JP6414057B2 - Photocurable resin and photocurable resin composition - Google Patents
Photocurable resin and photocurable resin composition Download PDFInfo
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- JP6414057B2 JP6414057B2 JP2015521402A JP2015521402A JP6414057B2 JP 6414057 B2 JP6414057 B2 JP 6414057B2 JP 2015521402 A JP2015521402 A JP 2015521402A JP 2015521402 A JP2015521402 A JP 2015521402A JP 6414057 B2 JP6414057 B2 JP 6414057B2
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- Prior art keywords
- formula
- photocurable resin
- represented
- acrylate
- meth
- Prior art date
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- 239000011347 resin Substances 0.000 title claims description 82
- 229920005989 resin Polymers 0.000 title claims description 82
- 239000011342 resin composition Substances 0.000 title claims description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 41
- -1 acrylate compound Chemical class 0.000 claims description 32
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 20
- 239000003999 initiator Substances 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 125000004185 ester group Chemical group 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 description 25
- 230000001070 adhesive effect Effects 0.000 description 25
- 239000005062 Polybutadiene Substances 0.000 description 24
- 229920002857 polybutadiene Polymers 0.000 description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 239000012299 nitrogen atmosphere Substances 0.000 description 19
- 150000001875 compounds Chemical class 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 12
- DPNXHTDWGGVXID-UHFFFAOYSA-N 2-isocyanatoethyl prop-2-enoate Chemical compound C=CC(=O)OCCN=C=O DPNXHTDWGGVXID-UHFFFAOYSA-N 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 9
- 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 9
- 239000005058 Isophorone diisocyanate Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 239000011521 glass Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000005056 polyisocyanate Substances 0.000 description 5
- 229920001228 polyisocyanate Polymers 0.000 description 5
- 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 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical class C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 4
- LUCXVPAZUDVVBT-UHFFFAOYSA-N methyl-[3-(2-methylphenoxy)-3-phenylpropyl]azanium;chloride Chemical compound Cl.C=1C=CC=CC=1C(CCNC)OC1=CC=CC=C1C LUCXVPAZUDVVBT-UHFFFAOYSA-N 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 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 4
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 3
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000004820 Pressure-sensitive adhesive Substances 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
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 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
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 2
- 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 2
- ROWKJAVDOGWPAT-UHFFFAOYSA-N Acetoin Chemical compound CC(O)C(C)=O ROWKJAVDOGWPAT-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 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
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- QNRMTGGDHLBXQZ-UHFFFAOYSA-N buta-1,2-diene Chemical group CC=C=C QNRMTGGDHLBXQZ-UHFFFAOYSA-N 0.000 description 2
- 150000001728 carbonyl compounds Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000000016 photochemical curing Methods 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 2
- UPPUJFRSINZXTE-UHFFFAOYSA-N (2,2,3,3,4-pentamethylpiperidin-1-yl) 2-methylprop-2-enoate Chemical compound CC1CCN(OC(=O)C(C)=C)C(C)(C)C1(C)C UPPUJFRSINZXTE-UHFFFAOYSA-N 0.000 description 1
- 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 1
- SWFHGTMLYIBPPA-UHFFFAOYSA-N (4-methoxyphenyl)-phenylmethanone Chemical compound C1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 SWFHGTMLYIBPPA-UHFFFAOYSA-N 0.000 description 1
- QXRRAZIZHCWBQY-UHFFFAOYSA-N 1,1-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1(CN=C=O)CCCCC1 QXRRAZIZHCWBQY-UHFFFAOYSA-N 0.000 description 1
- NXTLMBKGEDJACS-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)-3-methylbenzene Chemical compound CC1=CC=CC(CN=C=O)=C1CN=C=O NXTLMBKGEDJACS-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- 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
- 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
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-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
- 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 1
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- GYHPTPQZVBYHLC-UHFFFAOYSA-N 2-[2-[2-[2-(2-ethylhexanoyloxy)ethoxy]ethoxy]ethoxy]ethyl 2-ethylhexanoate Chemical compound CCCCC(CC)C(=O)OCCOCCOCCOCCOC(=O)C(CC)CCCC GYHPTPQZVBYHLC-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
- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical class OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-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
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- BUZICZZQJDLXJN-UHFFFAOYSA-N 3-azaniumyl-4-hydroxybutanoate Chemical compound OCC(N)CC(O)=O BUZICZZQJDLXJN-UHFFFAOYSA-N 0.000 description 1
- BVEYJWQCMOVMAR-UHFFFAOYSA-N 5-Hydroxy-4-octanone Chemical compound CCCC(O)C(=O)CCC BVEYJWQCMOVMAR-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 235000008098 Oxalis acetosella Nutrition 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene 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
- 244000126309 Trifolium dubium Species 0.000 description 1
- RVWADWOERKNWRY-UHFFFAOYSA-N [2-(dimethylamino)phenyl]-phenylmethanone Chemical compound CN(C)C1=CC=CC=C1C(=O)C1=CC=CC=C1 RVWADWOERKNWRY-UHFFFAOYSA-N 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 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
- 150000008366 benzophenones Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- JGCWKVKYRNXTMD-UHFFFAOYSA-N bicyclo[2.2.1]heptane;isocyanic acid Chemical compound N=C=O.N=C=O.C1CC2CCC1C2 JGCWKVKYRNXTMD-UHFFFAOYSA-N 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 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
- 239000003054 catalyst Substances 0.000 description 1
- 210000003109 clavicle Anatomy 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000002270 dispersing agent Substances 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
- 239000012776 electronic material Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- QKLCQKPAECHXCQ-UHFFFAOYSA-N ethyl phenylglyoxylate Chemical compound CCOC(=O)C(=O)C1=CC=CC=C1 QKLCQKPAECHXCQ-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- GFAZHVHNLUBROE-UHFFFAOYSA-N hydroxymethyl propionaldehyde Natural products CCC(=O)CO GFAZHVHNLUBROE-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002184 metal Substances 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
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- DVQHRBFGRZHMSR-UHFFFAOYSA-N sodium methyl 2,2-dimethyl-4,6-dioxo-5-(N-prop-2-enoxy-C-propylcarbonimidoyl)cyclohexane-1-carboxylate Chemical compound [Na+].C=CCON=C(CCC)[C-]1C(=O)CC(C)(C)C(C(=O)OC)C1=O DVQHRBFGRZHMSR-UHFFFAOYSA-N 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])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])[H] 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/81—Unsaturated isocyanates or isothiocyanates
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- 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
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/067—Polyurethanes; Polyureas
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—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
Description
本発明は、光硬化性樹脂および光硬化性樹脂組成物に関する。 The present invention relates to a photocurable resin and a photocurable resin composition.
近年、電子材料の接着剤や粘着剤として、光硬化性樹脂を用いた光硬化性樹脂組成物が知られている。
例えば、特許文献１には、「主鎖に水添ポリブタジエン骨格を有するポリオールを多官能性化合物を用いて高分子量化させ、次いで得られた分子量が１０，０００〜１００，０００の高分子量化水添ポリブタジエンポリオールの残存する水酸基に、該高分子量化水添ポリブタジエンポリオールの水酸基に対して２５ｍｏｌ％〜１００ｍｏｌ％の（メタ）アクリロイル基を導入させて得られるウレタン（メタ）アクリレートオリゴマー、および単官能（メタ）アクリレートを含有してなる放射線硬化型粘着剤組成物。」が記載されている（［請求項１］）。
また、特許文献２には、「複数の光硬化性官能基を有する水添ブタジエン系重合体、単一の光硬化性官能基を有するモノマー及び光重合開始剤を含有する光硬化性樹脂組成物の硬化物からなることを特徴とする粘着シート。」が記載されている（［請求項１］）。In recent years, a photocurable resin composition using a photocurable resin is known as an adhesive or pressure-sensitive adhesive for electronic materials.
For example, Patent Document 1 states that “a polyol having a hydrogenated polybutadiene skeleton in the main chain is made to have a high molecular weight using a polyfunctional compound, and then the high molecular weight water having a molecular weight of 10,000 to 100,000 is obtained. A urethane (meth) acrylate oligomer obtained by introducing 25 mol% to 100 mol% of a (meth) acryloyl group with respect to the hydroxyl group of the high molecular weight hydrogenated polybutadiene polyol, and a monofunctional ( Radiation curable pressure-sensitive adhesive composition containing (meth) acrylate "([Claim 1]).
Patent Document 2 discloses that “a photocurable resin composition containing a hydrogenated butadiene-based polymer having a plurality of photocurable functional groups, a monomer having a single photocurable functional group, and a photopolymerization initiator”. The pressure-sensitive adhesive sheet is characterized by comprising a cured product of "(Claim 1)".
しかしながら、特許文献１および２などに記載された光硬化性樹脂（ウレタン（メタ）アクリレートオリゴマー，水添ブタジエン系重合体）を用いた光硬化性樹脂組成物は、接着強度が低くなる場合があり、特に、高温高湿下での接着強度が劣ることが明らかとなった。 However, the photocurable resin composition using the photocurable resin (urethane (meth) acrylate oligomer, hydrogenated butadiene-based polymer) described in Patent Documents 1 and 2 may have low adhesive strength. In particular, it became clear that the adhesive strength under high temperature and high humidity was inferior.
そこで、本発明は、接着強度が高く、高温高湿下での接着性も良好な光硬化性樹脂組成物およびそれに用いる光硬化性樹脂を提供することを課題とする。 Then, this invention makes it a subject to provide the photocurable resin composition with high adhesive strength and the adhesiveness under high temperature, high humidity, and a photocurable resin used therefor.
本発明者らは、上記課題を解決するため鋭意検討した結果、末端に所定のウレタン結合を介して（メタ）アクリロイルオキシ基を有し、主鎖骨格に１，２−ブタジエン骨格由来の繰り返し単位を特定の割合で有し、かつ、ウレタン結合を２個以上有する光硬化性樹脂を用いることにより、接着強度が高く、高温高湿下での接着性も良好な光硬化性樹脂組成物となることを見出し、本発明を完成させた。
すなわち、以下の構成により上記課題を解決できることを見出した。As a result of intensive studies to solve the above problems, the present inventors have a (meth) acryloyloxy group at a terminal via a predetermined urethane bond, and a repeating unit derived from a 1,2-butadiene skeleton in the main chain skeleton. By using a photocurable resin having a specific ratio and having two or more urethane bonds, a photocurable resin composition having high adhesive strength and good adhesion under high temperature and high humidity is obtained. As a result, the present invention has been completed.
