JP6904406B2 - Cationic polymerization initiator and epoxy resin composition - Google Patents
Cationic polymerization initiator and epoxy resin composition Download PDFInfo
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- JP6904406B2 JP6904406B2 JP2019203132A JP2019203132A JP6904406B2 JP 6904406 B2 JP6904406 B2 JP 6904406B2 JP 2019203132 A JP2019203132 A JP 2019203132A JP 2019203132 A JP2019203132 A JP 2019203132A JP 6904406 B2 JP6904406 B2 JP 6904406B2
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- epoxy resin
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- resin composition
- cationic polymerization
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- 238000010538 cationic polymerization reaction Methods 0.000 title claims description 33
- 239000003505 polymerization initiator Substances 0.000 title claims description 32
- 239000003822 epoxy resin Substances 0.000 title description 52
- 229920000647 polyepoxide Polymers 0.000 title description 52
- 239000000203 mixture Substances 0.000 title description 42
- 125000004432 carbon atom Chemical group C* 0.000 claims description 25
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 description 40
- -1 benzyl cation Chemical class 0.000 description 17
- 125000003700 epoxy group Chemical group 0.000 description 17
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 12
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 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 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 9
- 159000000000 sodium salts Chemical class 0.000 description 9
- 125000001424 substituent group Chemical group 0.000 description 9
- 150000001450 anions Chemical class 0.000 description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium group Chemical group [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000012266 salt solution Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 5
- 229910018286 SbF 6 Inorganic materials 0.000 description 5
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 229920003986 novolac Polymers 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- 125000000732 arylene group Chemical group 0.000 description 4
- 238000001879 gelation Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 4
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 description 3
- VKALYYFVKBXHTF-UHFFFAOYSA-N 4-(methylsulfanyl)-m-cresol Chemical compound CSC1=CC=C(O)C=C1C VKALYYFVKBXHTF-UHFFFAOYSA-N 0.000 description 3
- QASBCTGZKABPKX-UHFFFAOYSA-N 4-(methylsulfanyl)phenol Chemical compound CSC1=CC=C(O)C=C1 QASBCTGZKABPKX-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 125000004450 alkenylene group Chemical group 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 2
- HMDQPBSDHHTRNI-UHFFFAOYSA-N 1-(chloromethyl)-3-ethenylbenzene Chemical compound ClCC1=CC=CC(C=C)=C1 HMDQPBSDHHTRNI-UHFFFAOYSA-N 0.000 description 2
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- DGUJJOYLOCXENZ-UHFFFAOYSA-N 4-[2-[4-(oxiran-2-ylmethoxy)phenyl]propan-2-yl]phenol Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 DGUJJOYLOCXENZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- PSBPNWBGNOWCCU-UHFFFAOYSA-N OB(O)O.S.S.S Chemical compound OB(O)O.S.S.S PSBPNWBGNOWCCU-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- SXJRAEVVVYLFBS-UHFFFAOYSA-O (4-hydroxyphenyl)methyl-methyl-phenylsulfanium Chemical compound OC1=CC=C(C[S+](C)C2=CC=CC=C2)C=C1 SXJRAEVVVYLFBS-UHFFFAOYSA-O 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- VTPQLJUADNBKRM-UHFFFAOYSA-N 1-(bromomethyl)-4-ethenylbenzene Chemical compound BrCC1=CC=C(C=C)C=C1 VTPQLJUADNBKRM-UHFFFAOYSA-N 0.000 description 1
- KKLSEIIDJBCSRK-UHFFFAOYSA-N 1-(chloromethyl)-2-ethenylbenzene Chemical compound ClCC1=CC=CC=C1C=C KKLSEIIDJBCSRK-UHFFFAOYSA-N 0.000 description 1
- XMWGTKZEDLCVIG-UHFFFAOYSA-N 1-(chloromethyl)naphthalene Chemical compound C1=CC=C2C(CCl)=CC=CC2=C1 XMWGTKZEDLCVIG-UHFFFAOYSA-N 0.000 description 1
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- HNRMPXKDFBEGFZ-UHFFFAOYSA-N 2,2-dimethylbutane Chemical compound CCC(C)(C)C HNRMPXKDFBEGFZ-UHFFFAOYSA-N 0.000 description 1
- IVIDDMGBRCPGLJ-UHFFFAOYSA-N 2,3-bis(oxiran-2-ylmethoxy)propan-1-ol Chemical compound C1OC1COC(CO)COCC1CO1 IVIDDMGBRCPGLJ-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- BBBUAWSVILPJLL-UHFFFAOYSA-N 2-(2-ethylhexoxymethyl)oxirane Chemical compound CCCCC(CC)COCC1CO1 BBBUAWSVILPJLL-UHFFFAOYSA-N 0.000 description 1
- CZAZXHQSSWRBHT-UHFFFAOYSA-N 2-(2-hydroxyphenyl)-3,4,5,6-tetramethylphenol Chemical compound OC1=C(C)C(C)=C(C)C(C)=C1C1=CC=CC=C1O CZAZXHQSSWRBHT-UHFFFAOYSA-N 0.000 description 1
- SNGZGCFWZHOVOS-UHFFFAOYSA-N 2-(2-methyloctoxymethyl)oxirane Chemical compound CCCCCCC(C)COCC1CO1 SNGZGCFWZHOVOS-UHFFFAOYSA-N 0.000 description 1
- XKOWGGVJZHBDJA-UHFFFAOYSA-N 2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl 7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1CC2OC2CC1C(=O)OCCC1CC2OC2CC1 XKOWGGVJZHBDJA-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- WAPRZVXVTPSWEB-UHFFFAOYSA-N 2-[(2-butan-2-ylphenoxy)methyl]oxirane Chemical compound CCC(C)C1=CC=CC=C1OCC1OC1 WAPRZVXVTPSWEB-UHFFFAOYSA-N 0.000 description 1
- HHRACYLRBOUBKM-UHFFFAOYSA-N 2-[(4-tert-butylphenoxy)methyl]oxirane Chemical compound C1=CC(C(C)(C)C)=CC=C1OCC1OC1 HHRACYLRBOUBKM-UHFFFAOYSA-N 0.000 description 1
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 description 1
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- DXLSPFDSUIZAON-UHFFFAOYSA-N 2-methyl-4-methylsulfanylphenol Chemical compound CSC1=CC=C(O)C(C)=C1 DXLSPFDSUIZAON-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- JGFZITGNFAVSKU-UHFFFAOYSA-N 3,5-dimethyl-4-(methylsulfanyl)phenol Chemical compound CSC1=C(C)C=C(O)C=C1C JGFZITGNFAVSKU-UHFFFAOYSA-N 0.000 description 1
- DVQAFBRTUVSZHA-UHFFFAOYSA-N 3-ethyl-4-methylsulfanylphenol Chemical compound CCC1=CC(O)=CC=C1SC DVQAFBRTUVSZHA-UHFFFAOYSA-N 0.000 description 1
- RRXFVFZYPPCDAW-UHFFFAOYSA-N 4-(7-oxabicyclo[4.1.0]heptan-4-ylmethoxymethyl)-7-oxabicyclo[4.1.0]heptane Chemical compound C1CC2OC2CC1COCC1CC2OC2CC1 RRXFVFZYPPCDAW-UHFFFAOYSA-N 0.000 description 1
- OEIZUSDQPOLYGQ-UHFFFAOYSA-N 4-(7-oxabicyclo[4.1.0]heptan-4-yloxy)-7-oxabicyclo[4.1.0]heptane Chemical compound C1CC2OC2CC1OC1CCC2OC2C1 OEIZUSDQPOLYGQ-UHFFFAOYSA-N 0.000 description 1
- MBMUWELGNWWSKI-UHFFFAOYSA-N 4-(oxiran-2-ylmethoxy)phenol Chemical compound C1=CC(O)=CC=C1OCC1OC1 MBMUWELGNWWSKI-UHFFFAOYSA-N 0.000 description 1
- WLHCBQAPPJAULW-UHFFFAOYSA-N 4-methylbenzenethiol Chemical compound CC1=CC=C(S)C=C1 WLHCBQAPPJAULW-UHFFFAOYSA-N 0.000 description 1
