JP2008127475A - Unsaturated group-containing urethane resin and actinic energy ray-curing resin composition containing the same - Google Patents
Unsaturated group-containing urethane resin and actinic energy ray-curing resin composition containing the same Download PDFInfo
- Publication number
- JP2008127475A JP2008127475A JP2006314398A JP2006314398A JP2008127475A JP 2008127475 A JP2008127475 A JP 2008127475A JP 2006314398 A JP2006314398 A JP 2006314398A JP 2006314398 A JP2006314398 A JP 2006314398A JP 2008127475 A JP2008127475 A JP 2008127475A
- Authority
- JP
- Japan
- Prior art keywords
- unsaturated group
- diisocyanate
- urethane resin
- containing urethane
- component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920002803 thermoplastic polyurethane Polymers 0.000 title claims abstract description 30
- 239000011342 resin composition Substances 0.000 title claims abstract description 16
- 150000002009 diols Chemical class 0.000 claims abstract description 29
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 23
- 239000004417 polycarbonate Substances 0.000 claims abstract description 23
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 9
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 8
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 8
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 239000004593 Epoxy Substances 0.000 claims description 9
- 230000001588 bifunctional effect Effects 0.000 claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 10
- -1 aliphatic diisocyanate compound Chemical class 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- 229920005862 polyol Polymers 0.000 description 7
- 150000003077 polyols Chemical class 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 6
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 5
- 125000005442 diisocyanate group Chemical group 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000007809 chemical reaction catalyst Substances 0.000 description 4
- 239000000976 ink Substances 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 description 2
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 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 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- KIQKWYUGPPFMBV-UHFFFAOYSA-N diisocyanatomethane Chemical compound O=C=NCN=C=O KIQKWYUGPPFMBV-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-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
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 1
- MTZUIIAIAKMWLI-UHFFFAOYSA-N 1,2-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC=C1N=C=O MTZUIIAIAKMWLI-UHFFFAOYSA-N 0.000 description 1
- ZTNJGMFHJYGMDR-UHFFFAOYSA-N 1,2-diisocyanatoethane Chemical compound O=C=NCCN=C=O ZTNJGMFHJYGMDR-UHFFFAOYSA-N 0.000 description 1
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- ZGDSDWSIFQBAJS-UHFFFAOYSA-N 1,2-diisocyanatopropane Chemical compound O=C=NC(C)CN=C=O ZGDSDWSIFQBAJS-UHFFFAOYSA-N 0.000 description 1
- PFUKECZPRROVOD-UHFFFAOYSA-N 1,3,5-triisocyanato-2-methylbenzene Chemical compound CC1=C(N=C=O)C=C(N=C=O)C=C1N=C=O PFUKECZPRROVOD-UHFFFAOYSA-N 0.000 description 1
- PQDIQKXGPYOGDI-UHFFFAOYSA-N 1,3,5-triisocyanatobenzene Chemical compound O=C=NC1=CC(N=C=O)=CC(N=C=O)=C1 PQDIQKXGPYOGDI-UHFFFAOYSA-N 0.000 description 1
- GNQKHBSIBXSFFD-UHFFFAOYSA-N 1,3-diisocyanatocyclohexane Chemical compound O=C=NC1CCCC(N=C=O)C1 GNQKHBSIBXSFFD-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- KIAZLPPFFCCZJS-UHFFFAOYSA-N 1,5-diisocyanato-2,3-dimethylbenzene Chemical compound CC1=CC(N=C=O)=CC(N=C=O)=C1C KIAZLPPFFCCZJS-UHFFFAOYSA-N 0.000 description 1
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- SIYBFAKKDKDECW-UHFFFAOYSA-N 1-ethoxy-2,4-diisocyanatobenzene Chemical compound CCOC1=CC=C(N=C=O)C=C1N=C=O SIYBFAKKDKDECW-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- DXUMYHZTYVPBEZ-UHFFFAOYSA-N 2,4,6-tris(trichloromethyl)-1,3,5-triazine Chemical compound ClC(Cl)(Cl)C1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 DXUMYHZTYVPBEZ-UHFFFAOYSA-N 0.000 description 1
- UXCIJKOCUAQMKD-UHFFFAOYSA-N 2,4-dichlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC(Cl)=C3SC2=C1 UXCIJKOCUAQMKD-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- DZDVHNPXFWWDRM-UHFFFAOYSA-N 2,4-diisocyanato-1-methoxybenzene Chemical compound COC1=CC=C(N=C=O)C=C1N=C=O DZDVHNPXFWWDRM-UHFFFAOYSA-N 0.000 description 1
- LCHAFMWSFCONOO-UHFFFAOYSA-N 2,4-dimethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC(C)=C3SC2=C1 LCHAFMWSFCONOO-UHFFFAOYSA-N 0.000 description 1
- QRHHZFRCJDAUNA-UHFFFAOYSA-N 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound C1=CC(OC)=CC=C1C1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 QRHHZFRCJDAUNA-UHFFFAOYSA-N 0.000 description 1
- CAYJDIDYXCENIR-UHFFFAOYSA-N 2-[5-(oxiran-2-ylmethoxy)pentoxymethyl]oxirane Chemical compound C1OC1COCCCCCOCC1CO1 CAYJDIDYXCENIR-UHFFFAOYSA-N 0.000 description 1
- HKJZKBBNMGMOJV-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane;prop-2-enoic acid Chemical compound OC(=O)C=C.C1OC1COCCCCCCOCC1CO1 HKJZKBBNMGMOJV-UHFFFAOYSA-N 0.000 description 1
- LSVJSOQIMZXASI-UHFFFAOYSA-N 2-[7-(oxiran-2-ylmethoxy)heptoxymethyl]oxirane Chemical compound C1OC1COCCCCCCCOCC1CO1 LSVJSOQIMZXASI-UHFFFAOYSA-N 0.000 description 1
- BCKFVXHJSVKKBD-UHFFFAOYSA-N 2-[8-(oxiran-2-ylmethoxy)octoxymethyl]oxirane Chemical compound C1OC1COCCCCCCCCOCC1CO1 BCKFVXHJSVKKBD-UHFFFAOYSA-N 0.000 description 1
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-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
- 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
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- SDQROPCSKIYYAV-UHFFFAOYSA-N 2-methyloctane-1,8-diol Chemical compound OCC(C)CCCCCCO SDQROPCSKIYYAV-UHFFFAOYSA-N 0.000 description 1
- QZWKEPYTBWZJJA-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine-4,4'-diisocyanate Chemical compound C1=C(N=C=O)C(OC)=CC(C=2C=C(OC)C(N=C=O)=CC=2)=C1 QZWKEPYTBWZJJA-UHFFFAOYSA-N 0.000 description 1
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 1
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 description 1
