(O)CC1=CC=CC=C1 GXELTROTKVKZBQ-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
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- WXPWZZHELZEVPO-UHFFFAOYSA-N (4-methylphenyl)-phenylmethanone Chemical compound C1=CC(C)=CC=C1C(=O)C1=CC=CC=C1 WXPWZZHELZEVPO-UHFFFAOYSA-N 0.000 description 1
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- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- WQQZMYRVHZZOEW-UHFFFAOYSA-N 1-benzyl-4-(2-methylphenyl)sulfanylbenzene Chemical compound CC1=CC=CC=C1SC(C=C1)=CC=C1CC1=CC=CC=C1 WQQZMYRVHZZOEW-UHFFFAOYSA-N 0.000 description 1
- 125000004818 1-methylbutylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- VETPHHXZEJAYOB-UHFFFAOYSA-N 1-n,4-n-dinaphthalen-2-ylbenzene-1,4-diamine Chemical compound C1=CC=CC2=CC(NC=3C=CC(NC=4C=C5C=CC=CC5=CC=4)=CC=3)=CC=C21 VETPHHXZEJAYOB-UHFFFAOYSA-N 0.000 description 1
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- CZNRFEXEPBITDS-UHFFFAOYSA-N 2,5-bis(2-methylbutan-2-yl)benzene-1,4-diol Chemical compound CCC(C)(C)C1=CC(O)=C(C(C)(C)CC)C=C1O CZNRFEXEPBITDS-UHFFFAOYSA-N 0.000 description 1
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- BSMGLVDZZMBWQB-UHFFFAOYSA-N 2-methyl-1-phenylpropan-1-one Chemical compound CC(C)C(=O)C1=CC=CC=C1 BSMGLVDZZMBWQB-UHFFFAOYSA-N 0.000 description 1
- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical compound CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-UHFFFAOYSA-N 0.000 description 1
- GAODDBNJCKQQDY-UHFFFAOYSA-N 2-methyl-4,6-bis(octylsulfanylmethyl)phenol Chemical compound CCCCCCCCSCC1=CC(C)=C(O)C(CSCCCCCCCC)=C1 GAODDBNJCKQQDY-UHFFFAOYSA-N 0.000 description 1
- 125000004819 2-methylbutylene group Chemical group [H]C([H])([H])C([H])(C([H])([H])[*:1])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- VTWDKFNVVLAELH-UHFFFAOYSA-N 2-methylcyclohexa-2,5-diene-1,4-dione Chemical compound CC1=CC(=O)C=CC1=O VTWDKFNVVLAELH-UHFFFAOYSA-N 0.000 description 1
- MWDGNKGKLOBESZ-UHFFFAOYSA-N 2-oxooctanal Chemical compound CCCCCCC(=O)C=O MWDGNKGKLOBESZ-UHFFFAOYSA-N 0.000 description 1
- HXIQYSLFEXIOAV-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1SC1=CC(C(C)(C)C)=C(O)C=C1C HXIQYSLFEXIOAV-UHFFFAOYSA-N 0.000 description 1
- PFANXOISJYKQRP-UHFFFAOYSA-N 2-tert-butyl-4-[1-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C PFANXOISJYKQRP-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- QRLSTWVLSWCGBT-UHFFFAOYSA-N 4-((4,6-bis(octylthio)-1,3,5-triazin-2-yl)amino)-2,6-di-tert-butylphenol Chemical compound CCCCCCCCSC1=NC(SCCCCCCCC)=NC(NC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=N1 QRLSTWVLSWCGBT-UHFFFAOYSA-N 0.000 description 1
- SRYYOKKLTBRLHT-UHFFFAOYSA-N 4-(benzylamino)phenol Chemical compound C1=CC(O)=CC=C1NCC1=CC=CC=C1 SRYYOKKLTBRLHT-UHFFFAOYSA-N 0.000 description 1
- YYVYAPXYZVYDHN-UHFFFAOYSA-N 9,10-phenanthroquinone Chemical compound C1=CC=C2C(=O)C(=O)C3=CC=CC=C3C2=C1 YYVYAPXYZVYDHN-UHFFFAOYSA-N 0.000 description 1
- PGDIJTMOHORACQ-UHFFFAOYSA-N 9-prop-2-enoyloxynonyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCCCCOC(=O)C=C PGDIJTMOHORACQ-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- RNPRWBJACGBYCX-UHFFFAOYSA-N C(C(=C)C)(=O)O.C(C(=C)C)(=O)O.C(C(=C)C)(=O)O.C(C(=C)C)(=O)O.NOC(=O)C(CO)CO.NOC(=O)C(CO)CO Chemical compound C(C(=C)C)(=O)O.C(C(=C)C)(=O)O.C(C(=C)C)(=O)O.C(C(=C)C)(=O)O.NOC(=O)C(CO)CO.NOC(=O)C(CO)CO RNPRWBJACGBYCX-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 235000006481 Colocasia esculenta Nutrition 0.000 description 1
- 240000004270 Colocasia esculenta var. antiquorum Species 0.000 description 1
- 229920001174 Diethylhydroxylamine Polymers 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- ZGFPUTOTEJOSAY-UHFFFAOYSA-N FC1=C([Ti])C(F)=CC=C1N1C=CC=C1 Chemical compound FC1=C([Ti])C(F)=CC=C1N1C=CC=C1 ZGFPUTOTEJOSAY-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- NQSMEZJWJJVYOI-UHFFFAOYSA-N Methyl 2-benzoylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 NQSMEZJWJJVYOI-UHFFFAOYSA-N 0.000 description 1
- KEQFTVQCIQJIQW-UHFFFAOYSA-N N-Phenyl-2-naphthylamine Chemical compound C=1C=C2C=CC=CC2=CC=1NC1=CC=CC=C1 KEQFTVQCIQJIQW-UHFFFAOYSA-N 0.000 description 1
- CKRZKMFTZCFYGB-UHFFFAOYSA-N N-phenylhydroxylamine Chemical compound ONC1=CC=CC=C1 CKRZKMFTZCFYGB-UHFFFAOYSA-N 0.000 description 1
- 229930192627 Naphthoquinone Natural products 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- CGRTZESQZZGAAU-UHFFFAOYSA-N [2-[3-[1-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]-2-methylpropan-2-yl]-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]-2-methylpropyl] 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCC(C)(C)C2OCC3(CO2)COC(OC3)C(C)(C)COC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 CGRTZESQZZGAAU-UHFFFAOYSA-N 0.000 description 1
- YPBNDGVRPOECEP-UHFFFAOYSA-N [2-hydroxy-3-[2-[2-hydroxy-3-(2-methylprop-2-enoyloxy)propoxy]ethoxy]propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)COCCOCC(O)COC(=O)C(C)=C YPBNDGVRPOECEP-UHFFFAOYSA-N 0.000 description 1
- IFBMOBFQBJZBMV-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphanyl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C IFBMOBFQBJZBMV-UHFFFAOYSA-N 0.000 description 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- VEBCLRKUSAGCDF-UHFFFAOYSA-N ac1mi23b Chemical compound C1C2C3C(COC(=O)C=C)CCC3C1C(COC(=O)C=C)C2 VEBCLRKUSAGCDF-UHFFFAOYSA-N 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 125000004976 cyclobutylene group Chemical group 0.000 description 1
- FWQJLFDJWHTPCJ-UHFFFAOYSA-N cyclodecane;methanol Chemical compound OC.OC.C1CCCCCCCCC1.C1CCCCCCCCC1.C1CCCCCCCCC1 FWQJLFDJWHTPCJ-UHFFFAOYSA-N 0.000 description 1
- 125000004956 cyclohexylene group Chemical group 0.000 description 1
- 125000004978 cyclooctylene group Chemical group 0.000 description 1
- 125000004979 cyclopentylene group Chemical group 0.000 description 1
- 125000004980 cyclopropylene group Chemical group 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- KQAHMVLQCSALSX-UHFFFAOYSA-N decyl(trimethoxy)silane Chemical compound CCCCCCCCCC[Si](OC)(OC)OC KQAHMVLQCSALSX-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 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 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002523 gelfiltration Methods 0.000 description 1
- 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 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 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 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- DZCCLNYLUGNUKQ-UHFFFAOYSA-N n-(4-nitrosophenyl)hydroxylamine Chemical compound ONC1=CC=C(N=O)C=C1 DZCCLNYLUGNUKQ-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002791 naphthoquinones Chemical class 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 229920013730 reactive polymer Polymers 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 239000000015 trinitrotoluene Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/04—Polymers provided for in subclasses C08C or C08F
- C08F290/048—Polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/22—Incorporating nitrogen atoms into the molecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/28—Reaction with compounds containing carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- 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
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/222—Catalysts containing metal compounds metal compounds not provided for in groups C08G18/225 - C08G18/26
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6204—Polymers of olefins
- C08G18/6208—Hydrogenated polymers of conjugated dienes
-
- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- 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
-
- 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 photocurable composition containing a terminal-modified (hydrogenated) polybutadiene, a (meth) acrylic acid ester monomer, and a radical photopolymerization initiator, and a cured product obtained by photocuring the photocurable composition.
- the present application is Japanese Patent Application No. 2013-208826 filed on October 4, 2013, Japanese Patent Application No. 2013-208832 filed on October 4, 2013, October 4, 2013. The priority is claimed to the Japanese patent application No. 2013-208833 filed, the contents of which are incorporated herein.
- a photocurable composition containing a polybutadiene or hydrogenated polybutadiene having a terminal portion modified with an acryloyl group or a methacryloyl group, a (meth) acrylic acid ester monomer, and a radical photopolymerization initiator is known. By curing these compositions with light, cured products that can be applied to various applications can be obtained.
- Patent Document 1 (A) 20 to 90% by mass of a reactive polymer having a (meth) acryloyl group at the terminal and (B) (meth) acrylic acid ester monomer of 80 to 10% by mass in total 100 parts by mass, (C) A photocurable composition containing 0.1 to 10 parts by mass of a photoradical polymerization initiator and a cured product thereof are disclosed.
- Patent Document 2 discloses an acrylate-terminated oligomer, an acrylate or methacrylate-terminated reactive diluent having 3 to 20 carbon atoms, 2-hydroxycyclohexylphenone, diethoxyacetophenone, 1- (4-dodecylphenyl) -2-hydroxy.
- a composition comprising a photoinitiator selected from the group comprising -2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and mixtures thereof.
- the present inventors have made a total of 100 parts by weight of 5 to 40% by weight of terminal-modified (hydrogenated) polybutadiene having a specific structure and 95 to 60% by weight of (meth) acrylate monomer, A photocurable composition containing 0.1 to 20 parts by weight of a radical photopolymerization initiator was found.
- the present invention was completed by finding that the photocurable composition can be photocured without yellowing, and that the resulting cured product exhibits good mechanical properties.
- the inventors have also found a photocurable composition comprising a terminal-modified (hydrogenated) polybutadiene having a specific structure, a (meth) acrylate monomer, and a photoradical polymerization initiator having a specific structure. It was. The photocurable composition can be photocured without yellowing, and the resulting cured product exhibits good mechanical properties.
- the present inventors have further found a photocurable composition containing a terminal-modified (hydrogenated) polybutadiene having a specific structure, tricyclodecane dimethanol di (meth) acrylate, and a photoradical polymerization initiator. The photocurable composition can be photocured without yellowing, and the resulting cured product exhibits good mechanical properties.
- the present invention relates to the following (1) to (10) photocurable compositions and photocured products.
- the terminal-modified (hydrogenated) polybutadiene represented by 5 to 40% by weight, and (B) (meth) acrylic acid ester monomer 95 to 60 wt% total 100 parts by weight, (C) A photocurable composition containing 0.1 to 20 parts by weight of a photoradical polymerization initiator.
- Formula [II] (Wherein R 1 represents a hydrogen atom or a methyl group, and R 2 and R 3 each independently represents a linear or branched C1-C10 alkylene group or a C1-C6 alkyl group)
- Formula [III] (Wherein A represents a polymer chain obtained by polymerizing butadiene or a polymer chain obtained by hydrogenating the polymer chain, and m represents 1 or 2).
- the photocurable composition according to (1) which is obtained by reacting a polybutadiene having a hydroxyl group at a terminal or a hydrogenated polybutadiene.
- (3) (A) Formula [I] (Wherein R 1 , R 2 , R 3 , A and m represent the same meaning as described above), terminal-modified (hydrogenated) polybutadiene represented by: (B) (meth) acrylic acid ester monomer, (C) Formula [IV] (Wherein, X represents any one selected from the group consisting of O, CH 2 , CH (CH 3 ), or C (CH 3 ) 2 , and R 4 and R 5 are each independently Represents a hydrogen atom, a methyl group, or a trimethylsilyl group.)
- a photocurable composition comprising: (4)
- the photo radical polymerization initiator represented by the formula [IV] is 2-hydroxy-1- (4- (4- (2-hydroxy-2-methyl-propionyl) -benzyl) -phenyl)
- a photocurable composition comprising: (8) A terminal-modified (hydrogenated) polybutadiene represented by the formula [I] Formula [II] (Wherein R 1 , R 2 and R 3 represent the same meaning as described above), Formula [III] (Wherein A and m represent the same meanings as described above)
- Sex composition (9)
- the terminal-modified (hydrogenated) polybutadiene represented by the formula [I] has a number average molecular weight (Mn) of 1,000 to 100,000, according to any one of (1) to (8).
- Photocurable composition (10) A cured product obtained by photocuring the photocurable composition according to any one of (1) to (9).
- a colorless and transparent cured product can be obtained by photocuring the photocurable composition of the present invention.
- the obtained cured product is hardly yellowed even when irradiated with light, and has high heat resistance.
- a cured product showing good mechanical properties is a material suitable for an optical material or the like.
- Examples of the “C1-C10 alkylene group having a straight or branched chain” for R 2 and R 3 include a methylene group, an ethylene group, a propylene group, a methylethylene group, a butylene group, a 1,2-dimethylethylene group, and a pentylene group. 1-methylbutylene group, 2-methylbutylene group, hexylene group and the like.
- the “C1-C6 alkyl group” of the “C3-C8 cycloalkylene group optionally having a C1-C6 alkyl group as a substituent” for R 2 and R 3 includes a methyl group, an ethyl group, n -Propyl group, isopropyl group, n-butyl group, 1-methyl-n-propyl group, 2-methyl-n-propyl group, t-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2 -Methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-
- Examples of the “C3-C8 cycloalkylene group optionally having a C1-C6 alkyl group as a substituent” for R 2 and R 3 include cyclopropylene, 2-methylcyclopropylene, cyclobutylene, 2,2- Examples thereof include dimethylcyclobutylene, cyclopentylene, 2,3-dimethylcyclopentylene, cyclohexylene, 1,3,3-trimethylcyclohexylene, cyclooctylene and the like.
- a complex thereof of R 2 and R 3 means “a C1-C10 alkylene group having a linear or branched chain and a C1-C6 alkyl group optionally having C3 to C8 as substituents.
- the photocurable composition of the present invention comprises 5 to 40% by weight of terminal-modified (hydrogenated) polybutadiene represented by the formula [I] as component (A), and (meth) acrylate monomer as component (B). Is contained in an amount of 0.1 to 20 parts by weight as a component (C) based on 100 parts by weight in total of 95 to 60% by weight.
- the photocurable composition of the present invention comprises a terminal-modified (hydrogenated) polybutadiene represented by the formula [I] as the component (A), a (meth) acrylate monomer as the component (B), and a formula as the component (C). It may contain a photo radical polymerization initiator represented by [IV].
- the amount of each component added is not particularly limited, but component (C) is added in an amount of 0.1 to 20 parts by weight of component (A) and 80 to 10% by weight of component (B).
- the content is preferably 1 to 20 parts by weight, and more preferably 3 to 7 parts by weight.
- the photocurable composition of the present invention comprises a terminal-modified (hydrogenated) polybutadiene represented by the formula [I] as the component (A), tricyclodecane dimethanol di (meth) acrylate as the component (B), and a component (C) may contain a radical photopolymerization initiator.
- the amount of each component added is not particularly limited, but component (C) is added in an amount of 0.1 to 20 parts by weight of component (A) and 80 to 10% by weight of component (B).
- the content is preferably 1 to 20 parts by weight.
- the photocurable composition of the present invention may further contain other components in addition to the component (A), the component (B), and the component (C).
- the component (A) contained in the photocurable composition of the present invention refers to a terminal-modified (hydrogenated) polybutadiene represented by the following formula [I].
- R 1 represents a hydrogen atom or a methyl group
- R 2 and R 3 each independently represent a linear or branched C1-C10 alkylene group or a C1-C6 alkyl group.
- A is obtained by polymerizing butadiene or by hydrogenating the polymer chain
- m represents 1 or 2.
- R 2 is preferably a linear C2 to C10 alkylene group, more preferably a linear C2 to C6 alkylene group, and even more preferably an ethylene group or a propylene group.
- R 3 is a linear C2 to C6 alkylene group, or a C1 to C10 alkylene group having a linear or branched chain and a C1 to C6 alkyl group optionally having C3 to C3 as a substituent.
- a group bonded to a C8 cycloalkylene group is preferred.
- a group in which a C1 to C10 alkylene group having a straight chain or a branched chain and a C3 to C8 cycloalkylene group optionally having a C1 to C6 alkyl group as a substituent are combined is represented by the following formula:
- the group represented by (1) or (2) is more preferable. In the formulas (1) and (2), * indicates a bonding position.
- the double line portion of the solid line and the dotted line represents a single bond or a double bond
- the double line part of the solid line and the dotted line is a double bond, it is a polybutadiene not added with hydrogen, and when it is a single bond, it means a hydrogenated polybutadiene.
- the double bond need not be 100% hydrogenated, and the residual rate of the double bond is not particularly limited.
- 1,4-bond repeating unit represented by the formula [V] has a double bond, a trans isomer, a cis isomer, or a mixture thereof may exist.
- the ratio of the repeating unit due to the 1,4-bond represented by the formula [V] and the 1,2-bond represented by the formula [VI] is 0 to 100 mol%. That is, in the present invention, the polymer chain represented by A may be a polymer having only 1,4-bonds or 1,2-bonds, and 1,4-bonds and 1,2-bonds are mixed. It may be a polymer. In particular, it is more preferable that the 1,2-bond ratio is 75 to 100 mol% and the 1,4-bond ratio is 25 to 0 mol%.
- the terminal-modified (hydrogenated) polybutadiene represented by the formula [I] preferably has a number average molecular weight of 1,000 to 100,000 according to GPC (gel filtration) method using polystyrene as an index. More preferably, it is from 1,000 to 10,000.
- the method for producing the terminal-modified (hydrogenated) polybutadiene represented by the formula [I] is not particularly limited, and can be produced by the method described in JP2011-116965A.
- the terminal-modified (hydrogenated) polybutadiene represented by the formula [I] is represented by the formula [II].
- R 1 , R 2 and R 3 represent the same meaning as described above
- the formula [III] (Wherein, A and m have the same meanings as described above) are preferably obtained by reacting a polybutadiene having a hydroxyl group at the polymer terminal or a hydrogenated polybutadiene.
- a method for obtaining the compound represented by the formula [II] and a method for reacting the compound represented by the formula [II] with the compound represented by the formula [III] are described in JP 2011-116965 A and the like. Known methods can be used.
- Specific examples of the compound represented by the formula [III] include NISSO-PB-G-1000, NISSO-PB-G-2000, NISSO-PB-G-3000, and hydrogenated products thereof.
- Examples thereof include PB-GI-1000, NISSO-PB-GI-2000, NISSO-PB-GI-3000 (all manufactured by Nippon Soda Co., Ltd.) and Poly bd R45HT (manufactured by Idemitsu Kosan Co., Ltd.). These can be used alone or in combination of two or more.
- the terminal-modified (hydrogenated) polybutadiene represented by the formula [I] is preferably a compound represented by Table 1, and more preferably a compound represented by Table 2.
- Table 1 R 1 , R 2 , A, and m represent the same meaning as described above, and in Table 2, R 1 , A, and m represent the same meaning as described above.
- Component (B) contained in the photocurable composition of the present invention is a (meth) acrylic acid ester monomer.
- (Meth) acrylic acid ester monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and benzyl (meth) Acrylate, phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, lauryl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, Isobornyl (meth) acrylate, 2,3-dibromopropyl (meth)
- the above (meth) acrylate monomers can be mentioned.
- a monofunctional (meth) acrylate monomer or a bifunctional (meth) acrylate monomer is preferable, and isobornyl (meth) acrylate is more preferable. More preferred are 1,6-hexanediol di (meth) acrylate and tricyclodecane dimethanol di (meth) acrylate. These can be used individually by 1 type or in mixture of 2 or more types.
- tricyclodecane dimethanol dimethyldimethacrylate is a bifunctional (meth) acrylate represented by the formula [VII].
- (Meth) acrylate is particularly preferred.
- R 4 each independently represents a hydrogen atom or a methyl group.
- Tricyclodecane dimethanol di (meth) acrylate is commercially available.
- the component (C) contained in the photocurable composition of the present invention is a photo radical polymerization initiator.
- radical photopolymerization initiators include alkylphenone photopolymerization initiators, benzophenone photopolymerization initiators, acylphosphine oxide photopolymerization initiators, titanocene photopolymerization initiators, and other photopolymerization initiators. it can.
- alkylphenone photopolymerization initiators include benzyl dimethyl ketal compounds such as 2,2-dimethoxy-1,2-diphenylethane-1-one (IRUGACURE (registered trademark) 651), 1-hydroxy-cyclohexyl-phenyl ketone (IRUGACURE® 184), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Darocur® 1173), 1- (4- (2-hydroxyethoxy) -phenyl)- 2-hydroxy-2-methylpropane (SB-PI 759), 1- (4- (2-hydroxyethoxy) -phenyl) -2-hydroxy-2-methyl-1-propan-1-one (IRUGACURE®) 2959), 2-hydroxy-1- (4- (4- (2-hydroxy-2-) ⁇ -hydroxyalkyl such as methyl-propionyl) -benzyl) -phenyl) -2-methyl-propan-1-one (IRUGACURE® 127), phenylglyoxylic acid methyl
- Benzophenone photopolymerization initiators include benzophenone (SB-PI 710), methyl-o-benzoylbenzoate (SB-PI 711), 4-methylbenzophenone (SB-PI 712), 4, 4′-bis (dimethylamino) ) Benzophenone (SB-PI 701), (4- (methylphenylthio) phenyl) -phenylmethane (SB-PI 705), and the like.
- Acylphosphine oxide photoinitiators include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (LUCIRIN® TPO), bis (2,4,6-trimethylbenzoyl) -phenylphosphine And an aqueous dispersion of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (IRUGACURE® 819DW) and the like.
- titanocene-based photopolymerization initiators bis ( ⁇ 5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium (IRUGACURE) (Registered trademark) 784).
- photopolymerization initiators include 1,2-octanedione, 1- (4- (phenylthio)-, 2- (O-benzoyloxime)) (IRUGACURE® OXE01), ethanone, 1- (9 Examples thereof include oxime esters such as -ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl)-, 1- (O-acetyloxime) (IRUGACURE (registered trademark) OXE02). These can be used individually by 1 type or in mixture of 2 or more types.
- a photoradical polymerization initiator represented by the formula [IV] is preferable.
- X represents any one selected from the group consisting of O, CH 2 , CH (CH 3 ), or C (CH 3 ) 2
- R 4 and R 5 are each independently Represents a hydrogen atom, a methyl group, or a trimethylsilyl group.
- 2-hydroxy-1- (4- (4- (2-hydroxy-2-methyl-propionyl) -benzyl) -phenyl) -2-methyl- Propan-1-one is preferred.
- 2-Hydroxy-1- (4- (4- (2-hydroxy-2-methyl-propionyl) -benzyl) -phenyl) -2-methyl-propan-1-one is a commercially available product (Ciba Specialty Chemicals ( Co., Ltd., trade name: IRUGACURE (registered trademark) 127) can be obtained
- a polymerization inhibitor can be mentioned.
- the polymerization inhibitor is not particularly limited.
- BHT 2,6-di-t-butyl-4-hydroxytoluene
- 2,6-di-t-butyl-4-methylphenol 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 3, 9-bis [2- (3- (3-t-butyl-4-hydroxy-5-methylphenyl) -propionyloxy) -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro (5,5) undecane, triethylene glycol-bis-3- (3-tert-butyl-4-hydroxy
- the photocurable composition of the present invention can be cured by light.
- ultraviolet rays for example, ultraviolet rays, visible light, X-rays, electron beams and the like can be used, but it is preferable to use ultraviolet rays. Since ultraviolet rays have high energy, the curing reaction can be accelerated by irradiating the curable composition with ultraviolet rays, the curing rate of the curable composition can be increased, and the unreacted curable composition in the cured product. The amount of objects can be reduced.
- the method of irradiating visible light is not particularly limited, and examples thereof include a method using an incandescent bulb or a fluorescent lamp.
- the method of irradiating ultraviolet rays is not particularly limited, and examples thereof include a metal halide lamp, a xenon lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, and an ultrahigh-pressure mercury lamp as an electrode system, and an excimer lamp, a metal halide lamp, and the like as an electrodeless system. be able to.
- the wavelength range is not particularly limited, but is preferably 150 nm to 400 nm, more preferably 200 nm to 380 nm.
- an inert gas atmosphere such as nitrogen gas or carbon dioxide gas or an atmosphere with a reduced oxygen concentration is preferable, but a normal air atmosphere is also possible.
- the irradiation atmosphere temperature can usually be 10 to 200 ° C.
- the curing conditions for completely curing the cured product can be selected as appropriate.
- IH-1000 terminal-modified hydrogenated polybutadiene
- the obtained IH-1000 was subjected to 1 H-NMR measurement, and two NH signals (4.55, 4.70 ppm) were confirmed. Further, IR measurement was performed, and absorption of urethane bonds of 1728 (CO) and 3339 cm ⁇ 1 (NH) was confirmed.
- Mn number average molecular weight
- Mn number average molecular weight
- P, 45 degreeC by a B-type viscosity meter was 3165. “Residual NCO (%)” indicates the weight (multiplier of the number of moles and 42.02 (NCO molecular weight)) of the isocyanate site in the weight of the compound in%.
- Example 1-1 (Preparation of photocurable composition A) 4.00 parts of end-modified hydrogenated polybutadiene (IH-1000) obtained in Production Example 1, 16.0 parts of isobornyl acrylate (trade name IBOA, manufactured by Daicel Ornex Co., Ltd.), 2-hydroxy-2 -1.00 parts of methyl-1-phenyl-propan-1-one (trade name DAROCUR (registered trademark) 1173, manufactured by Ciba Japan KK) and 2,6-di-t-butyl-4-hydroxytoluene 0 1 part was mixed (rotation revolution mixer: Awatori Rentaro (registered trademark), rotation 2000 rpm, 10 minutes, revolution 2200 rpm, 10 minutes) to obtain a photocurable composition A.
- IBOA isobornyl acrylate
- DAROCUR registered trademark
- Example 1-2 (Production of cured product A) Pour 4.00 g of the photocurable composition A obtained in Example 1-1 into an aluminum dish having a diameter of 6.5 cm, and irradiate with an ultrahigh pressure mercury lamp (10 mW; parallel light type) for 8 minutes. A cured product A having a thickness of 1.0 mm was obtained.
- Comparative Example 2-2 Manufacture of cured product C
- a cured product C having a thickness of 1.0 mm was obtained.
- test pieces were prepared by stacking 6 test pieces each having a thickness of 1 mm, and the hardness was measured with a durometer in accordance with JIS K7215. The obtained results are shown in Table 3.
- Example 2 Preparation of photocurable compositions A ′ to P ′) IH-1000, (meth) acrylic acid ester monomer, 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba Japan Co., Ltd., trade name IRGACURE (registered trademark) 184) and BHT are mixed (spinning revolving mixer: awatori smelting) Taro (registered trademark), rotation 2000 rpm, 10 minutes, revolution 2200 rpm, 10 minutes) to obtain photocurable compositions A ′ to P ′.
- test For each of the cured products A ′, B ′, E ′ to G ′, and I ′ to N ′, test specimens having a width of 5 mm, a length of 50 mm, and a thickness of about 1 mm were prepared. Shimadzu Corporation Autograph AGG-J A tensile test was conducted under the following conditions, and stress (MPa) and elastic modulus were measured. The results are shown in Table 4. Temperature: 24 ° C Humidity: 60% Distance between grips: 20mm Tensile speed: 20mm / min Tensile load Load cell: 5kN
- the elastic modulus is the tensile elastic modulus in the range of the test force (1-2N), and was calculated from the following calculation formula.
- Tensile modulus [ ⁇ test force (N) / cross-sectional area of test piece (mm 2 )] / [ ⁇ strain (mm) / distance between grips (mm)]
- Stress (MPa) Maximum point stress (MPa) In the above table, “-” indicates unmeasured.
- a colorless and transparent cured product can be obtained by photocuring the photocurable composition of the present invention.
- the obtained cured product is hardly yellowed even when irradiated with light, and exhibits good mechanical properties, so that it becomes a material suitable for an optical material or the like.
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Abstract
Description
本願は、2013年10月4日に出願された日本国特許出願第2013-208826号、2013年10月4日に出願された日本国特許出願第2013-208832号、2013年10月4日に出願された日本国特許出願第2013-208833号に対し優先権を主張し、その内容をここに援用する。
本発明者らは、また、特定の構造を有する末端変性(水素添加)ポリブタジエンと、(メタ)アクリル酸エステルモノマーと、特定の構造を有する光ラジカル重合開始剤を含む光硬化性組成物を見出した。該光硬化性組成物は、黄変することなく光硬化することができ、得られる硬化物は良好な機械特性を示す。
本発明者らは、さらに、特定の構造を有する末端変性(水素添加)ポリブタジエンと、トリシクロデカンジメタノールジ(メタ)アクリレートと、光ラジカル重合開始剤を含む光硬化性組成物を見出した。該光硬化性組成物は、黄変することなく光硬化することができ、得られる硬化物は良好な機械特性を示す。
(1)(A)式〔I〕
(B)(メタ)アクリル酸エステルモノマー95~60重量%の合計100重量部に対し、
(C)光ラジカル重合開始剤0.1~20重量部
を含む光硬化性組成物。
(2)式〔I〕で表される末端変性(水素添加)ポリブタジエンが、
式〔II〕
式〔III〕
(3)(A)式〔I〕
(B)(メタ)アクリル酸エステルモノマー、
(C)式〔IV〕
を含む光硬化性組成物。
(4)式〔IV〕で表される光ラジカル重合開始剤が、2-ヒドロキシ-1-(4-(4-(2-ヒドロキシ-2-メチル-プロピオニル)-ベンジル)-フェニル)-2-メチル-プロパン-1-オンである前記(3)に記載の光硬化性組成物。
(5)(A)式〔I〕で表される末端変性(水素添加)ポリブタジエン、および、(B)(メタ)アクリル酸エステルモノマーの合計100重量部に対し、(C)光ラジカル重合開始剤3~7重量部を含む前記(3)または(4)に記載の光硬化性組成物。
(6)式〔I〕で表される末端変性(水素添加)ポリブタジエンが、
式〔II〕
式〔III〕
(7)(A)式〔I〕
(B)トリシクロデカンジメタノールジ(メタ)アクリレート、および
(C)光ラジカル重合開始剤、
を含む光硬化性組成物。
(8)式〔I〕で表される末端変性(水素添加)ポリブタジエンが、
式〔II〕
式〔III〕
(9)式〔I〕で表される末端変性(水素添加)ポリブタジエンの数平均分子量(Mn)が1,000~100,000である前記(1)ないし(8)のいずれか1項に記載の光硬化性組成物。
(10)前記(1)~(9)のいずれか1項に記載の光硬化性組成物を光硬化させた硬化物。
本発明の光硬化性組成物は、成分(A)として式〔I〕で表される末端変性(水素添加)ポリブタジエンを5~40重量%と、成分(B)として(メタ)アクリル酸エステルモノマーを95~60重量%との合計100重量部に対し、成分(C)として光ラジカル重合開始剤を0.1~20重量部を含有する。
本発明の光硬化性組成物は、成分(A)として式〔I〕で表される末端変性(水素添加)ポリブタジエン、成分(B)として(メタ)アクリル酸エステルモノマー、成分(C)として式〔IV〕で表される光ラジカル重合開始剤を含有するものであってもよい。
この場合、各成分の添加量は特に制限されないが、成分(A)を20~90重量%および成分(B)を80~10重量%の合計100重量部に対し、成分(C)を0.1~20重量部含むのが好ましく、3~7重量部を含むのがより好ましい。
本発明の光硬化性組成物は、成分(A)として式〔I〕で表される末端変性(水素添加)ポリブタジエンと、成分(B)としてトリシクロデカンジメタノールジ(メタ)アクリレートと、成分(C)として光ラジカル重合開始剤を含有するものであってもよい。この場合、各成分の添加量は特に制限されないが、成分(A)を20~90重量%および成分(B)を80~10重量%の合計100重量部に対し、成分(C)を0.1~20重量部含むのが好ましい。
本発明の光硬化性組成物は、成分(A)、成分(B)、成分(C)以外に、さらに他の成分を含有していてもよい。
本発明の光硬化性組成物中に含まれる成分(A)は、以下の式〔I〕で表される末端変性(水素添加)ポリブタジエンをいう。
本発明の光硬化性組成物中に含まれる成分(B)は、(メタ)アクリル酸エステルモノマーである。(メタ)アクリル酸エステルモノマーとしては、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、ベンジル(メタ)アクリレート、フェノキシエチル(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、ラウリル(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、ジシクロペンタニル(メタ)アクリレート、ジシクロペンテニルオキシエチル(メタ)アクリレート、イソボルニル(メタ)アクリレート、2,3-ジブロモプロピル(メタ)アクリレート、2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、3-ヒドロキシプロピル(メタ)アクリレート、3-ジヒドロキシプロピル(メタ)アクリレート、2,3-ジヒドロキシプロピル(メタ)アクリレート、2-ヒドロキシエチル(メタ)アクリルアミド、3-メタクリロイルオキシプロピルトリメトキシシラン、11-メタクリロイルオキシウンデシルトリメトキシシラン、(メタ)アクリルアミド等の一官能性(メタ)アクリレートモノマーや、
本発明の光硬化性組成物中に含まれる成分(C)は、光ラジカル重合開始剤である。光ラジカル重合開始剤としては、アルキルフェノン系光重合開始剤、ベンゾフェノン系光重合開始剤、アシルフォスフィンオキサイド系光重合開始剤、チタノセン系光重合開始剤、その他の光重合開始剤を挙げることができる。
ベンゾフェノン系光重合開始剤としては、ベンゾフェノン(SB-PI 710)、メチル-o-ベンゾイルベンゾエート(SB-PI 711)、4-メチルベンゾフェノン(SB-PI 712)、4、4’-ビス(ジメチルアミノ)ベンゾフェノン(SB-PI 701)、(4-(メチルフェニルチオ)フェニル)-フェニルメタン(SB-PI 705)などを挙げることができる。
アシルフォスフィンオキサイド系光重合開始剤としては、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(LUCIRIN(登録商標) TPO)、ビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド(IRUGACURE(登録商標)819)、ビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイドの水分散体(IRUGACURE(登録商標)819DW)などを挙げることができる。
チタノセン系光重合開始剤としては、ビス(η5-2,4-シクロペンタジエン-1-イル)-ビス(2,6-ジフルオロ-3-(1H-ピロール-1-イル)-フェニル)チタニウム(IRUGACURE(登録商標)784)などを挙げることができる。
その他の光重合開始剤としては、1,2-オクタンジオン,1-(4-(フェニルチオ)-,2-(O-ベンゾイルオキシム))(IRUGACURE(登録商標) OXE01)、エタノン,1-(9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル)-,1-(O-アセチルオキシム)(IRUGACURE(登録商標) OXE02)などのオキシムエステルなどを挙げることができる。
これらは1種単独で、或いは、2種以上を混合して使用することができる。
本発明の光硬化性組成物は、その特性を損なわない範囲で、目的に応じて、他の成分を添加、配合する事が出来る。具体的には、重合禁止剤を挙げることができる。重合禁止剤は特に限定されないが、例えば、2,6-ジ-t-ブチル-4-ヒドロキシトルエン(BHT)、2,6-ジ-t-ブチル-4-メチルフェノール、2,2’-メチレンビス(4-メチル-6-t-ブチルフェノール)、4,4’-ブチリデンビス(3-メチル-6-t-ブチルフェノール)、4,4’-チオビス(3-メチル-6-t-ブチルフェノール)、3,9-ビス[2-(3-(3-t-ブチル-4-ヒドロキシ-5-メチルフェニル)-プロピオニロキシ)-1,1-ジメチルエチル]-2,4,8,10-テトラオキサスピロ(5,5)ウンデカン、トリエチレングリコール-ビス-3-(3-t-ブチル-4-ヒドロキシ-5-メチルフェニル)プロピオネート、n-オクタデシル-3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート、i-オクチル-3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート、ヘキサメチレンビス[3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート、4,6-ビス(オクチルチオメチル)-o-クレゾール、4,6-ビス(ドデシルチオメチル)-o-クレゾール、ペンタエリトリルテトラキス[3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート]、トリス(3,5-ジ-t-ブチルヒドロキシベンジル)イソシアヌレート、トリス(4-t-ブチル-2,6-ジメチル-5-ヒドロキシベンジル)イソシアヌレート、2,6-ジ-t-ブチル-4-(4,6-ビス(オクチルチオ)-1,3,5-トリアジン-2-イルアミノ)フェノール、チオジエチレンビス[3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート、N,N’-ヘキサン-1,6-ジイルビス[3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニルプロピオンアミド、3,3’,3’’,5,5’,5’’-ヘキサ-t-ブチル-a,a’,a’’-(メシチレン-2,4,6-トリイル)トリ-p-クレゾール、カルシウムジエチレンビス[[[3,5-ビス(1,1-ジメチルエチル)-4-ヒドロキシフェニル]メチル]ホスホネート]等のフェノール類;p-ベンゾキノン、アントラキノン、ナフトキノン、フェナンスラキノン、p-トルキノン、2,6-ジクロロキノン、2,5-ジフェニル-p-ベンゾキノン、2,5-ジアセトキシ-p-ベンゾキノン、2,5-ジカプロキシ-p-ベンゾキノン、2,5-ジアシロキシ-p-ベンゾキノン等のキノン類;ハイドロキノン、p-t-ブチルカテコール、2,5-ジ-t-ブチルハイドロキノン、モノ-t-ブチルハイドロキノン、モノメチルハイドロキノン、2,5-ジ-t-アミルハイドロキノン等のハイドロキノン類;フェニル-β-ナフチルアミン、p-ベンジルアミノフェノール、ジ-β-ナフチル-p-フェニレンジアミン、ジベンジルヒドロキシルアミン、フェニルヒドロキシルアミン、ジエチルヒドロキシルアミン等のアミン類;ジニトロベンゼン、トリニトロトルエン、ピクリン酸等のニトロ化合物;キノンジオキシム、シクロヘキサノンオキシム等のオキシム類;フェノチアジン、有機並びに無機の銅塩類等が挙げられるが、好ましくは、2,6-ジ-t-ブチル-4-ヒドロキシトルエンである。これらは1種単独で、或いは、2種以上を混合して使用することができる。
重合禁止剤の添加量は、本発明の特性を損なわない範囲であれば特に制限されない。通常、成分(A)と成分(B)の合計100重量部に対し、0.01~5重量部である。
本発明の光硬化性組成物は、光により硬化することができる。
実施例、比較例で使用する略語の意味は以下の通りである。
IH-1000: 製造例1で得られた末端変性水素添加ポリブタジエン
TEAI-1000: 日本曹達社製末端変性水素添加ポリブタジエン
HDDA: 1、6-ヘキサンジオールジアクリレート(東京化成工業製)
TCDDA: トリシクロデカンジメタノールジアクリレート(Sigma-Aldrich社製)
IRGACURE127: 2-ヒドロキシ-1-(4-(4-(2-ヒドロキシ-2-メチル-プロピオニル)-ベンジル)-フェニル)-2-メチル-プロパン-1-オン(チバ・ジャパン株式会社製)
IRGACURE184: 1-ヒドロキシ-シクロヘキシル-フェニルケトン(チバ・ジャパン株式会社製)
IRGACURE651: 2,2-ジメトキシ-1,2-ジフェニルエタン-1-オン(チバ・ジャパン株式会社製)
LUCIRIN TPO: 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(BASF社製)
DAROCUR1173: 2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オン(BASF社製)
DAROCUR MBF: フェニルグリオキシリックアシッドメチルエステル(BASF社製)
SB-PI 759: 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(Shuang-Bang Ind.crop.社製)
BHT: 2,6-ジ-t-ブチル-4-ヒドロキシトルエン(共同薬品社製)
空気雰囲気下でイソホロンジイソシアネート784部と、アルミキレートM6.95部と、ヒドロキシエチルアクリレート390部を混合し、65℃にて1時間反応させ、反応物Aを合成した。次に、空気雰囲気下にて、先に合成した反応物A1013部と、末端を水酸基で変性した水素添加ポリブタジエン(GI-1000,日本曹達社製)3000部と、アルミキレートM24.1部を混合し、65℃にて2時間反応させた。残存NCOが0.1%以下であることを確認して反応を終了し、末端変性水素添加ポリブタジエン(以下IH-1000と記載することがある)を得た。
得られたIH-1000について、1H-NMR測定をおこない、2つのNHシグナル(4.55、4.70ppm)を確認した。また、IR測定をおこない1728(CO)、3339cm-1(NH)のウレタン結合の吸収を確認した。得られたIH-1000について数平均分子量(Mn)をGPC法で測定したところ、3200であった。また、B型粘度計による粘度(P、45℃)は3165であった。
尚、「残存NCO(%)」とは、化合物の重量中に占めるイソシアネート部位の重量(モル数と42.02(NCO分子量)の乗数)を%で示したものである。
(光硬化性組成物Aの調製)
製造例1で得られた末端変性水素添加ポリブタジエン(IH-1000)4.00部と、イソボルニルアクリレート(ダイセル・オルネクス株式会社製、商品名IBOA)16.0部と、2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オン(チバ・ジャパン株式会社製、商品名DAROCUR(登録商標)1173)1.00部と、2,6-ジ-t-ブチル-4-ヒドロキシトルエン0.1部を混合(自転公転ミキサー:あわとり錬太郎(登録商標)、自転2000rpm、10分間、公転2200rpm、10分間)して光硬化性組成物Aを得た。
(硬化物Aの製造)
直径6.5cmのアルミ皿に実施例1-1で得られた光硬化性組成物A4.00gを流し込み、超高圧水銀灯(10mW;平行光タイプ)で8分間光照射を行って、厚さ約1.0mm厚の硬化物Aを得た。
(光硬化性組成物Bの調製)
製造例1で得られた末端変性水素添加ポリブタジエンA10.0部と、イソボルニルアクリレート(ダイセル・オルネクス株式会社製、商品名IBOA)10.0部と、2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オン(チバ・ジャパン株式会社製、商品名Darocur(登録商標)1173)1.0部と、2,6-ジ-t-ブチル-4-ヒドロキシトルエン0.1部を混合(自転公転ミキサー:あわとり錬太郎(登録商標)、自転2000rpm、10分間、公転2200rpm、10分間)して光硬化性組成物Bを得た。
(硬化物Bの製造)
直径6.5cmのアルミ皿に比較例1-1で得られた光硬化性組成物B4.00gを流し込み、超高圧水銀灯(10mW;平行光タイプ)で8分間光照射を行って、厚さ約1.0mm厚の硬化物Bを得た。
(光硬化性組成物Cの調製)
製造例1で得られた末端変性水素添加ポリブタジエンAの代わりにTEAI-1000(末端変性水素添加ポリブタジエン:日本曹達株式会社製)を使用した以外は、比較例1-1と同様にして光硬化性組成物Cを得た。
(硬化物Cの製造)
直径6.5cmのアルミ皿に比較例2-1で得られた光硬化性組成物C4.00gを流し込み、超高圧水銀灯(10mW;平行光タイプ)で8分間光照射を行って、厚さ約1.0mm厚の硬化物Cを得た。
(光硬化性組成物Dの調製)
製造例1で得られた末端変性水素添加ポリブタジエンA16.0部と、イソボルニルアクリレート(ダイセル・オルネクス株式会社製、商品名IBOA)4.0部と、2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オン(チバ・ジャパン株式会社製、商品名Darocur(登録商標)1173)1.0部と、2,6-ジ-t-ブチル-4-ヒドロキシトルエン0.1部を混合(自転公転ミキサー:あわとり錬太郎(登録商標)、自転2000rpm、10分間、公転2200rpm、10分間)して光硬化性組成物Dを得た。
(硬化物Dの製造)
直径6.5cmのアルミ皿に比較例3-1で得られた光硬化性組成物D4.00gを流し込み、超高圧水銀灯(10mW;平行光タイプ)で10分間光照射を行って、厚さ約1.0mm厚の硬化物Dを得た。
(光硬化性組成物Eの調製)
製造例1で得られた末端変性水素添加ポリブタジエンAの代わりにTEAI-1000(末端変性水素添加ポリブタジエン:日本曹達株式会社製)を使用した以外は、比較例3-1と同様にして光硬化性組成物Eを得た。
(硬化物Eの製造)
直径6.5cmのアルミ皿に比較例4-1で得られた光硬化性組成物E4.00gを流し込み、超高圧水銀灯(10mW;平行光タイプ)で10分間光照射を行って、厚さ約1.0mm厚の硬化物Eを得た。
硬化物A、B、C、D、Eについて、下記の条件で色相評価をおこなった。
(1)硬化物の色相評価試験
製造直後の硬化物A、B、C、D、Eについて、幅25mm、長さ50mm、厚さ約1mmの試験片を作成し、それぞれL*値、a*値、b*値を分光式色差計 (「SE-2000」:日本電色工業会社製)を用いて、反射法により測定した。得られた結果を表3に示す。
L*値、a*値、b*値とは、色を表す方法(表色系)の一種であり、明るさ(L*明度)と色調(a*=赤-緑、b*=黄-青)を3つの軸・指標で特定の色を数字として表すものである。
(2)紫外線照射後の硬化物の色相評価試験
幅25mm、長さ50mm、厚さ約1mmの硬化物A、B、C、D、Eそれぞれに対し、SUGA紫外線フェードメータU48(スガ試験機株式会社製)を用い、槽内温度約30℃、湿度50%下にて、500w/m2、300~700nmの照射条件で16時間照射を行った。16時間照射後の硬化物A、B、C、D、Eそれぞれについて、(1)と同じ条件で色相評価をおこなった。得られた結果を表3に示す。
製造直後の硬化物A、B、C、D、Eそれぞれについて、厚み1mmの試験片を6枚重ねた試験片を作成し、JIS K 7215に準じてデュロメータにより硬度を測定した。得られた結果を表3に示す。
(光硬化性組成物A’~P’の調製)
IH-1000と、(メタ)アクリル酸エステルモノマーと、1-ヒドロキシシクロヘキシルフェニルケトン(チバ・ジャパン株式会社製、商品名IRGACURE(登録商標)184)と、BHTを混合(自転公転ミキサー:あわとり錬太郎(登録商標)、自転2000rpm、10分間、公転2200rpm、10分間)して光硬化性組成物A’~P’を得た。
直径6.5cmのアルミ皿に光硬化性組成物A~G、I~Pをそれぞれ4.00gを流し込み、超高圧水銀灯(10mW;平行光タイプ)で5分間光照射を行って、厚さ約1.0mm厚の硬化物A’~G’、I’~P’を得た。
硬化物A’~G’、I’~P’について、下記の条件で色相評価をおこなった。
製造直後の硬化物A’~G’、I’~P’について、幅25mm、長さ50mm、厚さ約1mmの試験片を作成し、それぞれL*値、a*値、b*値を分光式色差計 (「SE-2000」:日本電色工業会社製)を用いて、反射法により測定した。得られた結果を表4に示す。
L*値、a*値、b*値とは、色を表す方法(表色系)の一種であり、明るさ(L*明度)と色調(a*=赤-緑、b*=黄-青)を3つの軸・指標で特定の色を数字として表すものである。
硬化物A’~D’、I’~P’それぞれについて、厚み1mmの試験片を6枚重ねた試験片を作成し、JIS K 7215に準じてデュロメータにより硬度を測定した。得られた結果を表4に示す。
硬化物A’、B’、E’~G’、I’~N’それぞれについて、幅5mm、長さ50mm、厚さ約1mmの試験片を作成し、株式会社島津製作所オートグラフAGG-Jを用いて以下の条件で引張試験をおこない、応力(MPa)、弾性率を測定した。結果を表4に示す。
温度:24℃
湿度:60%
つかみ具間距離:20mm
引張り速度:20mm/分
引張り荷重 ロードセル: 5kN
引張弾性率=〔Δ試験力(N)/試験片断面積(mm2)〕/〔Δひずみ(mm)/つかみ具間距離(mm)〕
応力(MPa)=最大点応力(MPa)
幅25mm、長さ50mm、厚さ約1mmの硬化物A’~D’、I’~P’それぞれに対し、SUGA紫外線フェードメータU48(スガ試験機株式会社製)を用い、槽内温度約30℃、湿度50%下にて、500w/m2、300~700nmの照射条件で照射を行った。48時間、96時間照射後の硬化物A~D、J~Pそれぞれについて、上記の色相評価試験と同じ条件で評価試験をおこなった。得られた結果を表6に示す。
(光硬化性組成物A”~H”の調製)
表3に示す組成で、末端変性水素添加ポリブタジエンと、(メタ)アクリル酸エステルモノマーと、2-ヒドロキシ-1-(4-(4-(2-ヒドロキシ-2-メチル-プロピオニル)-ベンジル)-フェニル)-2-メチル-プロパン-1-オン(チバ・ジャパン株式会社製、商品IRGACURE(登録商標)127)と、BHTを混合(自転公転ミキサー:あわとり錬太郎(登録商標)、自転2000rpm、10分間、公転2200rpm、10分間)して光硬化性組成物A”~H”を得た。
表4に示す組成で、末端変性水素添加ポリブタジエンと、(メタ)アクリル酸エステルモノマーと、光ラジカル重合開始剤と、ジブチルヒドロキシトルエン(以下BHTと記載することがある)を混合(自転公転ミキサー:あわとり錬太郎(登録商標)、自転2000rpm、10分間、公転2200rpm、10分間)して光硬化性組成物I”~U”を得た。
直径6.5cmのアルミ皿に光硬化性組成物A”~U”それぞれ4.00gを流し込み、超高圧水銀灯(10mW;平行光タイプ)で5分間光照射を行って、厚さ約1.0mm厚の硬化物A”~U”を得た。
得られた硬化物A”~I”、J”、L”~Q”、T”について、下記の条件で色相評価を行った。
製造直後の硬化物A”~I”、J”、L”~Q”、T”について、幅25mm、長さ50mm、厚さ約1mmの試験片を作成し、それぞれL*値、a*値、b*値を分光式色差計 (「SE-2000」:日本電色工業会社製)を用いて、反射法により測定した。得られた結果を表5に示す。
L*値、a*値、b*値とは、色を表す方法(表色系)の一種であり、明るさ(L*明度)と色調(a*=赤-緑、b*=黄-青)を3つの軸・指標で特定の色を数字として表すものである。
製造直後の硬化物A”~I”、J”、L”~Q”、T”それぞれについて、厚み1mmの試験片を6枚重ねた試験片を作成し、JIS K 7215に準じてデュロメータにより硬度を測定した。得られた結果を表9に示す。
硬化物A”~I”、J”、L”~Q”、T”それぞれについて、幅5mm、長さ50mm、厚さ約1mmの試験片を作成し、株式会社島津製作所オートグラフAGG-Jを用いて以下の条件で引張試験をおこない、ひずみ(%)を測定した。結果を表5に示す。
ひずみ(%)の値は以下の式から算出した。
ひずみ(%) = 100×(最大点変位/つかみ具間距離)
温度:24℃
湿度:60%
つかみ具間距離:20mm
引張り速度:20mm/分
引張り荷重 ロードセル:5kN
幅25mm、長さ50mm、厚さ約1mmの硬化物C”、I”~L”、N”、P”、T”それぞれに対し、SUGA紫外線フェードメータU48(スガ試験機株式会社製)を用い、槽内温度約30℃、湿度50%下にて、500w/m2、300~700nmの照射条件で照射を行った。48時間、96時間照射後の硬化物C”、I”~L”、N”、P”、T”それぞれについて、上記の色相評価試験と同じ条件で評価試験をおこなった。得られた結果を表10に示す。
幅25mm、長さ50mm、厚さ約1mmの硬化物C”、I” 、K” 、N” 、P”、R”、S”~U”それぞれを、槽内温度約130℃にて96時間保存した。96時間後、これら硬化物それぞれについて、上記の色相評価試験と同じ条件で評価試験を行った。得られた結果を表11に示す。
Claims (10)
- (A)式〔I〕
(B)(メタ)アクリル酸エステルモノマー95~60重量%の合計100重量部に対し、
(C)光ラジカル重合開始剤0.1~20重量部
を含む光硬化性組成物。 - 式〔I〕で表される末端変性(水素添加)ポリブタジエンが、
式〔II〕
式〔III〕
- 式〔IV〕で表される光ラジカル重合開始剤が、2-ヒドロキシ-1-(4-(4-(2-ヒドロキシ-2-メチル-プロピオニル)-ベンジル)-フェニル)-2-メチル-プロパン-1-オンである請求項3に記載の光硬化性組成物。
- (A)式〔I〕で表される末端変性(水素添加)ポリブタジエン、および、(B)(メタ)アクリル酸エステルモノマーの合計100重量部に対し、(C)光ラジカル重合開始剤3~7重量部を含む請求項3または4に記載の光硬化性組成物。
- 式〔I〕で表される末端変性(水素添加)ポリブタジエンの数平均分子量(Mn)が1,000~100,000である請求項1ないし8のいずれか1項に記載の光硬化性組成物。
- 請求項1ないし9のいずれか1項に記載の光硬化性組成物を光硬化させた硬化物。
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JP2017521505A (ja) * | 2014-05-08 | 2017-08-03 | アルケマ フランス | 硬化性ウレタン(メタ)アクリレートポリマー組成物および方法 |
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KR20160044013A (ko) | 2016-04-22 |
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