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 1
- ORTNTAAZJSNACP-UHFFFAOYSA-N 6-(oxiran-2-ylmethoxy)hexan-1-ol Chemical compound OCCCCCCOCC1CO1 ORTNTAAZJSNACP-UHFFFAOYSA-N 0.000 description 1
- NHJIDZUQMHKGRE-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-yl 2-(7-oxabicyclo[4.1.0]heptan-4-yl)acetate Chemical compound C1CC2OC2CC1OC(=O)CC1CC2OC2CC1 NHJIDZUQMHKGRE-UHFFFAOYSA-N 0.000 description 1
- QXALIERKYGCHHA-UHFFFAOYSA-N Bc(c(F)c(c(F)c1F)F)c1F Chemical compound Bc(c(F)c(c(F)c1F)F)c1F QXALIERKYGCHHA-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000004653 anthracenylene group Chemical group 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 1
- IDSLNGDJQFVDPQ-UHFFFAOYSA-N bis(7-oxabicyclo[4.1.0]heptan-4-yl) hexanedioate Chemical compound C1CC2OC2CC1OC(=O)CCCCC(=O)OC1CC2OC2CC1 IDSLNGDJQFVDPQ-UHFFFAOYSA-N 0.000 description 1
- DJUWPHRCMMMSCV-UHFFFAOYSA-N bis(7-oxabicyclo[4.1.0]heptan-4-ylmethyl) hexanedioate Chemical compound C1CC2OC2CC1COC(=O)CCCCC(=O)OCC1CC2OC2CC1 DJUWPHRCMMMSCV-UHFFFAOYSA-N 0.000 description 1
- JRPRCOLKIYRSNH-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,2-dicarboxylate Chemical compound C=1C=CC=C(C(=O)OCC2OC2)C=1C(=O)OCC1CO1 JRPRCOLKIYRSNH-UHFFFAOYSA-N 0.000 description 1
- KIKYOFDZBWIHTF-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohex-3-ene-1,2-dicarboxylate Chemical compound C1CC=CC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 KIKYOFDZBWIHTF-UHFFFAOYSA-N 0.000 description 1
- XFUOBHWPTSIEOV-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohexane-1,2-dicarboxylate Chemical compound C1CCCC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 XFUOBHWPTSIEOV-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- DNWBGZGLCKETOT-UHFFFAOYSA-N cyclohexane;1,3-dioxane Chemical compound C1CCCCC1.C1COCOC1 DNWBGZGLCKETOT-UHFFFAOYSA-N 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
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
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- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000011866 long-term treatment Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000006178 methyl benzyl group Chemical group 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000005562 phenanthrylene group Chemical group 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- QROGIFZRVHSFLM-UHFFFAOYSA-N prop-1-enylbenzene Chemical class CC=CC1=CC=CC=C1 QROGIFZRVHSFLM-UHFFFAOYSA-N 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000006410 propenylene group Chemical group 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000005920 sec-butoxy group Chemical group 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/55—Boron-containing compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は、カチオン重合開始剤およびそれを含むエポキシ樹脂組成物に関する。 The present invention relates to a cationic polymerization initiator and an epoxy resin composition containing the same.
エポキシ樹脂は、優れた機械特性、熱特性を有するため様々な分野で広く用いられており、例えば、樹脂特有の絶縁性や熱硬化性から、電子部品用の接着剤として利用されている。このような接着剤として使用されるエポキシ樹脂組成物は、通常、エポキシ樹脂と潜在性硬化剤とを含み、使用されるまでは、熱硬化性のエポキシ樹脂と潜在性硬化剤とが未反応の状態で安定に存在し、使用される際には、取扱い性に優れ且つ短時間で硬化することが要求される。
しかしながら、一般的に、貯蔵安定性に優れるエポキシ樹脂組成物は、硬化性が低く、硬化に高温処理または長時間処理が必要となる傾向がある。一方、硬化性が高いエポキシ樹脂組成物は、貯蔵安定性に劣る傾向がある。エポキシ樹脂組成物の硬化性と貯蔵安定性は、組成物中に配合される潜在硬化剤の性質に大きく影響を受けることが明らかとなっている。
Epoxy resins are widely used in various fields because they have excellent mechanical properties and thermal properties. For example, they are used as adhesives for electronic parts because of the insulating properties and thermosetting properties peculiar to resins. The epoxy resin composition used as such an adhesive usually contains an epoxy resin and a latent curing agent, and the thermosetting epoxy resin and the latent curing agent have not reacted until they are used. When it exists stably in a state and is used, it is required to have excellent handleability and cure in a short time.
However, in general, epoxy resin compositions having excellent storage stability tend to have low curability and require high-temperature treatment or long-term treatment for curing. On the other hand, the epoxy resin composition having high curability tends to be inferior in storage stability. It has been clarified that the curability and storage stability of the epoxy resin composition are greatly influenced by the properties of the latent curing agent blended in the composition.
このエポキシ樹脂の潜在性硬化剤としては、例えば、ｐ−ヒドロキシフェニル−ベンジル−メチルスルホニウムテトラキス（ペンタフルオロフェニル）ボレート等のスルホニウムボレート錯体が知られている（特許文献１参照）。 As a latent curing agent for this epoxy resin, for example, a sulfonium borate complex such as p-hydroxyphenyl-benzyl-methylsulfonium tetrakis (pentafluorophenyl) borate is known (see Patent Document 1).
しかし、昨今の電子部品の需要の高まりに応じて、より優れた硬化性を有しつつ、貯蔵安定性をも両立し得る新規なエポキシ樹脂組成物、およびそれを可能とする新規なカチオン重合開始剤が絶えず望まれているのが現状である。 However, in response to the recent increase in demand for electronic components, a new epoxy resin composition having better curability and storage stability can be achieved, and a new cationic polymerization that enables it. The current situation is that agents are in constant demand.
そこで、本発明は、エポキシ樹脂組成物の優れた硬化性と貯蔵安定性を両立することができるカチオン重合開始剤、および、それを含有するエポキシ樹脂組成物を提供することを課題とする。 Therefore, it is an object of the present invention to provide a cationic polymerization initiator capable of achieving both excellent curability and storage stability of an epoxy resin composition, and an epoxy resin composition containing the same.
本発明者は、スルホニウム残基に特定の置換基を導入し、且つ、対アニオンをテトラキス（ペンタフルオロフェニル）ボレートとする新規スルホニウムボレート錯体によれば、上記課題を解決できることを見出し、本発明を完成させるに至った。
すなわち、本発明は以下の通りである。
The present inventor has found that the above problems can be solved by a novel sulfonium borate complex in which a specific substituent is introduced into a sulfonium residue and the counter anion is tetrakis (pentafluorophenyl) borate. It came to be completed.
That is, the present invention is as follows.
[１] 下記一般式（１）で表されるカチオン重合開始剤。
[２] 上記［１］に記載のカチオン重合開始剤と、エポキシ基を有する化合物と、を含有するエポキシ樹脂組成物。
[３] 上記カチオン重合開始剤の含有量が、上記エポキシ基を有する化合物１００質量部に対して、０．１〜１０質量部である、上記［２］に記載のエポキシ樹脂組成物。
[1] A cationic polymerization initiator represented by the following general formula (1).
[2] An epoxy resin composition containing the cationic polymerization initiator according to the above [1] and a compound having an epoxy group.
[3] The epoxy resin composition according to the above [2], wherein the content of the cationic polymerization initiator is 0.1 to 10 parts by mass with respect to 100 parts by mass of the compound having an epoxy group.