- 125000004864 4-thiomethylphenyl group Chemical group 0.000 description 1
- ORTNTAAZJSNACP-UHFFFAOYSA-N 6-(oxiran-2-ylmethoxy)hexan-1-ol Chemical compound OCCCCCCOCC1CO1 ORTNTAAZJSNACP-UHFFFAOYSA-N 0.000 description 1
- YGIGBBHIZKMSAW-UHFFFAOYSA-N C(C1CO1)OCCCCOCC1CO1.C(C1CO1)OCCOCC1CO1 Chemical compound C(C1CO1)OCCCCOCC1CO1.C(C1CO1)OCCOCC1CO1 YGIGBBHIZKMSAW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZMDDERVSCYEKPQ-UHFFFAOYSA-N Ethyl (mesitylcarbonyl)phenylphosphinate Chemical compound C=1C=CC=CC=1P(=O)(OCC)C(=O)C1=C(C)C=C(C)C=C1C ZMDDERVSCYEKPQ-UHFFFAOYSA-N 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
- VWYHWAHYVKZKHI-UHFFFAOYSA-N N=C=O.N=C=O.C1=CC(N)=CC=C1C1=CC=C(N)C=C1 Chemical compound N=C=O.N=C=O.C1=CC(N)=CC=C1C1=CC=C(N)C=C1 VWYHWAHYVKZKHI-UHFFFAOYSA-N 0.000 description 1
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- VYGUBTIWNBFFMQ-UHFFFAOYSA-N [N+](#[C-])N1C(=O)NC=2NC(=O)NC2C1=O Chemical group [N+](#[C-])N1C(=O)NC=2NC(=O)NC2C1=O VYGUBTIWNBFFMQ-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- ZCGHEBMEQXMRQL-UHFFFAOYSA-N benzyl 2-carbamoylpyrrolidine-1-carboxylate Chemical compound NC(=O)C1CCCN1C(=O)OCC1=CC=CC=C1 ZCGHEBMEQXMRQL-UHFFFAOYSA-N 0.000 description 1
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 1
- NLUNLVTVUDIHFE-UHFFFAOYSA-N cyclooctylcyclooctane Chemical compound C1CCCCCCC1C1CCCCCCC1 NLUNLVTVUDIHFE-UHFFFAOYSA-N 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 238000009503 electrostatic coating Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- SXCBDZAEHILGLM-UHFFFAOYSA-N heptane-1,7-diol Chemical compound OCCCCCCCO SXCBDZAEHILGLM-UHFFFAOYSA-N 0.000 description 1
- TZMQHOJDDMFGQX-UHFFFAOYSA-N hexane-1,1,1-triol Chemical compound CCCCCC(O)(O)O TZMQHOJDDMFGQX-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- UFUASNAHBMBJIX-UHFFFAOYSA-N propan-1-one Chemical compound CC[C]=O UFUASNAHBMBJIX-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- AFCAKJKUYFLYFK-UHFFFAOYSA-N tetrabutyltin Chemical compound CCCC[Sn](CCCC)(CCCC)CCCC AFCAKJKUYFLYFK-UHFFFAOYSA-N 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- JQPMDTQDAXRDGS-UHFFFAOYSA-N triphenylalumane Chemical compound C1=CC=CC=C1[Al](C=1C=CC=CC=1)C1=CC=CC=C1 JQPMDTQDAXRDGS-UHFFFAOYSA-N 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
本発明は、例えばインキ、塗料、接着剤などに好適に使用される不飽和基含有ウレタン樹脂と、これを含有する活性エネルギー線硬化型樹脂組成物に関する。 The present invention relates to an unsaturated group-containing urethane resin suitably used for, for example, inks, paints, adhesives, and the like, and an active energy ray-curable resin composition containing the same.
不飽和基含有ウレタン樹脂は、柔軟性に富み、強靭な硬化膜を形成し得ることから、活性エネルギー線硬化型の樹脂として、例えばインキ、塗料、接着剤などに広く使用されている（例えば、特許文献１参照。）。
不飽和基含有ウレタン樹脂は、通常、ポリエステルポリオール、ポリエーテルポリオール、ポリカーボネートジオールなどのポリオール成分と、ジイソシアネート成分と、ラジカル重合性の水酸基含有不飽和モノマー成分とを反応させて得られるものであって、ポリオール成分およびジイソシアネート成分からなる繰り返し単位を樹脂骨格とし、この樹脂骨格の末端にラジカル重合性の水酸基含有不飽和モノマー成分が結合した構造となっている。
The unsaturated group-containing urethane resin is usually obtained by reacting a polyol component such as polyester polyol, polyether polyol or polycarbonate diol, a diisocyanate component, and a radical polymerizable hydroxyl group-containing unsaturated monomer component. In this structure, a repeating unit composed of a polyol component and a diisocyanate component is used as a resin skeleton, and a radical polymerizable hydroxyl group-containing unsaturated monomer component is bonded to the terminal of the resin skeleton.
しかしながら、形成される硬化膜の柔軟性や伸びなどを向上させようとして、上述の繰り返し単位からなる樹脂骨格を高分子量化すると、末端の水酸基含有不飽和モノマー成分の不飽和基含有ウレタン樹脂中における含有量（不飽和度）が相対的に低下してしまう。不飽和度が低下すると、不飽和基含有ウレタン樹脂の硬化速度の低下や、架橋密度が不十分となることによる硬化膜の表面硬度や耐汚染性の低下など、硬化性能の劣化が生じる傾向があった。 However, in order to improve the flexibility and elongation of the cured film to be formed, when the resin skeleton composed of the above-mentioned repeating units is increased in molecular weight, the terminal hydroxyl group-containing unsaturated monomer component in the unsaturated group-containing urethane resin Content (unsaturation degree) will fall relatively. When the degree of unsaturation decreases, the curing performance tends to deteriorate, such as the decrease in the curing rate of the unsaturated group-containing urethane resin and the decrease in the surface hardness and contamination resistance of the cured film due to insufficient crosslinking density. there were.
本発明は上記事情に鑑みてなされたもので、十分な硬化性能を備えるとともに、形成される硬化膜の柔軟性、伸びも優れる不飽和基含有ウレタン樹脂とこれを含む活性エネルギー線硬化型樹脂組成物の提供を課題とする。 The present invention has been made in view of the above circumstances, and has an unsaturated group-containing urethane resin having sufficient curing performance and excellent flexibility and elongation of a formed cured film, and an active energy ray-curable resin composition including the same. The issue is to provide goods.
本発明者は鋭意検討した結果、ポリイソシアネート（ｃ）に反応させる成分として、硬化膜に対して柔軟性や伸びを付与するポリカーボネートジオール（ａ）を選択するとともに、２個の水酸基と２個のエチレン性不飽和基とを含有する２官能エポキシ(メタ)アクリレート（ｂ）を使用することによって、硬化性能を劣化させることなく、柔軟性や伸びの良い硬化膜を形成できることに想到して、本発明を完成するに至った。
本発明の不飽和基含有ウレタン樹脂は、ポリカーボネートジオール（ａ）と、分子中に２個の水酸基と２個のエチレン性不飽和基とを含有する２官能エポキシ(メタ)アクリレート（ｂ）と、ポリイソシアネート（ｃ）とを反応させたことを特徴とする。
前記ポリカーボネートジオール（ａ）の数平均分子量は５００〜３０００であることが好ましい。
本発明の不飽和基含有ウレタン樹脂は、数平均分子量が１０００〜１０００００で、不飽和度が０．１〜１ｍｏｌ／ｋｇであることが好ましい。
本発明の活性エネルギー線硬化型樹脂組成物は、前記不飽和基含有ウレタン樹脂１００質量部に対して、光重合開始剤を０．１〜１５質量部配合したことを特徴とする。
As a result of intensive studies, the present inventor has selected a polycarbonate diol (a) that imparts flexibility and elongation to the cured film as a component to be reacted with the polyisocyanate (c), and two hydroxyl groups and two hydroxyl groups. By using a bifunctional epoxy (meth) acrylate (b) containing an ethylenically unsaturated group, it is conceived that a cured film having good flexibility and elongation can be formed without deteriorating the curing performance. The invention has been completed.
The unsaturated group-containing urethane resin of the present invention comprises a polycarbonate diol (a), a bifunctional epoxy (meth) acrylate (b) containing two hydroxyl groups and two ethylenically unsaturated groups in the molecule, It is characterized by reacting with polyisocyanate (c).
The number average molecular weight of the polycarbonate diol (a) is preferably 500 to 3,000.