That is, it has been found that the above problem can be solved by the following configuration.
（１）主鎖骨格に下記式（Ｉａ）〜（Ｉｃ）で表される繰り返し単位のうち、少なくとも下記式（Ｉｂ）で表される繰り返し単位を有する光硬化性樹脂であって、
下記式（Ｉａ）で表される繰り返し単位の含有量が、下記式（Ｉａ）〜（Ｉｃ）で表される全繰り返し単位に対して０〜４０モル％であり、
下記式（Ｉｂ）で表される繰り返し単位の含有量が、下記式（Ｉａ）〜（Ｉｃ）で表される全繰り返し単位に対して６０〜１００モル％であり、
下記式（Ｉｃ）で表される繰り返し単位の含有量が、下記式（Ｉａ）〜（Ｉｃ）で表される全繰り返し単位に対して０〜１０モル％であり、
末端の少なくとも１つに下記式（ＩＩａ）または下記式（ＩＩｂ）で表される構造を有し、
主鎖骨格に下記式（ＩＩＩ）で表されるウレタン結合を少なくとも２個以上有する、光硬化性樹脂。(1) A photocurable resin having at least a repeating unit represented by the following formula (Ib) among repeating units represented by the following formulas (Ia) to (Ic) in the main chain skeleton,
The content of the repeating unit represented by the following formula (Ia) is 0 to 40 mol% with respect to all the repeating units represented by the following formulas (Ia) to (Ic),
The content of the repeating unit represented by the following formula (Ib) is 60 to 100 mol% with respect to all the repeating units represented by the following formulas (Ia) to (Ic),
The content of the repeating unit represented by the following formula (Ic) is 0 to 10 mol% with respect to all the repeating units represented by the following formulas (Ia) to (Ic),
At least one of the terminals has a structure represented by the following formula (IIa) or the following formula (IIb);
A photocurable resin having at least two urethane bonds represented by the following formula (III) in the main chain skeleton.
（２）上記（１）に記載の光硬化性樹脂と、（メタ）アクリロイルオキシ基を１個有する単官能（メタ）アクリレート化合物と、光重合開始剤とを含有する光硬化性樹脂組成物。 (2) A photocurable resin composition comprising the photocurable resin according to (1) above, a monofunctional (meth) acrylate compound having one (meth) acryloyloxy group, and a photopolymerization initiator.
以下に示すように、本発明によれば、接着強度が高く、高温高湿下での接着性も良好な光硬化性樹脂組成物およびそれに用いる光硬化性樹脂を提供することができる。 As shown below, according to the present invention, it is possible to provide a photocurable resin composition having high adhesive strength and good adhesion under high temperature and high humidity, and a photocurable resin used therefor.
〔光硬化性樹脂〕
本発明の光硬化性樹脂は、主鎖骨格に後述する式（Ｉｂ）で表される所定の繰り返し単位を特定量有し、末端の少なくとも１つに後述する式（ＩＩａ）または式（ＩＩｂ）で表される構造を有し、主鎖骨格に後述する式（ＩＩＩ）で表されるウレタン結合を少なくとも２個以上有する、光硬化性樹脂である。[Photocurable resin]
The photocurable resin of the present invention has a specific amount of a predetermined repeating unit represented by the formula (Ib) described later in the main chain skeleton, and the formula (IIa) or the formula (IIb) described later at at least one of the terminals. And a photocurable resin having at least two urethane bonds represented by the formula (III) described later in the main chain skeleton.
＜主鎖骨格＞
（繰り返し単位）
本発明の光硬化性樹脂は、主鎖骨格に下記式（Ｉａ）〜（Ｉｃ）で表される繰り返し単位のうち、少なくとも下記式（Ｉｂ）で表される繰り返し単位を有する。
本発明においては、下記式（Ｉａ）で表される繰り返し単位の含有量は、下記式（Ｉａ）〜（Ｉｃ）で表される全繰り返し単位に対して０〜４０モル％であり、５〜３０モル％であるのが好ましい。
また、下記式（Ｉｂ）で表される繰り返し単位の含有量は、下記式（Ｉａ）〜（Ｉｃ）で表される全繰り返し単位に対して６０〜１００モル％であり、６５〜９５モル％であるのが好ましく、７０〜９５モル％であるのがより好ましい。
また、下記式（Ｉｃ）で表される繰り返し単位の含有量は、下記式（Ｉａ）〜（Ｉｃ）で表される全繰り返し単位に対して０〜１０モル％であり、０〜５モル％であるのが好ましい。<Main chain skeleton>
(Repeat unit)
The photocurable resin of the present invention has at least a repeating unit represented by the following formula (Ib) among repeating units represented by the following formulas (Ia) to (Ic) in the main chain skeleton.
In the present invention, the content of the repeating unit represented by the following formula (Ia) is 0 to 40 mol% with respect to all the repeating units represented by the following formulas (Ia) to (Ic), It is preferably 30 mol%.
Moreover, content of the repeating unit represented by the following formula (Ib) is 60 to 100 mol% with respect to all repeating units represented by the following formulas (Ia) to (Ic), and 65 to 95 mol%. It is preferable that it is 70 to 95 mol%.
Moreover, content of the repeating unit represented by the following formula (Ic) is 0 to 10 mol% with respect to all repeating units represented by the following formulas (Ia) to (Ic), and 0 to 5 mol%. Is preferred.
ここで、「全繰り返し単位に対するモル％」とは、モノマー（１，３−ブタジエン、１，２−ブタジエン、スチレン）の仕込み比から算出される値をいうが、本発明においては、１Ｈ−ＮＭＲ（プロトンＮＭＲ）から測定することができる。具体的には、１，２構造の−ＣＨ＝ＣＨ2−または−ＣＨ2−ＣＨ3のプロトンと、１，４構造の−ＣＨ＝ＣＨ−または−ＣＨ2−ＣＨ2−のプロトンの積分値により算出することができる。Here, “mol% with respect to all repeating units” refers to a value calculated from the charging ratio of monomers (1,3-butadiene, 1,2-butadiene, styrene). In the present invention, 1 H— It can be measured from NMR (proton NMR). Specifically, 1,2 structure -CH = CH 2 - or a proton of -CH 2 -CH 3, 1,4 structure -CH = CH- or -CH 2 -CH 2 - the integral value of proton Can be calculated.
また、上記式（Ｉａ）〜（Ｉｃ）で表される繰り返し単位の配列は、これらがランダムに配列されていても、ブロック的に配列されていても、あるいは、両者の混合であってもよい。 Moreover, the arrangement of the repeating units represented by the above formulas (Ia) to (Ic) may be arranged randomly, arranged in blocks, or a mixture of both. .
本発明においては、このような繰り返し単位、特に、上記式（Ｉｂ）で表される繰り返し単位を６０〜１００モル％有する光硬化性樹脂を用いることにより、高温高湿下での接着性が良好な光硬化性樹脂組成物となる。
これは、結晶構造を採らず、柔軟性が良好となり、高温高湿下においても基材の寸法変化などに追従することができるためと考えられる。このことは、後述する比較例５に示すように、上記式（Ｉｂ）で表される繰り返し単位のモル％を満たさない場合の結果、すなわち、上記式（Ｉａ）で表される繰り返し単位が多く含まれる場合は、光硬化性樹脂が結晶構造を採り、粘度が上昇するため、希釈剤が必要となり、その結果、接着性が低下するという結果からも推察することができる。In the present invention, by using a photocurable resin having 60 to 100 mol% of such a repeating unit, particularly the repeating unit represented by the above formula (Ib), the adhesiveness under high temperature and high humidity is good. A light-curable resin composition.
This is presumably because the crystal structure is not adopted, the flexibility is good, and the dimensional change of the substrate can be followed even under high temperature and high humidity. As shown in Comparative Example 5 described later, this is a result of not satisfying the mol% of the repeating unit represented by the above formula (Ib), that is, many repeating units represented by the above formula (Ia). If included, the photocurable resin takes a crystal structure and the viscosity increases, so that a diluent is required, and as a result, it can be inferred from the result that the adhesiveness is lowered.
（ウレタン結合）
本発明の光硬化性樹脂は、主鎖骨格に下記式（ＩＩＩ）で表されるウレタン結合を少なくとも２個以上有する。(Urethane bond)
The photocurable resin of the present invention has at least two urethane bonds represented by the following formula (III) in the main chain skeleton.
ここで、上記式（ＩＩＩ）で表されるウレタン結合は、後述する末端構造に含まれるウレタン結合とは異なり、主鎖骨格に含まれるウレタン結合であり、例えば、後述する調製方法に示すように、両末端に水酸基を有する水添ポリブタジエン系重合体とイソシアネート基を２個有するジイソシアネート化合物とを反応（二量化）させる際に生成する下記式（ＩＩＩａ）で表される構造に含まれるウレタン結合や、両末端に水酸基を有する水添ポリブタジエン系重合体とイソシアネート基を３個有するトリイソシアネート化合物（例えば、ジイソシアネート化合物のビウレット体、イソシアヌレート体、アタクト体など）とを反応（三量化）させる際に生成する下記式（ＩＩＩｂ）で表される構造に含まれるウレタン結合であるのが好ましい。 Here, the urethane bond represented by the formula (III) is a urethane bond contained in the main chain skeleton, unlike the urethane bond contained in the terminal structure described later. For example, as shown in the preparation method described later, A urethane bond contained in a structure represented by the following formula (IIIa) produced when a hydrogenated polybutadiene-based polymer having hydroxyl groups at both ends and a diisocyanate compound having two isocyanate groups are reacted (dimerized); When reacting (trimerizing) a hydrogenated polybutadiene-based polymer having hydroxyl groups at both ends and a triisocyanate compound having three isocyanate groups (for example, biuret, isocyanurate, and attack of a diisocyanate compound). A urethane bond contained in the structure represented by the following formula (IIIb) to be generated is preferable.
