JP6710892B2 - Curable resin composition - Google Patents
Curable resin composition Download PDFInfo
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- JP6710892B2 JP6710892B2 JP2015003900A JP2015003900A JP6710892B2 JP 6710892 B2 JP6710892 B2 JP 6710892B2 JP 2015003900 A JP2015003900 A JP 2015003900A JP 2015003900 A JP2015003900 A JP 2015003900A JP 6710892 B2 JP6710892 B2 JP 6710892B2
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- meth
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- resin composition
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims description 49
- -1 amine compound Chemical class 0.000 claims description 65
- 239000003822 epoxy resin Substances 0.000 claims description 40
- 229920000647 polyepoxide Polymers 0.000 claims description 40
- 150000003568 thioethers Chemical class 0.000 claims description 32
- 125000004432 carbon atom Chemical group C* 0.000 claims description 28
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 23
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 150000002430 hydrocarbons Chemical group 0.000 description 29
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 21
- 150000001875 compounds Chemical class 0.000 description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- 125000003396 thiol group Chemical group [H]S* 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 230000007423 decrease Effects 0.000 description 13
- 125000003700 epoxy group Chemical group 0.000 description 13
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 13
- 229920002799 BoPET Polymers 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000000758 substrate Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 239000003999 initiator Substances 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 150000001412 amines Chemical class 0.000 description 8
- 238000001723 curing Methods 0.000 description 8
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 7
- 239000004593 Epoxy Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 6
- 238000010438 heat treatment Methods 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 230000008719 thickening Effects 0.000 description 4
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 3
- 239000003759 ester based solvent Substances 0.000 description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 3
- 150000007529 inorganic bases Chemical class 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
- UIDDPPKZYZTEGS-UHFFFAOYSA-N 3-(2-ethyl-4-methylimidazol-1-yl)propanenitrile Chemical compound CCC1=NC(C)=CN1CCC#N UIDDPPKZYZTEGS-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 239000002318 adhesion promoter Substances 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 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
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 150000004291 polyenes Chemical class 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000006798 ring closing metathesis reaction Methods 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 125000000101 thioether group Chemical group 0.000 description 2
- 239000004034 viscosity adjusting agent Substances 0.000 description 2
- VJDHKUHTYJLWPV-UHFFFAOYSA-N (2-nitrophenyl)methyl 4-(2-methylprop-2-enoyloxy)piperidine-1-carboxylate Chemical compound C(C(=C)C)(=O)OC1CCN(CC1)C(=O)OCC1=C(C=CC=C1)[N+](=O)[O-] VJDHKUHTYJLWPV-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- RUEBPOOTFCZRBC-UHFFFAOYSA-N (5-methyl-2-phenyl-1h-imidazol-4-yl)methanol Chemical compound OCC1=C(C)NC(C=2C=CC=CC=2)=N1 RUEBPOOTFCZRBC-UHFFFAOYSA-N 0.000 description 1
- YBBLOADPFWKNGS-UHFFFAOYSA-N 1,1-dimethylurea Chemical class CN(C)C(N)=O YBBLOADPFWKNGS-UHFFFAOYSA-N 0.000 description 1
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 1
- FBHPRUXJQNWTEW-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=CN1CC1=CC=CC=C1 FBHPRUXJQNWTEW-UHFFFAOYSA-N 0.000 description 1
- XZKLXPPYISZJCV-UHFFFAOYSA-N 1-benzyl-2-phenylimidazole Chemical compound C1=CN=C(C=2C=CC=CC=2)N1CC1=CC=CC=C1 XZKLXPPYISZJCV-UHFFFAOYSA-N 0.000 description 1
- FODCFYIWOJIZQL-UHFFFAOYSA-N 1-methylsulfanyl-3,5-bis(trifluoromethyl)benzene Chemical compound CSC1=CC(C(F)(F)F)=CC(C(F)(F)F)=C1 FODCFYIWOJIZQL-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
- RUFZNDNBXKOZQV-UHFFFAOYSA-N 2,3-dihydro-1h-pyrrolo[1,2-a]benzimidazole Chemical compound C1=CC=C2N(CCC3)C3=NC2=C1 RUFZNDNBXKOZQV-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-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
- UGCSBIWAULODOR-UHFFFAOYSA-N 2-[2-(5,5-dimethoxycyclohexa-1,3-dien-1-yl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound COC1(CC(C=CC2=NC(=NC(=N2)C(Cl)(Cl)Cl)C(Cl)(Cl)Cl)=CC=C1)OC UGCSBIWAULODOR-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- UCRXZJYCOMRCER-UHFFFAOYSA-N 2-[n,n'-di(propan-2-yl)carbamimidoyl]-1,1,3,3-tetramethylguanidine Chemical compound CC(C)NC(=NC(C)C)N=C(N(C)C)N(C)C UCRXZJYCOMRCER-UHFFFAOYSA-N 0.000 description 1
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-UHFFFAOYSA-N 0.000 description 1
- PCKZAVNWRLEHIP-UHFFFAOYSA-N 2-hydroxy-1-[4-[[4-(2-hydroxy-2-methylpropanoyl)phenyl]methyl]phenyl]-2-methylpropan-1-one Chemical compound C1=CC(C(=O)C(C)(O)C)=CC=C1CC1=CC=C(C(=O)C(C)(C)O)C=C1 PCKZAVNWRLEHIP-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical compound CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 1
- NHCZYSDZAMNWGB-UHFFFAOYSA-N 3,4,6,7,8,9-hexahydro-2h-pyrimido[1,2-a]pyrimidine;2-(9-oxoxanthen-2-yl)propanoic acid Chemical compound C1CCN2CCCNC2=N1.C1=CC=C2C(=O)C3=CC(C(C(O)=O)C)=CC=C3OC2=C1 NHCZYSDZAMNWGB-UHFFFAOYSA-N 0.000 description 1
- SESYNEDUKZDRJL-UHFFFAOYSA-N 3-(2-methylimidazol-1-yl)propanenitrile Chemical compound CC1=NC=CN1CCC#N SESYNEDUKZDRJL-UHFFFAOYSA-N 0.000 description 1
- SZUPZARBRLCVCB-UHFFFAOYSA-N 3-(2-undecylimidazol-1-yl)propanenitrile Chemical compound CCCCCCCCCCCC1=NC=CN1CCC#N SZUPZARBRLCVCB-UHFFFAOYSA-N 0.000 description 1
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- WPYCRFCQABTEKC-UHFFFAOYSA-N C(C1OC1)Oc1cccc(OCC2OC2)c1 Chemical compound C(C1OC1)Oc1cccc(OCC2OC2)c1 WPYCRFCQABTEKC-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- KLJLQTJYNGGTIU-FOWTUZBSSA-N [(e)-1-phenylethylideneamino] benzoate Chemical compound C=1C=CC=CC=1C(/C)=N/OC(=O)C1=CC=CC=C1 KLJLQTJYNGGTIU-FOWTUZBSSA-N 0.000 description 1
- AGJXDKGTTMVHOU-UHFFFAOYSA-N [4-(hydroxymethyl)-1h-imidazol-5-yl]methanol Chemical compound OCC=1N=CNC=1CO AGJXDKGTTMVHOU-UHFFFAOYSA-N 0.000 description 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- XTKDAFGWCDAMPY-UHFFFAOYSA-N azaperone Chemical compound C1=CC(F)=CC=C1C(=O)CCCN1CCN(C=2N=CC=CC=2)CC1 XTKDAFGWCDAMPY-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- VGZKCAUAQHHGDK-UHFFFAOYSA-M bis(4-tert-butylphenyl)iodanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C1=CC(C(C)(C)C)=CC=C1[I+]C1=CC=C(C(C)(C)C)C=C1 VGZKCAUAQHHGDK-UHFFFAOYSA-M 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 1
- OZLBDYMWFAHSOQ-UHFFFAOYSA-N diphenyliodanium Chemical compound C=1C=CC=CC=1[I+]C1=CC=CC=C1 OZLBDYMWFAHSOQ-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Epoxy Resins (AREA)
Description
本発明は、寒冷地においても基材に対する密着性が優れ、且つ、得られた硬化膜が柔軟性を有する硬化性樹脂組成物に関するものである。 The present invention relates to a curable resin composition that has excellent adhesion to a substrate even in cold regions and that the obtained cured film has flexibility.
従来、エポキシ樹脂を主成分とする塗料等の無機基材に対する密着性を向上させるために、シランカップリング剤を添加する技術がある(例えば特許文献1)。しかしながら、シランカップリング剤の多くは沸点が低く、熱硬化樹脂に対しては多量に添加する必要があった。また、密着性向上効果も充分とは言えず、例えばチタン・ジルコニウム等の塩や、リン酸エステル、ウレタン樹脂等の密着性助剤も同時に添加することによって初めて実用レベルで求められる密着性を達成できる場合も多かった。この場合、これら密着性助剤の配合は工程数が増加するだけでなく、塗料特性を損なわないような密着性助剤種の選定や、その添加量の厳密な最適化作業も必要であるという問題点があった。 Conventionally, there is a technique of adding a silane coupling agent in order to improve adhesion to an inorganic base material such as a coating material containing an epoxy resin as a main component (for example, Patent Document 1). However, most of the silane coupling agents have low boiling points, and it was necessary to add a large amount to the thermosetting resin. In addition, the effect of improving the adhesion is not sufficient. For example, the adhesion required at a practical level can be achieved only by simultaneously adding a salt such as titanium and zirconium or an adhesion aid such as a phosphate ester or a urethane resin. It was often possible. In this case, not only the number of steps of compounding these adhesion promoters increases, but it is also necessary to select adhesion promoter species that do not impair the coating properties and strictly optimize the addition amount. There was a problem.
そこで、特許文献2には、多官能チオール化合物と特定のチオエーテル含有アルコキシシラン誘導体を、エポキシ樹脂組成物、及び、二重結合を複数個有する多官能ポリエンと混合した硬化性樹脂組成物が提案されている。この硬化性樹脂組成物は、シランカップリング剤を使用する場合のように、その他の密着性助剤等を添加する必要が無く、無機基材に対して優れた密着性を発揮することができる。 Therefore, Patent Document 2 proposes a curable resin composition in which a polyfunctional thiol compound and a specific thioether-containing alkoxysilane derivative are mixed with an epoxy resin composition and a polyfunctional polyene having a plurality of double bonds. ing. Unlike the case of using a silane coupling agent, this curable resin composition can exhibit excellent adhesion to an inorganic base material without the need to add other adhesion aids or the like. ..