The unsaturated group-containing urethane resin of the present invention preferably has a number average molecular weight of 1,000 to 100,000 and an unsaturation degree of 0.1 to 1 mol / kg.
The active energy ray-curable resin composition of the present invention is characterized in that 0.1 to 15 parts by mass of a photopolymerization initiator is blended with 100 parts by mass of the unsaturated group-containing urethane resin.
本発明によれば、十分な硬化性能を備えるとともに、形成される硬化膜の柔軟性、伸びも優れる不飽和基含有ウレタン樹脂とこれを含む活性エネルギー線硬化型樹脂組成物を提供できる。 ADVANTAGE OF THE INVENTION According to this invention, while providing sufficient hardening performance, the softness | flexibility of the cured film formed and the unsaturated group containing urethane resin which is excellent in elongation, and the active energy ray hardening-type resin composition containing this can be provided.
以下、本発明を詳細に説明する。
本発明の不飽和基含有ウレタン樹脂は、ポリカーボネートジオール（ａ）（以下、（ａ）成分という場合がある。）と、分子中に２個の水酸基と２個のエチレン性不飽和基とを含有する２官能エポキシ(メタ)アクリレート（ｂ）（以下、（ｂ）成分ということがある。）と、ポリイソシアネート（ｃ）（以下、（ｃ）成分ということがある。）とを反応させたものである。
Hereinafter, the present invention will be described in detail.
The unsaturated group-containing urethane resin of the present invention contains a polycarbonate diol (a) (hereinafter sometimes referred to as component (a)), and two hydroxyl groups and two ethylenically unsaturated groups in the molecule. A reaction between a bifunctional epoxy (meth) acrylate (b) (hereinafter also referred to as component (b)) and polyisocyanate (c) (hereinafter also referred to as component (c)) It is.
ポリカーボネートジオール（ａ）とは、カーボネート結合を介してポリオールに由来する炭化水素基が連結した高分子鎖と、この高分子鎖の両末端に結合した水酸基とを有するものであって、例えば下記式（ａ−１）の構造のものが挙げられる。 The polycarbonate diol (a) has a polymer chain in which a hydrocarbon group derived from a polyol is connected via a carbonate bond, and a hydroxyl group bonded to both ends of the polymer chain. The thing of the structure of (a-1) is mentioned.
式（ａ−１）中のｌ、ｍ、ｎの値には特に制限はないが、ポリカーボネートジオール（ａ）は数平均分子量が５００〜３０００であることが好ましいため、このような数平均分子量となる値であることが好ましい。使用するポリカーボネートジオール（ａ）の数平均分子量がこの範囲未満であると、形成される硬化膜の柔軟性、伸びが乏しくなる場合があり、この範囲を超えると ポリカーボネートジオール（ａ）の結晶性が強くなり、その粘度も上昇するため、製造上取り扱いが困難になる場合がある。 Although there is no restriction | limiting in particular in the value of l, m, n in Formula (a-1), since it is preferable that the polycarbonate diol (a) is 500-3000, such a number average molecular weight and It is preferable that If the number average molecular weight of the polycarbonate diol (a) to be used is less than this range, the cured film formed may have poor flexibility and elongation, and if this range is exceeded, the crystallinity of the polycarbonate diol (a) may be reduced. Since it becomes strong and its viscosity increases, handling in manufacturing may be difficult.
なお、式（ａ−１）中のｌおよびｍの値は、原料として使用されるポリオールの種類により決まる整数であって、ポリオールとしては、炭素数が２〜１０の直鎖および側鎖を持つジオールが挙げられる。具体的には、エチレングリコール、１，３−プロパンジオール、１，４−ブタンジオール、１，５−ペンタンジオール、１，６−ヘキサンジオール、１，７−ヘプタンジオール、１，８−オクタンジオール、１，９−ノナンジオール、１，１０−デカンジオール、３−メチル−１，５−ペンタンジオール、ネオペンチルグリコール、２−メチル−１，８−オクタンジオール、１，４−シクロヘキサンジメタノールなどが挙げられ、これらのうち２種以上を併用したものであってもよい。これらのなかでは、１，５−ペンタンジオールおよび／または１，６−ヘキサンジオールとのポリカーボネートジオールが好ましい。
また、（ａ）成分としては、１種の化合物を単独で使用してもよいし、２種以上を併用してもよい。
In addition, the value of 1 and m in Formula (a-1) is an integer determined by the kind of polyol used as a raw material, Comprising: As a polyol, it has a C2-C10 linear and side chain. Diols are mentioned. Specifically, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-methyl-1,8-octanediol, 1,4-cyclohexanedimethanol, etc. Of these, two or more of them may be used in combination. Of these, polycarbonate diols with 1,5-pentanediol and / or 1,6-hexanediol are preferred.
Moreover, as a component (a), 1 type of compounds may be used independently and 2 or more types may be used together.
分子中に２個の水酸基と２個のエチレン性不飽和基とを含有する２官能エポキシ（メタ）アクリレート（ｂ）とは、例えば下記式（ｂ−２）で表されるような化合物であって、具体的には、プロピレングリコールジグリシジルエーテルの（メタ）アクリル酸付加物、１，６ヘキサンジオールジグリシジルエーテルの（メタ）アクリル酸付加物、エチレングリコールジグリシジルエーテルの（メタ）アクリル酸付加物、１，４−ブタンジオールジグリシジルエーテルの（メタ）アクリル酸付加物、１，５−ペンタンジオールジグリシジルエーテルの（メタ）アクリル酸付加物、１，７−ヘプタンジオールジグリシジルエーテルの（メタ）アクリル酸付加物、１，８−オクタンジオールジグリシジルエーテルの（メタ）アクリル酸付加物などが挙げられる。また、そのほかにも、ネオペンチルグリコールジグリシジルエーテルの（メタ）アクリル酸付加物、ビスフェノールＡジグリシジルエーテルの（メタ）アクリル酸付加物、水添ビスフェノールＡジグリシジルエーテルの（メタ）アクリル酸付加物などが挙げられる。これらのなかでは、プロピレングリコールジグリシジルエーテルのアクリル酸付加物、１，６ヘキサンジオールジグリシジルエーテルのアクリル酸付加物が好ましい。 The bifunctional epoxy (meth) acrylate (b) containing two hydroxyl groups and two ethylenically unsaturated groups in the molecule is, for example, a compound represented by the following formula (b-2). Specifically, (meth) acrylic acid addition product of propylene glycol diglycidyl ether, (meth) acrylic acid addition product of 1,6 hexanediol diglycidyl ether, (meth) acrylic acid addition of ethylene glycol diglycidyl ether 1,4-Butanediol diglycidyl ether (meth) acrylic acid adduct, 1,5-pentanediol diglycidyl ether (meth) acrylic acid adduct, 1,7-heptanediol diglycidyl ether (meth ) Acrylic acid adduct, 1,8-octanediol diglycidyl ether (meth) acrylic acid adduct, etc. It is. In addition, (meth) acrylic acid adduct of neopentyl glycol diglycidyl ether, (meth) acrylic acid adduct of bisphenol A diglycidyl ether, (meth) acrylic acid adduct of hydrogenated bisphenol A diglycidyl ether Etc. Among these, an acrylic acid adduct of propylene glycol diglycidyl ether and an acrylic acid adduct of 1,6 hexanediol diglycidyl ether are preferable.
式（ｂ−１）中、ｐは整数であり、好ましくは２〜６である。
また、（ｂ）成分としては、１種の化合物を単独で使用してもよいし、２種以上を併用してもよい。
In formula (b-1), p is an integer, preferably 2-6.
As the component (b), one type of compound may be used alone, or two or more types may be used in combination.