本発明によれば、エポキシ樹脂組成物の優れた硬化性と貯蔵安定性を両立することができるカチオン重合開始剤、および、それを含有するエポキシ樹脂組成物を提供することができる。 According to the present invention, it is possible to provide a cationic polymerization initiator capable of achieving both excellent curability and storage stability of an epoxy resin composition, and an epoxy resin composition containing the same.
［カチオン重合開始剤］
本発明のカチオン重合開始剤は、下記一般式（１）で表される化合物である。
[Cationic polymerization initiator]
The cationic polymerization initiator of the present invention is a compound represented by the following general formula (1).
このようなカチオン重合開始剤を用いることにより、エポキシ樹脂組成物の優れた硬化性と貯蔵安定性を両立することができる。
これは、詳細には明らかではないが、本発明者は以下のように推測している。
すなわち、スルホニウム残基において、硫黄原子に結合するベンジル基のベンゼン環に電子供与基であるビニルを導入したことにより、重合時に発生するベンジルカチオンを共鳴安定化させ、開始剤活性を向上させることができ、一方で、この電子供与基であるビニル基は環を形成していないため立体障害を受けづらく、カウンターアニオンであるテトラキス（ペンタフルオロフェニル）ボレートがスルホニウムイオンおよび発生したベンジルカチオンに接近し易くしているため、貯蔵時にはＳ−Ｃ間の結合が安定しており、熱等の外部環境による影響を受けにくいと考えられる。
また、上記カチオン開始剤においては、対アニオンがテトラキス（ペンタフルオロフェニル）ボレートであり、電子吸引基であるフッ素原子の影響によりホウ素の求核性が著しく低い状態であり、スルホニウムカチオンのカチオン性が非常に高い状態であることから、ＳｂＦ６ −やＢＦ４ −等と比較すると硬化性に優れる。
By using such a cationic polymerization initiator, it is possible to achieve both excellent curability and storage stability of the epoxy resin composition.
This is not clear in detail, but the present inventor speculates as follows.
That is, at the sulfonium residue, by introducing vinyl, which is an electron donating group, into the benzene ring of the benzyl group bonded to the sulfur atom, the benzyl cation generated during polymerization can be resonance-stabilized and the initiator activity can be improved. On the other hand, since the vinyl group, which is an electron donating group, does not form a ring, it is less susceptible to steric damage, and the counter anion tetrakis (pentafluorophenyl) borate easily approaches the sulfonium ion and the generated benzyl cation. Therefore, it is considered that the bond between SC is stable during storage and is not easily affected by the external environment such as heat.
Further, in the above-mentioned cation initiator, the counter anion is tetrakis (pentafluorophenyl) borate, the nucleophilicity of boron is remarkably low due to the influence of the fluorine atom which is an electron-withdrawing group, and the cation property of the sulfonium cation is high. because it is very high state, SbF 6 - or BF 4 -, etc. as compared with excellent curability.
一般式（１）において、Ｒ１は、水酸基、Ｒ５Ｏ基、Ｒ５ＣＯＯ基、Ｒ５ＮＨＣＯＯ基またはＲ５ＯＣＯＯ基であり、Ｒ５は、置換基を有していてもよい、芳香族炭化水素基または脂肪族炭化水素基である。 In the general formula (1), R 1 is a hydroxyl group, an R 5 O group, an R 5 COO group, an R 5 NHCOO group or an R 5 OCOO group, and R 5 is an aromatic group which may have a substituent. It is a group hydrocarbon group or an aliphatic hydrocarbon group.
芳香族炭化水素基としては、例えば、アリール基、アラルキル基、アリーレン基が挙げられる。
アリール基としては、例えば、炭素数６〜１４（好ましくは炭素数６〜１０）のものが挙げられ、具体的には、フェニル基、ナフチル基、アントリル基、フェナントリル基、ビフェニル基等が挙げられる。中でも、フェニル基が好ましい。
アラルキル基としては、例えば、炭素数７〜１３（好ましくは炭素数７〜１１）のものが挙げられ、具体的には、ベンジル基、フェネチル基、フェニルプロピル基等が挙げられる。中でも、ベンジル基が好ましい。
アリーレン基としては、例えば、炭素数６〜１４（好ましくは炭素数６〜１０）のものが挙げられ、具体的には、フェニレン基、ナフチレン基、アントリレン基、フェナントリレン基、ビフェニレン基が挙げられる。中でも、フェニレン基が好ましい。アリーレン基は、アリール基、アラルキル基等の１価の基と結合することでＲ５を構成する。
Examples of the aromatic hydrocarbon group include an aryl group, an aralkyl group, and an arylene group.
Examples of the aryl group include those having 6 to 14 carbon atoms (preferably 6 to 10 carbon atoms), and specific examples thereof include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group and a biphenyl group. .. Of these, a phenyl group is preferable.
Examples of the aralkyl group include those having 7 to 13 carbon atoms (preferably 7 to 11 carbon atoms), and specific examples thereof include a benzyl group, a phenethyl group, a phenylpropyl group and the like. Of these, a benzyl group is preferable.
Examples of the arylene group include those having 6 to 14 carbon atoms (preferably 6 to 10 carbon atoms), and specific examples thereof include a phenylene group, a naphthylene group, an anthrylene group, a phenanthrylene group, and a biphenylene group. Of these, a phenylene group is preferable. Arylene groups constitutes the R 5 by coupling an aryl group, a monovalent group such as an aralkyl group.
芳香族炭化水素基は、さらに任意の炭素原子の位置に、例えば、炭素数１〜４の低級アルキル基、ヒドロキシル基、アミノ基、ニトロ基、ハロゲン原子等の１以上の置換基を有してもよい。
置換基を有する芳香族炭化水素基としては、例えば、トリル基、キシリル基、フェノキシ基等の、置換基を有するアリール基；メチルベンジル基、エチルベンジル基、メチルフェネチル基等の、置換基を有するアラルキル基；メチルフェニレン基、ジメチルフェニレン基、メチルナフチレン基等の、置換基を有するアリーレン基が挙げられる。中でも、フェノキシ基が好ましい。
The aromatic hydrocarbon group further has one or more substituents such as a lower alkyl group having 1 to 4 carbon atoms, a hydroxyl group, an amino group, a nitro group, and a halogen atom at the position of an arbitrary carbon atom. May be good.
Examples of the aromatic hydrocarbon group having a substituent include an aryl group having a substituent such as a tolyl group, a xsilyl group and a phenoxy group; and having a substituent such as a methylbenzyl group, an ethylbenzyl group and a methylphenethyl group. Aralkyl group; examples thereof include an arylene group having a substituent such as a methylphenylene group, a dimethylphenylene group and a methylnaphthylene group. Of these, a phenoxy group is preferable.
脂肪族炭化水素基としては、例えば、アルキル基、シクロアルキル基、アルケニル基、アルケニレン基、アルコキシ基が挙げられる。
アルキル基としては、例えば、炭素数１〜１８（好ましくは炭素数１〜６）の直鎖または分岐状のものが挙げられ、具体的には、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基が挙げられる。中でも、メチル基が好ましい。
シクロアルキル基としては、例えば、炭素数３〜１０（好ましくは炭素数３〜６）のものが挙げられ、具体的には、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基が挙げられる。
アルケニル基としては、例えば、炭素数２〜１８（好ましくは炭素数２〜６）の直鎖または分岐状のものが挙げられ、具体的には、ビニル基、１−プロペニル基、アリル基、イソプロペニル基、１−ブテニル基、２−ブテニル基、アクリロイル基が挙げられる。
アルケニレン基としては、例えば、炭素数２〜１８（好ましくは炭素数２〜６）の直鎖または分岐状のものが挙げられ、具体的には、ビニレン基、プロペニレン基、ブタジエニレン基が挙げられる。アルケニレン基は、アルキル基、シクロアルキル基等の１価の基と結合することでＲ５を構成する。
アルコキシ基としては、例えば、炭素数１〜１８（好ましくは炭素数１〜６）の直鎖または分岐状のものが挙げられ、具体的には、メトキシ基、エトキシ基、ｎ−プロポキシ基、イソプロポキシ基、ｎ−ブトキシ基、ｓｅｃ−ブトキシ基、ｔｅｒｔ−ブトキシ基が挙げられる。中でも、メトキシ基が好ましい。
Examples of the aliphatic hydrocarbon group include an alkyl group, a cycloalkyl group, an alkenyl group, an alkenylene group and an alkoxy group.