しかしながら、特許文献2のように多官能チオール化合物及び特定のチオエーテル含有アルコキシシラン誘導体を、エポキシ樹脂組成物、及び、二重結合を複数個有する多官能ポリエンと混合した硬化性樹脂組成物は、無機基材に対する密着性に優れ、樹脂組成物の貯蔵安定性に優れるものの、寒冷地においては硬化膜が柔軟性に乏しいため屈曲時にクラックが生じやすく、更に、密着性に乏しいといった課題があることが判明した。 However, as in Patent Document 2, a curable resin composition obtained by mixing a polyfunctional thiol compound and a specific thioether-containing alkoxysilane derivative with an epoxy resin composition and a polyfunctional polyene having a plurality of double bonds is an inorganic compound. Although it has excellent adhesion to the substrate and excellent storage stability of the resin composition, in a cold region the cured film has poor flexibility, so cracks tend to occur during bending, and there is also the problem of poor adhesion. found.
本発明は上記実状に鑑みて成し遂げられたものであり、その目的は、寒冷地においても基材に対する密着性が優れ、且つ、得られた硬化膜が柔軟性を有する材料を提供することにある。 The present invention has been accomplished in view of the above circumstances, and an object thereof is to provide a material having excellent adhesion to a substrate even in a cold region, and a cured film obtained having flexibility. ..
本発明は次の〔1〕から〔3〕である。
〔1〕(A)下記一般式(1)であるチオエーテル含有(メタ)アクリレート誘導体と、(B)分子量が50000以下であり、下記一般式(11)で表される多官能エポキシ樹脂と、(C)分子量が90〜700であるアミン化合物と、を含有し、前記(A)成分と前記(B)成分との質量比((A)/(B))が0.05〜30であり、前記(A)成分と前記(B)成分との合計質量100質量部に対し、前記(C)成分が0.01〜50質量部配合されてなる、硬化性樹脂組成物。
(式中のaは1〜2の整数であり、bは1〜2の整数であり、a+b=3である。R1は下記式2で表される3価の基であり、R2は下記式3または下記式4で表される2価の基である。R3は炭素数が1〜12の炭化水素基である。)
(式中のR4は−CH2−、−CH2CH2−、または−CH2CH(CH3)−である。)
(R5は水素原子またはメチル基である。)
(R5は水素原子またはメチル基である。)
なお、本発明において、分子量とは重量平均分子量のことである。
[1] (A) A thioether-containing (meth)acrylate derivative represented by the following general formula (1), and (B) a polyfunctional epoxy resin having a molecular weight of 50,000 or less and represented by the following general formula (11): C) an amine compound having a molecular weight of 90 to 700, and a mass ratio ((A)/(B)) of the component (A) and the component (B) is 0.05 to 30, A curable resin composition obtained by mixing 0.01 to 50 parts by mass of the component (C) with respect to 100 parts by mass of the total amount of the component (A) and the component (B).
(In the formula, a is an integer of 1-2, b is an integer of 1-2, and a+b=3. R 1 is a trivalent group represented by the following formula 2 and R 2 is It is a divalent group represented by the following formula 3 or the following formula 4. R 3 is a hydrocarbon group having 1 to 12 carbon atoms.)
(-CH 2 R 4 in the formula -, - CH 2 CH 2 - , or -CH 2 CH (CH 3) - and is.)
(R 5 is a hydrogen atom or a methyl group.)
(R 5 is a hydrogen atom or a methyl group.)
In addition, in this invention, a molecular weight is a weight average molecular weight.
〔2〕本発明の硬化性樹脂組成物は、前記(A)〜(C)成分に加えて、さらに下記(D)成分を含有させることもできる。(D)成分としては、分子量が200〜50000である多官能(メタ)アクリレート化合物を含有させることができる。当該(D)成分は、前記(A)成分と前記(B)成分との合計質量100質量部に対し、2〜300質量部配合する。 [2] The curable resin composition of the present invention may further contain the following component (D) in addition to the components (A) to (C). As the component (D), a polyfunctional (meth)acrylate compound having a molecular weight of 200 to 50,000 can be contained. The component (D) is added in an amount of 2 to 300 parts by mass based on 100 parts by mass of the total amount of the components (A) and (B).
〔3〕本発明の硬化性樹脂組成物は、前記(A)〜(D)成分に加えて、さらに下記(E)成分を含有させることもできる。(E)成分としては、光開始剤を含有させることができる。当該(E)成分は、前記(A)成分と前記(D)成分との合計質量100質量部に対し、0.01〜10質量部配合する。 [3] The curable resin composition of the present invention may further contain the following component (E) in addition to the components (A) to (D). A photoinitiator can be contained as the component (E). The component (E) is added in an amount of 0.01 to 10 parts by mass based on 100 parts by mass of the total amount of the components (A) and (D).
なお、本発明において「(メタ)アクリレート」とは、アクリレートとメタクリレートの双方を含む総称を意味する。また、本発明において数値範囲を示す「○○〜××」とは、その下限値(「○○」)や上限値(「××」)を含む概念である。すなわち、正確には「○○以上××以下」を意味する。 In addition, in this invention, "(meth)acrylate" means a general term including both acrylate and methacrylate. Further, in the present invention, “XX to XX” indicating a numerical range is a concept including the lower limit value (“XX”) and the upper limit value (“XX”). That is, to be precise, it means “more than XX and less than XX”.
本発明の硬化性樹脂組成物によれば、特定のチオエーテル含有(メタ)アクリレート誘導体(A)を密着性向上作用の有効成分としながら、特定の分子量の多官能エポキシ樹脂(B)と、特定の分子量のアミン化合物(C)がバランス良く配合されている。それにより、従来のシランカップリング剤を使用する場合のようにその他の密着性助剤等を添加することなく、基材に対する密着性に優れる。特に、従来の多官能チオール化合物を使用した硬化性樹脂組成物では不十分であった、寒冷地における基材に対する密着性にも優れ、且つ、得られた硬化膜が柔軟性を有する。 According to the curable resin composition of the present invention, a specific thioether-containing (meth)acrylate derivative (A) is used as an active ingredient for improving the adhesiveness, and a polyfunctional epoxy resin (B) having a specific molecular weight and The amine compound (C) having a molecular weight is blended in a good balance. As a result, the adhesiveness to the substrate is excellent without adding other adhesiveness aids and the like as in the case of using a conventional silane coupling agent. In particular, a curable resin composition using a conventional polyfunctional thiol compound was not sufficient, and the adhesiveness to a base material in cold regions was excellent, and the obtained cured film had flexibility.
以下に、本発明について詳しく説明する。本発明の硬化性樹脂組成物は、下記(A)、(B)、及び(C)成分を必須成分とし、必要に応じて(D)成分、さらに(E)成分も含有する硬化性樹脂組成物である。 The present invention will be described in detail below. The curable resin composition of the present invention comprises the following components (A), (B), and (C) as essential components, and optionally a component (D) and further a component (E). It is a thing.
<チオエーテル含有(メタ)アクリレート誘導体((A)成分)>
(A)成分であるチオエーテル含有(メタ)アクリレート誘導体とは、下記式1で表される化合物である。
(式中のaは1〜2の整数であり、bは1〜2の整数であり、a+b=3である。R1は下記式2で表される3価の基であり、R2は下記式3または下記式4で表される2価の基である。R3は炭素数が1〜12の炭化水素基である。)
(式中のR4は−CH2−、−CH2CH2−、または−CH2CH(CH3)−である。)
(R5は水素原子またはメチル基である。)
(R5は水素原子またはメチル基である。)
<Thioether-containing (meth)acrylate derivative ((A) component)>
The thioether-containing (meth)acrylate derivative as the component (A) is a compound represented by the following formula 1.
(In the formula, a is an integer of 1-2, b is an integer of 1-2, and a+b=3. R 1 is a trivalent group represented by the following formula 2 and R 2 is It is a divalent group represented by the following formula 3 or the following formula 4. R 3 is a hydrocarbon group having 1 to 12 carbon atoms.)
(-CH 2 R 4 in the formula -, - CH 2 CH 2 - , or -CH 2 CH (CH 3) - and is.)
(R 5 is a hydrogen atom or a methyl group.)
(R 5 is a hydrogen atom or a methyl group.)
上記式1中のR3である炭素数が1〜12の炭化水素基としては、直鎖のアルキル基、側鎖を持つアルキル基、環状のアルキル基が挙げられる。 Examples of the hydrocarbon group having 1 to 12 carbon atoms, which is R 3 in the above formula 1, include a linear alkyl group, an alkyl group having a side chain, and a cyclic alkyl group.
上記式2中のR4は、メチレン基、エチレン基、イソプロピレン基であり、密着性向上効果が高くなることから、エチレン基、イソプロピレン基が特に好ましい。 R 4 in the above formula 2 is a methylene group, an ethylene group, or an isopropylene group, and an ethylene group and an isopropylene group are particularly preferable because the effect of improving the adhesion is enhanced.
<多官能エポキシ樹脂((B)成分)>
(B)成分である多官能エポキシ樹脂とは、2個以上のエポキシ基(オキシラン環)を有する有機化合物である。多官能エポキシ樹脂の分子量は200〜50000、好ましくは200〜48000、より好ましくは200〜46000である。分子量が200より小さくても密着性に関しては問題ないが、多官能エポキシ樹脂の揮発性が高くなり、臭気が強くなる傾向がある。一方、分子量が50000より大きいと、他の成分に対する溶解性が低くなって、基材に対する密着性が低下する可能性がある。
<Polyfunctional epoxy resin (component (B))>
The polyfunctional epoxy resin as the component (B) is an organic compound having two or more epoxy groups (oxirane ring). The molecular weight of the polyfunctional epoxy resin is 200 to 50,000, preferably 200 to 48,000, and more preferably 200 to 46,000. Even if the molecular weight is less than 200, there is no problem in terms of adhesion, but the volatility of the polyfunctional epoxy resin is high and the odor tends to be strong. On the other hand, when the molecular weight is more than 50,000, the solubility with respect to other components may be low and the adhesion to the substrate may be reduced.