ポリイソシアネート（ｃ）としては特に制限はないが、例えば、脂肪族系ジイソシアネート化合物、脂環族系ジイソシアネート化合物、芳香族系ジイソシアネート化合物などのジイソシアネート化合物が好ましく使用できる。具体的には、トリレンジイソシアネート、４，４’−ジフェニルメタンジイソシアネート、キシリレンジイソシアネート、キシレンジイソシアネート、ヘキサメチレンジイソシアネート、リジンジイソシアネート、４，４’−メチレンビス（シクロヘキシルイソシアネート）、メチルシクロヘキサン−２，４（又は２，６）−ジイソシアネート、１，３−（イソシアネートメチル）シクロヘキサン、イソホロンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、ダイマー酸ジイソシアネート、ジアニシジンジイソシアネート、フェニルジイソシアネート、ハロゲン化フェニルジイソシアネート、メチレンジイソシアネート、エチレンジイソシアネート、ブチレンジイソシアネート、プロピレンジイソシアネート、オクタデシレンジイソシアネート、１，５−ナフタレンジイソシアネート、ポリメチレンポリフェニレンジイソシアネート、トリフェニルメタントリイソシアネート、ナフタレンジイソシアネート、トリレンジイソシアネート重合体、ジフェニルメタンジイソシアネートの重合体、ヘキサメチレンジイソシアネートの重合体、３−フェニル−２−エチレンジイソシアネート、クメン−２，４−ジイソシアネート、４−メトキシ−１，３−フェニレンジイソシアネート、４−エトキシ−１，３−フェニレンジイソシアネート、２，４’−ジイソシアネートジフェニルエーテル、５，６−ジメチル−１，３−フェニレンジイソシアネート、４，４’−ジイソシアネートジフェニルエーテル、ベンジジンジイゾシアネート、９，１０−アンスラセンジイソシアネート、４，４’−ジイソシアネートベンジル、３，３’−ジメチル−４，４’−ジイソシアネートジフェニルメタン、２，６−ジメチル−４，４’−ジイソシアネートジフェニル、３，３’−ジメトキシ−４，４’−ジイソシアネートジフェニル、１，４−アンスラセンジイソシアネート、フェニレンジイソシアネート、２，４，６−トリレントリイソシアネート、２，４，４’−トリイソシアネートジフェニルエーテル、１，４−テトラメチレンジイソシアネート、１，６−ヘキサメチレンジイソシアネート、１，１０−デカメチレンジイソシアネート、１，３−シクロヘキシレンジイソシアネート、４，４’−メチレン−ビス（シクロヘキシルイソシアネート）などを挙げることができる。 Although there is no restriction | limiting in particular as polyisocyanate (c), For example, diisocyanate compounds, such as an aliphatic diisocyanate compound, an alicyclic diisocyanate compound, and an aromatic diisocyanate compound, can be used preferably. Specifically, tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4 (or 2,6) -diisocyanate, 1,3- (isocyanatomethyl) cyclohexane, isophorone diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate, dianisidine diisocyanate, phenyl diisocyanate, halogenated phenyl diisocyanate, methylene diisocyanate, ethylene diisocyanate, butylene diisocyanate, Propylene diisocyanate, octadecile Diisocyanate, 1,5-naphthalene diisocyanate, polymethylene polyphenylene diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, tolylene diisocyanate polymer, polymer of diphenylmethane diisocyanate, polymer of hexamethylene diisocyanate, 3-phenyl-2-ethylene diisocyanate , Cumene-2,4-diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-ethoxy-1,3-phenylene diisocyanate, 2,4′-diisocyanate diphenyl ether, 5,6-dimethyl-1,3-phenylene Diisocyanate, 4,4'-diisocyanate diphenyl ether, benzidine diisocyanate, 9,10-anthracene diisocyanate 4,4'-diisocyanate benzyl, 3,3'-dimethyl-4,4'-diisocyanate diphenylmethane, 2,6-dimethyl-4,4'-diisocyanate diphenyl, 3,3'-dimethoxy-4,4 ' -Diisocyanate diphenyl, 1,4-anthracene diisocyanate, phenylene diisocyanate, 2,4,6-tolylene triisocyanate, 2,4,4'-triisocyanate diphenyl ether, 1,4-tetramethylene diisocyanate, 1,6-hexa Examples include methylene diisocyanate, 1,10-decamethylene diisocyanate, 1,3-cyclohexylene diisocyanate, and 4,4′-methylene-bis (cyclohexyl isocyanate).
その他には、（ｃ）成分として、トリフェニルメタン−４，４’，４”−トリイソシアネート、１，３，５−トリイソシアナトベンゼン、２，４，６−トリイソシアナトトルエン、４，４’−ジメチルジフェニルメタン−２，２’，５，５’−テトライソシアネートなどの３個以上のイソシアネ−ト基を有するポリイソシアネート化合物；エチレングリコール、プロピレングリコール、１，４−ブチレングリコール、ポリアルキレングリコール、トリメチロ−ルプロパン、ヘキサントリオ−ルなどのポリオールの水酸基に対してイソシアネート基が過剰量となる量のポリイソシアネート化合物を反応させてなる付加物；ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、トリレンジイソシアネート、キシリレンジイソシアネート、４，４’−ジフェニルメタンジイソシアネート、４，４’−メチレンビス（シクロヘキシルイソシアネート）などのビューレットタイプ付加物、イソシアヌル環タイプ付加物なども使用できる。
これら（ｃ）成分としては、１種の化合物を単独で使用してもよいし、２種以上を併用してもよい。
In addition, as component (c), triphenylmethane-4,4 ′, 4 ″ -triisocyanate, 1,3,5-triisocyanatobenzene, 2,4,6-triisocyanatotoluene, 4,4 Polyisocyanate compounds having three or more isocyanate groups such as '-dimethyldiphenylmethane-2,2', 5,5'-tetraisocyanate; ethylene glycol, propylene glycol, 1,4-butylene glycol, polyalkylene glycol, Addition products obtained by reacting an excess amount of a polyisocyanate compound with a hydroxyl group of a polyol such as trimethylolpropane or hexanetriol; hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, xylylene diisocyanate 4 , 4′-diphenylmethane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate) and other burette type adducts, isocyanuric ring type adducts, and the like can also be used.
As these (c) components, one type of compound may be used independently and 2 or more types may be used together.
上述した（ａ）〜（ｃ）成分を反応させた不飽和基含有ウレタン樹脂によれば、（ｃ）成分と反応させる成分として、上述のポリカーボネートジオール（ａ）と、分子中に２個の水酸基と２個のエチレン性不飽和基とを含有する２官能エポキシ(メタ)アクリレート（ｂ）を併用している。そのために、（ｂ）成分に由来する十分な硬化性能を備えるとともに、（ａ）成分に由来する優れた柔軟性、伸びを有する硬化膜を形成することができる。
ここで（ｃ）成分と反応させる成分として、仮に（ｂ）成分のみを使用した場合には、得られる不飽和基含有ウレタン樹脂は、（ｂ）成分に由来する不飽和度が高いものとなるため、硬化性能には優れる傾向にある。しかしながら、形成された硬化膜は柔軟性や伸びが不十分となり、膜性能は良好ではない。また、（ｃ）成分と反応させる成分として、仮に（ａ）成分のみを使用した場合には、不飽和基含有ウレタン樹脂は（ｂ）成分に由来する不飽和基を含有しないため、硬化自体が困難となる。また、（ａ）成分の代わりにポリカーボネートジオール以外の他のジオールを使用した場合や、（ｂ）成分の代わりに２個の水酸基を含有しないような２官能エポキシ(メタ)アクリレートを使用した場合にも、硬化性能などが不十分となる。
According to the unsaturated group-containing urethane resin obtained by reacting the components (a) to (c) described above, as the component to be reacted with the component (c), the above-mentioned polycarbonate diol (a) and two hydroxyl groups in the molecule And a bifunctional epoxy (meth) acrylate (b) containing two ethylenically unsaturated groups. Therefore, while providing sufficient curing performance derived from the component (b), a cured film having excellent flexibility and elongation derived from the component (a) can be formed.