本発明においては、このようなウレタン結合を主鎖骨格に２個以上有する光硬化性樹脂を用いることにより、接着強度が高い光硬化性樹脂組成物となる。
これは、末端構造に含まれるウレタン結合とは別に、主鎖骨格にウレタン結合を含むことにより、隣接する光硬化性樹脂の主鎖骨格に含まれるウレタン結合のＮ−Ｈ基同士で水素結合が生じやすくなったためと考えられる。このことは、後述する比較例６に示すように、主鎖骨格にウレタン結合を有さない場合の結果からも推察することができる。
また、接着強度および硬化物物性がより高くなる理由から、主鎖骨格におけるウレタン結合は、２〜１０個であるのが好ましい。In this invention, it becomes a photocurable resin composition with high adhesive strength by using the photocurable resin which has two or more of such urethane bonds in the principal chain skeleton.
This is because, apart from the urethane bond contained in the terminal structure, by including a urethane bond in the main chain skeleton, hydrogen bonds are formed between the N—H groups of the urethane bond contained in the main chain skeleton of the adjacent photocurable resin. This is thought to be because it is more likely to occur. This can also be inferred from the results when the main chain skeleton does not have a urethane bond, as shown in Comparative Example 6 described later.
Moreover, it is preferable that the number of urethane bonds in the main chain skeleton is 2 to 10 because the adhesive strength and the physical properties of the cured product become higher.
＜末端構造＞
本発明の光硬化性樹脂は、末端の少なくとも１つに下記式（ＩＩａ）または下記式（ＩＩｂ）で表される構造を有する。<Terminal structure>
The photocurable resin of the present invention has a structure represented by the following formula (IIa) or the following formula (IIb) at at least one of the terminals.
本発明においては、このような末端構造を有する光硬化性樹脂を用いることにより、接着強度が高く、高温高湿下での接着性が良好な光硬化性樹脂組成物となる。
これは、末端構造に含まれるウレタン結合が、酸素原子を介して主鎖と結合した構造を採ることにより、意外にも光硬化後の重合度（架橋密度）が高くなり、アミノ基の電子供与性によりラジカルが発生し易くなったためと考えられる。このことは、後述する比較例１〜３に示すように、下記式（ＩＶ）で表される構造を末端に有する場合には重合度が低く、接着強度が劣る結果からも推察することができる。In the present invention, by using a photocurable resin having such a terminal structure, a photocurable resin composition having high adhesive strength and good adhesiveness under high temperature and high humidity is obtained.
This is because, by adopting a structure in which the urethane bond contained in the terminal structure is bonded to the main chain via an oxygen atom, the degree of polymerization (crosslink density) after photocuring is unexpectedly increased, and the electron donation of the amino group This is thought to be because radicals were easily generated due to the nature. This can be inferred from the result that the degree of polymerization is low and the adhesive strength is inferior when having a structure represented by the following formula (IV) at the end, as shown in Comparative Examples 1 to 3 described later. .
また、本発明においては、高温高湿下での接着性がより良好となり、硬化物の伸びも良好となる理由から、上記式（ＩＩａ）または上記式（ＩＩｂ）で表される末端構造を２個以上有しているのが好ましく、上記式（ＩＩａ）で表される末端構造を２個以上有しているのがより好ましい。 In the present invention, the terminal structure represented by the above formula (IIa) or the above formula (IIb) is 2 for the reason that the adhesiveness under high temperature and high humidity becomes better and the elongation of the cured product becomes better. It is preferable to have at least one, and it is more preferable to have two or more terminal structures represented by the above formula (IIa).
＜調製方法＞
本発明の光硬化性樹脂の調製方法は特に限定されないが、例えば、末端に水酸基を有する水添ポリブタジエン系重合体（以下、「水酸基末端水添ポリブタジエン（ａ）」という。）と、イソシアネート基および（メタ）アクリロイルオキシ基を有する化合物（ｂ）と、イソシアネート基を２個以上有するポリイソシアネート化合物（ｃ）とを反応させる方法が好ましく、より具体的には、水酸基末端水添ポリブタジエン（ａ）とポリイソシアネート化合物（ｃ）とを、水酸基とイソシアネート基との当量比（水酸基／イソシアネート基）が１より大きい値（例えば、１．１〜２）で反応させ、高分子量化した後に、残存する水酸基と化合物（ｂ）のイソシアネート基とを反応させ、（メタ）アクリロイルオキシ基を導入する方法が好ましい。
ここで、「（メタ）アクリロイルオキシ基」とは、アクリロイルオキシ基および／またはメタクリロイルオキシ基を意味する。<Preparation method>
The method for preparing the photocurable resin of the present invention is not particularly limited. For example, a hydrogenated polybutadiene polymer having a hydroxyl group at the terminal (hereinafter referred to as “hydroxyl-terminated hydrogenated polybutadiene (a)”), an isocyanate group, and A method of reacting the compound (b) having a (meth) acryloyloxy group with the polyisocyanate compound (c) having two or more isocyanate groups is preferred, and more specifically, the hydroxyl group-terminated hydrogenated polybutadiene (a) and After the polyisocyanate compound (c) is reacted with an equivalent ratio of hydroxyl group to isocyanate group (hydroxyl group / isocyanate group) greater than 1 (for example, 1.1 to 2) to increase the molecular weight, the remaining hydroxyl group And the isocyanate group of compound (b) are reacted to introduce a (meth) acryloyloxy group.
Here, the “(meth) acryloyloxy group” means an acryloyloxy group and / or a methacryloyloxy group.
＜水酸基末端水添ポリブタジエン（ａ）＞
上記水酸基末端水添ポリブタジエン（ａ）としては、上述した式（Ｉａ）〜（Ｉｃ）で表される繰り返し単位のモル％を満たす観点から、例えば、下記式（ａ１）および（ａ２）で表される両末端水酸基水素化ポリブタジエンが好適に挙げられる。<Hydroxyl-terminated hydrogenated polybutadiene (a)>
The hydroxyl group-terminated hydrogenated polybutadiene (a) is represented by, for example, the following formulas (a1) and (a2) from the viewpoint of satisfying the mol% of the repeating units represented by the formulas (Ia) to (Ic) described above. Suitable examples include both-end hydroxylated polybutadiene.
上記水添ポリブタジエン系重合体（ａ）の数平均分子量は、１０００〜１００００であるがの好ましく、１５００〜５０００であるのがより好ましい。
ここで、数平均分子量は、ポリスチレン換算によるゲルパーミエーションクロマトグラフィー（ＧＰＣ）測定により求めた値である。The number average molecular weight of the hydrogenated polybutadiene polymer (a) is preferably 1000 to 10,000, and more preferably 1500 to 5,000.
Here, the number average molecular weight is a value determined by gel permeation chromatography (GPC) measurement in terms of polystyrene.
＜化合物（ｂ）＞
上記化合物（ｂ）としては、上述した式（ＩＩａ）または式（ＩＩｂ）で表される末端構造を導入する観点から、下記式（ｂ１）または下記式（ｂ２）で表される化合物、例えば、２−イソシアネートエチル（メタ）アクリレート、１，１−（ビスアクリロイルオキシメチル）エチルイソシアネートを用いる。<Compound (b)>
As the compound (b), from the viewpoint of introducing the terminal structure represented by the formula (IIa) or the formula (IIb) described above, a compound represented by the following formula (b1) or the following formula (b2), for example, 2-isocyanatoethyl (meth) acrylate, 1,1- (bisacryloyloxymethyl) ethyl isocyanate is used.
＜ポリイソシアネート化合物（Ｃ）＞
上記ポリイソシアネート化合物（Ｃ）は、分子内にイソシアネート基を２個有するものであれば特に限定されない。
ポリイソシアネート化合物としては、具体的には、例えば、ＴＤＩ（例えば、２，４−トリレンジイソシアネート（２，４−ＴＤＩ）、２，６−トリレンジイソシアネート（２，６−ＴＤＩ））、ＭＤＩ（例えば、４，４′−ジフェニルメタンジイソシアネート（４，４′−ＭＤＩ）、２，４′−ジフェニルメタンジイソシアネート（２，４′−ＭＤＩ））、１，４−フェニレンジイソシアネート、キシリレンジイソシアネート（ＸＤＩ）、テトラメチルキシリレンジイソシアネート（ＴＭＸＤＩ）、トリジンジイソシアネート（ＴＯＤＩ）、１，５−ナフタレンジイソシアネート（ＮＤＩ）、トリフェニルメタントリイソシアネートなどの芳香族ジイソシアネート；ヘキサメチレンジイソシアネート（ＨＤＩ）、トリメチルヘキサメチレンジイソシアネート（ＴＭＨＤＩ）、リジンジイソシアネート、ノルボルナンジイソシアネート（ＮＢＤＩ）などの脂肪族ジイソシアネート；トランスシクロヘキサン−１，４−ジイソシアネート、イソホロンジイソシアネート（ＩＰＤＩ）、ビス（イソシアネートメチル）シクロヘキサン（Ｈ6ＸＤＩ）、ジシクロヘキシルメタンジイソシアネート（Ｈ12ＭＤＩ）などの脂環式ジイソシアネート；上述したジイソシアネートのイソシアヌレート体、ビウレット体、アダクト体；等が挙げられ、これらを１種単独で用いてもよく、２種以上を併用してもよい。<Polyisocyanate compound (C)>
The polyisocyanate compound (C) is not particularly limited as long as it has two isocyanate groups in the molecule.
Specific examples of the polyisocyanate compound include TDI (for example, 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI)), MDI ( For example, 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI)), 1,4-phenylene diisocyanate, xylylene diisocyanate (XDI), tetra Aromatic diisocyanates such as methylxylylene diisocyanate (TMXDI), tolidine diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI), triphenylmethane triisocyanate; hexamethylene diisocyanate (HDI), trimethylhexamethylene Isocyanate (TMHDI), lysine diisocyanate, aliphatic diisocyanates such as norbornane diisocyanate (NBDI); trans-cyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), bis (isocyanatomethyl) cyclohexane (H 6 XDI), dicyclohexylmethane diisocyanate ( Alicyclic diisocyanates such as H 12 MDI); isocyanurates, biurets and adducts of the above-mentioned diisocyanates; these may be used alone or in combination of two or more. .
〔光硬化性樹脂組成物〕
本発明の光硬化性樹脂組成物は、上述した本発明の光硬化性樹脂（以下、「光硬化性樹脂（Ａ）」ともいう。）と、（メタ）アクリロイルオキシ基を１個有する単官能（メタ）アクリレート化合物（Ｂ）と、光重合開始剤（Ｃ）とを含有する光硬化性樹脂組成物である。[Photocurable resin composition]
The photocurable resin composition of the present invention is a monofunctional resin having the above-described photocurable resin of the present invention (hereinafter also referred to as “photocurable resin (A)”) and one (meth) acryloyloxy group. It is a photocurable resin composition containing a (meth) acrylate compound (B) and a photopolymerization initiator (C).
＜光硬化性樹脂（Ａ）＞
上記光硬化性樹脂（Ａ）は、上述した本発明の光硬化性樹脂と同様であるが、本発明の光硬化性樹脂組成物における上記光硬化性樹脂（Ａ）の含有量は、１０〜８０質量％であるのが好ましく、２０〜６５質量％であるのがより好ましい。<Photocurable resin (A)>
The photocurable resin (A) is the same as the photocurable resin of the present invention described above, but the content of the photocurable resin (A) in the photocurable resin composition of the present invention is 10 to 10. It is preferably 80% by mass, more preferably 20 to 65% by mass.
＜単官能（メタ）アクリレート化合物（Ｂ）＞
上記単官能（メタ）アクリレート化合物（Ｂ）は、（メタ）アクリロイルオキシ基を１個有する化合物であれば特に限定されず、その具体例としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ベンジル（メタ）アクリレート、カルビトール（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、グリシジル（メタ）アクリレート、ラウリル（メタ）アクリレート、トリデシル（メタ）アクリレート、ステアリル（メタ）アクリレート、エトキシエチル（メタ）アクリレート、メトキシエチル（メタ）アクリレート、アリル（メタ）アクリレート、３−メトキシブチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、イソボルニル（メタ）アクリレート、イソデシル（メタ）アクリレート等が挙げられ、これらを１種単独で用いてもよく、２種以上を併用してもよい。
これらのうち、上記光硬化性樹脂（Ａ）への相溶性が良好となり、耐候性にも優れる理由から、ジシクロペンテニル（メタ）アクリレート、イソボルニル（メタ）アクリレート、イソデシル（メタ）アクリレートであるのが好ましい。<Monofunctional (meth) acrylate compound (B)>
The monofunctional (meth) acrylate compound (B) is not particularly limited as long as it is a compound having one (meth) acryloyloxy group. Specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, Butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, carbitol (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate , Stearyl (meth) acrylate, ethoxyethyl (meth) acrylate, methoxyethyl (meth) acrylate, allyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, isooctyl (meth) acrylate, pheno Ciethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, isodecyl (meth) acrylate, and the like may be used. These may be used alone or in combination of two or more. .
Among these, the compatibility with the photocurable resin (A) is good, and because of excellent weather resistance, it is dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, isodecyl (meth) acrylate. Is preferred.
上記単官能（メタ）アクリレート化合物（Ｂ）の含有量は、上記光硬化性樹脂（Ａ）１００質量部に対して、１０〜２００質量部であるのが好ましく、３０〜１００質量部であるのがより好ましい。 The content of the monofunctional (meth) acrylate compound (B) is preferably 10 to 200 parts by mass, and 30 to 100 parts by mass with respect to 100 parts by mass of the photocurable resin (A). Is more preferable.
＜光重合開始剤（Ｃ）＞
上記光重合開始剤（Ｃ）としては、例えば、アルキルフェノン系化合物、ベンゾインエーテル系化合物、ベンゾフェノン系化合物のようなカルボニル化合物、硫黄化合物、アゾ化合物、パーオキサイド化合物、ホスフィンオキサイド系化合物等が挙げられる。
より具体的には、例えば、アセトフェノン、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、ベンゾインイソプロピルエーテル、アセトイン、ブチロイン、トルオイン、ベンジル、ベンゾフェノン、ｐ−メトキシベンゾフェノン、ジエトキシアセトフェノン、α，α−ジメトキシ−α−フェニルアセトフェノン、メチルフェニルグリオキシレート、エチルフェニルグリオキシレート、４，４′−ビス（ジメチルアミノベンゾフェノン）、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、下記式（１）で表される１−ヒドロキシシクロヘキシルフェニルケトンなどのカルボニル化合物；テトラメチルチウラムモノスルフィド、テトラメチルチウラムジスルフィドなどの硫黄化合物；アゾビスイソブチロニトリル、アゾビス−２，４−ジメチルバレロなどのアゾ化合物；ベンゾイルパーオキサイド、ジターシャリーブチルパーオキサイドなどのパーオキサイド化合物：等が挙げられ、これらを１種単独で用いてもよく、２種以上を併用してもよい。<Photopolymerization initiator (C)>
Examples of the photopolymerization initiator (C) include carbonyl compounds such as alkylphenone compounds, benzoin ether compounds, and benzophenone compounds, sulfur compounds, azo compounds, peroxide compounds, phosphine oxide compounds, and the like. .
More specifically, for example, acetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, acetoin, butyroin, toluoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, α, α-dimethoxy-α -Phenylacetophenone, methylphenylglyoxylate, ethylphenylglyoxylate, 4,4'-bis (dimethylaminobenzophenone), 2-hydroxy-2-methyl-1-phenylpropan-1-one, the following formula (1) A carbonyl compound such as 1-hydroxycyclohexyl phenyl ketone; a sulfur compound such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; azobisisobutyronitrite And azo compounds such as azobis-2,4-dimethylvalero; peroxide compounds such as benzoyl peroxide and ditertiary butyl peroxide, and the like. These may be used alone or in combination of two or more. You may use together.
これらのうち、光安定性、光開裂の高効率性、上記光硬化性樹脂（Ａ）との相溶性、低揮発、低臭気という観点から、１−ヒドロキシシクロヘキシルフェニルケトン、２−ヒドロキシ−２−メチル−１−フェニル−プロパン−１−オン、１−［４−（２−ヒドロキシエトキシ）−フェニル］−２−ヒドロキシ−２−メチル−１−プロパン−１−オンが好ましい。
１−ヒドロキシシクロヘキシルフェニルケトンの市販品としては、例えば、イルガキュア１８４（チバスペシャリティケミカルズ社製）が挙げられる。Among these, from the viewpoint of light stability, high efficiency of photocleavage, compatibility with the photocurable resin (A), low volatility, and low odor, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2- Methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one are preferred.
Examples of commercially available 1-hydroxycyclohexyl phenyl ketone include Irgacure 184 (manufactured by Ciba Specialty Chemicals).
上記光重合開始剤（Ｃ）の含有量は、上記光硬化性樹脂（Ａ）１００質量部に対して１〜１０質量部であるのが好ましく、２〜８質量部であるのがより好ましい。 The content of the photopolymerization initiator (C) is preferably 1 to 10 parts by mass and more preferably 2 to 8 parts by mass with respect to 100 parts by mass of the photocurable resin (A).
＜エステル基含有（メタ）アクリレート＞
本発明の光硬化性樹脂組成物は、硬化後の靱性が良好となる理由から、下記式で表される、エステル基含有（メタ）アクリレート（Ｄ）を用いるのが好ましい。<Ester group-containing (meth) acrylate>
The photocurable resin composition of the present invention preferably uses an ester group-containing (meth) acrylate (D) represented by the following formula because the toughness after curing is good.
このようなエステル基含有（メタ）アクリレート（Ｄ）としては、市販品として、「プラクセルＦＡ−１」、「プラクセルＦＡ−２」、「プラクセルＦＡ−２Ｄ」、「プラクセルＦＡ−３」、「プラクセルＦＡ−４」、「プラクセルＦＡ−５」、「プラクセルＦＭ−１」、「プラクセルＦＭ−２」、「プラクセルＦＭ−２Ｄ」、「プラクセルＦＭ−３」、「プラクセルＦＭ−４」、「プラクセルＦＭ−５」（いずれもダイセル化学社製）等を用いることができる。 As such an ester group-containing (meth) acrylate (D), “Placcel FA-1”, “Placcel FA-2”, “Placcel FA-2D”, “Placcel FA-3”, “Placcel” are commercially available. "FA-4", "Plaxel FA-5", "Plaxel FM-1", "Plaxel FM-2", "Plaxel FM-2D", "Plaxel FM-3", "Plaxel FM-4", "Plaxel FM −5 ”(all manufactured by Daicel Chemical Industries, Ltd.) and the like can be used.
上記エステル基含有（メタ）アクリレート（Ｄ）の含有量は、上記光硬化性樹脂（Ａ）１００質量部に対して１〜５０質量部であるのが好ましく、５〜２０質量部であるのがより好ましい。 It is preferable that content of the said ester group containing (meth) acrylate (D) is 1-50 mass parts with respect to 100 mass parts of said photocurable resins (A), and it is 5-20 mass parts. More preferred.
＜溶剤、添加剤＞
本発明の光硬化性樹脂組成物は、作業性の観点から、溶剤を含有していてもよい。
溶剤としては、具体的には、例えば、エタノール、イソプロパノール、ブタノール、トルエン、キシレン、アセトン、メチルエチルケトン、酢酸エチル、酢酸ブチル、シクロヘキサノン等が挙げられる。<Solvent, additive>
The photocurable resin composition of the present invention may contain a solvent from the viewpoint of workability.
Specific examples of the solvent include ethanol, isopropanol, butanol, toluene, xylene, acetone, methyl ethyl ketone, ethyl acetate, butyl acetate, and cyclohexanone.
また、本発明の光硬化性樹脂組成物は、本発明の目的を損なわない範囲で、種々の添加剤、例えば、充填剤、老化防止剤、酸化防止剤、帯電防止剤、難燃剤、接着性付与剤、レベリング剤、分散剤、消泡剤、艶消し剤、光安定剤（例えば、ヒンダードアミン系化合物等）、染料、顔料等を含有することができる。 In addition, the photocurable resin composition of the present invention has various additives such as a filler, an anti-aging agent, an antioxidant, an antistatic agent, a flame retardant, and adhesiveness, as long as the object of the present invention is not impaired. An imparting agent, a leveling agent, a dispersant, an antifoaming agent, a matting agent, a light stabilizer (for example, a hindered amine compound), a dye, a pigment, and the like can be contained.
＜調製方法＞
本発明の光硬化性樹脂組成物の調製方法は特に限定されず、例えば、反応容器に上記の各必須成分と任意成分とを入れ、減圧下で混合ミキサー等のかくはん機を用いて十分に混練する方法等により製造することができる。<Preparation method>
The method for preparing the photocurable resin composition of the present invention is not particularly limited. For example, the above-mentioned essential components and optional components are placed in a reaction vessel, and are sufficiently kneaded using a stirrer such as a mixing mixer under reduced pressure. It can manufacture by the method to do.
以下、実施例を用いて、本発明の光硬化性樹脂組成物について詳細に説明する。ただし、本発明はこれに限定されるものではない。 Hereinafter, the photocurable resin composition of the present invention will be described in detail using examples. However, the present invention is not limited to this.
＜光硬化性樹脂（Ａ−１）の合成＞
水酸基末端水添ポリブタジエン（ＧＩ−３０００、日本曹達社製）１００ｇと、２−イソシアナトエチルアクリラート（昭和電工社製）２．３ｇと、ヘキサメチレンジイソシアネート３．７ｇとを混合し、窒素雰囲気下で７０℃２時間反応させ、光硬化性樹脂（Ａ−１）を合成した。
なお、合成した光硬化性樹脂（Ａ−１）は、上記式（Ｉａ）で表される繰り返し単位の含有量が上記式（Ｉａ）〜（Ｉｃ）で表される全繰り返し単位に対して１５モル％であり、かつ、上記式（Ｉｂ）で表される繰り返し単位の含有量が上記式（Ｉａ）〜（Ｉｃ）で表される全繰り返し単位に対して８５モル％であり、また、上記式（ＩＩａ）で表される末端構造（式（ＩＩａ）中のＲ1は水素原子）を有し、上記式（ＩＩＩ）で表されるウレタン結合を２個有していることを確認した。<Synthesis of Photocurable Resin (A-1)>
100 g of hydroxyl-terminated hydrogenated polybutadiene (GI-3000, manufactured by Nippon Soda Co., Ltd.), 2.3 g of 2-isocyanatoethyl acrylate (manufactured by Showa Denko KK), and 3.7 g of hexamethylene diisocyanate were mixed in a nitrogen atmosphere. At 70 ° C. for 2 hours to synthesize a photocurable resin (A-1).
The synthesized photocurable resin (A-1) has a content of the repeating unit represented by the above formula (Ia) of 15 with respect to all the repeating units represented by the above formulas (Ia) to (Ic). And the content of the repeating unit represented by the above formula (Ib) is 85 mol% with respect to all the repeating units represented by the above formulas (Ia) to (Ic). It was confirmed that it had a terminal structure represented by formula (IIa) (R 1 in formula (IIa) was a hydrogen atom) and had two urethane bonds represented by formula (III).
＜光硬化性樹脂（Ａ−２）の合成＞
水酸基末端水添ポリブタジエン（ＧＩ−３０００、日本曹達社製）１００ｇと、ヘキサメチレンジイソシアネート３．７ｇとを混合し、窒素雰囲気下で７０℃２時間反応させた。
次いで、２−イソシアナトエチルアクリラート（昭和電工社製）２．３ｇを混合し、窒素雰囲気下で７０℃２時間反応させ、光硬化性樹脂（Ａ−２）を合成した。
なお、合成した光硬化性樹脂（Ａ−２）は、上記式（Ｉａ）で表される繰り返し単位の含有量が上記式（Ｉａ）〜（Ｉｃ）で表される全繰り返し単位に対して１５モル％であり、かつ、上記式（Ｉｂ）で表される繰り返し単位の含有量が上記式（Ｉａ）〜（Ｉｃ）で表される全繰り返し単位に対して８５モル％であり、また、上記式（ＩＩａ）で表される末端構造（式（ＩＩａ）中のＲ1は水素原子）を有し、上記式（ＩＩＩ）で表されるウレタン結合を２個有していることを確認した。<Synthesis of photocurable resin (A-2)>
100 g of hydroxyl-terminated hydrogenated polybutadiene (GI-3000, manufactured by Nippon Soda Co., Ltd.) and 3.7 g of hexamethylene diisocyanate were mixed and reacted at 70 ° C. for 2 hours in a nitrogen atmosphere.
Subsequently, 2.3 g of 2-isocyanatoethyl acrylate (manufactured by Showa Denko) was mixed and reacted at 70 ° C. for 2 hours in a nitrogen atmosphere to synthesize a photocurable resin (A-2).
In addition, the synthesized photocurable resin (A-2) has a content of the repeating unit represented by the above formula (Ia) of 15 with respect to all the repeating units represented by the above formulas (Ia) to (Ic). And the content of the repeating unit represented by the above formula (Ib) is 85 mol% with respect to all the repeating units represented by the above formulas (Ia) to (Ic). It was confirmed that it had a terminal structure represented by formula (IIa) (R 1 in formula (IIa) was a hydrogen atom) and had two urethane bonds represented by formula (III).
＜光硬化性樹脂（Ａ−３）の合成＞
水酸基末端水添ポリブタジエン（ＧＩ−３０００、日本曹達社製）１００ｇと、イソホロンジイソシアネート（Ｅｖｏｎｉｃ社製）３．９ｇとを混合し、窒素雰囲気下で７０℃２時間反応させた。
次いで、２−イソシアナトエチルアクリラート（昭和電工社製）２．４ｇを混合し、窒素雰囲気下で７０℃２時間反応させ、光硬化性樹脂（Ａ−３）を合成した。
なお、合成した光硬化性樹脂（Ａ−３）は、上記式（Ｉａ）で表される繰り返し単位の含有量が上記式（Ｉａ）〜（Ｉｃ）で表される全繰り返し単位に対して１５モル％であり、かつ、上記式（Ｉｂ）で表される繰り返し単位の含有量が上記式（Ｉａ）〜（Ｉｃ）で表される全繰り返し単位に対して８５モル％であり、また、上記式（ＩＩａ）で表される末端構造（式（ＩＩａ）中のＲ1は水素原子）を有し、上記式（ＩＩＩ）で表されるウレタン結合を４個有していることを確認した。<Synthesis of photocurable resin (A-3)>
100 g of hydroxyl-terminated hydrogenated polybutadiene (GI-3000, manufactured by Nippon Soda Co., Ltd.) and 3.9 g of isophorone diisocyanate (produced by Evonic) were mixed and reacted at 70 ° C. for 2 hours in a nitrogen atmosphere.
Subsequently, 2.4 g of 2-isocyanatoethyl acrylate (manufactured by Showa Denko KK) was mixed and reacted at 70 ° C. for 2 hours under a nitrogen atmosphere to synthesize a photocurable resin (A-3).
The synthesized photocurable resin (A-3) has a content of the repeating unit represented by the above formula (Ia) of 15 with respect to all the repeating units represented by the above formulas (Ia) to (Ic). And the content of the repeating unit represented by the above formula (Ib) is 85 mol% with respect to all the repeating units represented by the above formulas (Ia) to (Ic). It was confirmed that it had a terminal structure represented by the formula (IIa) (R 1 in the formula (IIa) was a hydrogen atom) and had four urethane bonds represented by the formula (III).
＜光硬化性樹脂（Ａ−４）の合成＞
水酸基末端水添ポリブタジエン（ＧＩ−３０００、日本曹達社製）１００ｇと、イソホロンジイソシアネート（Ｅｖｏｎｉｃ社製）３．９ｇと、触媒としてペンタメチルピペリジニルメタクリレート（ＦＡ−７１１ＭＭ、日立化成工業社製）０．１ｇとを混合し、窒素雰囲気下で７０℃２時間反応させた。
次いで、２−イソシアナトエチルアクリラート（昭和電工社製）２．４ｇを混合し、窒素雰囲気下で７０℃２時間反応させ、光硬化性樹脂（Ａ−４）を合成した。
なお、合成した光硬化性樹脂（Ａ−４）は、上記式（Ｉａ）で表される繰り返し単位の含有量が上記式（Ｉａ）〜（Ｉｃ）で表される全繰り返し単位に対して１５モル％であり、かつ、上記式（Ｉｂ）で表される繰り返し単位の含有量が上記式（Ｉａ）〜（Ｉｃ）で表される全繰り返し単位に対して８５モル％であり、また、上記式（ＩＩａ）で表される末端構造（式（ＩＩａ）中のＲ1は水素原子）を有し、上記式（ＩＩＩ）で表されるウレタン結合を４個有していることを確認した。<Synthesis of photocurable resin (A-4)>
100 g of hydroxyl-terminated hydrogenated polybutadiene (GI-3000, manufactured by Nippon Soda Co., Ltd.), 3.9 g of isophorone diisocyanate (Evonic), and pentamethylpiperidinyl methacrylate (FA-711MM, manufactured by Hitachi Chemical Co., Ltd.) as a catalyst 0.1 g was mixed and reacted at 70 ° C. for 2 hours under a nitrogen atmosphere.
Subsequently, 2.4 g of 2-isocyanatoethyl acrylate (manufactured by Showa Denko KK) was mixed and reacted at 70 ° C. for 2 hours in a nitrogen atmosphere to synthesize a photocurable resin (A-4).
In addition, the synthesized photocurable resin (A-4) has a content of the repeating unit represented by the above formula (Ia) of 15 with respect to all the repeating units represented by the above formulas (Ia) to (Ic). And the content of the repeating unit represented by the above formula (Ib) is 85 mol% with respect to all the repeating units represented by the above formulas (Ia) to (Ic). It was confirmed that it had a terminal structure represented by the formula (IIa) (R 1 in the formula (IIa) was a hydrogen atom) and had four urethane bonds represented by the formula (III).
＜光硬化性樹脂（Ａ−５）の合成＞
水酸基末端水添ポリブタジエン（ＧＩ−３０００、日本曹達社製）１００ｇと、イソホロンジイソシアネート（Ｅｖｏｎｉｃ社製）３．９ｇとを混合し、窒素雰囲気下で７０℃２時間反応させた。
次いで、１，１−（ビスアクリロイルオキシメチル）エチルイソシアネート（昭和電工社製）４．２３ｇを混合し、窒素雰囲気下で７０℃２時間反応させ、光硬化性樹脂（Ａ−５）を合成した。
なお、合成した光硬化性樹脂（Ａ−５）は、上記式（Ｉａ）で表される繰り返し単位の含有量が上記式（Ｉａ）〜（Ｉｃ）で表される全繰り返し単位に対して１５モル％であり、かつ、上記式（Ｉｂ）で表される繰り返し単位の含有量が上記式（Ｉａ）〜（Ｉｃ）で表される全繰り返し単位に対して８５モル％であり、また、上記式（ＩＩｂ）で表される末端構造（式（ＩＩｂ）中のＲ1は水素原子）を有し、上記式（ＩＩＩ）で表されるウレタン結合を４個有していることを確認した。<Synthesis of photocurable resin (A-5)>
100 g of hydroxyl-terminated hydrogenated polybutadiene (GI-3000, manufactured by Nippon Soda Co., Ltd.) and 3.9 g of isophorone diisocyanate (produced by Evonic) were mixed and reacted at 70 ° C. for 2 hours in a nitrogen atmosphere.