Examples of the alkyl group include linear or branched ones having 1 to 18 carbon atoms (preferably 1 to 6 carbon atoms), and specifically, methyl group, ethyl group, n-propyl group and isopropyl. Examples thereof include a group, an n-butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group. Of these, a methyl group is preferable.
Examples of the cycloalkyl group include those having 3 to 10 carbon atoms (preferably 3 to 6 carbon atoms), and specific examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
Examples of the alkenyl group include a linear or branched group having 2 to 18 carbon atoms (preferably 2 to 6 carbon atoms), and specifically, a vinyl group, a 1-propenyl group, an allyl group and an iso. Examples thereof include a propenyl group, a 1-butenyl group, a 2-butenyl group and an acryloyl group.
Examples of the alkenylene group include a linear or branched group having 2 to 18 carbon atoms (preferably 2 to 6 carbon atoms), and specific examples thereof include a vinylene group, a propenylene group, and a butadienylene group. Alkenylene group, an alkyl group, constituting R 5 by binding to a monovalent group such as a cycloalkyl group.
Examples of the alkoxy group include a linear or branched group having 1 to 18 carbon atoms (preferably 1 to 6 carbon atoms), and specifically, a methoxy group, an ethoxy group, an n-propoxy group, and an iso group. Examples thereof include a propoxy group, an n-butoxy group, a sec-butoxy group, and a tert-butoxy group. Of these, the methoxy group is preferable.
Ｒ５Ｏ基においては、好ましいＲ５として、メチル基、メトキシ基、フェニル基、フェノキシ基が挙げられ、中でも、メチル基がより好ましい。
Ｒ５ＣＯＯ基においては、好ましいＲ５として、メチル基、ベンジル基、フェニル基が挙げられ、中でも、メチル基がより好ましい。
Ｒ５ＮＨＣＯＯ基においては、好ましいＲ５として、メチル基、メトキシ基、フェニル基、フェノキシ基、フェニレン基が挙げられ、中でも、フェニル基がより好ましい。
Ｒ５ＯＣＯＯ基においては、好ましいＲ５として、メチル基、フェニル基、フェニレン基が挙げられ、中でも、フェニル基がより好ましい。
Among the R 5 O groups, preferred R 5 includes a methyl group, a methoxy group, a phenyl group and a phenoxy group, and among them, the methyl group is more preferable.
In the R 5 COO group, preferred R 5 includes a methyl group, a benzyl group and a phenyl group, and among them, the methyl group is more preferable.
In the R 5 NHCOO group, preferred R 5 includes a methyl group, a methoxy group, a phenyl group, a phenoxy group and a phenylene group, and among them, a phenyl group is more preferable.
In the R 5 OCOO group, preferred R 5 includes a methyl group, a phenyl group and a phenylene group, and among them, a phenyl group is more preferable.
Ｒ５Ｏ基、Ｒ５ＣＯＯ基、Ｒ５ＮＨＣＯＯ基およびＲ５ＯＣＯＯ基のうち、なかでも、Ｒ５ＣＯＯ基、Ｒ５ＮＨＣＯＯ基およびＲ５ＯＣＯＯ基がより好ましい。これらの基は、電子吸引性基を有することから電子吸引性が高いためである。これにより、スルホニウムイオンのカチオン性がより向上し、硬化性により優れる。特に、電子吸引性基の電子吸引性が高いものほど硬化性により優れる。 Of the R 5 O group, the R 5 COO group, the R 5 NHCOO group and the R 5 OCOO group, the R 5 COO group, the R 5 NHCOO group and the R 5 OCOO group are more preferable. This is because these groups have high electron-withdrawing properties because they have electron-withdrawing groups. As a result, the cation property of the sulfonium ion is further improved, and the curability is more excellent. In particular, the higher the electron attraction of the electron attraction group, the better the curability.
Ｒ１としては、硬化性により優れるという観点から、水酸基、Ｒ５ＣＯＯ基、Ｒ５ＮＨＣＯＯ基、または、Ｒ５ＯＣＯＯ基が好ましく、水酸基がより好ましい。
Ｒ１の配置は、スルホニウムイオンに対し、オルト位、メタ位、パラ位のいずれであってもよく、硬化性により優れるという観点から、パラ位であるのが好ましい。
As R 1 , from the viewpoint of being more excellent in curability, a hydroxyl group, an R 5 COO group, an R 5 NHCOO group, or an R 5 OCOO group is preferable, and a hydroxyl group is more preferable.
The arrangement of R 1 may be any of the ortho-position, the meta-position, and the para-position with respect to the sulfonium ion, and is preferably the para-position from the viewpoint of being more excellent in curability.
一般式（１）において、Ｒ２およびＲ３は、それぞれ独立して、水素原子または炭素数１〜６のアルキル基であり、好ましくは水素原子または炭素数１〜３のアルキル基である。アルキル基としては、例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基が挙げられる。中でも、水素原子またはメチル基が好ましい。 In the general formula (1), R 2 and R 3 are independently hydrogen atoms or alkyl groups having 1 to 6 carbon atoms, preferably hydrogen atoms or alkyl groups having 1 to 3 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group. Of these, a hydrogen atom or a methyl group is preferable.
一般式（１）において、Ｒ４は、水素原子または炭素数１〜６のアルキル基であり、好ましくは水素原子または炭素数１〜３のアルキル基である。アルキル基としては、例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基が挙げられる。中でも、メチル基が好ましい。 In the general formula (1), R 4 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group. Of these, a methyl group is preferable.
一般式（１）において、スルホニウム残基のベンジル基に結合するビニル基は、ベンジル位に対し、オルト位、メタ位、パラ位のいずれであってもよく、硬化性により優れるという観点から、パラ位であるのが好ましい。 In the general formula (1), the vinyl group bonded to the benzyl group of the sulfonium residue may be in any of the ortho-position, the meta-position and the para-position with respect to the benzyl position, and from the viewpoint of being more excellent in curability, para. It is preferably a rank.
一般式（１）で表されるカチオン重合開始剤は、単独でまたは２種以上を組み合わせて用いることができる。 The cationic polymerization initiator represented by the general formula (1) can be used alone or in combination of two or more.
一般式（１）で表されるカチオン重合開始剤は、その製造方法について特に制限されない。例えば、下記一般式（２）で表される化合物とハロゲン化メチルスチレンとを反応させてハライド中間体を得た後、このハライド中間体とテトラキス（ペンタフルオロフェニル）ボレートのナトリウム塩水溶液とを混合し、反応させることで得られる。 The cationic polymerization initiator represented by the general formula (1) is not particularly limited in its production method. For example, a compound represented by the following general formula (2) is reacted with methylstyrene halide to obtain a halide intermediate, and then this halide intermediate is mixed with an aqueous sodium salt solution of tetrakis (pentafluorophenyl) borate. It is obtained by reacting.
（一般式（２）中のＲ１、Ｒ２、Ｒ３およびＲ４の定義は、一般式（１）中におけるＲ１、Ｒ２、Ｒ３およびＲ４の定義と同じである。） (Definition of the general formula (2) R 1 in, R 2, R 3 and R 4 are as defined for R 1, R 2, R 3 and R 4 in the general formula (1).)