Here, when only the component (b) is used as the component to be reacted with the component (c), the obtained unsaturated group-containing urethane resin has a high degree of unsaturation derived from the component (b). Therefore, the curing performance tends to be excellent. However, the formed cured film has insufficient flexibility and elongation, and the film performance is not good. In addition, when only the component (a) is used as the component to be reacted with the component (c), the unsaturated group-containing urethane resin does not contain the unsaturated group derived from the component (b), so that the curing itself is not performed. It becomes difficult. When a diol other than polycarbonate diol is used instead of component (a), or when bifunctional epoxy (meth) acrylate that does not contain two hydroxyl groups is used instead of component (b) However, the curing performance is insufficient.
本発明の不飽和基含有ウレタン樹脂としては、数平均分子量が１０００〜１０００００で、不飽和度が０．１〜１ｍｏｌ／ｋｇであるものが好ましい。数平均分子量が上記範囲未満では形成される硬化膜の柔軟性や伸びが不十分となる傾向があり、上記範囲を超えると結晶性、粘度が非常に高くなるため製造安定性の確保が難しくなる傾向がある。また、不飽和度が上記範囲未満では硬化性能が不十分となったり、形成される硬化膜の架橋密度が小さくなり、十分な表面硬化性が得られなったりする傾向があり、上記範囲を超えると十分な表面硬化性は得られるが、硬化膜が硬くなり、柔軟性、伸びに乏しくなる傾向がある。より好ましい数平均分子量は１００００〜５００００で、不飽和度は０．１〜０．５ｍｏｌ／ｋｇである。
なお、不飽和度とは、樹脂１ｋｇを製造するにあたって必要な（ｂ）成分のモル数をαｍｏｌとし、（ｂ）成分１分子中に含まれるラジカル重合性不飽和結合の数をβ個とした場合、α×βで計算される値である。
The unsaturated group-containing urethane resin of the present invention preferably has a number average molecular weight of 1000 to 100,000 and an unsaturation degree of 0.1 to 1 mol / kg. If the number average molecular weight is less than the above range, the flexibility and elongation of the cured film to be formed tend to be insufficient, and if it exceeds the above range, the crystallinity and the viscosity become very high, making it difficult to ensure production stability. Tend. Further, if the degree of unsaturation is less than the above range, the curing performance tends to be insufficient, or the crosslinking density of the formed cured film tends to be small, and sufficient surface curability tends to be obtained, which exceeds the above range. And sufficient surface curability can be obtained, but the cured film tends to be hard and tend to be poor in flexibility and elongation. A more preferred number average molecular weight is 10,000 to 50,000, and an unsaturation degree is 0.1 to 0.5 mol / kg.
The degree of unsaturation means that the number of moles of component (b) necessary for producing 1 kg of resin is α mol, and the number of radical polymerizable unsaturated bonds contained in one molecule of component (b) is β. In this case, the value is calculated by α × β.
本発明の不飽和基含有ウレタン樹脂は、上述した（ａ）〜（ｃ）成分を有機溶媒に投入し、反応させることにより製造できる。
反応温度は、通常２０〜２５０℃であり、５０〜１５０℃の範囲が好ましい。また、反応はイソシアネート残基が無くなくなるまで適宜行えばよく、反応時間は通常１０分間〜２４時間である。有機溶媒としては、例えば、炭化水素系、ケトン系、エーテル系、エステル系などの各種溶媒を使用できる。また、反応時には、必要に応じてイソシアネート基と水酸基との反応触媒を添加することができ、このような反応触媒としては、オレイン酸鉛、テトラブチルスズ、三塩化アンチモン、トリフェニルアルミニウム、トリオクチルアルミニウム、ナフテン酸亜鉛、ナフテン酸ジルコニウム、ジブチルスズジラウレート、テトラ−ｎ−ブチル−１，３−ジアセチルオキシジスタノキサン、１，４−ジアザ［２，２，２］ビシクロオクタン、Ｎ−エチルモルホリンなどを挙げることができる。
The unsaturated group-containing urethane resin of the present invention can be produced by introducing the above-described components (a) to (c) into an organic solvent and reacting them.
The reaction temperature is usually 20 to 250 ° C, preferably 50 to 150 ° C. Further, the reaction may be carried out as appropriate until the isocyanate residue disappears, and the reaction time is usually 10 minutes to 24 hours. As the organic solvent, for example, various solvents such as hydrocarbon, ketone, ether and ester can be used. Further, during the reaction, a reaction catalyst of an isocyanate group and a hydroxyl group can be added as necessary. Examples of such a reaction catalyst include lead oleate, tetrabutyltin, antimony trichloride, triphenylaluminum, and trioctylaluminum. , Zinc naphthenate, zirconium naphthenate, dibutyltin dilaurate, tetra-n-butyl-1,3-diacetyloxydistanoxane, 1,4-diaza [2,2,2] bicyclooctane, N-ethylmorpholine, etc. be able to.
（ａ）成分、（ｂ）成分、（ｃ）成分の比率は、不飽和基含有ウレタン樹脂に要求される不飽和度、数平均分子量などに応じて決定すればよいが、例えば、数平均分子量が１０００〜１０００００で、不飽和度が０．１〜１ｍｏｌ／ｋｇの不飽和基含有ウレタン樹脂を製造するためには、（ａ）〜（ｃ）成分の総合計量（固形分）を１００質量％とした場合に、（ａ）成分が６０〜９０質量％、（ｂ）成分が２．５〜１５質量％、（ｃ）成分が５〜２５質量％であることが好ましい。
また、反応触媒を使用する場合には、通常、（ａ）〜（ｃ）成分の総合計量（固形分）１００質量部に対して０．００５〜０．５質量部の範囲で使用する。
The ratio of the component (a), the component (b), and the component (c) may be determined according to the degree of unsaturation and the number average molecular weight required for the unsaturated group-containing urethane resin. Is 1000 to 100,000, and in order to produce an unsaturated group-containing urethane resin having an unsaturation degree of 0.1 to 1 mol / kg, the total measurement (solid content) of the components (a) to (c) is 100% by mass. It is preferable that (a) component is 60-90 mass%, (b) component is 2.5-15 mass%, and (c) component is 5-25 mass%.
Moreover, when using a reaction catalyst, it is normally used in 0.005-0.5 mass part with respect to 100 mass parts of total measurement (solid content) of (a)-(c) component.