Subsequently, 4.21 g of 1,1- (bisacryloyloxymethyl) ethyl isocyanate (manufactured by Showa Denko KK) was mixed and reacted at 70 ° C. for 2 hours in a nitrogen atmosphere to synthesize a photocurable resin (A-5). .
In addition, the synthesized photocurable resin (A-5) has a content of the repeating unit represented by the above formula (Ia) of 15 with respect to all the repeating units represented by the above formulas (Ia) to (Ic). And the content of the repeating unit represented by the above formula (Ib) is 85 mol% with respect to all the repeating units represented by the above formulas (Ia) to (Ic). It was confirmed that it had a terminal structure represented by the formula (IIb) (R 1 in the formula (IIb) was a hydrogen atom) and four urethane bonds represented by the above formula (III).
＜光硬化性樹脂（Ａ−６）の合成＞
水酸基末端水添ポリブタジエン（ＧＩ−３０００、日本曹達製）９５ｇと水酸基末端水添ポリイソプレン（ｐｏｌｙ ｉｐ）６．２５ｇとイソホロンジイソシアネート４．０７ｇを混合し、窒素雰囲気下で７０℃３時間反応させた。
次いで、２−イソシアナトエチルアクリラート（昭和電工社製）２．４ｇを混合し、窒素雰囲気下で７０℃２時間反応させ、光硬化性樹脂（Ａ−６）を合成した。
なお、合成した光硬化性樹脂（Ａ−６）は、上記式（Ｉａ）で表される繰り返し単位の含有量が上記式（Ｉａ）〜（Ｉｃ）で表される全繰り返し単位に対して１４．２５モル％であり、かつ、上記式（Ｉｂ）で表される繰り返し単位の含有量が上記式（Ｉａ）〜（Ｉｃ）で表される全繰り返し単位に対して８０．７５モル％であり、上記式（Ｉｃ）で表される繰り返し単位の含有量が上記式（Ｉａ）〜（Ｉｃ）で表される全繰り返し単位に対して５モル％であり、また、上記式（ＩＩａ）で表される末端構造（式（ＩＩａ）中のＲ1は水素原子）を有し、上記式（ＩＩＩ）で表されるウレタン結合を４個有していることを確認した。<Synthesis of photocurable resin (A-6)>
Hydroxyl-terminated hydrogenated polybutadiene (GI-3000, manufactured by Nippon Soda) (95 g), hydroxyl-terminated hydrogenated polyisoprene (poly ip) (6.25 g) and isophorone diisocyanate (4.07 g) were mixed and reacted at 70 ° C. for 3 hours in a nitrogen atmosphere. .
Subsequently, 2.4 g of 2-isocyanatoethyl acrylate (manufactured by Showa Denko KK) was mixed and reacted at 70 ° C. for 2 hours in a nitrogen atmosphere to synthesize a photocurable resin (A-6).
In addition, as for the synthesize | combined photocurable resin (A-6), content of the repeating unit represented by the said Formula (Ia) is 14 with respect to all the repeating units represented by the said Formula (Ia)-(Ic). And the content of the repeating unit represented by the above formula (Ib) is 80.75 mol% with respect to all the repeating units represented by the above formulas (Ia) to (Ic). The content of the repeating unit represented by the above formula (Ic) is 5 mol% with respect to all the repeating units represented by the above formulas (Ia) to (Ic), and is represented by the above formula (IIa). It was confirmed that the terminal structure (R 1 in the formula (IIa) is a hydrogen atom) and four urethane bonds represented by the formula (III) are included.
＜光硬化性樹脂（Ａ−７）の合成＞
水酸基末端水添ポリブタジエン（Ｉｂで表される繰り返し単位が１００モル％のもの）１００ｇとイソホロンジイソシアネート３．９ｇを混合し、窒素雰囲気下で７０℃３時間反応させた。
次いで、２−イソシアナトエチルアクリラート（昭和電工社製）２．４ｇを混合し、窒素雰囲気下で７０℃２時間反応させ、光硬化性樹脂（Ａ−７）を合成した。
なお、合成した光硬化性樹脂（Ａ−７）は、上記式（Ｉｂ）で表される繰り返し単位の含有量が上記式（Ｉａ）〜（Ｉｃ）で表される全繰り返し単位に対して１００モル％であり、また、上記式（ＩＩａ）で表される末端構造（式（ＩＩａ）中のＲ1は水素原子）を有し、上記式（ＩＩＩ）で表されるウレタン結合を４個有していることを確認した。<Synthesis of photocurable resin (A-7)>
100 g of hydroxyl-terminated hydrogenated polybutadiene (having a repeating unit represented by Ib of 100 mol%) and 3.9 g of isophorone diisocyanate were mixed and reacted at 70 ° C. for 3 hours in a nitrogen atmosphere.
Subsequently, 2.4 g of 2-isocyanatoethyl acrylate (manufactured by Showa Denko) was mixed and reacted at 70 ° C. for 2 hours in a nitrogen atmosphere to synthesize a photocurable resin (A-7).
The synthesized photocurable resin (A-7) has a content of the repeating unit represented by the above formula (Ib) of 100 with respect to all the repeating units represented by the above formulas (Ia) to (Ic). It has a terminal structure represented by the above formula (IIa) (R 1 in formula (IIa) is a hydrogen atom), and has four urethane bonds represented by the above formula (III). I confirmed that
＜光硬化性樹脂（Ｅ−１）の合成＞
水酸基末端固形水添ポリブタジエン（ポリテールＨ、三菱化学株式会社）１００ｇをトルエン１００ｇに溶解させた後、２−ヒドロキシエチルアクリラート（東京化成工業社製）１．５ｇおよびイソホロンジイソシアネート１１．８ｇを混合し、窒素雰囲気下で７０℃２時間反応させた。
次いで、ジシクロペンテニルアクリレート３０ｇを溶解させた後にトルエン層を留去し、光硬化性樹脂（Ｅ−１）を合成した。
なお、合成した光硬化性樹脂（Ｅ−１）は、上記式（Ｉａ）で表される繰り返し単位の含有量が上記式（Ｉａ）〜（Ｉｃ）で表される全繰り返し単位に対して８０モル％であり、かつ、上記式（Ｉｂ）で表される繰り返し単位の含有量が上記式（Ｉａ）〜（Ｉｃ）で表される全繰り返し単位に対して２０モル％であり、また、上記式（ＩＶ）で表される末端構造（式（ＩＶ）中のＲ1は水素原子）を有し、上記式（ＩＩＩ）で表されるウレタン結合を６個有していることを確認した。<Synthesis of photocurable resin (E-1)>
After 100 g of hydroxyl-terminated solid hydrogenated polybutadiene (polytail H, Mitsubishi Chemical Corporation) is dissolved in 100 g of toluene, 1.5 g of 2-hydroxyethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 11.8 g of isophorone diisocyanate are mixed. The mixture was reacted at 70 ° C. for 2 hours under a nitrogen atmosphere.
Next, after dissolving 30 g of dicyclopentenyl acrylate, the toluene layer was distilled off to synthesize a photocurable resin (E-1).
The synthesized photocurable resin (E-1) has a content of the repeating unit represented by the above formula (Ia) of 80 with respect to all the repeating units represented by the above formulas (Ia) to (Ic). And the content of the repeating unit represented by the above formula (Ib) is 20 mol% with respect to all the repeating units represented by the above formulas (Ia) to (Ic). It was confirmed that it had a terminal structure represented by the formula (IV) (R 1 in the formula (IV) was a hydrogen atom) and had 6 urethane bonds represented by the formula (III).
＜光硬化性樹脂（Ｅ−２）の合成＞
水酸基末端水添ポリブタジエン（ＧＩ−３０００、日本曹達社製）１００ｇと、２−ヒドロキシエチルアクリラート（東京化成工業社製）１．５ｇと、イソホロンジイソシアネート８．８ｇとを混合し、窒素雰囲気下で７０℃２時間反応させ、光硬化性樹脂（Ｅ−２）を合成した。
なお、合成した光硬化性樹脂（Ｅ−２）は、上記式（Ｉａ）で表される繰り返し単位の含有量が上記式（Ｉａ）〜（Ｉｃ）で表される全繰り返し単位に対して１５モル％であり、かつ、上記式（Ｉｂ）で表される繰り返し単位の含有量が上記式（Ｉａ）〜（Ｉｃ）で表される全繰り返し単位に対して８５モル％であり、また、上記式（ＩＶ）で表される末端構造（式（ＩＶ）中のＲ1は水素原子）を有し、上記式（ＩＩＩ）で表されるウレタン結合を４個有していることを確認した。<Synthesis of photocurable resin (E-2)>
100 g of hydroxyl-terminated hydrogenated polybutadiene (GI-3000, manufactured by Nippon Soda Co., Ltd.), 1.5 g of 2-hydroxyethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), and 8.8 g of isophorone diisocyanate are mixed in a nitrogen atmosphere. It was made to react at 70 degreeC for 2 hours, and the photocurable resin (E-2) was synthesize | combined.
In addition, the synthesized photocurable resin (E-2) has a content of the repeating unit represented by the above formula (Ia) of 15 with respect to all the repeating units represented by the above formulas (Ia) to (Ic). And the content of the repeating unit represented by the above formula (Ib) is 85 mol% with respect to all the repeating units represented by the above formulas (Ia) to (Ic). It was confirmed that it had a terminal structure represented by the formula (IV) (R 1 in the formula (IV) is a hydrogen atom) and four urethane bonds represented by the formula (III).
＜光硬化性樹脂（Ｅ−３）の合成＞
まず、トリレンジイソシアネート３．４８ｇと、２−ヒドロキシエチルアクリラート２．３２ｇとを混合し、窒素雰囲気下６０℃３時間で反応させハーフアダクト体を得た。
次いで、水酸基末端水添ポリブタジエン（ＧＩ−３０００、日本曹達社製）１００ｇと、トリレンジイソシアネート２．１７ｇとを混合し、窒素雰囲気下７０℃２時間で反応させた後、先に調製したハーフアダクト体２．５ｇを混合し、７０℃２時間で反応させ、光硬化性樹脂（Ｅ−３）を合成した。
なお、合成した光硬化性樹脂（Ｅ−３）は、上記式（Ｉａ）で表される繰り返し単位の含有量が上記式（Ｉａ）〜（Ｉｃ）で表される全繰り返し単位に対して１５モル％であり、かつ、上記式（Ｉｂ）で表される繰り返し単位の含有量が上記式（Ｉａ）〜（Ｉｃ）で表される全繰り返し単位に対して８５モル％であり、また、上記式（ＩＶ）で表される末端構造（式（ＩＶ）中のＲ1は水素原子）を有し、上記式（ＩＩＩ）で表されるウレタン結合を２個有していることを確認した。<Synthesis of photocurable resin (E-3)>
First, 3.48 g of tolylene diisocyanate and 2.32 g of 2-hydroxyethyl acrylate were mixed and reacted in a nitrogen atmosphere at 60 ° C. for 3 hours to obtain a half adduct.
Next, 100 g of hydroxyl-terminated hydrogenated polybutadiene (GI-3000, manufactured by Nippon Soda Co., Ltd.) and 2.17 g of tolylene diisocyanate were mixed and reacted in a nitrogen atmosphere at 70 ° C. for 2 hours, and then the half adduct prepared previously. 2.5 g of the body was mixed and reacted at 70 ° C. for 2 hours to synthesize a photocurable resin (E-3).
In addition, the synthesized photocurable resin (E-3) has a content of the repeating unit represented by the above formula (Ia) of 15 with respect to all the repeating units represented by the above formulas (Ia) to (Ic). And the content of the repeating unit represented by the above formula (Ib) is 85 mol% with respect to all the repeating units represented by the above formulas (Ia) to (Ic). It was confirmed that it had a terminal structure represented by formula (IV) (R 1 in formula (IV) was a hydrogen atom) and had two urethane bonds represented by formula (III).
＜光硬化性樹脂（Ｅ−４）の合成＞
水酸基末端固形水添ポリブタジエン（ポリテールＨ、三菱化学株式会社）１００ｇをトルエン１００部に溶解させ、２−イソシアナトエチルアクリラート（昭和電工社製）１１ｇを混合し、窒素雰囲気下で７０℃２時間反応させた。
次いで、ジシクロペンテニルアクリレート３０部を溶解させた後にトルエン層を留去し、光硬化性樹脂（Ｅ−４）を合成した。
なお、合成した光硬化性樹脂（Ｅ−４）は、上記式（Ｉａ）で表される繰り返し単位の含有量が上記式（Ｉａ）〜（Ｉｃ）で表される全繰り返し単位に対して８０モル％であり、かつ、上記式（Ｉｂ）で表される繰り返し単位の含有量が上記式（Ｉａ）〜（Ｉｃ）で表される全繰り返し単位に対して２０モル％であり、また、上記式（ＩＩａ）で表される末端構造（式（ＩＩａ）中のＲ1は水素原子）を有し、上記式（ＩＩＩ）で表されるウレタン結合を有していないことを確認した。<Synthesis of photocurable resin (E-4)>
100 g of hydroxyl-terminated solid hydrogenated polybutadiene (Polytail H, Mitsubishi Chemical Corporation) is dissolved in 100 parts of toluene, 11 g of 2-isocyanatoethyl acrylate (manufactured by Showa Denko KK) is mixed, and 70 ° C. for 2 hours under a nitrogen atmosphere. Reacted.
Next, after dissolving 30 parts of dicyclopentenyl acrylate, the toluene layer was distilled off to synthesize a photocurable resin (E-4).
In addition, the synthesized photocurable resin (E-4) has a content of the repeating unit represented by the above formula (Ia) of 80 with respect to all the repeating units represented by the above formulas (Ia) to (Ic). And the content of the repeating unit represented by the above formula (Ib) is 20 mol% with respect to all the repeating units represented by the above formulas (Ia) to (Ic). It was confirmed that it had a terminal structure represented by the formula (IIa) (R 1 in the formula (IIa) is a hydrogen atom) and did not have a urethane bond represented by the above formula (III).
＜光硬化性樹脂（Ｅ−５）の合成＞
水酸基末端固形水添ポリブタジエン（ポリテールＨ、三菱化学株式会社）１００ｇをトルエン１００ｇに溶解させた後、２−イソシアナトエチルアクリラート（昭和電工社製）３．５ｇおよびイソホロンジイソシアネート６ｇを混合し、窒素雰囲気下で７０℃２時間反応させた。
次いで、ジシクロペンテニルアクリレート３０ｇを溶解させた後にトルエン層を留去し、光硬化性樹脂（Ｅ−５）を合成した。
なお、合成した光硬化性樹脂（Ｅ−５）は、上記式（Ｉａ）で表される繰り返し単位の含有量が上記式（Ｉａ）〜（Ｉｃ）で表される全繰り返し単位に対して８０モル％であり、かつ、上記式（Ｉｂ）で表される繰り返し単位の含有量が上記式（Ｉａ）〜（Ｉｃ）で表される全繰り返し単位に対して２０モル％であり、また、上記式（ＩＩａ）で表される末端構造（式（ＩＩａ）中のＲ1は水素原子）を有し、上記式（ＩＩＩ）で表されるウレタン結合を４個有していることを確認した。<Synthesis of photocurable resin (E-5)>
After 100 g of hydroxyl-terminated solid hydrogenated polybutadiene (Polytail H, Mitsubishi Chemical Corporation) was dissolved in 100 g of toluene, 3.5 g of 2-isocyanatoethyl acrylate (manufactured by Showa Denko KK) and 6 g of isophorone diisocyanate were mixed, and nitrogen was added. The reaction was performed at 70 ° C. for 2 hours under an atmosphere.
Next, after dissolving 30 g of dicyclopentenyl acrylate, the toluene layer was distilled off to synthesize a photocurable resin (E-5).
In addition, the synthesized photocurable resin (E-5) has a content of the repeating unit represented by the above formula (Ia) of 80 with respect to all the repeating units represented by the above formulas (Ia) to (Ic). And the content of the repeating unit represented by the above formula (Ib) is 20 mol% with respect to all the repeating units represented by the above formulas (Ia) to (Ic). It was confirmed that it had a terminal structure represented by the formula (IIa) (R 1 in the formula (IIa) was a hydrogen atom) and had four urethane bonds represented by the formula (III).
＜光硬化性樹脂（Ｅ−６）の合成＞
水酸基末端水添ポリブタジエン（ＧＩ−３０００、日本曹達社製）１００ｇと、２−イソシアナトエチルアクリラート（昭和電工社製）７．５ｇとを混合し、窒素雰囲気下７０℃２時間で反応させ、光硬化性樹脂（Ｅ−６）を合成した。
なお、合成した光硬化性樹脂（Ｅ−６）は、上記式（Ｉａ）で表される繰り返し単位の含有量が上記式（Ｉａ）〜（Ｉｃ）で表される全繰り返し単位に対して１５モル％であり、かつ、上記式（Ｉｂ）で表される繰り返し単位の含有量が上記式（Ｉａ）〜（Ｉｃ）で表される全繰り返し単位に対して８５モル％であり、また、上記式（ＩＩａ）で表される末端構造（式（ＩＩａ）中のＲ1は水素原子）を有し、上記式（ＩＩＩ）で表されるウレタン結合を有していないことを確認した。<Synthesis of photocurable resin (E-6)>
100 g of hydroxyl-terminated hydrogenated polybutadiene (GI-3000, manufactured by Nippon Soda Co., Ltd.) and 7.5 g of 2-isocyanatoethyl acrylate (manufactured by Showa Denko) were mixed and reacted in a nitrogen atmosphere at 70 ° C. for 2 hours. A photocurable resin (E-6) was synthesized.
The synthesized photocurable resin (E-6) has a content of the repeating unit represented by the above formula (Ia) of 15 with respect to all the repeating units represented by the above formulas (Ia) to (Ic). And the content of the repeating unit represented by the above formula (Ib) is 85 mol% with respect to all the repeating units represented by the above formulas (Ia) to (Ic). It was confirmed that it had a terminal structure represented by the formula (IIa) (R 1 in the formula (IIa) is a hydrogen atom) and did not have a urethane bond represented by the above formula (III).
〔実施例１〜１０、比較例１〜６〕
下記第１表に示す各成分を、第１表に示す組成（質量部）で、かくはん機を用いて混合し、第１表に示される各光硬化性樹脂組成物を得た。
次いで、得られた各組成物を以下に示す硬化条件で硬化させた硬化物を得た。
（硬化条件）
光照射装置（ＧＳ ＵＶＳＹＳＴＥＭ ＴＹＰＥ Ｓ２５０―０１、ジーエス・ユアサ ライティング社製）を用い、光源としてメタルハイドロランプを使用し、波長２５０〜３８０ｎｍの紫外線を光量１２０ｍＷ／ｃｍで積算光量１０００ｍＪ／ｃｍ2となるよう照射し、硬化物を得た。[Examples 1 to 10, Comparative Examples 1 to 6]
Each component shown in the following Table 1 was mixed using a stirrer with the composition (parts by mass) shown in Table 1 to obtain each photocurable resin composition shown in Table 1.
Subsequently, the hardened | cured material which hardened each obtained composition on the hardening conditions shown below was obtained.
(Curing conditions)
Using a light irradiation device (GS UVSYSTEM TYPE S250-01, manufactured by GS Yuasa Lighting Co., Ltd.), a metal hydrolamp is used as a light source, and an ultraviolet ray having a wavelength of 250 to 380 nm is a light amount of 120 mW / cm and an integrated light amount of 1000 mJ / cm 2. Irradiated to obtain a cured product.
＜重合度＞
各光硬化性樹脂組成物およびその硬化物について、それぞれＦＴ−ＩＲを用いて測定し、以下の方法により重合度を算出した。
すなわち、８１０ｃｍ-1のピーク強度の変化について、硬化前（組成物）の初期状態を重合度０とし、硬化（重合）が進行し、バンド強度が０となる状態を重合度１００として、重合度を測定した。結果を第１表に示す。<Degree of polymerization>
About each photocurable resin composition and its hardened | cured material, it measured using FT-IR, respectively, and computed the polymerization degree with the following method.
That is, regarding the change in the peak intensity at 810 cm −1, the degree of polymerization is defined by setting the initial state before curing (composition) as 0 degree of polymerization, curing (polymerization) progressing, and setting the band intensity as 0 as degree of polymerization 100. Was measured. The results are shown in Table 1.
＜接着強度＞
各光硬化性樹脂組成物を接着面積φ５ｍｍ、接着厚み０．３ｍｍとなるようにガラス基板に塗布し、上記ガラス基板と直行するように他のガラス基板を貼り合わせた後、上述した硬化条件で硬化させ、接着サンプルを作製した。
接着強度は、接着サンプルの一方のガラス基板を固定して、他のガラス基板を引張り試験速度５ｍｍ／ｍｉｎにて引張り、これらのガラス基板が剥がれたときの最大値を接着強度した。結果を第１表に示す。<Adhesive strength>
Each photocurable resin composition was applied to a glass substrate so that the adhesion area was 5 mm and the adhesion thickness was 0.3 mm, and another glass substrate was bonded so as to be orthogonal to the glass substrate. Cured to produce an adhesive sample.
For the adhesive strength, one glass substrate of the adhesive sample was fixed, the other glass substrate was pulled at a tensile test speed of 5 mm / min, and the maximum value when these glass substrates were peeled was defined as the adhesive strength. The results are shown in Table 1.
＜高温高湿下での接着強度＞
上記で作製した接着試料を６５℃９５％ＲＨの高温高湿環境下に置き、１００時間経過した後の接着強度を上記と同様の方法で測定した。結果を第１表に示す。<Adhesive strength under high temperature and high humidity>
The adhesive sample prepared above was placed in a high-temperature and high-humidity environment of 65 ° C. and 95% RH, and the adhesive strength after 100 hours was measured by the same method as described above. The results are shown in Table 1.
上記第１表に示す成分のうち、上述した光硬化性樹脂（Ａ−１）〜（Ａ−７）および（Ｅ−１）〜（Ｅ−６）以外については、以下のとおりである。
・単官能アクリレート（Ｂ−１）：ジシクロペンテニルアクリレート
・単官能アクリレート（Ｂ−２）：イソボルニルアクリレート
・単官能アクリレート（Ｂ−３）：イソデシルアクリレート
・エステル基含有アクリレート（Ｄ−１）：不飽和脂肪酸ヒドロキシアルキルエステル修飾ε-カプロラクトン（プラクセルＦＭ１、ダイセル社製）
・エステル基含有アクリレート（Ｄ−２）：不飽和脂肪酸ヒドロキシアルキルエステル修飾ε-カプロラクトン（プラクセルＦＭ３、ダイセル社製）
・光重合開始剤（Ｃ−１）：イルガキュア１８４（ＢＡＳＦ社製）
・液状可塑剤（Ｆ−１）：エステル系可塑剤（ＴｅｇＭｅＲ ８０４、HallStar社製）
・液状可塑剤（Ｆ−２）：ポリエチレン系可塑剤（Ｖｅｒｓａｆｌｏｅ ＥＶ、Ｓｈａｍｒｏｃｋ社製）Among the components shown in Table 1, the components other than the photocurable resins (A-1) to (A-7) and (E-1) to (E-6) described above are as follows.
Monofunctional acrylate (B-1): Dicyclopentenyl acrylate Monofunctional acrylate (B-2): Isobornyl acrylate Monofunctional acrylate (B-3): Isodecyl acrylate Ester group-containing acrylate (D-1 ): Unsaturated fatty acid hydroxyalkyl ester modified ε-caprolactone (Placcel FM1, manufactured by Daicel Corporation)
Ester group-containing acrylate (D-2): unsaturated fatty acid hydroxyalkyl ester modified ε-caprolactone (Placcel FM3, manufactured by Daicel)
Photopolymerization initiator (C-1): Irgacure 184 (manufactured by BASF)
Liquid plasticizer (F-1): Ester plasticizer (TegMeR 804, manufactured by HallStar)
Liquid plasticizer (F-2): Polyethylene plasticizer (Versafloe EV, manufactured by Shamrock)
上記第１表に示す結果より、主鎖骨格における上記式（Ｉｂ）で表される繰り返し単位のモル％にかかわらず、上記式（ＩＶ）で表される末端構造を有する光硬化性樹脂を用いた場合には、重合度が低く、接着強度が劣り、高温高湿下での接着強度も低くなることが分かった（比較例１〜３）。
また、主鎖骨格におけるウレタン結合の有無にかかわらず、主鎖骨格における上記式（Ｉｂ）で表される繰り返し単位のモル％を満たしていない光硬化性樹脂を用いた場合には、重合度は高くなるが、接着強度が劣り、高温高湿下での接着強度も低くなることが分かった（比較例４および５）。
また、主鎖骨格にウレタン結合を有していない光硬化性樹脂を用いた場合には、重合度は高くなるが、接着強度が劣り、高温高湿下での接着強度も低くなることが分かった（比較例６）。From the results shown in Table 1, the photocurable resin having the terminal structure represented by the formula (IV) is used regardless of the mol% of the repeating unit represented by the formula (Ib) in the main chain skeleton. It was found that the degree of polymerization was low, the adhesive strength was poor, and the adhesive strength under high temperature and high humidity was also low (Comparative Examples 1 to 3).
In addition, regardless of the presence or absence of a urethane bond in the main chain skeleton, when using a photocurable resin that does not satisfy the mol% of the repeating unit represented by the above formula (Ib) in the main chain skeleton, the degree of polymerization is Although it became high, it turned out that adhesive strength is inferior and the adhesive strength under high temperature, high humidity also becomes low (comparative examples 4 and 5).
In addition, when a photo-curing resin that does not have a urethane bond in the main chain skeleton is used, the degree of polymerization is increased, but the adhesive strength is poor, and the adhesive strength under high temperature and high humidity is also low. (Comparative Example 6).
これに対し、主鎖骨格に上記式（Ｉｂ）で表される繰り返し単位を特定の割合で有し、上記式（ＩＩａ）または上記式（ＩＩｂ）で表される末端構造を有し、主鎖骨格にウレタン結合を少なくとも２個以上有する光硬化性樹脂（Ａ）を用いた場合には、いずれも重合度が高く、接着強度が高くなり、高温高湿下での接着性も良好となることが分かった（実施例１〜１０）。 On the other hand, the main chain skeleton has a repeating unit represented by the above formula (Ib) at a specific ratio, has a terminal structure represented by the above formula (IIa) or the above formula (IIb), and the main clavicle. When using a photocurable resin (A) having at least two urethane bonds, the degree of polymerization is high, the adhesive strength is high, and the adhesiveness under high temperature and high humidity is also good. Was found (Examples 1 to 10).
Claims (1)
式中、Ｒ 1 は水素原子またはメチル基を表し、Ｒ 3 は炭素数２〜６のアルキレン基を表し、ｒは３〜８の整数を表し、ｓは１〜５の整数を表す。
前記光硬化性樹脂が、主鎖骨格に下記式（Ｉａ）〜（Ｉｃ）で表される繰り返し単位のうち、少なくとも下記式（Ｉｂ）で表される繰り返し単位を有する光硬化性樹脂であり、
下記式（Ｉａ）で表される繰り返し単位の含有量が、下記式（Ｉａ）〜（Ｉｃ）で表される全繰り返し単位に対して０〜４０モル％であり、
下記式（Ｉｂ）で表される繰り返し単位の含有量が、下記式（Ｉａ）〜（Ｉｃ）で表される全繰り返し単位に対して６０〜１００モル％であり、
下記式（Ｉｃ）で表される繰り返し単位の含有量が、下記式（Ｉａ）〜（Ｉｃ）で表される全繰り返し単位に対して０〜１０モル％であり、
末端の少なくとも１つに下記式（ＩＩａ）または下記式（ＩＩｂ）で表される構造を有し、
主鎖骨格に下記式（ＩＩＩ）で表されるウレタン結合を少なくとも２個以上有する、光硬化性樹脂である、光硬化性樹脂組成物。
式（Ｉａ）〜式（Ｉｃ）中、破線と実線との二重線は単結合または二重結合を表し、式（ＩＩａ）および式（ＩＩｂ）中、Ｒ 1 はそれぞれ独立に水素原子またはメチル基を表し、式（ＩＩａ）中、ｎは１〜７の整数を表し、式（ＩＩａ）、式（ＩＩｂ）および式（ＩＩＩ）中、＊は主鎖との結合位置を表す。 A photocurable resin, a monofunctional (meth) acrylate compound having one (meth) acryloyloxy group, a photopolymerization initiator, and an ester group-containing (meth) acrylate represented by the following formula :
In the formula, R 1 represents a hydrogen atom or a methyl group, R 3 represents an alkylene group having 2 to 6 carbon atoms, r represents an integer of 3 to 8, and s represents an integer of 1 to 5.
The photocurable resin is a photocurable resin having at least a repeating unit represented by the following formula (Ib) among repeating units represented by the following formulas (Ia) to (Ic) in the main chain skeleton,
The content of the repeating unit represented by the following formula (Ia) is 0 to 40 mol% with respect to all the repeating units represented by the following formulas (Ia) to (Ic),
The content of the repeating unit represented by the following formula (Ib) is 60 to 100 mol% with respect to all the repeating units represented by the following formulas (Ia) to (Ic),
The content of the repeating unit represented by the following formula (Ic) is 0 to 10 mol% with respect to all the repeating units represented by the following formulas (Ia) to (Ic),
At least one of the terminals has a structure represented by the following formula (IIa) or the following formula (IIb);
A photocurable resin composition which is a photocurable resin having at least two urethane bonds represented by the following formula (III) in the main chain skeleton .
In the formulas (Ia) to (Ic), the double line between the broken line and the solid line represents a single bond or a double bond, and in the formulas (IIa) and (IIb), each R 1 is independently a hydrogen atom or methyl. In the formula (IIa), n represents an integer of 1 to 7, and in the formula (IIa), the formula (IIb) and the formula (III), * represents a bonding position with the main chain.
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