一般式（２）で表される化合物としては、例えば、４−（メチルチオ）フェノール、４−（メチルチオ）−ｍ−クレゾール、４−（メチルチオ）−２−メチルフェノール、２，６−ジメチル−４−（メチルチオ）フェノール、３,５−ジメチル−４−（メチルチオ）フェノール、３−エチル−４−(メチルチオ)フェノール等が挙げられる。 Examples of the compound represented by the general formula (2) include 4- (methylthio) phenol, 4- (methylthio) -m-cresol, 4- (methylthio) -2-methylphenol, and 2,6-dimethyl-4. -(Methylthio) phenol, 3,5-dimethyl-4- (methylthio) phenol, 3-ethyl-4- (methylthio) phenol and the like can be mentioned.
また、ハロゲン化メチルスチレンとしては、例えば、４−（クロロメチル）スチレン、３−（クロロメチル）スチレン、２−(クロロメチル)スチレン、４−（ブロモメチル）スチレン等が挙げられる。 Examples of the halogenated methylstyrene include 4- (chloromethyl) styrene, 3- (chloromethyl) styrene, 2- (chloromethyl) styrene, 4- (bromomethyl) styrene and the like.
［エポキシ樹脂組成物］
本発明のエポキシ樹脂組成物は、上述した一般式（１）で表されるカチオン重合開始剤と、後述するエポキシ基を有する化合物を含有する樹脂組成物である。
＜エポキシ基を有する化合物＞
エポキシ基を有する化合物としては、エポキシ基を有するモノマーまたはポリマーのいずれでもよい。
[Epoxy resin composition]
The epoxy resin composition of the present invention is a resin composition containing the above-mentioned cationic polymerization initiator represented by the general formula (1) and a compound having an epoxy group described later.
<Compound with epoxy group>
The compound having an epoxy group may be either a monomer having an epoxy group or a polymer.
（エポキシ基を有するモノマー）
エポキシ基を有するモノマーとしては、特に限定されず、例えば、単官能グリシジルエーテル類、多官能脂肪族グリシジルエーテル類、多官能芳香族グリシジルエーテル類、グリシジルエステル類、脂環式エポキシ化合物等が挙げられる。
(Monomer having an epoxy group)
The monomer having an epoxy group is not particularly limited, and examples thereof include monofunctional glycidyl ethers, polyfunctional aliphatic glycidyl ethers, polyfunctional aromatic glycidyl ethers, glycidyl esters, and alicyclic epoxy compounds. ..
単官能グリシジルエーテル類としては、例えば、アリルグリシジルエーテル、ブチルグリシジルエーテル、フェニルグリシジルエーテル、２−エチルヘキシルグリシジルエーテル、ｓｅｃ−ブチルフェニルグリシジルエーテル、ｔｅｒｔ−ブチルフェニルグリシジルエーテル、２−メチルオクチルグリシジルエーテル等が挙げられる。 Examples of the monofunctional glycidyl ethers include allyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, 2-ethylhexyl glycidyl ether, sec-butylphenyl glycidyl ether, tert-butylphenyl glycidyl ether, 2-methyloctyl glycidyl ether and the like. Can be mentioned.
多官能脂肪族グリシジルエーテル類としては、例えば、１，６−ヘキサンジオールグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、グリセロールジグリシジルエーテル、グリセロールトリグリシジルエーテル、エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル等が挙げられる。 Examples of polyfunctional aliphatic glycidyl ethers include 1,6-hexanediol glycidyl ether, trimethylpropan triglycidyl ether, neopentyl glycol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, and ethylene glycol diglycidyl ether. , Polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether and the like.
多官能芳香族グリシジルエーテル類としては、例えば、ビスフェノールＡグリシジルエーテル、ビスフェノールＦグリシジルエーテル、ブロモ化ビスフェノールＡグリシジルエーテル、ビフェノールグリシジルエーテル、テトラメチルビフェノールグリシジルエーテル、レゾルシングリシジルエーテル、ハイドロキノングリシジルエーテル、ジヒドロキシナフタレングリシジルエーテル、ビスフェノールノボラック樹脂グリシジルエーテル、フェノールノボラック樹脂グリシジルエーテル、クレゾールノボラック樹脂グリシジルエーテル、ジシクロペンタジエンフェノール樹脂グリシジルエーテル、テルペンフェノール樹脂グリシジルエーテル、ナフトールノボラック樹脂グリシジルエーテル等が挙げられる。 Examples of the polyfunctional aromatic glycidyl ethers include bisphenol A glycidyl ether, bisphenol F glycidyl ether, bromoized bisphenol A glycidyl ether, biphenol glycidyl ether, tetramethyl biphenol glycidyl ether, resolving ricidyl ether, hydroquinone glycidyl ether, and dihydroxynaphthalene glycidyl. Examples thereof include ether, bisphenol novolac resin glycidyl ether, phenol novolac resin glycidyl ether, cresol novolac resin glycidyl ether, dicyclopentadienephenol resin glycidyl ether, terpenphenol resin glycidyl ether, naphthol novolac resin glycidyl ether and the like.
グリシジルエステル類としては、例えば、グリシジルアクリレート、グリシジルメタクリレート、ジグリシジルフタレート、ジグリシジルヘキサヒドロフタレート、ジグリシジルテトラヒドロフタレート、ジメチルジグリシジルヘキサヒドロフタレート等が挙げられる。 Examples of glycidyl esters include glycidyl acrylate, glycidyl methacrylate, diglycidyl phthalate, diglycidyl hexahydrophthalate, diglycidyl tetrahydrophthalate, dimethyl diglycidyl hexahydrophthalate and the like.
脂環式エポキシ化合物としては、例えば、３，４−エポキシシクロヘキシルメチル−３，４−エポキシシクロヘキサンカルボキシレート、３，４−エポキシシクロヘキシルエチル−３，４−エポキシシクロヘキサンカルボキシレート、ビニルシクロヘキセンジオキシド、アリルシクロヘキセンジオキシド、３，４−エポキシ−４−メチルシクロヘキシル−２−プロピレンオキシド、２−（３，４−エポキシシクロヘキシル−５，５−スピロ−３，４−エポキシ）シクロヘキサン−ｍ−ジオキサン、ビス（３，４−エポキシシクロヘキシル）アジペート、ビス（３，４−エポキシシクロヘキシルメチル）アジペート、ビス（３，４−エポキシシクロヘキシル）エーテル、ビス（３，４−エポキシシクロヘキシルメチル）エーテル、ビス（３，４−エポキシシクロヘキシル）ジエチルシロキサン等が挙げられる。
エポキシ基を有するモノマーは、単独でまたは２種以上を混合して用いることができる。
Examples of the alicyclic epoxy compound include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexenedioxide, and allyl. Cyclohexene dioxide, 3,4-epoxy-4-methylcyclohexyl-2-propylene oxide, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-m-dioxane, bis ( 3,4-Epoxycyclohexyl) adipate, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxycyclohexyl) ether, bis (3,4-epoxycyclohexylmethyl) ether, bis (3,4-) Epoxycyclohexyl) diethylsiloxane and the like can be mentioned.
The monomer having an epoxy group can be used alone or in combination of two or more.
（エポキシ基を有するポリマー）
エポキシ基を有するポリマーとしては、エポキシ基を２個以上有するものであれば特に制限されない。例えば、ビスフェノールＡ型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、ジアミノジフェニルメタン型エポキシ樹脂、アミノフェノール型エポキシ樹脂、ナフタレン型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、ビフェニル型エポキシ樹脂、水添ビフェノール型エポキシ樹脂、脂環式エポキシ樹脂が挙げられる。
エポキシ基を有するポリマーはそれぞれ単独でまたは２種以上を組み合わせて使用することができる。
(Polymer with epoxy group)
The polymer having an epoxy group is not particularly limited as long as it has two or more epoxy groups. For example, bisphenol A type epoxy resin, dicyclopentadiene type epoxy resin, diaminodiphenylmethane type epoxy resin, aminophenol type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, biphenyl type epoxy resin, hydrogenated biphenol type epoxy resin, An alicyclic epoxy resin can be mentioned.
The polymers having an epoxy group can be used alone or in combination of two or more.
＜カチオン重合開始剤の含有量＞
エポキシ樹脂組成物中、一般式（１）で表されるカチオン重合開始剤の含有量は、硬化性がより良好となる観点から、エポキシ基を有する化合物１００質量部に対して、０．１〜１０質量部であるのが好ましく、０．１〜５質量部であるのがより好ましい。
<Content of cationic polymerization initiator>
The content of the cationic polymerization initiator represented by the general formula (1) in the epoxy resin composition is 0.1 to 1 to 100 parts by mass with respect to 100 parts by mass of the compound having an epoxy group from the viewpoint of better curability. It is preferably 10 parts by mass, more preferably 0.1 to 5 parts by mass.
本発明のエポキシ樹脂組成物は、硬化剤として、一般式（１）で表されるカチオン重合開始剤のほか、従来公知の他のカチオン重合開始剤をさらに含有してもよい。また、本発明のエポキシ樹脂組成物は、発明の効果を損なわない範囲で、ルイス酸等の従来公知の硬化促進剤をさらに含有してもよい。 The epoxy resin composition of the present invention may further contain, as a curing agent, a cationic polymerization initiator represented by the general formula (1) and other conventionally known cationic polymerization initiators. Further, the epoxy resin composition of the present invention may further contain a conventionally known curing accelerator such as Lewis acid as long as the effects of the present invention are not impaired.
＜任意成分＞
また、本発明のエポキシ樹脂組成物は、上述した各成分以外に、必要に応じて、さらに添加剤を含有することができる。添加剤としては、例えば、充填剤（フィラー）、シランカップリング剤、反応性希釈剤、可塑剤、チクソトロピー性付与剤、顔料、染料、老化防止剤、酸化防止剤、帯電防止剤、難燃剤、接着性付与剤、分散剤、溶剤が挙げられる。充填剤としては、シリカ、マイカ等が挙げられる。
また、本発明のエポキシ樹脂組成物は発明の効果を損なわない範囲でオニウム塩、塩基などの安定化剤をさらに含有してもよい。
<Arbitrary ingredient>
In addition to the above-mentioned components, the epoxy resin composition of the present invention may further contain additives, if necessary. Additives include, for example, fillers, silane coupling agents, reactive diluents, plasticizers, thixotropic agents, pigments, dyes, antioxidants, antioxidants, antistatic agents, flame retardants, etc. Examples include adhesive-imparting agents, dispersants, and solvents. Examples of the filler include silica and mica.
Further, the epoxy resin composition of the present invention may further contain a stabilizer such as an onium salt or a base as long as the effects of the present invention are not impaired.
＜エポキシ樹脂組成物の製造方法＞
本発明のエポキシ樹脂組成物は、その製造について特に制限されない。本発明のエポキシ樹脂組成物は、例えば、上述したエポキシ基を有する化合物、一般式（１）で表されるカチオン重合開始剤、並びに、必要に応じて添加される硬化促進剤等の添加剤を混合し、減圧下または窒素雰囲気下において混合ミキサー等の撹拌装置を用いて混練して、均一に分散させることによって、１液型のエポキシ樹脂組成物として得ることができる。
<Manufacturing method of epoxy resin composition>
The epoxy resin composition of the present invention is not particularly limited in its production. The epoxy resin composition of the present invention contains, for example, the above-mentioned compound having an epoxy group, a cationic polymerization initiator represented by the general formula (1), and additives such as a curing accelerator added as needed. A one-component epoxy resin composition can be obtained by mixing, kneading under reduced pressure or under a nitrogen atmosphere using a stirring device such as a mixing mixer, and uniformly dispersing.
［用途］
本発明のエポキシ樹脂組成物は、例えば、接着剤用、塗料用、土木建築用、電気用、輸送機用、医療用、包装用、繊維用、スポーツ・レジャー用として使用することができる。特に、エポキシ樹脂組成物中に配合される一般式（１）で表されるカチオン重合開始剤は、対アニオンがテトラキス（ペンタフルオロフェニル）ボレートであることから、対アニオンンがＳｂＦ６ −やＢＦ４ −等である場合と比較して重合時にフッ素イオンの生成が少ないという利点を有する。したがって、電子材料（例えば、金属の薄膜を加工して形成された回路パターンを基板上に有する各種表示デバイス）の表面に塗布して用いる接着剤用途に好ましく用いることができる。その中でも、ＡＣＦ（異方導電性フィルム）の組成物としてより好ましく用いられる。
[Use]
The epoxy resin composition of the present invention can be used, for example, for adhesives, paints, civil engineering and construction, electricity, transport aircraft, medical use, packaging, textiles, and sports / leisure. In particular, in the cationic polymerization initiator represented by the general formula (1) blended in the epoxy resin composition, since the counter anion is tetrakis (pentafluorophenyl) borate, the counter anion is SbF 6 − or BF 4 It has the advantage that less fluoride ions are generated during polymerization as compared with the case of − etc. Therefore, it can be preferably used as an adhesive used by applying it to the surface of an electronic material (for example, various display devices having a circuit pattern formed by processing a thin metal film on a substrate). Among them, it is more preferably used as a composition of ACF (anisotropic conductive film).
［硬化処理］
本発明のエポキシ樹脂組成物は、加熱により硬化させることができる。
本発明のエポキシ樹脂組成物を硬化させる際の温度は、例えば、エポキシ基を有するポリマーとしてＡＤＥＫＡ社製ビスフェノールＡ型エポキシ樹脂ＥＰ４１００Ｅを用いた場合、１００〜２５０℃であるのが好ましく、１２０〜２００℃であるのがより好ましい。
本発明において、「硬化性」は、エポキシ樹脂組成物のゲル化時間（ゲルタイム）で評価される。例えば、後述する安田式ゲルタイムテスターを使用する方法で測定することができる。
本発明のエポキシ樹脂組成物のゲル化時間は、例えば、エポキシ基を有するポリマーとしてＡＤＥＫＡ社製ビスフェノールＡ型エポキシ樹脂ＥＰ４１００Ｅを用いた場合、１５０℃で３０秒未満であることが好ましく、２０秒未満であることがより好ましい。
[Case-hardening]
The epoxy resin composition of the present invention can be cured by heating.
The temperature at which the epoxy resin composition of the present invention is cured is preferably 100 to 250 ° C., preferably 120 to 200 ° C., for example, when ADEKA's bisphenol A type epoxy resin EP4100E is used as the polymer having an epoxy group. More preferably, it is ° C.
In the present invention, "curability" is evaluated by the gelation time (gel time) of the epoxy resin composition. For example, it can be measured by a method using a Yasuda-type gel time tester described later.
The gelation time of the epoxy resin composition of the present invention is preferably less than 30 seconds at 150 ° C., preferably less than 20 seconds, when, for example, ADEKA's bisphenol A type epoxy resin EP4100E is used as the polymer having an epoxy group. Is more preferable.
以下、実施例を示して、本発明を具体的に説明する。ただし、本発明はこれらに限定されるものではない。本明細書において、実施例１、２、４を、それぞれ、参考例１、２、４と読み替えるものとする。 Hereinafter, the present invention will be specifically described with reference to Examples. However, the present invention is not limited thereto. In the present specification, Examples 1, 2 and 4 shall be read as Reference Examples 1, 2 and 4, respectively.