本発明の活性エネルギー線硬化型樹脂組成物（以下、樹脂組成物という。）は、上述の不飽和基含有ウレタン樹脂１００質量部に対して、光重合開始剤を０．１〜１５質量部配合することにより得られる。また、この樹脂組成物は、通常、インキ、塗料、接着剤などとして対象物に塗布されるものであるため、塗布性、取り扱い性などの観点から、例えば先に例示したような有機溶媒を適量含有していてもよい。
光重合開始剤としては、例えば、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソブチルエーテル、ジエトキシアセトフェノン、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、ベンジルジメチルケタール、１−ヒドロキシシクロヘキシル−フェニルケトン、２−メチル−２−モルフォリノ（４−チオメチルフェニル）プロパン−１−オン、２−ベンジル−２−ジメチルアミノ−１−（４−モルホリノフェニル）ブタノン、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、２，４，６−トリメチルベンゾイルフェニルエトキシフォスフィンオキサイド、ベンゾフェノン、ｏ−ベンゾイル安息香酸メチル、ヒドロキシベンゾフェノン、２−イソプロピルチオキサントン、２，４−ジメチルチオキサントン、２，４−ジエチルチオキサントン、２，４−ジクロロチオキサントン、２，４，６−トリス（トリクロロメチル）−Ｓ−トリアジン、２−メチル−４，６−ビス（トリクロロ）−Ｓ−トリアジン、２−（４−メトキシフェニル）−４、６−ビス（トリクロロメチル）−Ｓ−トリアジン、鉄−アレン錯体、チタノセン化合物などが挙げられ、これらのうち１種以上を使用できる。
The active energy ray-curable resin composition (hereinafter referred to as a resin composition) of the present invention contains 0.1 to 15 parts by mass of a photopolymerization initiator with respect to 100 parts by mass of the unsaturated group-containing urethane resin. Can be obtained. In addition, since this resin composition is usually applied to an object as ink, paint, adhesive, etc., an appropriate amount of an organic solvent as exemplified above is used from the viewpoints of applicability, handleability, and the like. You may contain.
Examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1- Hydroxycyclohexyl-phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 2,4,6 -Trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide, benzophenone, methyl o-benzoylbenzoate, hydroxybenzophenone, 2-isopropylthioxan 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 2,4,6-tris (trichloromethyl) -S-triazine, 2-methyl-4,6-bis (trichloro ) -S-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -S-triazine, iron-allene complex, titanocene compound, etc., and one or more of these can be used. .
樹脂組成物には、さらに、光重合開始剤と組み合わせて増感色素を併用してもよい。また、必要に応じて、染料、顔料、各種添加剤（重合禁止剤、レベリング剤、消泡剤、タレ止め剤、付着向上剤、塗面改質剤、可塑剤、含窒素化合物など）、架橋剤（例えば、エポキシ樹脂など）などを含んでいてもよい。 A sensitizing dye may be used in combination with the photopolymerization initiator in the resin composition. If necessary, dyes, pigments, various additives (polymerization inhibitors, leveling agents, antifoaming agents, sagging inhibitors, adhesion improvers, coating surface modifiers, plasticizers, nitrogen-containing compounds, etc.), crosslinking An agent (such as an epoxy resin) may be included.
このような樹脂組成物は、例えば、塗料、インキ、接着剤、エッチングレジスト材、ソルダーレジスト材、メッキレジスト材、フォトビアビルドアップ絶縁材、刷板材（平板や凸版用製版材、オフセット印刷用ＰＳ板）情報記録材料、レリーフ像作製材料、光ファイバー用被覆材などに使用することができる。
樹脂組成物を対象物に塗布する際には、スプレー塗装、静電塗装、スピン塗装、浸漬塗装、ローラー塗装、カーテンフロー塗装、シルク印刷などの方法で行えばよい。また、その際の膜厚には特に制限はないが、通常０．５〜１００μｍであり、好ましくは１〜５０μｍである。
樹脂組成物を硬化させる活性エネルギー線には特に制限はなく、例えば紫外線、可視光線、レーザー光（近赤外線、可視光レーザー、紫外線レーザー等）が挙げられ、その照射量は、通常０．２〜２，０００ｍＪ／ｃｍ２、好ましくは１〜１，０００ｍＪ／ｃｍ２である。
Such resin compositions include, for example, paints, inks, adhesives, etching resist materials, solder resist materials, plating resist materials, photovia build-up insulating materials, printing plate materials (plate and letterpress plate making materials, PS for offset printing) Plate) can be used for information recording materials, relief image forming materials, optical fiber coating materials, and the like.
When the resin composition is applied to an object, spray coating, electrostatic coating, spin coating, dip coating, roller coating, curtain flow coating, silk printing, or the like may be used. Moreover, there is no restriction | limiting in particular in the film thickness in that case, Usually, it is 0.5-100 micrometers, Preferably it is 1-50 micrometers.
There is no restriction | limiting in particular in the active energy ray which hardens a resin composition, For example, an ultraviolet-ray, visible light, a laser beam (near infrared rays, visible light laser, an ultraviolet laser etc.) is mentioned, The irradiation amount is 0.2 ~ normally. It is 2,000 mJ / cm 2 , preferably 1 to 1,000 mJ / cm 2 .
以下、本発明について実施例を挙げて具体的に説明する。
［実施例１］
温度計、冷却管、攪拌装置を備えた１Ｌの４口フラスコに、表１に示すように、１，５−ペンタンジオールと１，６−ヘキサンジオールとのポリカーボネートジオール（旭化成ケミカルズ社製ＰＣＤＬ Ｔ−５６５２、数平均分子量：２０００）３４１ｇと、１，６−ヘキサンジオールジグリシジルエーテルのアクリル酸付加物（昭和高分子社製リポキシＳＰ−１６ＬＤＡ）１７ｇと、イソホロンジイソシアネート４３ｇと、ジブチルスズジラウレート（反応触媒）０．２ｇ、メチルエチルケトン（有機溶媒）４００ｇとを投入し、７０℃において約２４時間攪拌し、反応させた。反応後、赤外線吸収スペクトルによりイソシアネート残基が観測されなくなったのを確認した。
このようにして、数平均分子量３００００、不飽和度０．２３ｍｏｌ／ｋｇの不飽和基含有ウレタン樹脂を固形分として５０質量％含有する樹脂液を得た。
ついで、この樹脂液中の不飽和基含有ウレタン樹脂（固形分）１００質量部に対して、１．５質量部の光重合開始剤（チバスペシャリティケミカルズ社製イルガキュア１８４、１−ヒドロキシシクロヘキシル−フェニルケトン）を加えて樹脂組成物を調製し、この樹脂組成物をガラス板上に約１００μｍの膜厚でコーティングした。その後、４０℃において２４時間放置して、メチルエチルケトンを完全に揮発させてから、紫外線を１００ｍＪ／ｃｍ２照射して硬化膜を形成した。そして、この硬化膜について、下記の方法により表面硬化性（指触比較）、柔軟性、伸びを評価した。結果を表１に示す。
Hereinafter, the present invention will be specifically described with reference to examples.
[Example 1]
As shown in Table 1, a polycarbonate diol of 1,5-pentanediol and 1,6-hexanediol (PCDL T-manufactured by Asahi Kasei Chemicals Corporation) was added to a 1 L four-necked flask equipped with a thermometer, a condenser, and a stirrer. 5652, number average molecular weight: 2000) 341 g, 1,6-hexanediol diglycidyl ether acrylic acid adduct (Showa Polymers Lipoxy SP-16LDA) 17 g, isophorone diisocyanate 43 g, dibutyltin dilaurate (reaction catalyst) 0.2 g and 400 g of methyl ethyl ketone (organic solvent) were added, and the mixture was stirred at 70 ° C. for about 24 hours to be reacted. After the reaction, it was confirmed by the infrared absorption spectrum that no isocyanate residue was observed.
Thus, the resin liquid which contains 50 mass% of unsaturated group containing urethane resins of the number average molecular weight 30000 and unsaturation degree 0.23 mol / kg as solid content was obtained.
Next, 1.5 parts by mass of a photopolymerization initiator (Irgacure 184, 1-hydroxycyclohexyl-phenylketone manufactured by Ciba Specialty Chemicals Co., Ltd.) with respect to 100 parts by mass of the unsaturated group-containing urethane resin (solid content) in the resin liquid. ) Was prepared, and this resin composition was coated on a glass plate with a film thickness of about 100 μm. Thereafter, the film was allowed to stand at 40 ° C. for 24 hours to completely volatilize methyl ethyl ketone, and then irradiated with ultraviolet rays at 100 mJ / cm 2 to form a cured film. And about this cured film, surface curability (finger touch comparison), a softness | flexibility, and elongation were evaluated by the following method. The results are shown in Table 1.