多官能エポキシ樹脂のエポキシ当量は80〜6000g/mol、好ましくは85〜5500g/mol、より好ましくは90〜5000g/molとする。エポキシ当量が80g/molより小さいと、単位体積あたりのエポキシ基が過剰になって、(A)チオエーテル含有(メタ)アクリレート誘導体のチオール基と未反応のエポキシ基が多量に残存することで、硬化性樹脂組成物からなる硬化膜の靭性が低下し、密着性が低下するおそれがある。一方、エポキシ当量が6000g/molより大きいと、エポキシ基濃度が著しく低いことから(A)チオエーテル含有(メタ)アクリレート誘導体のチオール基との反応効率が低下することで、硬化性樹脂組成物からなる硬化膜の靭性が低下し、基材に対する密着性が低下するおそれがある。 The epoxy equivalent of the polyfunctional epoxy resin is 80 to 6000 g/mol, preferably 85 to 5500 g/mol, more preferably 90 to 5000 g/mol. When the epoxy equivalent is less than 80 g/mol, the epoxy group per unit volume becomes excessive, and a large amount of the thiol group of the (A) thioether-containing (meth)acrylate derivative and the unreacted epoxy group remain, and thus curing. The toughness of the cured film made of the resin composition may decrease, and the adhesion may decrease. On the other hand, when the epoxy equivalent is more than 6000 g/mol, the epoxy group concentration is remarkably low, so that the reaction efficiency with the thiol group of the (A) thioether-containing (meth)acrylate derivative is lowered, and thus the curable resin composition is formed. The toughness of the cured film may decrease, and the adhesion to the substrate may decrease.
(B)成分である多官能エポキシ樹脂としては、例えばグリシジルエーテル型エポキシ樹脂、グリシジルエステル型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、又は二重結合含有化合物の二重結合を過酸化物で酸化して得られる酸化型エポキシ樹脂などが挙げられる。これら中でも、室温での反応性が遅く可使用時間が長くなることから、グリシジルエーテル型エポキシ樹脂やグリシジルエステル型エポキシ樹脂が好ましい。なお、多官能エポキシ樹脂は、1種のみを単独で使用することもできるし、2種以上を混合使用することもできる。 As the polyfunctional epoxy resin as the component (B), for example, a glycidyl ether type epoxy resin, a glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, or a double bond-containing compound obtained by oxidizing a double bond with a peroxide is used. The obtained oxidation type epoxy resin etc. are mentioned. Among these, a glycidyl ether type epoxy resin and a glycidyl ester type epoxy resin are preferable because they have a low reactivity at room temperature and a long usable time. The polyfunctional epoxy resins may be used alone or in combination of two or more.
〔グリシジルエーテル型エポキシ樹脂〕
グリシジルエーテル型エポキシ樹脂としては、エピクロロヒドリンと下記一般式(5)で表される化合物との反応生成物が好ましい。
(式中のcは2〜30の整数であり、R6は炭素数2〜200の炭化水素基(β1)、炭素数2〜300のエーテル酸素(−O−)と炭化水素基のみからなる基(β2)、イソシアヌレート環(β3)、イソシアヌレート環と炭化水素基のみからなる基(β4)である。)
[Glycidyl ether type epoxy resin]
As the glycidyl ether type epoxy resin, a reaction product of epichlorohydrin and a compound represented by the following general formula (5) is preferable.
(C in the formula is an integer of 2 to 30, and R 6 is composed of a hydrocarbon group (β1) having 2 to 200 carbon atoms, an ether oxygen (—O—) having 2 to 300 carbon atoms, and a hydrocarbon group only. A group (β2), an isocyanurate ring (β3), and a group (β4) consisting only of an isocyanurate ring and a hydrocarbon group.)
上記一般式(5)で表される化合物の中でも、cが2〜20であり、且つR6が炭素数2〜150の炭化水素基からなる基である化合物(β1−1)、又はcが2〜20であり、且つR6が炭素数2〜150の炭化水素基とエーテル酸素(−O−)のみからなる基であり化合物(β2−1)が、他の成分との溶解性が高いという理由で好ましい。(β1−1)としては、例えば炭素数2〜10のアルキレンジオール、グリセリン、ペンタエリスリトール、トリメチロールプロパン、フェノールノボラック、ビスフェノールA等が挙げられる。(β2−1)としては、例えばポリエチレングリコール、ポリプロピレングリコール、又はジペンタエリスリトール等が挙げられる。 Among the compounds represented by the general formula (5), the compound (β1-1) in which c is 2 to 20 and R 6 is a hydrocarbon group having 2 to 150 carbon atoms, or c is 2 to 20 and R 6 is a group consisting only of a hydrocarbon group having 2 to 150 carbon atoms and ether oxygen (—O—), and the compound (β2-1) has high solubility with other components. Therefore, it is preferable. Examples of (β1-1) include alkylenediol having 2 to 10 carbon atoms, glycerin, pentaerythritol, trimethylolpropane, phenol novolac, bisphenol A and the like. Examples of (β2-1) include polyethylene glycol, polypropylene glycol, dipentaerythritol, and the like.
上記のエピクロロヒドリンと一般式(5)で表される化合物との反応は、エピクロロヒドリンと一般式(5)で表される化合物の水酸基とが付加反応して得られるクロロヒドリンを、酸化ナトリウム等の塩基で閉環しエポキシ樹脂を得ることができる。また、グリシジルエーテル型エポキシ樹脂は前記の閉環反応の後得られたエポキシ樹脂のエポキシ基の一部を開環重合させたエポキシ樹脂でもよい。 The reaction between the epichlorohydrin and the compound represented by the general formula (5) is performed by adding chlorohydrin obtained by addition reaction between epichlorohydrin and the hydroxyl group of the compound represented by the general formula (5), The epoxy resin can be obtained by ring closure with a base such as sodium oxide. The glycidyl ether type epoxy resin may be an epoxy resin obtained by ring-opening polymerization of a part of the epoxy groups of the epoxy resin obtained after the ring-closing reaction.
エピクロロヒドリンと一般式(5)で表される化合物の反応生成物は、下記一般式(6)の構造となる。
(式中のcは2〜30の整数であり、R6は炭素数2〜200の炭化水素基(β1)、炭素数2〜300のエーテル酸素(−O−)と炭化水素基のみからなる基(β2)、イソシアヌレート環(β3)、又はイソシアヌレート環と炭化水素基のみからなる基(β4)である。)
The reaction product of epichlorohydrin and the compound represented by the general formula (5) has the structure of the following general formula (6).
(C in the formula is an integer of 2 to 30, and R 6 is composed of a hydrocarbon group (β1) having 2 to 200 carbon atoms, an ether oxygen (—O—) having 2 to 300 carbon atoms, and a hydrocarbon group only. A group (β2), an isocyanurate ring (β3), or a group (β4) consisting only of an isocyanurate ring and a hydrocarbon group.)
〔グリシジルエステル型エポキシ樹脂〕
グリシジルエステル型エポキシ樹脂は、グリシジル(メタ)アクリレート等のエポキシ基を有するモノマーを単独あるいは炭素数4〜25のアルキル(メタ)アクリレートと共重合して得られる重量平均分子量3000〜20000のポリマー又はエピクロロヒドリンと、下記一般式(7)で表される化合物との反応生成物などである。
(式中のdは2〜8の整数であり、R7は炭素数2〜20の炭化水素基(β5)、炭素数2〜30のエーテル酸素(−O−)と炭化水素基のみからなる基(β6)、イソシアヌレート環(β7)、又はイソシアヌレート環と炭化水素基のみからなる基(β8)のいずれかである。)
[Glycidyl ester type epoxy resin]
The glycidyl ester type epoxy resin is a polymer having a weight average molecular weight of 3,000 to 20,000 or obtained by copolymerizing a monomer having an epoxy group such as glycidyl (meth)acrylate alone or with an alkyl (meth)acrylate having 4 to 25 carbon atoms. Examples include reaction products of chlorohydrin and a compound represented by the following general formula (7).
(D in the formula is an integer of 2 to 8, and R 7 is composed only of a hydrocarbon group having 2 to 20 carbon atoms (β5), an ether oxygen having 2 to 30 carbon atoms (-O-), and a hydrocarbon group. It is either a group (β6), an isocyanurate ring (β7), or a group (β8) consisting only of an isocyanurate ring and a hydrocarbon group.)
エピクロロヒドリンと一般式(7)で表される化合物との反応は、エピクロロヒドリンと一般式(7)の化合物のカルボキシル基とが付加反応して得られるクロロヒドリンを、水酸化ナトリウム等の塩基で閉環しグリシジルエステル型エポキシ樹脂を得ることができる。また、グリシジルエステル型エポキシ樹脂のエポキシ基の一部を開環重合させたエポキシ樹脂も使用することができる。 The reaction between epichlorohydrin and the compound represented by the general formula (7) is performed by adding chlorohydrin obtained by addition reaction between epichlorohydrin and the carboxyl group of the compound of the general formula (7) to sodium hydroxide or the like. The glycidyl ester type epoxy resin can be obtained by ring closure with the base. An epoxy resin obtained by ring-opening polymerization of a part of the epoxy groups of the glycidyl ester type epoxy resin can also be used.
上記一般式(7)で表される化合物の中でも、dが2〜4であり、且つR7が炭素数2〜10の炭化水素基からなる基であり化合物(β5−1)、dが2〜6であり、且つR7が炭素数2〜30のエーテル酸素(−O−)と炭化水素基のみからなる基であり化合物(β6−1)、又はdが3であり、且つR7がイソシアヌレート環と炭化水素基のみからなる基である化合物(β8−1)が、溶解性が高いという理由で好ましく挙げられる。 Among the compounds represented by the general formula (7), d is 2 to 4 and R 7 is a group consisting of a hydrocarbon group having 2 to 10 carbon atoms, and the compound (β5-1), d is 2 To 6 and R 7 is a group consisting of only ether oxygen (—O—) having 2 to 30 carbon atoms and a hydrocarbon group and is a compound (β6-1), or d is 3 and R 7 is The compound (β8-1), which is a group consisting of an isocyanurate ring and a hydrocarbon group, is preferred because of its high solubility.
(β5−1)としては、例えばヒドロフタル酸やトリメリット酸等が挙げられる。(β6−1)としては、例えばペンタエリスリトールと無水トリメリット酸との反応物が挙げられる。(β8−1)としては、例えば1,3,5−トリス(2−カルボキシエチル)イソシアヌレート等が挙げられる。 Examples of (β5-1) include hydrophthalic acid and trimellitic acid. Examples of (β6-1) include a reaction product of pentaerythritol and trimellitic anhydride. Examples of (β8-1) include 1,3,5-tris(2-carboxyethyl)isocyanurate.
エピクロロヒドリンと一般式(7)で表される化合物の反応生成物は、下記一般式(8)の構造となる。
(式中のdは2〜8の整数であり、R7は炭素数2〜20の炭化水素基(β5)、炭素数2〜30のエーテル酸素(−O−)と炭化水素基のみからなる基(β6)、イソシアヌレート環(β7)、又はイソシアヌレート環と炭化水素基のみからなる基(β8)のいずれかである。)
The reaction product of epichlorohydrin and the compound represented by the general formula (7) has a structure of the following general formula (8).
(D in the formula is an integer of 2 to 8, and R 7 is composed only of a hydrocarbon group having 2 to 20 carbon atoms (β5), an ether oxygen having 2 to 30 carbon atoms (-O-), and a hydrocarbon group. It is either a group (β6), an isocyanurate ring (β7), or a group (β8) consisting only of an isocyanurate ring and a hydrocarbon group.)
<アミン化合物((C)成分)>
(C)成分であるアミン化合物は、チオール基とエポキシ基との反応を促進(触媒)するために添加される。(C)成分であるアミン化合物としては、分子量が90〜700、好ましくは100〜690、より好ましくは110〜680の、単官能アミンや複数個のアミノ基とを有するポリアミンが挙げられる。アミン化合物の分子量が90未満では、アミンの揮発性が高くなり、臭気やボイドの原因となるだけではなく、加熱硬化時のアミン濃度が低くなるため架橋反応が進行し難くなり密着性が低下し易くなる。アミン化合物の分子量が700を超えると、耐水性が低くなり密着性が低下し易くなる。
<Amine compound ((C) component)>
The amine compound as the component (C) is added to accelerate (catalyze) the reaction between the thiol group and the epoxy group. Examples of the amine compound as the component (C) include monofunctional amines having a molecular weight of 90 to 700, preferably 100 to 690, and more preferably 110 to 680, and polyamines having a plurality of amino groups. When the molecular weight of the amine compound is less than 90, the volatility of the amine increases, which not only causes odor and voids, but also lowers the amine concentration at the time of heat curing, which makes it difficult for the crosslinking reaction to proceed and the adhesion decreases. It will be easier. When the molecular weight of the amine compound exceeds 700, the water resistance becomes low and the adhesiveness tends to deteriorate.
単官能アミンとしては、1級アミン、2級アミン、又は3級アミンが挙げられる。ポリアミンとしては、1級アミン、2級アミン、3級アミン、複合アミンが挙げられる。複合アミンとは、1級アミノ基、2級アミノ基、3級アミノ基のうち2種以上を有するアミンのことである。このような複合アミンとしては、イミダゾリン化合物、イミダゾール化合物、N置換ピペラジン化合物、N,N−ジメチル尿素誘導体等が挙げられる。なお、アミン化合物は、1種のみを単独で使用することもできるし、2種以上を混合使用することもできる。 Examples of monofunctional amines include primary amines, secondary amines, and tertiary amines. Examples of polyamines include primary amines, secondary amines, tertiary amines, and complex amines. The complex amine is an amine having two or more kinds of primary amino group, secondary amino group and tertiary amino group. Examples of such complex amines include imidazoline compounds, imidazole compounds, N-substituted piperazine compounds, N,N-dimethylurea derivatives and the like. The amine compounds may be used alone or in combination of two or more.
また、アミン化合物は、触媒活性を調整するために予め有機酸との塩を形成していても良い。アミン化合物と予め反応させる有機酸としては、炭素数1〜20でカルボキシル基を分子中に1〜5個有するステアリン酸や2−エチルヘキサン酸等の脂肪族カルボン酸、炭素数1〜20でカルボキシル基を分子中に1〜10個有するピロメリット酸、トリメリット酸、安息香酸等の芳香族カルボン酸、又はイソシアヌル酸が挙げられる。また、(C)成分であるアミン化合物は、触媒活性を調整するために(B)成分である多官能エポキシ樹脂とのアダクトを形成した後に配合されても良い。 Further, the amine compound may previously form a salt with an organic acid in order to adjust the catalytic activity. As the organic acid to be preliminarily reacted with the amine compound, aliphatic carboxylic acids such as stearic acid and 2-ethylhexanoic acid having 1 to 5 carbon atoms and 1 to 5 carboxyl groups in the molecule, and carboxylic acids having 1 to 20 carbon atoms. Examples thereof include aromatic carboxylic acids such as pyromellitic acid, trimellitic acid, and benzoic acid having 1 to 10 groups in the molecule, or isocyanuric acid. Further, the amine compound as the component (C) may be blended after forming an adduct with the polyfunctional epoxy resin as the component (B) in order to adjust the catalytic activity.
〔イミダゾール化合物〕
アミン化合物の中でも、イミダゾール化合物が最も保存安定性と低温における硬化時間の両立に適している。また、フェノール樹脂等でコーティングしたイミダゾール化合物も用いることができる。
[Imidazole compound]
Among the amine compounds, the imidazole compound is most suitable for satisfying both the storage stability and the curing time at low temperature. Also, an imidazole compound coated with a phenol resin or the like can be used.
当該イミダゾール化合物は、下記一般式(9)で表される化合物である。
(R9はシアノ基、炭素数1〜10の炭化水素基、2,3−ジアミノトリアジンで置換された炭素数1〜10の炭化水素基、炭素数1〜4のアルコキシ基、又は水素原子であり、R8、R10、R11は炭素数1〜20の炭化水素基、炭素数1〜4のアルコキシ基、又は水素原子であり、R8〜R11が結合して環を形成している場合には炭素数2〜8の炭化水素基である。)
The imidazole compound is a compound represented by the following general formula (9).
(R 9 is a cyano group, a hydrocarbon group having 1 to 10 carbon atoms, a hydrocarbon group having 1 to 10 carbon atoms substituted with 2,3-diaminotriazine, an alkoxy group having 1 to 4 carbon atoms, or a hydrogen atom. R 8 , R 10 , and R 11 are a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydrogen atom, and R 8 to R 11 are bonded to each other to form a ring. When it is present, it is a hydrocarbon group having 2 to 8 carbon atoms.)
具体的には、2−メチルイミダゾール、2−ウンデシルイミダゾール、2−ヘプタデシルイミダゾール、2−フェニルイミダゾール、1,2−ジメチルイミダゾール、2−フェニル−4−メチルイミダゾール、1−ベンジル−2−メチルイミダゾール、1−ベンジル−2−フェニルイミダゾール、2−エチル−4−メチルイミダゾール、1−(2−シアノエチル)−2−メチルイミダゾール、1−(2−シアノエチル)−2−ウンデシルイミダゾール、1−(2−シアノエチル)−2−エチル−4−メチルイミダゾール、1−(2−シアノエチル−2−フェニルイミダゾール、1−(2−シアノエチル)−2−エチル−4−メチルイミダゾール、2,3−ジヒドロ−1H−ピロロ[1,2−a]ベンズイミダゾール、2,4−ジアミノ−6−[2−メチルイミダゾリル−(1)]エチル−s−トリアジン、2,4−ジアミノ−6−[2’−ウンデシルイミダゾリル−(1’)]−エチル−s−トリアジン、2,4−ジアミノ−6−[2’−エチル−4'−メチルイミダゾリル−(1')]−エチル−s−トリアジン、2−フェニル−4,5−ジヒドロキシメチルイミダゾール、2−フェニル−4−メチル−5−ヒドロキシメチルイミダゾールが挙げられる。 Specifically, 2-methyl imidazole, 2-undecyl imidazole, 2-heptadecyl imidazole, 2-phenyl imidazole, 1,2-dimethyl imidazole, 2-phenyl-4-methyl imidazole, 1-benzyl-2-methyl Imidazole, 1-benzyl-2-phenylimidazole, 2-ethyl-4-methylimidazole, 1-(2-cyanoethyl)-2-methylimidazole, 1-(2-cyanoethyl)-2-undecylimidazole, 1-( 2-cyanoethyl)-2-ethyl-4-methylimidazole, 1-(2-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole,2,3-dihydro-1H -Pyrrolo[1,2-a]benzimidazole,2,4-diamino-6-[2-methylimidazolyl-(1)]ethyl-s-triazine,2,4-diamino-6-[2'-undecyl Imidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2-phenyl- Examples include 4,5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole.
<多官能(メタ)アクリレート化合物((D)成分)>
本発明の硬化性樹脂組成物は、(A)チオエーテル含有(メタ)アクリレート誘導体、(B)多官能エポキシ樹脂、及び(C)アミン化合物があれば、熱により硬化する。一方、本発明の硬化性樹脂組成物に光硬化性あるいは光熱二段階硬化性を付与したい場合には、(D)成分として多官能(メタ)アクリレート化合物を添加すればよい。
<Polyfunctional (meth)acrylate compound ((D) component)>
The curable resin composition of the present invention is cured by heat if (A) thioether-containing (meth)acrylate derivative, (B) polyfunctional epoxy resin, and (C) amine compound are present. On the other hand, when it is desired to impart photocurability or photothermal two-step curability to the curable resin composition of the present invention, a polyfunctional (meth)acrylate compound may be added as the component (D).
本発明において多数ある二重結合含有化合物の中でも、(D)成分として多官能(メタ)アクリレートを選択した理由は、本発明の硬化性樹脂組成物における(A)チオエーテル含有(メタ)アクリレート誘導体と室温では反応しにくく可使用時間を長く設定できること、(A)チオエーテル含有(メタ)アクリレート誘導体と反応した際に強靭な硬化物を形成すること、(C)アミン化合物により(A)チオエーテル含有(メタ)アクリレート誘導体との反応が触媒されにくいこと、(B)多官能エポキシ樹脂と反応しないこと等が挙げられる。 Among the many double bond-containing compounds in the present invention, the reason for selecting the polyfunctional (meth)acrylate as the component (D) is that the (A) thioether-containing (meth)acrylate derivative in the curable resin composition of the present invention is It is difficult to react at room temperature and the usable time can be set long, a tough cured product is formed when it reacts with (A) thioether-containing (meth)acrylate derivative, (C) amine compound (A) thioether-containing (meth) ) It is difficult to catalyze the reaction with the acrylate derivative, and it does not react with the (B) polyfunctional epoxy resin.
このような多官能(メタ)アクリレートとしては、下記一般式(10)で表される化合物が好ましく挙げられる。なお、(D)成分である多官能(メタ)アクリレートは、1種のみを単独で使用することもできるし、2種以上を混合使用することもできる。 As such a polyfunctional (meth)acrylate, a compound represented by the following general formula (10) is preferable. In addition, the polyfunctional (meth)acrylate which is a (D)component can also be used individually by 1 type, and can also mix and use 2 or more types.
(式中のeは2〜30の整数であり、R12は炭素数2〜200の炭化水素基(ε1)、炭素数2〜300のエーテル酸素(−O−)と炭化水素基のみからなる基(ε2)、イソシアヌレート環(ε3)、又はイソシアヌレート環と炭化水素基のみからなる基(ε4)であり、R13は水素原子またはメチル基である。)
(E in the formula is an integer of 2 to 30, and R 12 is composed only of a hydrocarbon group having 2 to 200 carbon atoms (ε1), an ether oxygen having 2 to 300 carbon atoms (-O-), and a hydrocarbon group. A group (ε2), an isocyanurate ring (ε3), or a group (ε4) consisting only of an isocyanurate ring and a hydrocarbon group, and R 13 is a hydrogen atom or a methyl group.)
また、(D)多官能(メタ)アクリレートとしては、ポリマータイプのものも好適に用いることができる。ポリマータイプの多官能(メタ)アクリレートとしては、グリシジル(メタ)アクリレート等のエポキシ基を有する(メタ)アクリレート化合物単独あるいは共重合体に、(メタ)アクリル酸のようにエポキシ基と反応する基を有する(メタ)アクリレート化合物を反応させて得られるポリマー、ヒドロキシエチル(メタ)アクリレート等の水酸基を有する(メタ)アクリレート化合物単独あるいは共重合体に、2−メチルプロペン酸2−イソシアナトエチルのように水酸基と反応する基を有する(メタ)アクリレート化合物を反応させて得られるポリマー、(メタ)アクリル酸等のカルボキシル基を有する(メタ)アクリレート化合物単独あるいは共重合体に、グリシジル(メタ)アクリレートのようにカルボキシル基と反応する基を有する(メタ)アクリレート化合物を反応させて得られるポリマー等が挙げられる。 Further, as the (D) polyfunctional (meth)acrylate, a polymer type can also be preferably used. As the polymer-type polyfunctional (meth)acrylate, a (meth)acrylate compound having an epoxy group such as glycidyl (meth)acrylate is used alone or in a copolymer, and a group that reacts with an epoxy group such as (meth)acrylic acid is added. A polymer obtained by reacting a (meth)acrylate compound having, a (meth)acrylate compound having a hydroxyl group such as hydroxyethyl (meth)acrylate, or a copolymer, with a 2-methylpropenoate 2-isocyanatoethyl A polymer obtained by reacting a (meth)acrylate compound having a group capable of reacting with a hydroxyl group, or a (meth)acrylate compound having a carboxyl group such as (meth)acrylic acid, alone or in a copolymer, may be used as glycidyl (meth)acrylate. Examples thereof include polymers obtained by reacting a (meth)acrylate compound having a group that reacts with a carboxyl group.
(D)多官能(メタ)アクリレート化合物の分子量は200〜50000、好ましくは220〜40000、より好ましくは240〜30000とする。(D)多官能(メタ)アクリレート化合物の分子量が200より小さくても密着性に関しては問題ないが、揮発性が高くなり臭気が強くなる傾向がある。一方、分子量が50000より大きいと、他の成分に対する溶解性が低くなる可能性がある。 The molecular weight of the (D) polyfunctional (meth)acrylate compound is 200 to 50,000, preferably 220 to 40,000, and more preferably 240 to 30,000. Even if the molecular weight of the polyfunctional (meth)acrylate compound (D) is less than 200, there is no problem in terms of adhesion, but the volatility tends to be high and the odor tends to be strong. On the other hand, if the molecular weight is larger than 50,000, the solubility in other components may be low.
また、(D)多官能(メタ)アクリレートの(メタ)アクリレート当量は80〜6000g/mol、好ましくは80〜4500、より好ましくは85〜3000とする。(メタ)アクリレート当量が80g/molより小さいと、単位体積あたりの(メタ)アクリロキシ基が過剰になって(A)チオエーテル含有(メタ)アクリレート誘導体のチオール基と未反応の(メタ)アクリロキシ基が多量に残存することで、硬化性樹脂組成物からなる硬化膜の靭性が低下し、密着性が低下するおそれがある。一方、(メタ)アクリレート当量が6000g/molより大きくなると、(メタ)アクリロキシ基濃度が著しく低いことから(A)チオエーテル含有(メタ)アクリレート誘導体のチオール基との反応効率が低下することで、硬化性樹脂組成物からなる硬化膜の靭性が低下し、密着性が低下するおそれがある。 The (meth)acrylate equivalent of the (D) polyfunctional (meth)acrylate is 80 to 6000 g/mol, preferably 80 to 4500, and more preferably 85 to 3000. When the (meth)acrylate equivalent is less than 80 g/mol, the (meth)acryloxy group per unit volume becomes excessive, and the thiol group of the (A) thioether-containing (meth)acrylate derivative and the unreacted (meth)acryloxy group become When a large amount remains, the toughness of the cured film made of the curable resin composition may decrease, and the adhesion may decrease. On the other hand, when the (meth)acrylate equivalent is more than 6000 g/mol, the reaction efficiency with the thiol group of the (A) thioether-containing (meth)acrylate derivative is lowered because the (meth)acryloxy group concentration is remarkably low, and thus the curing The toughness of the cured film made of the resin composition may decrease, and the adhesion may decrease.
<光開始剤((E)成分)>
(E)成分である光開始剤は、チオール基と(メタ)アクリロキシ基との反応を促進するために添加される。光開始剤としては、光ラジカル開始剤、光カチオン開始剤、光アニオン開始剤等である。光ラジカル開始剤は、反応時間を短縮する際に用いることが好ましく、光カチオン開始剤は、硬化収縮を小さくする際に用いることが好ましく、光アニオン開始剤は、電子回路等の分野での接着性を付与する際に用いることが好ましい。
<Photoinitiator ((E) component)>
The photoinitiator as the component (E) is added to accelerate the reaction between the thiol group and the (meth)acryloxy group. Examples of the photoinitiator include a photo radical initiator, a photo cation initiator, a photo anion initiator and the like. The photo radical initiator is preferably used for shortening the reaction time, the photo cation initiator is preferably used for reducing curing shrinkage, and the photo anion initiator is used for adhesion in the field of electronic circuits and the like. It is preferably used when imparting the property.
光ラジカル開始剤としては、例えば、2,2−ジメトキシ−1,2−ジフェニルエタン−1−オン、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、2−ヒドロキシ−1−{4−[4−(2−ヒドロキシ−2−メチル−プロピオニル)−ベンジル]−フェニル}−2−メチル−プロパン−1−オン、2−メチル−1−[4−(メチルチオ)フェニル]−2−モルフォリノプロパン−1−オン、ビス(2,4,6−トリメチルベンゾイル)−フェニルフォスフィンオキサイド、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等が挙げられる。 Examples of the photoradical initiator include 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-. 1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2- Hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, Examples thereof include bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.
光カチオン開始剤としては、例えば、ビス(4−tert−ブチルフェニル)ヨードニウムヘキサフルオロホスファート、ビス(4−tert−ブチルフェニル)ヨードニウムトリフルオロメタンスルホナート、シクロプロピルジフェニルスルホニウムテトラフルオロボラート、ジフェニルヨードニウムヘキサフルオロホスファート、ジフェニルヨードニウムヘキサフルオロアルセナート、2−(3,3−ジメトキシスチリル) −4,6−ビス(トリクロロメチル)-1,3,5-トリアジン、トリフェニルスルホニウムテトラフルオロボラート、トリフェニルスルホニウムブロミド、トリ−p−トリルスルホニウムヘキサフルオロホスファート、トリ−p−トリルスルホニウムトリフルオロメタンスルホナート等が挙げられる。 Examples of the photocationic initiator include bis(4-tert-butylphenyl)iodonium hexafluorophosphate, bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, cyclopropyldiphenylsulfonium tetrafluoroborate, diphenyliodonium. Hexafluorophosphate, diphenyliodonium hexafluoroarsenate, 2-(3,3-dimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, triphenylsulfonium tetrafluoroborate, tri Examples thereof include phenylsulfonium bromide, tri-p-tolylsulfonium hexafluorophosphate, tri-p-tolylsulfonium trifluoromethanesulfonate and the like.
光アニオン開始剤としては、例えば、アセトフェノンO−ベンゾイルオキシム、ニフェジピン、2−(9−オキソキサンテン−2−イル)プロピオン酸1,5,7−トリアザビシクロ[4.4.0]デカ−5−エン、2−ニトロフェニルメチル4−メタクリロイルオキシピペリジン−1−カルボキシラート 、1,2−ジイソプロピル−3−〔ビス(ジメチルアミノ)メチレン〕グアニジウム2−(3−ベンゾイルフェニル)プロピオナート、1,2−ジシクロヘキシル−4,4,5,5−テトラメチルビグアニジウムn-ブチルトリフェニルボラート等が挙げられる。 Examples of the photoanion initiator include acetophenone O-benzoyl oxime, nifedipine, and 1,5,7-triazabicyclo[4.4.0]deca-5-(9-oxoxanthen-2-yl)propionate. -Ene, 2-nitrophenylmethyl 4-methacryloyloxypiperidine-1-carboxylate, 1,2-diisopropyl-3-[bis(dimethylamino)methylene]guanidinium 2-(3-benzoylphenyl)propionate, 1,2- Examples thereof include dicyclohexyl-4,4,5,5-tetramethylbiguanidinium n-butyltriphenylborate.
<組成比(配合バランス)>
本発明の硬化性樹脂組成物は、(A)チオエーテル含有(メタ)アクリレート誘導体と(B)多官能エポキシ樹脂との質量比((A)/(B))が0.05〜30となるように配合する。ここで、「(A)/(B)」とは、(A)チオエーテル含有(メタ)アクリレート誘導体の質量を(B)多官能エポキシ樹脂の質量で除した値である。最適な(A)/(B)の値は、硬化性樹脂組成物に求められる特性や、(A)チオエーテル含有(メタ)アクリレート誘導体や(B)多官能エポキシ樹脂および場合によっては添加される(D)多官能(メタ)アクリレート化合物の構造によって異なる。硬化性樹脂組成物を硬化した後の特性は、厳密には硬化性樹脂組成物単位重量中の(チオール基数)/(エポキシ基数+(メタ)アクリロキシ基数)(以下、チオール/(エポキシ+エン)比と称す)の値に影響を受ける。例えば、チオール/(エポキシ+エン)比が0.5〜1.5の範囲にあれば、密な架橋を形成し易く、且つ強靭な硬化物になり易い。一方、チオール/(エポキシ+エン)比が0.1以上0.5未満、あるいは1.5を超え2.0以下であれば、柔軟で粘着質な硬化物を得ることができる。チオール/(エポキシ+エン)比が0.1未満、あるいは2.0を超えるとゲル化し難くなり、密着性が低下する傾向がある。
<Composition ratio (blending balance)>
The curable resin composition of the present invention has a mass ratio ((A)/(B)) of (A) thioether-containing (meth)acrylate derivative to (B) polyfunctional epoxy resin of 0.05 to 30. Blend into. Here, "(A)/(B)" is a value obtained by dividing the mass of the (A) thioether-containing (meth)acrylate derivative by the mass of the (B) polyfunctional epoxy resin. The optimum value of (A)/(B) is added to the properties required for the curable resin composition, the (A) thioether-containing (meth)acrylate derivative, the (B) polyfunctional epoxy resin and, in some cases, added ( D) Depends on the structure of the polyfunctional (meth)acrylate compound. Strictly speaking, the property of the curable resin composition after curing is (the number of thiol groups)/(the number of epoxy groups+the number of (meth)acryloxy groups) (hereinafter, thiol/(epoxy+ene)) in the unit weight of the curable resin composition. It is affected by the value of the ratio). For example, when the thiol/(epoxy+ene) ratio is in the range of 0.5 to 1.5, dense crosslinks are likely to be formed, and a tough cured product is likely to be obtained. On the other hand, when the thiol/(epoxy+ene) ratio is 0.1 or more and less than 0.5 or more than 1.5 and 2.0 or less, a flexible and tacky cured product can be obtained. When the thiol/(epoxy+ene) ratio is less than 0.1 or exceeds 2.0, gelation becomes difficult and the adhesiveness tends to decrease.
また、本発明の硬化性樹脂組成物は、(A)チオエーテル含有(メタ)アクリレート誘導体と(B)多官能エポキシ樹脂との合計質量((A)+(B))100質量部に対し、(C)アミン化合物が0.01〜50質量部、好ましくは0.01〜45質量部となるように配合する。((A)+(B))100質量部に対して(C)成分の配合量が0.01質量部未満では、チオール基とエポキシ基の反応が進行するのに時間を要するため硬化不良を起こし、50質量部を超えると架橋密度が低くなり密着性が低下する傾向がある。 Further, the curable resin composition of the present invention is (A) thioether-containing (meth)acrylate derivative and (B) polyfunctional epoxy resin total mass ((A) + (B)) to 100 parts by mass, The C) amine compound is added in an amount of 0.01 to 50 parts by mass, preferably 0.01 to 45 parts by mass. If the amount of the component (C) is less than 0.01 parts by mass with respect to 100 parts by mass of ((A)+(B)), it takes time for the reaction of the thiol group and the epoxy group to proceed, resulting in poor curing. If it exceeds 50 parts by mass, the crosslinking density tends to be low and the adhesion tends to be low.
また、この硬化性樹脂組成物に対して(D)多官能(メタ)アクリレート化合物も配合する場合は、(A)チオエーテル含有(メタ)アクリレート誘導体と(B)多官能エポキシ樹脂との合計質量((A)+(B))100質量部に対し、(D)多官能(メタ)アクリレート化合物が2〜300質量部、好ましくは2〜250質量部となるように配合する。((A)+(B))100質量部に対して(D)成分の配合量が2質量部未満では、光硬化性を付与することが難しく、300質量部を超えると、密着性が低下する傾向がある。 When the (D) polyfunctional (meth)acrylate compound is also added to the curable resin composition, the total mass of the (A) thioether-containing (meth)acrylate derivative and the (B) polyfunctional epoxy resin ( The (D) polyfunctional (meth)acrylate compound is added in an amount of 2 to 300 parts by weight, preferably 2 to 250 parts by weight, based on 100 parts by weight of (A)+(B). If the blending amount of the component (D) is less than 2 parts by mass with respect to 100 parts by mass of ((A)+(B)), it is difficult to impart photocurability, and if it exceeds 300 parts by mass, the adhesion decreases. Tend to do.
さらにこの硬化性樹脂組成物に対して(E)光開始剤も配合する場合は、(A)チオエーテル含有(メタ)アクリレート誘導体と(D)多官能(メタ)アクリレート化合物との合計質量((A)+(D))100質量部に対して(E)光開始剤を0.01〜10質量部配合する。((A)+(D))100質量部に対して(E)成分が0.01質量部未満では、チオール基と(メタ)アクリロキシ基との反応促進作用が小さく、10質量部を超えると架橋密度が低くなり密着性が低下する場合がある。 When (E) a photoinitiator is also added to the curable resin composition, the total mass of the (A) thioether-containing (meth)acrylate derivative and the (D) polyfunctional (meth)acrylate compound ((A )+(D)) 100 parts by mass, 0.01 to 10 parts by mass of the (E) photoinitiator is blended. When the amount of the component (E) is less than 0.01 parts by mass with respect to 100 parts by mass of ((A)+(D)), the reaction promoting action between the thiol group and the (meth)acryloxy group is small, and when it exceeds 10 parts by mass. The cross-linking density may be low and the adhesion may be low.
<硬化膜の形成>
本発明の硬化性樹脂組成物は、基材上に塗工し、硬化させることで、硬化膜を形成することができる。本発明の硬化性樹脂組成物は、(A)チオエーテル含有(メタ)アクリレート誘導体のチオエーテル基に起因して基材に対して密着性を発揮する。したがって、基材としては、チオエーテル基と化学的な結合を形成する(化学的な親和力の高い)基材、例えば、遷移金属あるいはその合金や珪素化合物、リン化合物、硫黄化合物、又はホウ素化合物等の無機基材、不飽和結合(芳香環を含む)を有する有機物、水酸基やカルボキシル基を有する有機物、又はプラズマやUVオゾン処理された有機物等への密着性向上効果に優れる。具体的には、無機基材としては、ガラス、シリコン、各種金属などが挙げられる。有機基材として、ポリ(メタ)アクリル系樹脂、トリアセテートセルロース(TAC)系樹脂、ポリエチレンテレフタレート(PET)やポリブチレンテレフタレート等のポリエステル系樹脂、ポリカーボネート系樹脂、ポリイミド系樹脂、ポリエチレンやポリプロピレン等のポリオレフィン系樹脂、ポリカーボネート、ポリイミド、ABS樹脂、ポリビニルアルコール、塩化ビニル系樹脂、ポリアセタールなどが好ましく挙げられる。また、本発明の硬化性樹脂組成物は、(A)チオエーテル含有(メタ)アクリレート誘導体が特定の炭化水素基を有することで、硬化膜が柔軟性に優れる。そのため、寒冷条件化でも硬化膜が基材に追従しやすく、基材に対する密着性に優れる。したがって、特に、寒冷条件下で使用され得るフレキシブルな基材のコーティングに特に好適に使用することができる。
<Cured film formation>
The curable resin composition of the present invention can be applied on a substrate and cured to form a cured film. The curable resin composition of the present invention exhibits adhesion to a substrate due to the thioether group of the (A) thioether-containing (meth)acrylate derivative. Therefore, as a base material, a base material that forms a chemical bond with a thioether group (has a high chemical affinity), such as a transition metal or its alloy, a silicon compound, a phosphorus compound, a sulfur compound, or a boron compound, is used. It has an excellent effect of improving the adhesion to an inorganic substrate, an organic substance having an unsaturated bond (including an aromatic ring), an organic substance having a hydroxyl group or a carboxyl group, or an organic substance treated with plasma or UV ozone. Specifically, examples of the inorganic base material include glass, silicon, various metals and the like. As an organic base material, poly(meth)acrylic resin, triacetate cellulose (TAC) resin, polyester resin such as polyethylene terephthalate (PET) or polybutylene terephthalate, polycarbonate resin, polyimide resin, polyolefin such as polyethylene or polypropylene Preferred examples include resin, polycarbonate, polyimide, ABS resin, polyvinyl alcohol, vinyl chloride resin, and polyacetal. Further, in the curable resin composition of the present invention, since the (A) thioether-containing (meth)acrylate derivative has a specific hydrocarbon group, the cured film has excellent flexibility. Therefore, the cured film easily follows the substrate even under cold conditions and has excellent adhesion to the substrate. Therefore, it can be particularly suitably used for coating a flexible substrate that can be used under cold conditions.
硬化性樹脂組成物は、加熱により硬化させることができる。加熱温度は、25〜250℃程度とされる。また、硬化性樹脂組成物が(D)成分を含む場合には、光を照射することにより硬化させることもできる。照射する光としては、UV(紫外線)やEB(電子線)などの活性エネルギー線等が挙げられる。硬化性樹脂組成物が(D)成分を含む場合には、加熱による硬化工程と、光の照射による硬化工程との二段階の工程を経て硬化させることもできる。 The curable resin composition can be cured by heating. The heating temperature is about 25 to 250°C. Further, when the curable resin composition contains the component (D), it can be cured by irradiation with light. Examples of the light to be applied include active energy rays such as UV (ultraviolet ray) and EB (electron beam). When the curable resin composition contains the component (D), it can be cured through a two-step process including a curing process by heating and a curing process by irradiation with light.
本発明の硬化性樹脂組成物は、反応系を均一にし、塗工を容易にするために有機溶媒で希釈して使用してもよい。そのような有機溶媒としては、アルコール系溶剤、芳香族炭化水素系溶剤、エーテル系溶剤、エステル系溶剤及びエーテルエステル系溶剤、ケトン系溶剤、リン酸エステル系溶剤が挙げられる。これらの有機溶媒は硬化性樹脂組成物100質量部に対して、10000質量部未満の配合量に抑えることが好ましいが、基本的に溶剤は硬化膜になる時点では揮発しているため、硬化膜の物性に大きな影響は与えない。ただし、チオール基、エポキシ基、又は(メタ)アクリロイル基と反応する官能基を有する化合物、及びアミン化合物は溶剤として用いることで本発明の効果を損なうおそれがある。 The curable resin composition of the present invention may be used by diluting it with an organic solvent in order to make the reaction system uniform and facilitate coating. Examples of such organic solvents include alcohol solvents, aromatic hydrocarbon solvents, ether solvents, ester solvents and ether ester solvents, ketone solvents, and phosphate ester solvents. It is preferable to control the amount of these organic solvents to be less than 10000 parts by mass with respect to 100 parts by mass of the curable resin composition. It does not affect the physical properties of. However, the compound having a functional group that reacts with a thiol group, an epoxy group, or a (meth)acryloyl group, and an amine compound may impair the effects of the present invention when used as a solvent.
また、本発明の硬化性樹脂組成物は、粘度を調整する目的でシリカ粉末等の粘度調整剤を配合しても良い。これらの粘度調整剤は、硬化性樹脂組成物100質量部に対して、300質量部未満の配合量に抑えることが好ましい。この値が、粘度調整剤の配合量が300質量部を超えると、密着性が低下する可能性がある。 Further, the curable resin composition of the present invention may contain a viscosity modifier such as silica powder for the purpose of adjusting the viscosity. These viscosity modifiers are preferably contained in an amount of less than 300 parts by mass with respect to 100 parts by mass of the curable resin composition. If this value exceeds 300 parts by mass, the adhesiveness may decrease.
また、本発明の硬化性樹脂組成物は、通常の塗料や接着剤に用いられるような各種添加剤を添加しても良い。このような添加剤としては、塗工面を平滑にするための界面活性剤、可使用時間を長くするためのアルミニウム塩、光反応性を向上させるための光ラジカル発生剤、光塩基発生剤、光酸発生剤等が挙げられる。これらの添加剤は、硬化性樹脂組成物100質量部に対して、80質量部未満の配合量に抑えることが好ましい。これらの添加剤の配合量が80質量部を超えると、密着性が低下する可能性がある。 Further, the curable resin composition of the present invention may be added with various additives used in ordinary paints and adhesives. Examples of such additives include a surfactant for smoothing the coated surface, an aluminum salt for increasing the usable time, a photoradical generator for improving photoreactivity, a photobase generator, and a light source. An acid generator etc. are mentioned. It is preferable to control the amount of these additives to be less than 80 parts by mass with respect to 100 parts by mass of the curable resin composition. If the blending amount of these additives exceeds 80 parts by mass, the adhesiveness may decrease.
次に、実施例及び比較例を挙げて、本発明をさらに具体的に説明するが、本発明はこれに限られるものではない。本実施例及び比較例で用いた試薬は、次のとおりである。なお、Mwは重量平均分子量を示す。 Next, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The reagents used in this example and comparative examples are as follows. In addition, Mw shows a weight average molecular weight.
<(A)成分>
(A−1:チオエーテル含有(メタ)アクリレート誘導体)
(A-1: Thioether-containing (meth)acrylate derivative)
(A−2:チオエーテル含有(メタ)アクリレート誘導体)
(A−3:チオエーテル含有(メタ)アクリレート誘導体)
(A−4:チオエーテル含有(メタ)アクリレート誘導体)
(A−5:チオエーテル含有(メタ)アクリレート誘導体)
(A−6:多価チオール化合物)
(A−7:多価チオール化合物)
(A−8:チオエーテル含有アルコキシシラン誘導体)
(A−9:チオエーテル含有アルコキシシラン誘導体)
<多官能エポキシ樹脂((B)成分)>
(B−1、Mw:5500)
(B-1, Mw:5500)
(B−2、Mw:220)
(B−3、Mw:18000)
グリシジルメタクリレートとシクロヘキシルメタクリレートの共重合体(50wt%メチルイソブチルケトン溶液をヘキサンで再沈した白色固体)
(B-3, Mw:18000)
Copolymer of glycidyl methacrylate and cyclohexyl methacrylate (white solid obtained by reprecipitating 50 wt% methyl isobutyl ketone solution with hexane)
(B−4、Mw:45000)
グリシジルメタクリレートとシクロヘキシルメタクリレートの共重合体(50wt%メチルイソブチルケトン溶液をヘキサンで再沈した白色固体)
(B-4, Mw: 45000)
Copolymer of glycidyl methacrylate and cyclohexyl methacrylate (white solid obtained by reprecipitating 50 wt% methyl isobutyl ketone solution with hexane)
<アミン化合物((C)成分)>
(C−1、Mw:110)
(C-1, Mw: 110)
(C−2、Mw:102)
N,N−ジメチル−1,3−プロパンジアミン
(C-2, Mw: 102)
N,N-dimethyl-1,3-propanediamine
(C−3、Mw:680)
n1、n2、n3は1〜5の整数であり、平均が3.5混合物
(C-3, Mw:680)
n1, n2, and n3 are integers from 1 to 5, with an average of 3.5 mixture
<多官能(メタ)アクリレート化合物((D)成分)>
(D−1、Mw:352)
(D-1, Mw:352)
(D−2、Mw:246)
(D−3、Mw:5000)
nは平均13
(D-3, Mw: 5000)
n is 13 on average
(D−4、Mw:22000)
グリシジルメタクリレートとシクロヘキシルメタクリレートの共重合体にD−3を触媒としメタクリル酸を当モル付加したポリマー(50wt%メチルイソブチルケトン溶液をヘキサンで再沈した白色固体)。
(D-4, Mw: 22000)
Polymer obtained by adding equimolar amount of methacrylic acid using D-3 as a catalyst to a copolymer of glycidyl methacrylate and cyclohexyl methacrylate (white solid obtained by reprecipitating a 50 wt% methyl isobutyl ketone solution with hexane).
<光開始剤((E)成分)>
(E−1、Mw:204)
1−ヒドロキシ−シクロヘキシル−フェニル−ケトン
<Photoinitiator ((E) component)>
(E-1, Mw:204)
1-hydroxy-cyclohexyl-phenyl-ketone
(E−2、Mw:348)
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
(E-2, Mw: 348)
2,4,6-Trimethylbenzoyl-diphenyl-phosphine oxide
(E−3、Mw:407)
2−(9−オキソキサンテン−2−イル)プロピオン酸1,5,7−トリアザビシクロ[4.4.0]デカ−5−エン
(E-3, Mw:407)
1,5,7-Triazabicyclo[4.4.0]dec-5-ene 2-(9-oxoxanthen-2-yl)propionate
表1〜表4に示す配合バランスで(A)〜(D)成分をそれぞれ混合し、スパチュラで均一になるまで撹拌し、実施例及び比較例の硬化性樹脂組成物のサンプルを得た。得られた実施例及び比較例の各硬化性樹脂組成物のサンプルに対して以下の密着性1(室温密着性)、密着性2(寒冷地密着性)、柔軟性及び保存安定性の評価を行った。また、実施例2−1〜2−9及び実施例3−1〜3−5の各硬化性樹脂組成物のサンプルに対しては、更に光硬化性の評価も行った。その結果を表1〜表4に示す。 The components (A) to (D) were mixed in the compounding balances shown in Tables 1 to 4 and stirred until they were uniform with a spatula to obtain samples of the curable resin compositions of Examples and Comparative Examples. The following adhesion 1 (room temperature adhesion), adhesion 2 (adhesion in cold regions), flexibility and storage stability were evaluated for each of the obtained curable resin composition samples of Examples and Comparative Examples. went. Further, the photocurability of the samples of the curable resin compositions of Examples 2-1 to 2-9 and Examples 3-1 to 3-5 was also evaluated. The results are shown in Tables 1 to 4.
[評価用試験片の作製]
密着性1、密着性2、柔軟性評価用試験片は、次のように得た。硬化性樹脂組成物の各サンプルを、25mm幅のPETフィルム上にダイコーターで100ミクロンの厚みに塗布し、その上に別のPETフィルムを重ねた後、150℃、1時間の条件で硬化させ評価用試験片を得た。なお、PETフィルムとしては、東レ(株)製、ルミラーU46−100を用いた。
[Preparation of test pieces for evaluation]
Adhesion 1, adhesion 2, and test pieces for evaluating flexibility were obtained as follows. Each sample of the curable resin composition was applied on a PET film having a width of 25 mm to a thickness of 100 μm by a die coater, another PET film was superposed thereon, and then cured at 150° C. for 1 hour. An evaluation test piece was obtained. As the PET film, Lumirror U46-100 manufactured by Toray Industries, Inc. was used.
[密着性1(室温密着性)]
上記評価用試験片を、25℃24時間静置した後、5分以内にJIS K6854−3に規定されるT型はく離法で測定し、以下の通り評価した。
◎:引っ張り強度が5N/25mm以上(PETフィルムが破断)
○:引っ張り強度が5N/25mm以上(PETフィルムは破断せず)
×:5N/25mm未満
[Adhesion 1 (room temperature adhesion)]
The above-mentioned test piece for evaluation was allowed to stand for 24 hours at 25° C., and then measured within 5 minutes by the T-type peeling method specified in JIS K6854-3, and evaluated as follows.
⊚: Tensile strength is 5 N/25 mm or more (PET film is broken)
◯: Tensile strength is 5 N/25 mm or more (PET film does not break)
X: less than 5 N/25 mm
[密着性2(寒冷地密着性)]
上記評価用試験片を、−10℃24時間静置した後、5分以内にJIS K6854−3に規定されるT型はく離法で測定し、以下の通り評価した。
◎:引っ張り強度が5N/25mm以上(PETフィルムが破断)
○:引っ張り強度が5N/25mm以上(PETフィルムは破断せず)
×:5N/25mm未満
[Adhesion 2 (adhesion in cold regions)]
The above-mentioned test piece for evaluation was allowed to stand at -10°C for 24 hours and then measured within 5 minutes by the T-type peeling method specified in JIS K6854-3, and evaluated as follows.
⊚: Tensile strength is 5 N/25 mm or more (PET film is broken)
◯: Tensile strength is 5 N/25 mm or more (PET film does not break)
X: less than 5 N/25 mm
[柔軟性]
上記評価用試験片を、−10℃24時間静置した後、5分以内に直径8mmの棒に1分間巻きつけ、以下の通り評価した。
○:クラック0本
×:クラック1本以上
[Flexibility]
The above-mentioned test piece for evaluation was allowed to stand at -10°C for 24 hours, and then wound on a rod having a diameter of 8 mm for 1 minute within 5 minutes and evaluated as follows.
○: 0 cracks ×: 1 or more cracks
[保存安定性]
各実施例及び比較例の硬化性樹脂組成物のサンプルについて、混合した直後に25℃における粘度(混合後の粘度)を測定するとともに、40℃で12時間加熱した後再度粘度(加熱後の粘度)を測定し、加熱後の粘度を混合直後の粘度で除して増粘率を算出し、以下の通り評価した。なお、粘度は、東機産業株式会社製のR型粘度計を用い、下記条件にて測定した。
使用ロータ:1°34′×R24
測定範囲:0.5183〜103.7 Pa・s
◎:増粘率1.0〜1.8
○:増粘率1.8〜10
×:増粘率上記範囲以外
[Storage stability]
For the samples of the curable resin compositions of Examples and Comparative Examples, the viscosity at 25° C. (viscosity after mixing) was measured immediately after mixing, and after heating at 40° C. for 12 hours, the viscosity (viscosity after heating) was measured again. ) Was measured, the viscosity after heating was divided by the viscosity immediately after mixing to calculate the thickening rate, and the evaluation was made as follows. The viscosity was measured under the following conditions using an R-type viscometer manufactured by Toki Sangyo Co., Ltd.
Rotor used: 1°34' x R24
Measuring range: 0.5183 to 103.7 Pa·s
A: Thickening rate 1.0 to 1.8
◯: Thickening rate 1.8 to 10
X: Thickening rate outside the above range
[光硬化性]
硬化性樹脂組成物の各サンプルを、幅25mm、長さ150mmのPETフィルム上にダイコーターで100ミクロンの厚みに塗布し、その上に別のPETフィルムを重ねた後、高圧水銀灯で500mJ/cm2(i線換算)の光を照射して評価用試験片を得た。この試験片の一方のPETフィルムを幅方向に引っ張り、他方のPETフィルムに対する相対的な変位(幅方向のズレ)を以下の通り評価した。なお、PETフィルムとしては、東レ(株)製、ルミラーU46−100を用いた。
◎:ズレ無し
○:ズレ2mm以内
×:ズレ3mm以上
[Photocurable]
Each sample of the curable resin composition was applied on a PET film having a width of 25 mm and a length of 150 mm to a thickness of 100 μm by a die coater, another PET film was overlaid thereon, and then 500 mJ/cm with a high pressure mercury lamp. The test piece for evaluation was obtained by irradiating light of 2 (i line conversion). One PET film of this test piece was pulled in the width direction, and the relative displacement (deviation in the width direction) with respect to the other PET film was evaluated as follows. As the PET film, Lumirror U46-100 manufactured by Toray Industries, Inc. was used.
◎: No deviation ○: Within 2 mm deviation ×: Over 3 mm deviation
実施例の結果より、(A)成分として上記一般式(1)であるチオエーテル含有(メタ)アクリレート誘導体、(B)成分として分子量が200〜50000である多官能エポキシ樹脂、及び(C)成分として分子量が90〜700であるアミン化合物を含む硬化性樹脂組成物について、室温及び寒冷条件下における高い密着性、良好な柔軟性、及び優れた保存安定性が確認された。一方、(A)成分として上記一般式(1)と一部に共通の構造を有する別の材料を用いた比較例1−5〜1−8では、寒冷条件下における密着性と柔軟性に欠ける。ここで、実施例1−7及び実施例1−10〜1−13と、比較例1−5とを対比から、(A)成分として、上記一般式(1)においてR3が炭化水素基であるチオエーテル含有(メタ)アクリレート誘導体を用いることで、硬化性樹脂組成物の柔軟性が得られ、寒冷条件化での密着性に優れることが分かる。 From the results of Examples, as the component (A), the thioether-containing (meth)acrylate derivative represented by the general formula (1), as the component (B), a polyfunctional epoxy resin having a molecular weight of 200 to 50,000, and as the component (C). Regarding the curable resin composition containing an amine compound having a molecular weight of 90 to 700, high adhesion under room temperature and cold conditions, good flexibility, and excellent storage stability were confirmed. On the other hand, in Comparative Examples 1-5 to 1-8 in which another material having a structure partially common to the general formula (1) is used as the component (A), adhesiveness and flexibility under cold conditions are lacking. .. Here, from comparison of Examples 1-7 and Examples 1-10 to 1-13 with Comparative Example 1-5, as the component (A), in the general formula (1), R 3 is a hydrocarbon group. It can be seen that by using a certain thioether-containing (meth)acrylate derivative, flexibility of the curable resin composition can be obtained and the adhesiveness under cold conditions is excellent.
また、実施例1−1〜1−5と比較例1−1及び1−2との対比より、(A)成分と(B)成分の質量比((A)/(B))は、0.05〜30とすることが明らかとなった。(A)/(B)がこの範囲を満たさない比較例1−1及び1−2では、寒冷条件下のみならず常温でも密着性が劣る。このうち、成分(B)に対して成分(A)が少なすぎる比較例1−1では、柔軟性も欠ける。 From the comparison between Examples 1-1 to 1-5 and Comparative Examples 1-1 and 1-2, the mass ratio ((A)/(B)) of the component (A) and the component (B) was 0. It became clear that it was set to 0.05 to 30. In Comparative Examples 1-1 and 1-2 in which (A)/(B) does not satisfy this range, the adhesion is poor not only under cold conditions but also at room temperature. Among these, Comparative Example 1-1 in which the amount of the component (A) is too small with respect to the component (B) also lacks flexibility.
また、実施例1−6〜1−9と比較例1−3及び1−4との対比より、(C)成分を、(A)成分と(B)成分との合計質量100質量部に対して0.05〜30質量部配合することが明らかとなった。(C)成分が配合されていない比較例1−3では密着性に欠ける。(C)成分が過剰に配合されている比較例1−4では、保存安定性に乏しい。 Further, from the comparison between Examples 1-6 to 1-9 and Comparative Examples 1-3 and 1-4, the component (C) was added to the total mass of the component (A) and the component (B) of 100 parts by mass. It became clear that 0.05 to 30 parts by mass was added. In Comparative Example 1-3 in which the component (C) is not blended, the adhesiveness is poor. In Comparative Example 1-4 in which the component (C) is excessively blended, the storage stability is poor.
また、実施例2−1〜2−9にて、(D)成分を添加することで、室温及び寒冷条件下における高い密着性、良好な柔軟性、及び優れた保存安定性に加えて光硬化性を付与できることが確認された。また、実施例3−1〜3−5にて、さらに(E)成分を添加しても室温及び寒冷条件下における高い密着性、良好な柔軟性、優れた保存安定性及び光硬化性を備えることが確認された。 Further, in Examples 2-1 to 2-9, by adding the component (D), in addition to high adhesiveness at room temperature and cold conditions, good flexibility, and excellent storage stability, photocuring is performed. It was confirmed that sex can be imparted. Further, in Examples 3-1 to 3-5, even if the component (E) is further added, it has high adhesiveness at room temperature and cold conditions, good flexibility, excellent storage stability, and photocurability. It was confirmed.
Claims (3)
(B)分子量が50000以下であり、下記一般式(11)で表される多官能エポキシ樹脂と、
(C)分子量が90〜700であるアミン化合物と、を含有し、
前記(A)成分と前記(B)成分との質量比((A)/(B))が0.05〜30であり、
前記(A)成分と前記(B)成分との合計質量100質量部に対し、前記(C)成分が0.01〜50質量部配合されてなる、硬化性樹脂組成物。
(式中のaは1〜2の整数であり、bは1〜2の整数であり、a+b=3である。R1は下記式2で表される3価の基であり、R2は下記式3または下記式4で表される2価の基である。R3は炭素数が1〜12の炭化水素基である。)
(式中のR4は−CH2−、−CH2CH2−、または−CH2CH(CH3)−である。)
(R5は水素原子またはメチル基である。)
(R5は水素原子またはメチル基である。)
(B) a polyfunctional epoxy resin having a molecular weight of 50,000 or less and represented by the following general formula (11):
(C) an amine compound having a molecular weight of 90 to 700,
The mass ratio ((A)/(B)) of the component (A) and the component (B) is 0.05 to 30,
A curable resin composition obtained by mixing 0.01 to 50 parts by mass of the component (C) with respect to 100 parts by mass of the total amount of the component (A) and the component (B).
(In the formula, a is an integer of 1-2, b is an integer of 1-2, and a+b=3. R 1 is a trivalent group represented by the following formula 2 and R 2 is It is a divalent group represented by the following formula 3 or the following formula 4. R 3 is a hydrocarbon group having 1 to 12 carbon atoms.)
(-CH 2 R 4 in the formula -, - CH 2 CH 2 - , or -CH 2 CH (CH 3) - and is.)
(R 5 is a hydrogen atom or a methyl group.)
(R 5 is a hydrogen atom or a methyl group.)
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