［エポキシ樹脂組成物の製造］
実施例１〜４、比較例１〜７として、下記表１に示す各成分を、それぞれ同表に示す配合比で混合し、エポキシ樹脂組成物を製造した。表中の各成分の数値は「質量部」を表す。
[Manufacturing of epoxy resin composition]
As Examples 1 to 4 and Comparative Examples 1 to 7, each component shown in Table 1 below was mixed at the blending ratio shown in the same table to prepare an epoxy resin composition. The numerical value of each component in the table represents "part by mass".
表１に示す各成分の詳細は以下のとおりである。
・ エポキシ樹脂（Ａ）：ビスフェノールＡ型エポキシ樹脂（商品名ＥＰ４１００Ｅ、ＡＤＥＫＡ社製）
The details of each component shown in Table 1 are as follows.
-Epoxy resin (A): Bisphenol A type epoxy resin (trade name EP4100E, manufactured by ADEKA Corporation)
・ 硬化剤（１）：下記式で表されるカチオン重合開始剤
硬化剤（１）は次のようにして調製した。
４−（クロロメチル）スチレン１５２．６２ｇと４−（メチルチオ）フェノール１４０．２ｇとを、メタノール中において、室温で２４時間反応させた。反応後、ろ過および乾燥をし、白色結晶を得た。次いで、得られた白色結晶１００ｇに酢酸エチル１００gを混合し、さらにテトラキス（ペンタフルオロフェニル）ボレートのナトリウム塩水溶液（固形分１０％）２４５０gを混合し、室温で６時間反応させた。反応後、有機層を水洗した後に有機層を濃縮し、硬化剤（１）を得た。
The curing agent (1) was prepared as follows.
152.62 g of 4- (chloromethyl) styrene and 140.2 g of 4- (methylthio) phenol were reacted in methanol at room temperature for 24 hours. After the reaction, it was filtered and dried to obtain white crystals. Next, 100 g of ethyl acetate was mixed with 100 g of the obtained white crystals, and 2450 g of an aqueous sodium salt solution (solid content 10%) of tetrakis (pentafluorophenyl) borate was further mixed, and the mixture was reacted at room temperature for 6 hours. After the reaction, the organic layer was washed with water and then concentrated to obtain a curing agent (1).
・ 硬化剤（２）：下記式で表されるカチオン重合開始剤
硬化剤（２）は次のようにして調製した。
４−（クロロメチル）スチレン１５２．６２ｇと４−（メチルチオ）−ｍ−クレゾール１５４．２３ｇとを、メタノール中において、室温で２４時間反応させた。反応後、ろ過および乾燥をし、白色結晶を得た。次いで、得られた白色結晶１００ｇに酢酸エチル１００ｇを混合し、さらにテトラキス（ペンタフルオロフェニル）ボレートのナトリウム塩水溶液（固形分１０％）２３５０ｇを混合し、室温で６時間反応させた。反応後、有機層を水洗した後に有機層を濃縮し、硬化剤（２）を得た。
The curing agent (2) was prepared as follows.
152.62 g of 4- (chloromethyl) styrene and 154.23 g of 4- (methylthio) -m-cresol were reacted in methanol at room temperature for 24 hours. After the reaction, it was filtered and dried to obtain white crystals. Next, 100 g of ethyl acetate was mixed with 100 g of the obtained white crystals, and 2350 g of an aqueous sodium salt solution (solid content 10%) of tetrakis (pentafluorophenyl) borate was further mixed, and the mixture was reacted at room temperature for 6 hours. After the reaction, the organic layer was washed with water and then concentrated to obtain a curing agent (2).
・ 硬化剤（３）：下記式で表されるカチオン重合開始剤
硬化剤（３）は次のようにして調製した。
３−（クロロメチル）スチレン１５２．６２ｇと４−（メチルチオ）−ｍ−クレゾール１５４．２３ｇとを、メタノール中において、室温で２４時間反応させた。反応後、ろ過および乾燥をし、白色結晶を得た。次いで、得られた白色結晶１００ｇに酢酸エチル１００ｇを混合し、さらにテトラキス（ペンタフルオロフェニル）ボレートのナトリウム塩水溶液（固形分１０％）２３５０ｇを混合し、室温で６時間反応させた。反応後に、有機層を水洗した後に有機層を濃縮し、硬化剤（３）を得た。
The curing agent (3) was prepared as follows.
152.62 g of 3- (chloromethyl) styrene and 154.23 g of 4- (methylthio) -m-cresol were reacted in methanol at room temperature for 24 hours. After the reaction, it was filtered and dried to obtain white crystals. Next, 100 g of ethyl acetate was mixed with 100 g of the obtained white crystals, and 2350 g of an aqueous sodium salt solution (solid content 10%) of tetrakis (pentafluorophenyl) borate was further mixed, and the mixture was reacted at room temperature for 6 hours. After the reaction, the organic layer was washed with water and then concentrated to obtain a curing agent (3).
・ 硬化剤（４）：下記式で表されるカチオン重合開始剤
硬化剤（４）は次のようにして調製した。
上記硬化剤（１）の合成例において、テトラキス（ペンタフルオロフェニル）ボレートのナトリウム塩水溶液（固形分１０％）をヘキサフルオロアンチモン酸ナトリウム水溶液（固形分１０％）９００ｇに変更した以外は、硬化剤（１）と同じように合成を行い、硬化剤（４）を得た。
The curing agent (4) was prepared as follows.
In the synthesis example of the above-mentioned curing agent (1), the curing agent was changed from the sodium salt aqueous solution (solid content 10%) of tetrakis (pentafluorophenyl) borate to 900 g of the sodium hexafluoroantimonate aqueous solution (solid content 10%). Synthesis was carried out in the same manner as in (1) to obtain a curing agent (4).
・ 硬化剤（５）：下記式で表されるカチオン重合開始剤
硬化剤（５）は次のようにして調製した。
上記硬化剤（１）の合成例において、テトラキス（ペンタフルオロフェニル）ボレートのナトリウム塩水溶液（固形分１０％）を４フッ化ホウ酸ナトリウム水溶液（固形分１０％）３８２ｇに変更した以外は、硬化剤（１）と同じように合成を行い、硬化剤（５）を得た。
The curing agent (5) was prepared as follows.
In the synthesis example of the curing agent (1), curing was performed except that the sodium salt aqueous solution (solid content 10%) of tetrakis (pentafluorophenyl) borate was changed to 382 g of the sodium tetrafluorate borate aqueous solution (solid content 10%). Synthesis was carried out in the same manner as in the agent (1) to obtain a curing agent (5).
・ 硬化剤（６）：下記式で表されるカチオン重合開始剤
硬化剤（６）は次のようにして調製した。
上記硬化剤（２）の合成例において、テトラキス（ペンタフルオロフェニル）ボレートのナトリウム塩水溶液（固形分１０％）をヘキサフルオロアンチモン酸ナトリウム水溶液（固形分１０％）９０５ｇに変更した以外は、硬化剤（２）と同じように合成を行い、硬化剤（６）を得た。
The curing agent (6) was prepared as follows.
In the synthesis example of the curing agent (2), the curing agent was changed from the sodium salt aqueous solution (solid content 10%) of tetrakis (pentafluorophenyl) borate to 905 g of the sodium hexafluoroantimonate aqueous solution (solid content 10%). Synthesis was carried out in the same manner as in (2) to obtain a curing agent (6).
・ 硬化剤（７）：下記式で表されるカチオン重合開始剤（ＳＩ−１００Ｌ、三新化学工業社製）
・ 硬化剤（８）：下記式で表されるカチオン重合開始剤
硬化剤（８）は次のようにして調製した。
ベンジルクロライド１０ｇと４−（メチルチオ）フェノール１１．０７ｇとをメタノール中において室温で２４時間反応させ、クロライド中間体を得た。さらに中間体１０ｇとテトラキス（ペンタフルオロフェニル）ボレートのナトリウム塩水溶液（固形分１０％）２６３ｇとを混合し、硬化剤（８）を得た。
The curing agent (8) was prepared as follows.
10 g of benzyl chloride and 11.07 g of 4- (methylthio) phenol were reacted in methanol at room temperature for 24 hours to obtain a chloride intermediate. Further, 10 g of the intermediate and 263 g of an aqueous sodium salt solution (solid content 10%) of tetrakis (pentafluorophenyl) borate were mixed to obtain a curing agent (8).
・ 硬化剤（９）：下記式で表されるカチオン重合開始剤
硬化剤（９）は次のようにして調製した。
１−（クロロメチル）ナフタレン１０ｇと４−メチルチオフェノール７．９ｇとをメタノール中において室温で２４時間反応させ、クロライド中間体を得た。さらに中間体１０ｇとテトラキス（ペンタフルオロフェニル）ボレートのナトリウム塩水溶液（固形分１０％）２２０．１６ｇとを混合し、硬化剤（９）を得た。
The curing agent (9) was prepared as follows.
10 g of 1- (chloromethyl) naphthalene and 7.9 g of 4-methylthiophenol were reacted in methanol at room temperature for 24 hours to obtain a chloride intermediate. Further, 10 g of the intermediate and 220.16 g of an aqueous sodium salt solution (solid content 10%) of tetrakis (pentafluorophenyl) borate were mixed to obtain a curing agent (9).
［評価］
得られた各エポキシ樹脂組成物について、それぞれ、下記の方法でゲルタイム（硬化性）、貯蔵安定性およびフッ素イオン濃度を測定した。結果を表１に示す。
（１）ゲルタイム（硬化性評価）
得られた各組成物について、安田式ゲルタイムテスター（株式会社安田精機製作所製、Ｎｏ．１５３ゲルタイムテスター）を用いて１５０℃でのゲルタイムを測定した。安田式ゲルタイムテスターは、オイルバス中、試料を入れた試験管の中でローターを回転させ、ゲル化が進み一定のトルクが掛かると磁気カップリング機構によりローターが落ちタイマーが止まる装置である。
（２）貯蔵安定性
得られた各組成物を４０℃のオーブンに入れて、初期および２時間経過後の粘度をそれぞれ測定し、その増加率を粘度上昇率とした。粘度は、４０℃において、Ｅ型粘度計 ＶＩＳＣＯＮＩＣ ＥＨＤ型（東機産業社製）を用いて測定した。次いで、得られた初期粘度および２時間後の粘度の値を下記式に当てはめて、粘度上昇率を算出した。
（粘度上昇率）＝（２時間後の粘度）／（初期粘度）
（３）フッ素イオン濃度
各硬化剤のフッ素イオン濃度：硬化剤０．５ｇを純水５０ｍＬ中に投入し、１００℃１０時間加熱抽出を行い、得られた抽出液をメンブレンフィルター（ＯｎＧｕａｒｄＲＰ、Ｄｉｏｎｅｘ社製）にてろ過を行った。得られた濾液に対し、イオンクロマトグラフ（ＩＣＳ−１６００、Ｄｉｏｎｅｘ社製）を用いてフッ素イオン濃度の分析を行った。
[Evaluation]
For each of the obtained epoxy resin compositions, the gel time (curability), storage stability and fluorine ion concentration were measured by the following methods. The results are shown in Table 1.
(1) Gel time (evaluation of curability)
The gel time of each of the obtained compositions was measured at 150 ° C. using a Yasuda-type gel time tester (No. 153 gel time tester manufactured by Yasuda Seiki Seisakusho Co., Ltd.). The Yasuda-type gel time tester is a device that rotates the rotor in a test tube containing a sample in an oil bath, and when gelation progresses and a constant torque is applied, the rotor drops due to a magnetic coupling mechanism and the timer stops.
(2) Storage stability Each of the obtained compositions was placed in an oven at 40 ° C., and the viscosities were measured at the initial stage and after 2 hours, respectively, and the rate of increase was taken as the rate of increase in viscosity. The viscosity was measured at 40 ° C. using an E-type viscometer VISCONIC EHD type (manufactured by Toki Sangyo Co., Ltd.). Then, the obtained initial viscosity and the value of the viscosity after 2 hours were applied to the following formulas to calculate the viscosity increase rate.
(Viscosity increase rate) = (Viscosity after 2 hours) / (Initial viscosity)
(3) Fluoride ion concentration Fluoride ion concentration of each curing agent: 0.5 g of the curing agent was put into 50 mL of pure water, heat extraction was performed at 100 ° C. for 10 hours, and the obtained extract was used as a membrane filter (OnGuardRP, Dionex). Manufactured by). The obtained filtrate was analyzed for fluorine ion concentration using an ion chromatograph (ICS-1600, manufactured by Dionex).
表１に示す結果から明らかなように、実施例１〜４のエポキシ樹脂組成物は、ゲル化時間（１５０℃）がいずれも３０秒未満であり、また貯蔵安定性にも優れていた。
実施例１〜４と比較例１〜４とを比較すると、一般式（１）で表されるカチオン重合開始剤を含有する実施例１〜４は、硬化性において、対アニオンがＳｂＦ６ −やＢＦ４ −である比較例１〜４よりも顕著に優れていた。
また、実施例１〜４と比較例５とを比較すると、一般式（１）で表されるカチオン重合開始剤を含有する実施例１〜４は、硬化性において、スルホニウム残基にビニル基を有さず、且つ、対アニオンがＳｂＦ６ −である比較例５よりも顕著に優れていた。
さらに、比較例１〜５のカチオン重合開始剤は、いずれも対アニオンがテトラキス（ペンタフルオロフェニル）ボレートではなくＳｂＦ６ −やＢＦ４ −であるため、重合時に生成するフッ素イオン濃度が高い結果となった。
一方、実施例１〜４と比較例６とを比較すると、比較例６は、貯蔵安定性については実施例１〜４と同程度であったものの、硬化性が実施例１〜４よりも劣る結果となった。
実施例１〜４と比較例７とを比較すると、比較例７は硬化性については実施例１〜４と同程度であったものの、貯蔵安定性が実施例１〜４よりも劣る結果となった。
As is clear from the results shown in Table 1, the epoxy resin compositions of Examples 1 to 4 had a gelation time (150 ° C.) of less than 30 seconds, and were also excellent in storage stability.
Comparing Examples 1 to 4 with Comparative Examples 1 to 4, in Examples 1 to 4 containing the cationic polymerization initiator represented by the general formula (1), the counter anion was SbF 6 − or BF 4 - and is than Comparative examples 1 to 4 had remarkably excellent.
Further, comparing Examples 1 to 4 with Comparative Example 5, Examples 1 to 4 containing the cationic polymerization initiator represented by the general formula (1) have a vinyl group at the sulfonium residue in terms of curability. It was not present and was significantly superior to Comparative Example 5 in which the counter anion was SbF 6 −.
Further, the cationic polymerization initiator of Comparative Examples 1 to 5 are all SbF 6 not even counter anion tetrakis (pentafluorophenyl) borate - and BF 4 - for the is a result fluorine ion concentration is higher generated during the polymerization became.
On the other hand, when Examples 1 to 4 and Comparative Example 6 are compared, Comparative Example 6 has the same storage stability as Examples 1 to 4, but its curability is inferior to that of Examples 1 to 4. The result was.
Comparing Examples 1 to 4 with Comparative Example 7, Comparative Example 7 had the same degree of curability as Examples 1 to 4, but the storage stability was inferior to that of Examples 1 to 4. It was.
Claims (1)
（一般式（１）において、Ｒ 2 およびＲ 4 は、それぞれ独立して、炭素数１〜３のアルキル基である。） A cationic polymerization initiator represented by the following general formula (1).
(In the general formula (1), R 2 and R 4 are independently alkyl groups having 1 to 3 carbon atoms. )
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