＜評価方法＞
（１）表面硬化性
硬化膜の表面を指で触わる指触評価により実施し、３段階で評価した。
タックが全く認められないものを「○」、明らかにタックが認められるものを「×」とし、これらの間の感触のものを「△」として、表に示した。
（２）柔軟性
ガラス板から剥離した硬化膜について、１８０度折り曲げを繰り返し、折り曲げ回数３回以下で折り目にクラックまたは割れが発生した場合を「×」、４〜１０回で発生した場合を「△」、１０回折り曲げてもクラックまたは割れが発生しない場合を「○」として、表に示した。
（３）伸び
ＪＩＳ Ｋ６２５１「加硫ゴムおよび熱可塑性ゴム引っ張り特性の求め方」の試験方法により行い、伸び率が２００％以下の場合を「×」、２００〜３００％の場合を「△」、３００％以上の場合を「○」として、表に示した。
<Evaluation method>
(1) Surface curing property It implemented by the finger touch evaluation which touches the surface of a cured film with a finger, and evaluated in three steps.
The case where no tack was recognized was shown in the table as “◯”, the case where tack was clearly recognized as “x”, and the feel between them as “Δ”.
(2) Flexibility About the cured film peeled from the glass plate, 180 degree bending was repeated, and the case where cracking or cracking occurred on the crease when the number of bendings was 3 times or less was “x”, and the case where it occurred 4 to 10 times. A case where no cracks or cracks were generated even after being bent 10 times was shown as “◯” in the table.
(3) Elongation Performed according to the test method of JIS K6251 “Method of obtaining tensile properties of vulcanized rubber and thermoplastic rubber”, “x” when the elongation is 200% or less, “△” when 200 to 300%. The case of 300% or more is shown in the table as “◯”.
［実施例２〜５および比較例１〜４］
温度計、冷却管、攪拌装置を備えた１Ｌの４口フラスコに投入する成分の種類および質量を表１に示すように変更した以外は、実施例１と同様にして樹脂液を調製し、さらに硬化膜を形成し、評価した。なお、実施例４および５、比較例２〜４では、反応温度を７０℃ではなく８０℃にした。結果を表１に示す。
[Examples 2 to 5 and Comparative Examples 1 to 4]
A resin solution was prepared in the same manner as in Example 1 except that the types and masses of components to be charged into a 1 L four-necked flask equipped with a thermometer, a condenser, and a stirring device were changed as shown in Table 1. A cured film was formed and evaluated. In Examples 4 and 5 and Comparative Examples 2 to 4, the reaction temperature was set to 80 ° C. instead of 70 ° C. The results are shown in Table 1.
表中の各成分の詳細は以下のとおりである。
ポリカーボネートジオール（１）：１，５−ペンタンジオールと１，６−ヘキサンジオールとのポリカーボネートジオール（旭化成ケミカルズ社製ＰＣＤＬ Ｔ−５６５２、数平均分子量：２０００）
ポリカーボネートジオール（２）：１，６−ヘキサンジオールのポリカーボネートジオール（日本ポリウレタン社製ニッポランＮ−９８０Ｒ、数平均分子量：２０００）
ポリカーボネートジオール（３）：１，５−ペンタンジオールと１，６−ヘキサンジオールとのポリカーボネートジオール（旭化成ケミカルズ社製ＰＣＤＬ Ｔ−５６５０Ｊ、数平均分子量：８００）
ポリカプロラクトンジオール：ダイセル化学社製ＰＣＬ−２２０Ｎ、数平均分子量２０００
１，６−ヘキサンジオールグリシジルエーテルのアクリル酸付加物：昭和高分子社製リポキシＳＰ−１６ＬＤＡ
プロピレングリコールジグリシジルエーテルのアクリル酸付加物：共栄社化学社製エポキシエステル７０ＰＡ
グリシジルメタクリレートのアクリル酸付加物：新中村化学社製ＮＫエステル７０１Ａ
The details of each component in the table are as follows.
Polycarbonate diol (1): Polycarbonate diol of 1,5-pentanediol and 1,6-hexanediol (PCDL T-5562 manufactured by Asahi Kasei Chemicals Corporation, number average molecular weight: 2000)
Polycarbonate diol (2): 1,6-hexanediol polycarbonate diol (Nipporan N-980R, number average molecular weight: 2000, manufactured by Nippon Polyurethane)
Polycarbonate diol (3): Polycarbonate diol of 1,5-pentanediol and 1,6-hexanediol (PCDL T-5650J, manufactured by Asahi Kasei Chemicals Corporation, number average molecular weight: 800)
Polycaprolactone diol: PCL-220N manufactured by Daicel Chemical Industries, number average molecular weight 2000
Acrylic acid adduct of 1,6-hexanediol glycidyl ether: Lipoxy SP-16LDA manufactured by Showa Polymer Co., Ltd.
Acrylic acid adduct of propylene glycol diglycidyl ether: Epoxy ester 70PA manufactured by Kyoeisha Chemical Co., Ltd.
Acrylic acid adduct of glycidyl methacrylate: NK ester 701A manufactured by Shin-Nakamura Chemical Co., Ltd.
表１から明らかなように、（ｃ）成分と反応させる成分として、ポリカーボネートジオール（ａ）と、分子中に２個の水酸基と２個のエチレン性不飽和基とを含有する２官能エポキシ(メタ)アクリレート（ｂ）とを併用した各実施例の不飽和基含有ウレタン樹脂は、十分な硬化性能を備え、また、柔軟性、伸びに優れる硬化膜を形成することができた。
As is apparent from Table 1, as the component to be reacted with the component (c), a polycarbonate diol (a) and a bifunctional epoxy (meta) containing two hydroxyl groups and two ethylenically unsaturated groups in the molecule. ) The unsaturated group-containing urethane resin of each example used in combination with acrylate (b) was able to form a cured film having sufficient curing performance and excellent in flexibility and elongation.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006314398A JP5068513B2 (en) | 2006-11-21 | 2006-11-21 | Unsaturated group-containing urethane resin and active energy ray-curable resin composition containing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006314398A JP5068513B2 (en) | 2006-11-21 | 2006-11-21 | Unsaturated group-containing urethane resin and active energy ray-curable resin composition containing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2008127475A true JP2008127475A (en) | 2008-06-05 |
| JP5068513B2 JP5068513B2 (en) | 2012-11-07 |
Family
ID=39553652
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2006314398A Active JP5068513B2 (en) | 2006-11-21 | 2006-11-21 | Unsaturated group-containing urethane resin and active energy ray-curable resin composition containing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5068513B2 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009154224A1 (en) * | 2008-06-20 | 2009-12-23 | ハンツマン・アドヴァンスト・マテリアルズ・（スイッツランド）・ゲーエムベーハー | Active-energy-ray-curable sealing agent composition, and member having sealing layer attached thereto |
| JP2010053231A (en) * | 2008-08-27 | 2010-03-11 | Aica Kogyo Co Ltd | Resin composition and molded product |
| WO2010147090A1 (en) | 2009-06-15 | 2010-12-23 | 東洋インキ製造株式会社 | Urethane resin, adhesive curable with actinic energy rays, and back protective sheet for solar cell |
| WO2012026475A1 (en) * | 2010-08-25 | 2012-03-01 | 宇部興産株式会社 | Aqueous polyurethane resin dispersion, manufacturing method therefor, and use therefor |
| JP2012111852A (en) * | 2010-11-25 | 2012-06-14 | Toyo Ink Sc Holdings Co Ltd | Urethane resin containing (meth)acryloyl group, active energy ray curable adhesive containing the urethane resin and back surface protective sheet for solar cell |
| JP2013166877A (en) * | 2012-02-16 | 2013-08-29 | Nitto Denko Corp | Method for producing radiation-curable self-adhesive composition, radiation-curable self-adhesive composition obtained by the production method, and self-adhesive sheet using the self-adhesive composition |
| WO2014106939A1 (en) * | 2013-01-07 | 2014-07-10 | 宇部興産株式会社 | Aqueous resin dispersion and use of same |
| WO2015133535A1 (en) * | 2014-03-05 | 2015-09-11 | グンゼ株式会社 | Laminate body |
| JP2016505648A (en) * | 2012-11-16 | 2016-02-25 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Polyurethane, its dispersions, their production and use |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11104758B2 (en) | 2018-06-29 | 2021-08-31 | 3M Innovative Properties Company | Orthodontic articles prepared using a polycarbonate diol, and methods of making same |
| CN112367959A (en) | 2018-06-29 | 2021-02-12 | 3M创新有限公司 | Orthodontic articles comprising cured free-radically polymerizable compositions having improved strength in aqueous environments |
| JP2021523247A (en) | 2018-06-29 | 2021-09-02 | スリーエム イノベイティブ プロパティズ カンパニー | A photopolymerizable composition comprising a polycarbonate diol, an article, and a polyurethane methacrylate polymer prepared using the method. |
| EP3813764A2 (en) | 2018-06-29 | 2021-05-05 | 3M Innovative Properties Company | Orthodontic articles prepared using a polycarbonate diol, polymerizable compositions, and methods of making the articles |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004035715A (en) * | 2002-07-03 | 2004-02-05 | Mitsubishi Rayon Co Ltd | Composition curable with active energy rays, for optical disc, and optical disc |
-
2006
- 2006-11-21 JP JP2006314398A patent/JP5068513B2/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004035715A (en) * | 2002-07-03 | 2004-02-05 | Mitsubishi Rayon Co Ltd | Composition curable with active energy rays, for optical disc, and optical disc |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2505576C2 (en) * | 2008-06-20 | 2014-01-27 | Хантсман Эдванст Матириалз (Свитзеленд) Гмбх | Composition of sealing agent curable by highly active radiation and component with sealing layer |
| CN102066517A (en) * | 2008-06-20 | 2011-05-18 | 亨斯迈先进材料（瑞士）有限公司 | Active-energy-ray-curable sealing agent composition, and member having sealing layer attached thereto |
| JPWO2009154224A1 (en) * | 2008-06-20 | 2011-12-01 | ハンツマン・アドヴァンスト・マテリアルズ・（スイッツランド）・ゲーエムベーハー | Active energy ray-curable sealant composition and member with seal layer |
| WO2009154224A1 (en) * | 2008-06-20 | 2009-12-23 | ハンツマン・アドヴァンスト・マテリアルズ・（スイッツランド）・ゲーエムベーハー | Active-energy-ray-curable sealing agent composition, and member having sealing layer attached thereto |
| US8404757B2 (en) | 2008-06-20 | 2013-03-26 | Huntsman International Llc | Radiation curable sealing agent composition and member with sealing layer |
| KR101623770B1 (en) * | 2008-06-20 | 2016-05-24 | 훈츠만 어드밴스트 머티리얼스(스위처랜드) 게엠베하 | Active-Energy-Ray-Curable Sealing Agent Composition, And Member Having Sealing Layer Attached Thereto |
| JP2010053231A (en) * | 2008-08-27 | 2010-03-11 | Aica Kogyo Co Ltd | Resin composition and molded product |
| WO2010147090A1 (en) | 2009-06-15 | 2010-12-23 | 東洋インキ製造株式会社 | Urethane resin, adhesive curable with actinic energy rays, and back protective sheet for solar cell |
| US8404969B2 (en) | 2009-06-15 | 2013-03-26 | Toyo Ink Sc Holdings Co., Ltd. | Urethane resin, actinic energy ray curable adhesive, and back protective sheet for solar cell |
| WO2012026475A1 (en) * | 2010-08-25 | 2012-03-01 | 宇部興産株式会社 | Aqueous polyurethane resin dispersion, manufacturing method therefor, and use therefor |
| JP2012111852A (en) * | 2010-11-25 | 2012-06-14 | Toyo Ink Sc Holdings Co Ltd | Urethane resin containing (meth)acryloyl group, active energy ray curable adhesive containing the urethane resin and back surface protective sheet for solar cell |
| JP2013166877A (en) * | 2012-02-16 | 2013-08-29 | Nitto Denko Corp | Method for producing radiation-curable self-adhesive composition, radiation-curable self-adhesive composition obtained by the production method, and self-adhesive sheet using the self-adhesive composition |
| JP2016505648A (en) * | 2012-11-16 | 2016-02-25 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Polyurethane, its dispersions, their production and use |
| WO2014106939A1 (en) * | 2013-01-07 | 2014-07-10 | 宇部興産株式会社 | Aqueous resin dispersion and use of same |
| WO2015133535A1 (en) * | 2014-03-05 | 2015-09-11 | グンゼ株式会社 | Laminate body |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5068513B2 (en) | 2012-11-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5068513B2 (en) | Unsaturated group-containing urethane resin and active energy ray-curable resin composition containing the same | |
| WO2009154224A1 (en) | Active-energy-ray-curable sealing agent composition, and member having sealing layer attached thereto | |
| JP4953381B2 (en) | Reactive polyurethane compound, method for producing the same, resin composition and cured product thereof | |
| TW200523285A (en) | Photocrosslinkable polyurethanes | |
| JP5482234B2 (en) | Urethane-modified acrylic resin and coating agent and adhesive using the same | |
| JP2007314768A (en) | Photocurable resin composition and photocurable coating | |
| JP2016194061A (en) | Active energy ray-curable resin composition and method for producing the same, coating agent using the same, and sheet | |
| JP2011162646A (en) | Curable composition | |
| JP3830330B2 (en) | Photosensitive material | |
| KR20090100382A (en) | Aqueous urethane resin composition | |
| JPS63275619A (en) | Composition for coating optical fiber | |
| JP3301447B2 (en) | Urethane / unsaturated organo oligomers and method for producing the same | |
| JP7054753B1 (en) | Hardcourt resin composition | |
| JP2017048301A (en) | Urethane (meth)acrylate, active energy ray-curable composition and cured product thereof | |
| WO1997000276A1 (en) | Active energy ray-curable resin compositions, a cured article and an optical lens obtained therefrom, and novel (meth)acrylate compounds therefor | |
| JP2019081830A (en) | Method for producing urethane acrylate resin and method for producing photocuring composition | |
| DE4027770A1 (en) | LIQUID, RADIANT-COVERABLE COATING MEASUREMENT FOR THE COATING OF GLASS SURFACES | |
| JP3436410B2 (en) | Active energy ray-curable adhesive | |
| JP4017055B2 (en) | (Meth) acrylic acid ester and resin composition using the same | |
| JP3995191B2 (en) | Urethane (meth) acrylate and active energy ray-curable urethane (meth) acrylate composition containing the same | |
| JP3741085B2 (en) | Photocurable resin composition | |
| JP2001305726A (en) | Photosensitive composition | |
| JP2000219850A (en) | Composition for adhesive, and cured product thereof | |
| JP2005097373A (en) | Energy ray-curable resin composition and coating material using the same | |
| JP4017056B2 (en) | (Meth) acrylic acid ester and resin composition using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20090811 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120508 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120702 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20120724 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20120815 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150824 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5068513 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |