JP2017002124A - Thermosetting resin composition, and prepreg, laminate and printed wiring board prepared therewith - Google Patents
Thermosetting resin composition, and prepreg, laminate and printed wiring board prepared therewith Download PDFInfo
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- JP2017002124A JP2017002124A JP2015114694A JP2015114694A JP2017002124A JP 2017002124 A JP2017002124 A JP 2017002124A JP 2015114694 A JP2015114694 A JP 2015114694A JP 2015114694 A JP2015114694 A JP 2015114694A JP 2017002124 A JP2017002124 A JP 2017002124A
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- general formula
- resin composition
- thermosetting resin
- compound
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- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 42
- 239000011342 resin composition Substances 0.000 title claims abstract description 40
- -1 maleimide compound Chemical class 0.000 claims abstract description 66
- 229920005989 resin Polymers 0.000 claims abstract description 38
- 239000011347 resin Substances 0.000 claims abstract description 38
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 28
- 239000003822 epoxy resin Substances 0.000 claims abstract description 27
- 229920001955 polyphenylene ether Polymers 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 125000005843 halogen group Chemical group 0.000 claims description 12
- 230000002378 acidificating effect Effects 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 125000001424 substituent group Chemical group 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 7
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical group NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 125000001118 alkylidene group Chemical group 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 125000001033 ether group Chemical group 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 3
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 239000004593 Epoxy Substances 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 abstract description 3
- 150000002367 halogens Chemical class 0.000 abstract description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 21
- 229910052802 copper Inorganic materials 0.000 description 13
- 239000010949 copper Substances 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 239000003063 flame retardant Substances 0.000 description 9
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 8
- 229920003986 novolac Polymers 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000011889 copper foil Substances 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- 239000011256 inorganic filler Substances 0.000 description 7
- 229910003475 inorganic filler Inorganic materials 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical class N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 6
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 6
- 238000005530 etching Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 229920002223 polystyrene Polymers 0.000 description 6
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 5
- 239000004305 biphenyl Substances 0.000 description 5
- 235000010290 biphenyl Nutrition 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 4
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 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 4
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 4
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 229920006026 co-polymeric resin Polymers 0.000 description 4
- 229930003836 cresol Natural products 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000011810 insulating material Substances 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 3
- 229940018563 3-aminophenol Drugs 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012796 inorganic flame retardant Substances 0.000 description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 3
- 239000000347 magnesium hydroxide Substances 0.000 description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- XOJRVZIYCCJCRD-UHFFFAOYSA-N 1-[4-[4-(2,5-dioxopyrrol-1-yl)phenoxy]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1OC1=CC=C(N2C(C=CC2=O)=O)C=C1 XOJRVZIYCCJCRD-UHFFFAOYSA-N 0.000 description 2
- GUIACFHOZIQGKX-UHFFFAOYSA-N 1-[4-[4-(2,5-dioxopyrrol-1-yl)phenyl]sulfonylphenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=C(S(=O)(=O)C=2C=CC(=CC=2)N2C(C=CC2=O)=O)C=C1 GUIACFHOZIQGKX-UHFFFAOYSA-N 0.000 description 2
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 2
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 2
- XFDUHJPVQKIXHO-UHFFFAOYSA-N 3-aminobenzoic acid Chemical compound NC1=CC=CC(C(O)=O)=C1 XFDUHJPVQKIXHO-UHFFFAOYSA-N 0.000 description 2
- PDCMTKJRBAZZHL-UHFFFAOYSA-N 5-aminobenzene-1,3-diol Chemical compound NC1=CC(O)=CC(O)=C1 PDCMTKJRBAZZHL-UHFFFAOYSA-N 0.000 description 2
- ZXLYUNPVVODNRE-UHFFFAOYSA-N 6-ethenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=C)=N1 ZXLYUNPVVODNRE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 239000005456 alcohol based solvent Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229960004050 aminobenzoic acid Drugs 0.000 description 2
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
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- 239000007809 chemical reaction catalyst Substances 0.000 description 2
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- 238000005553 drilling Methods 0.000 description 2
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- 239000000806 elastomer Substances 0.000 description 2
- 239000004210 ether based solvent Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
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- 229920005992 thermoplastic resin Polymers 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- QYOJZFBQEAZNEW-UHFFFAOYSA-N 1-(2-methylphenyl)pyrrole-2,5-dione Chemical compound CC1=CC=CC=C1N1C(=O)C=CC1=O QYOJZFBQEAZNEW-UHFFFAOYSA-N 0.000 description 1
- XAZPKEBWNIUCKF-UHFFFAOYSA-N 1-[4-[4-[2-[4-[4-(2,5-dioxopyrrol-1-yl)phenoxy]phenyl]propan-2-yl]phenoxy]phenyl]pyrrole-2,5-dione Chemical compound C=1C=C(OC=2C=CC(=CC=2)N2C(C=CC2=O)=O)C=CC=1C(C)(C)C(C=C1)=CC=C1OC(C=C1)=CC=C1N1C(=O)C=CC1=O XAZPKEBWNIUCKF-UHFFFAOYSA-N 0.000 description 1
- HHVCCCZZVQMAMT-UHFFFAOYSA-N 1-hydroxy-3-phenylpyrrole-2,5-dione Chemical compound O=C1N(O)C(=O)C=C1C1=CC=CC=C1 HHVCCCZZVQMAMT-UHFFFAOYSA-N 0.000 description 1
- SEULWJSKCVACTH-UHFFFAOYSA-N 1-phenylimidazole Chemical compound C1=NC=CN1C1=CC=CC=C1 SEULWJSKCVACTH-UHFFFAOYSA-N 0.000 description 1
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- YIUOAAUFVBZQPM-UHFFFAOYSA-N 2-methyl-1,3,5-triazine Chemical compound CC1=NC=NC=N1 YIUOAAUFVBZQPM-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
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- MOSSLXZUUKTULI-UHFFFAOYSA-N 3-[3-(2,5-dioxopyrrol-3-yl)-4-methylphenyl]pyrrole-2,5-dione Chemical compound CC1=CC=C(C=2C(NC(=O)C=2)=O)C=C1C1=CC(=O)NC1=O MOSSLXZUUKTULI-UHFFFAOYSA-N 0.000 description 1
- ZAJAQTYSTDTMCU-UHFFFAOYSA-N 3-aminobenzenesulfonic acid Chemical compound NC1=CC=CC(S(O)(=O)=O)=C1 ZAJAQTYSTDTMCU-UHFFFAOYSA-N 0.000 description 1
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 1
- KBZFDRWPMZESDI-UHFFFAOYSA-N 5-aminobenzene-1,3-dicarboxylic acid Chemical compound NC1=CC(C(O)=O)=CC(C(O)=O)=C1 KBZFDRWPMZESDI-UHFFFAOYSA-N 0.000 description 1
- 0 C*C(CC(*)=CC=C1)=C1NC(CC(N1c2ccccc2)=O)C1=O Chemical compound C*C(CC(*)=CC=C1)=C1NC(CC(N1c2ccccc2)=O)C1=O 0.000 description 1
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- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
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- 125000002723 alicyclic group Chemical group 0.000 description 1
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- 238000004458 analytical method Methods 0.000 description 1
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- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical class [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
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- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 1
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- 239000006185 dispersion Substances 0.000 description 1
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Abstract
Description
本発明は、ハロゲンフリーであり、耐熱性、誘電特性、成形性及び難燃性が高度に両立した熱硬化性樹脂組成物、並びにそれを用いたプリプレグ、積層板及びプリント配線板に関する。 The present invention relates to a thermosetting resin composition that is halogen-free and highly compatible with heat resistance, dielectric properties, moldability, and flame retardancy, and a prepreg, laminate, and printed wiring board using the same.
熱硬化性樹脂は、その特有な架橋構造が高い耐熱性及び寸法安定性を発現するため、電子部品等の高い信頼性を要求される分野において広く使用されているが、特に銅張積層板及び層間絶縁材料においては、近年の高密度化への要求から、微細配線形成のための高い銅箔接着性、ドリル又は打ち抜きによる穴あけ等の加工をする際の加工性などが必要とされる。 Thermosetting resins are widely used in fields requiring high reliability such as electronic parts because their unique cross-linked structure expresses high heat resistance and dimensional stability. Interlayer insulating materials require high copper foil adhesion for forming fine wiring and workability when processing such as drilling or punching due to the recent demand for higher density.
また、近年では、大量のデータを高速で処理するために、コンピュータ、情報機器端末等で、信号の高周波化が進んでいる。用いる周波数が高くなるにつれて、電気信号の伝送損失が大きくなる。そのため、銅張積層板及び層間絶縁材料においては、低い比誘電率及び低い誘電正接が要求されている。 In recent years, in order to process a large amount of data at high speed, the frequency of signals has been increased in computers, information equipment terminals, and the like. As the frequency used increases, the transmission loss of electrical signals increases. For this reason, the copper clad laminate and the interlayer insulating material are required to have a low relative dielectric constant and a low dielectric loss tangent.
さらに、近年、環境意識の高まりから、電子機器及び電子部品についても環境への配慮が不可欠となっている。電子部品をはじめとするプラスチック製品全般に用いられているハロゲン系難燃剤は、最も代表的な臭素系難燃剤であるデカブロモジフェニルオキサイドが焼却時に有毒な臭素化ジベンゾダイオキシンとフランを生成させることが報告されて以来、その安全性が疑われている。したがって、環境問題への配慮の点から、従来のハロゲンを含む臭素系難燃剤を使用しないハロゲンフリー製品の導入が進められている。 Furthermore, in recent years, due to increasing environmental awareness, consideration for the environment is indispensable for electronic devices and electronic components. Halogen-based flame retardants used in plastic products, including electronic parts, can produce toxic brominated dibenzodioxins and furans when incinerated, the most typical brominated flame retardant, decabromodiphenyl oxide. Since being reported, its safety has been suspected. Therefore, in consideration of environmental problems, the introduction of halogen-free products that do not use conventional brominated flame retardants containing halogen is being promoted.
ハロゲン系化合物を含まずに難燃性を付与する方法としては、通常、リン含有難燃剤と比較的多量の無機充填材とを併用する方法が使われている。ここで用いられる無機充填材としては、水酸化アルミニウム、シリカ等が選択されることが多い。
また、同様に環境問題への配慮の点から、鉛を含まない鉛フリーはんだの導入も進んでおり、従来よりも高温で行われる鉛フリーはんだプロセスに対応するため、銅張積層板及び層間絶縁材料には高耐熱性及び低熱膨張性が要求されている。
As a method for imparting flame retardancy without containing a halogen compound, a method using a phosphorus-containing flame retardant in combination with a relatively large amount of an inorganic filler is usually used. As the inorganic filler used here, aluminum hydroxide, silica or the like is often selected.
Similarly, lead-free solders that do not contain lead are also being introduced from the viewpoint of environmental issues, and copper-clad laminates and interlayer insulation are required to support lead-free solder processes that are performed at higher temperatures than before. The material is required to have high heat resistance and low thermal expansion.
特許文献１には、鉛フリーはんだに対応した高耐熱性及び誘電特性に優れた樹脂組成物として、特定の２官能ポリフェニレンエーテル樹脂と、熱硬化性樹脂と、熱硬化性樹脂の硬化剤を含有してなる樹脂組成物が開示されている。 Patent Document 1 contains a specific bifunctional polyphenylene ether resin, a thermosetting resin, and a thermosetting resin curing agent as a resin composition with high heat resistance and excellent dielectric properties corresponding to lead-free solder. A resin composition is disclosed.
特許文献１の技術によると、耐熱性及び誘電特性を改善することができるが、耐熱性、誘電特性、成形性及び難燃性をより高度に両立した材料が望まれていた。
本発明は、上記の問題点に鑑みてなされたものであり、ハロゲンフリーであり、耐熱性、誘電特性、成形性及び難燃性が高度に両立した熱硬化性樹脂組成物、並びにそれを用いたプリプレグ、積層板及びプリント配線板を提供することを課題とする。
According to the technique of Patent Document 1, although heat resistance and dielectric properties can be improved, a material having higher compatibility between heat resistance, dielectric properties, moldability and flame retardancy has been desired.
The present invention has been made in view of the above problems, and is a halogen-free thermosetting resin composition having high compatibility between heat resistance, dielectric properties, moldability and flame retardancy, and uses the same. It is an object to provide a prepreg, a laminated board, and a printed wiring board.
本発明者等は上記の課題を解決すべく検討を進めた結果、下記の本発明により当該課題を解決できることを見出した。
すなわち、本発明は、以下の［１］〜［９］を提供するものである。
［１］（Ａ）重量平均分子量が２０００〜１７０００であるポリフェニレンエーテル樹脂、（Ｂ）分子中にＮ−置換マレイミド基を有するマレイミド化合物、（Ｃ）硬化剤及び（Ｄ）１分子中に少なくとも２個のエポキシ基を有するエポキシ樹脂を含有する、熱硬化性樹脂組成物。
［２］（Ａ）ポリフェニレンエーテル樹脂が、下記一般式（１）で表される構造単位を有する、上記［１］に記載の熱硬化性樹脂組成物。
As a result of investigations to solve the above problems, the present inventors have found that the problems can be solved by the following present invention.
That is, the present invention provides the following [1] to [9].
[1] (A) polyphenylene ether resin having a weight average molecular weight of 2000 to 17000, (B) a maleimide compound having an N-substituted maleimide group in the molecule, (C) a curing agent, and (D) at least 2 in one molecule. A thermosetting resin composition comprising an epoxy resin having an epoxy group.
[2] The thermosetting resin composition according to [1], wherein the (A) polyphenylene ether resin has a structural unit represented by the following general formula (1).
（一般式（１）中、Ｒ１〜Ｒ４は各々独立に、水素原子、ハロゲン原子又は炭素数１〜６のアルキル基を示す。）
［３］（Ａ）ポリフェニレンエーテル樹脂の含有量が、固形分換算の（Ｂ）〜（Ｄ）成分の総和１００質量部に対して、０．１〜５０質量部である、上記［１］又は［２］に記載の熱硬化性樹脂組成物。
［４］（Ｂ）分子中にＮ−置換マレイミド基を有するマレイミド化合物が、（ｂ−１）１分子中に少なくとも２個のＮ−置換マレイミド基を有するマレイミド化合物と、（ｂ−２）下記一般式（２）で表される酸性置換基を有するアミン化合物とを反応させて得られた不飽和マレイミド基を有する化合物である、上記［１］〜［３］のいずれか１項に記載の熱硬化性樹脂組成物。
(In general formula (1), R < 1 > -R < 4 > shows a hydrogen atom, a halogen atom, or a C1-C6 alkyl group each independently.)
[3] The above [1], wherein the content of (A) polyphenylene ether resin is 0.1 to 50 parts by mass with respect to 100 parts by mass of the total of the components (B) to (D) in terms of solid content The thermosetting resin composition according to [2].
[4] (B) a maleimide compound having an N-substituted maleimide group in the molecule is (b-1) a maleimide compound having at least two N-substituted maleimide groups in one molecule; The compound according to any one of the above [1] to [3], which is a compound having an unsaturated maleimide group obtained by reacting with an amine compound having an acidic substituent represented by the general formula (2). Thermosetting resin composition.
（一般式（２）中、Ｒ５は各々独立に、水酸基、カルボキシ基及びスルホン酸基から選ばれる酸性置換基を示し、Ｒ６は各々独立に、水素原子、炭素数１〜５の脂肪族炭化水素基又はハロゲン原子を示し、ｘは１〜５の整数、ｙは０〜４の整数で、かつｘとｙの和は５である。）
［５］（Ｂ）分子中にＮ−置換マレイミド基を有するマレイミド化合物が、下記一般式（３）で表される化合物及び下記一般式（４）で表される化合物から選ばれる１種以上を含む、上記［１］〜［４］のいずれか１項に記載の熱硬化性樹脂組成物。
(In General Formula (2), each R 5 independently represents an acidic substituent selected from a hydroxyl group, a carboxy group, and a sulfonic acid group, and each R 6 independently represents a hydrogen atom or an aliphatic group having 1 to 5 carbon atoms. A hydrocarbon group or a halogen atom, x is an integer of 1 to 5, y is an integer of 0 to 4, and the sum of x and y is 5.
[5] (B) The maleimide compound having an N-substituted maleimide group in the molecule contains at least one selected from a compound represented by the following general formula (3) and a compound represented by the following general formula (4): The thermosetting resin composition according to any one of [1] to [4] above.
（一般式（３）中、Ｒ５、Ｒ６、ｘ及びｙは一般式（２）と同じものを示し、Ｒ７は各々独立に、水素原子、炭素数１〜５の脂肪族炭化水素基又はハロゲン原子を示す。） (In General Formula (3), R 5 , R 6 , x and y are the same as those in General Formula (2), and R 7 is independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. Or a halogen atom.)
（一般式（４）中、Ｒ５、Ｒ６、ｘ及びｙは一般式（２）と同じものを示し、Ｒ８及びＲ９は各々独立に、水素原子、炭素数１〜５の脂肪族炭化水素基又はハロゲン原子を示し、Ａはアルキレン基、アルキリデン基、エーテル基、スルフォニル基又は下記式（５）で表される２価の基を示す。） (In General Formula (4), R 5 , R 6 , x and y are the same as those in General Formula (2), and R 8 and R 9 are each independently a hydrogen atom, an aliphatic group having 1 to 5 carbon atoms. A hydrocarbon group or a halogen atom, and A represents an alkylene group, an alkylidene group, an ether group, a sulfonyl group, or a divalent group represented by the following formula (5).
［６］（Ｃ）硬化剤が、ジシアンジアミドである、上記［１］〜［５］のいずれか１項に記載の熱硬化性樹脂組成物。
［７］上記［１］〜［６］のいずれか１項に記載の熱硬化性樹脂組成物を、基材に含浸又は塗工し、加熱乾燥して得られるプリプレグ。
［８］上記［７］に記載のプリプレグを用いてなる積層板。
［９］上記［８］に記載の積層板を回路加工してなるプリント配線板。
[6] The thermosetting resin composition according to any one of [1] to [5], wherein (C) the curing agent is dicyandiamide.
[7] A prepreg obtained by impregnating or coating the thermosetting resin composition according to any one of the above [1] to [6] on a base material and drying by heating.
[8] A laminate using the prepreg according to [7] above.
[9] A printed wiring board obtained by subjecting the laminated board according to [8] to circuit processing.
本発明によれば、ハロゲンフリーであり、耐熱性、誘電特性、成形性及び難燃性が高度に両立した熱硬化性樹脂組成物、並びにそれを用いたプリプレグ、積層板及びプリント配線板を提供することができる。 According to the present invention, there are provided a thermosetting resin composition that is halogen-free and highly compatible with heat resistance, dielectric properties, moldability, and flame retardancy, and a prepreg, laminate, and printed wiring board using the same. can do.
以下、本発明の具体的な実施形態について、詳細に説明するが、本発明は、以下の実施形態に何ら限定されるものではなく、本発明の目的の範囲内において、適宜変更を加えて実施することができる。 Hereinafter, specific embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and may be implemented with appropriate modifications within the scope of the object of the present invention. can do.
［熱硬化性樹脂組成物］
本発明の熱硬化性樹脂組成物は、（Ａ）重量平均分子量が２０００〜１７０００であるポリフェニレンエーテル樹脂（以下、単に「（Ａ）ポリフェニレンエーテル樹脂」又は「（Ａ）成分」ともいう）、（Ｂ）分子中にＮ−置換マレイミド基を有するマレイミド化合物（以下、「（Ｂ）成分」ともいう）、（Ｃ）硬化剤（以下、「（Ｃ）成分」ともいう）及び（Ｄ）１分子中に少なくとも２個のエポキシ基を有するエポキシ樹脂（以下、「（Ｄ）エポキシ樹脂」又は「（Ｄ）成分」ともいう）を含有するものである。
[Thermosetting resin composition]
The thermosetting resin composition of the present invention comprises (A) a polyphenylene ether resin having a weight average molecular weight of 2000 to 17000 (hereinafter also simply referred to as “(A) polyphenylene ether resin” or “(A) component”), ( B) Maleimide compound having an N-substituted maleimide group in the molecule (hereinafter also referred to as “component (B)”), (C) a curing agent (hereinafter also referred to as “component (C)”), and (D) 1 molecule It contains an epoxy resin having at least two epoxy groups (hereinafter also referred to as “(D) epoxy resin” or “(D) component”).
＜（Ａ）ポリフェニレンエーテル樹脂＞
（Ａ）ポリフェニレンエーテル樹脂としては、重量平均分子量が２０００〜１７０００であるポリフェニレンエーテル樹脂であれば、特に制限なく用いることができる。
本発明の熱硬化性樹脂組成物は、（Ａ）ポリフェニレンエーテル樹脂を必須成分とすることにより、高耐熱性及び良好な成形性を確保しつつ、低い比誘電率及び誘電正接を付与することができる。
<(A) Polyphenylene ether resin>
(A) As a polyphenylene ether resin, if it is a polyphenylene ether resin whose weight average molecular weight is 2000-17000, it can be especially used without a restriction | limiting.
The thermosetting resin composition of the present invention can impart low dielectric constant and dielectric loss tangent while ensuring high heat resistance and good moldability by using (A) polyphenylene ether resin as an essential component. it can.
（Ａ）ポリフェニレンエーテル樹脂の重量平均分子量は、耐熱性、誘電特性、成形性及び難燃性の観点から、２０００〜１７０００であり、好ましくは２２００〜１６５００、より好ましくは２４００〜１６０００である。
本発明の熱硬化性樹脂組成物は、この（Ａ）ポリフェニレンエーテル樹脂を必須成分とすることにより、高耐熱性及び良好な成形性を確保しつつ、低い比誘電率、低い誘電正接を付与することができる。一方、重量平均分子量が２０００未満では機械強度が弱くなるため耐熱性が低下する。この耐熱性の低下は、プリント配線板においては、リフロー実装時のクラック、デラミネーション等の原因となる。また、重量平均分子量が１７０００を超えると、樹脂の粘度が高くなりすぎ、銅張積層板、及びプリント配線板のプレス成形時に十分な樹脂流動が得られず、成形不具合の原因になり得る。
また、特に優れた成形性を得る観点からは、（Ａ）ポリフェニレンエーテル樹脂の重量平均分子量は、好ましくは２０００〜１５０００、より好ましくは２２００〜１００００、更に好ましくは２３００〜５０００である。
また、特に優れた誘電特性を得る観点からは、（Ａ）ポリフェニレンエーテル樹脂の重量平均分子量は、好ましくは３０００〜１７０００、より好ましくは８０００〜１６５００、更に好ましくは１３０００〜１６５００である。
なお、重量平均分子量はゲルパーミエーションクロマトグラフィー（ＧＰＣ）による標準ポリスチレン換算値から求めることができ、具体的には、実施例に記載の方法で測定することができる。
(A) The weight average molecular weight of polyphenylene ether resin is 2000-17000 from a viewpoint of heat resistance, a dielectric characteristic, a moldability, and a flame retardance, Preferably it is 2100-16500, More preferably, it is 2400-16000.
The thermosetting resin composition of the present invention provides a low relative dielectric constant and a low dielectric loss tangent while ensuring high heat resistance and good moldability by using the polyphenylene ether resin (A) as an essential component. be able to. On the other hand, if the weight average molecular weight is less than 2,000, the mechanical strength becomes weak and the heat resistance decreases. This decrease in heat resistance causes cracks, delamination, etc. during reflow mounting in a printed wiring board. On the other hand, if the weight average molecular weight exceeds 17000, the viscosity of the resin becomes too high, and sufficient resin flow cannot be obtained at the time of press molding of the copper-clad laminate and the printed wiring board, which may cause molding defects.
Moreover, from the viewpoint of obtaining particularly excellent moldability, the weight average molecular weight of the (A) polyphenylene ether resin is preferably 2000 to 15000, more preferably 2200 to 10,000, and still more preferably 2300 to 5000.
From the viewpoint of obtaining particularly excellent dielectric properties, the weight average molecular weight of the (A) polyphenylene ether resin is preferably 3000 to 17000, more preferably 8000 to 16500, and still more preferably 13,000 to 16500.
In addition, a weight average molecular weight can be calculated | required from the standard polystyrene conversion value by a gel permeation chromatography (GPC), and can be specifically measured by the method as described in an Example.
（Ａ）ポリフェニレンエーテル樹脂としては、下記一般式（１）で表される構造単位を有するものが挙げられる。 (A) As polyphenylene ether resin, what has a structural unit represented by following General formula (1) is mentioned.
一般式（１）中、Ｒ１〜Ｒ４は各々独立に、水素原子、ハロゲン原子又は炭素数１〜６のアルキル基を示し、炭素数１〜３のアルキルであってもよく、メチル基又はエチル基であってもよい。
一般式（１）で表される構造単位は、耐熱性、誘電特性、成形性及び難燃性の観点並びに入手容易性の観点から、下記一般式（１’）で表される構造単位が好ましい。
In general formula (1), R 1 to R 4 each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms, which may be an alkyl having 1 to 3 carbon atoms, a methyl group or It may be an ethyl group.
The structural unit represented by the general formula (1) is preferably a structural unit represented by the following general formula (1 ′) from the viewpoints of heat resistance, dielectric properties, moldability and flame retardancy, and availability. .
（Ａ）ポリフェニレンエーテル樹脂１分子中における、前記一般式（１’）で表される構造単位の含有量は、好ましくは５０質量％以上、より好ましくは８０質量％以上、更に好ましくは９０質量％以上、特に好ましくは実質的に１００質量％である。 (A) The content of the structural unit represented by the general formula (1 ′) in one molecule of the polyphenylene ether resin is preferably 50% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass. As described above, it is particularly preferably 100% by mass.
（Ａ）ポリフェニレンエーテル樹脂としては、市販品を用いてもよい。市販品の（Ａ）ポリフェニレンエーテル樹脂としては、「ＳＡ９０」、「ＳＡ１２０」等（ＳＡＢＩＣジャパン合同会社製）が、商業的に入手可能である。 (A) As polyphenylene ether resin, you may use a commercial item. Commercially available (A) polyphenylene ether resins such as “SA90” and “SA120” (manufactured by SABIC Japan GK) are commercially available.
＜（Ｂ）分子中にＮ−置換マレイミド基を有するマレイミド化合物＞
（Ｂ）成分としては、分子中にＮ−置換マレイミド基を有するマレイミド化合物であれば、特に制限なく用いることができ、例えば、１分子中に１個のＮ−置換マレイミド基を有するマレイミド化合物、１分子中に２個のＮ−置換マレイミド基を有するマレイミド化合物等が挙げられる。
<(B) Maleimide compound having N-substituted maleimide group in molecule>
As the component (B), any maleimide compound having an N-substituted maleimide group in the molecule can be used without particular limitation. For example, a maleimide compound having one N-substituted maleimide group in one molecule, Examples include maleimide compounds having two N-substituted maleimide groups in one molecule.
１分子中に１個のＮ−置換マレイミド基を有するマレイミド化合物としては、例えば、Ｎ−フェニルマレイミド、Ｎ−ヒドロキシフェニルマレイミド等が挙げられる。
１分子中に２個のＮ−置換マレイミド基を有するマレイミド化合物としては、例えば、ビス（４−マレイミドフェニル）メタン、ポリ（マレイミドフェニル）メタン、ビス（４−マレイミドフェニル）エーテル、ビス（４−マレイミドフェニル）スルホン、３，３’−ジメチル−５，５’−ジエチル−４，４’−ジフェニルメタンビスマレイミド、４−メチル−１，３−フェニレンビスマレイミド、ｍ−フェニレンビスマレイミド、２，２−ビス［４−（４−マレイミドフェノキシ）フェニル］プロパン等が挙げられる。
これらの中でも、反応率が高く、より高耐熱性化できる観点から、ビス（４−マレイミドフェニル）メタン、ｍ−フェニレンビスマレイミド及びビス（４−マレイミドフェニル）スルホンが好ましく、安価である点から、ｍ−フェニレンビスマレイミド及びビス（４−マレイミドフェニル）メタンがより好ましく、溶剤への溶解性の点から、ビス（４−マレイミドフェニル）メタンが更に好ましい。
これらの（Ｂ）成分は、単独で又は２種類以上を組み合わせて使用することができる。
Examples of the maleimide compound having one N-substituted maleimide group in one molecule include N-phenylmaleimide and N-hydroxyphenylmaleimide.
Examples of maleimide compounds having two N-substituted maleimide groups in one molecule include bis (4-maleimidophenyl) methane, poly (maleimidophenyl) methane, bis (4-maleimidophenyl) ether, and bis (4- Maleimidophenyl) sulfone, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide, 4-methyl-1,3-phenylenebismaleimide, m-phenylenebismaleimide, 2,2- And bis [4- (4-maleimidophenoxy) phenyl] propane.
Among these, bis (4-maleimidophenyl) methane, m-phenylenebismaleimide and bis (4-maleimidophenyl) sulfone are preferable from the viewpoint that the reaction rate is high and higher heat resistance can be achieved. m-phenylene bismaleimide and bis (4-maleimidophenyl) methane are more preferred, and bis (4-maleimidophenyl) methane is more preferred from the viewpoint of solubility in a solvent.
These (B) components can be used individually or in combination of 2 or more types.
（Ｂ）成分は、（ｂ−１）前記１分子中に少なくとも２個のＮ−置換マレイミド基を有するマレイミド化合物（以下、「（ｂ−１）マレイミド化合物」ともいう）と、（ｂ−２）下記一般式（２）で表される酸性置換基を有するアミン化合物（以下、「（ｂ−２）アミノ化合物」ともいう）とを反応させて得られた、酸性置換基と不飽和マレイミド基とを有する化合物であることが好ましい。 The component (B) comprises (b-1) a maleimide compound having at least two N-substituted maleimide groups in one molecule (hereinafter also referred to as “(b-1) maleimide compound”), and (b-2). ) An acidic substituent and an unsaturated maleimide group obtained by reacting an amine compound having an acidic substituent represented by the following general formula (2) (hereinafter also referred to as “(b-2) amino compound”) It is preferable that it is a compound which has these.
一般式（２）中、Ｒ５は各々独立に、水酸基、カルボキシ基及びスルホン酸基から選ばれる酸性置換基を示し、Ｒ６は各々独立に、水素原子、炭素数１〜５の脂肪族炭化水素基又はハロゲン原子を示し、ｘは１〜５の整数、ｙは０〜４の整数で、かつｘとｙの和は５である。 In general formula (2), R 5 each independently represents an acidic substituent selected from a hydroxyl group, a carboxy group, and a sulfonic acid group, and R 6 each independently represents a hydrogen atom or an aliphatic carbon atom having 1 to 5 carbon atoms. A hydrogen group or a halogen atom is shown, x is an integer of 1 to 5, y is an integer of 0 to 4, and the sum of x and y is 5.
（ｂ−２）アミノ化合物としては、例えば、ｍ−アミノフェノール、ｐ−アミノフェノール、ｏ−アミノフェノール、ｐ−アミノ安息香酸、ｍ−アミノ安息香酸、ｏ−アミノ安息香酸、ｏ−アミノベンゼンスルホン酸、ｍ−アミノベンゼンスルホン酸、ｐ−アミノベンゼンスルホン酸、３，５−ジヒドロキシアニリン、３，５−ジカルボキシアニリン等が挙げられる。これらの中でも、溶解性及び合成の収率の点から、ｍ−アミノフェノール、ｐ−アミノフェノール、ｐ−アミノ安息香酸、ｍ−アミノ安息香酸及び３，５−ジヒドロキシアニリンが好ましく、耐熱性の点から、ｏ−アミノフェノール、ｍ−アミノフェノール、ｐ−アミノフェノール等のアミノフェノール類がより好ましく、誘電特性の点から、ｐ−アミノフェノールが更に好ましい。
これらの（ｂ−２）アミノ化合物は、単独で又は２種類以上を組み合わせて使用することができる。
(B-2) Examples of amino compounds include m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, o-aminobenzoic acid, o-aminobenzenesulfone. Examples include acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, 3,5-dicarboxyaniline and the like. Among these, m-aminophenol, p-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid and 3,5-dihydroxyaniline are preferable from the viewpoint of solubility and synthetic yield, and heat resistance Therefore, aminophenols such as o-aminophenol, m-aminophenol, and p-aminophenol are more preferable, and p-aminophenol is more preferable from the viewpoint of dielectric properties.
These (b-2) amino compounds can be used alone or in combination of two or more.
（ｂ−１）マレイミド化合物と（ｂ−２）アミノ化合物との使用量比は、（ｂ−１）マレイミド化合物のマレイミド基当量と（ｂ−２）アミン化合物の−ＮＨ２基換算の当量との当量比が次式：
１．０＜（マレイミド基当量）／（−ＮＨ２基換算の当量）≦１０．０
に示す範囲であることが好ましく、該当量比が２．０〜１０．０の範囲であることがより好ましく、４．０〜９．０の範囲であることが更に好ましく、６．０〜８．５の範囲であることが特に好ましい。該当量比を上記範囲内とすることにより、溶剤への溶解性が不足したり、ゲル化を起こしたり、熱硬化性樹脂の耐熱性が低下することがない。
The amount ratio of (b-1) maleimide compound to (b-2) amino compound is (b-1) maleimide group equivalent of maleimide compound and (b-2) equivalent of —NH 2 group of amine compound. The equivalent ratio of:
1.0 <(maleimide group equivalent) / (-NH 2 group equivalent) ≦ 10.0
Is preferable, the corresponding amount ratio is more preferably in the range of 2.0 to 10.0, still more preferably in the range of 4.0 to 9.0, and 6.0 to 8 is more preferable. A range of .5 is particularly preferred. By setting the corresponding ratio within the above range, the solubility in the solvent is not insufficient, gelation occurs, and the heat resistance of the thermosetting resin does not decrease.
（ｂ−１）マレイミド化合物と（ｂ−２）アミノ化合物との反応で使用される有機溶媒は特に制限されないが、例えば、エタノール、プロパノール、ブタノ−ル、メチルセロソルブ、ブチルセロソルブ、プロピレングリコールモノメチルエーテル等のアルコール系溶媒；アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶媒；テトラヒドロフラン等のエーテル系溶媒；トルエン、キシレン、メシチレン等の芳香族系溶媒；ジメチルホルムアミド、ジメチルアセトアミド、Ｎ−メチルピロリドン等の窒素含有溶媒；ジメチルスルホキシド等の硫黄含有溶媒などが挙げられ、これらは単独で又は２種以上を混合して使用できる。
これらの有機溶媒の中でも、溶解性の点から、シクロヘキサノン、プロピレングリコールモノメチルエーテル及びメチルセロソルブが好ましく、低毒性である点から、シクロヘキサノン及びプロピレングリコールモノメチルエーテルがより好ましく、揮発性が高くプリプレグの製造時に残溶媒として残りにくい点から、プロピレングリコールモノメチルエーテルが更に好ましい。
有機溶媒の使用量は、（ｂ−１）マレイミド化合物と（ｂ−２）アミン化合物の総和１００質量部当たり、１０〜１０００質量部とすることが好ましく、３０〜５００質量部とすることがより好ましく、５０〜２００質量部とすることが更に好ましい。有機溶媒の使用量を１０質量部以上とすることにより、溶解性が十分となり、１０００質量部以下とすることにより、反応時間が長すぎることがなくなる。
The organic solvent used in the reaction between (b-1) maleimide compound and (b-2) amino compound is not particularly limited, and examples thereof include ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, and the like. Alcohol solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc .; ether solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene, mesitylene; dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. A nitrogen-containing solvent, such as dimethyl sulfoxide, and the like. These may be used alone or in admixture of two or more.
Among these organic solvents, cyclohexanone, propylene glycol monomethyl ether and methyl cellosolve are preferable from the viewpoint of solubility, and cyclohexanone and propylene glycol monomethyl ether are more preferable from the viewpoint of low toxicity. Propylene glycol monomethyl ether is more preferred because it is difficult to remain as a residual solvent.
The amount of the organic solvent used is preferably 10 to 1000 parts by mass, more preferably 30 to 500 parts by mass, per 100 parts by mass of the sum of (b-1) maleimide compound and (b-2) amine compound. Preferably, it is more preferable to set it as 50-200 mass parts. When the amount of the organic solvent used is 10 parts by mass or more, the solubility becomes sufficient, and when it is 1000 parts by mass or less, the reaction time is not too long.
（ｂ−１）マレイミド化合物と（ｂ−２）アミノ化合物との反応温度は、５０〜２００℃であることが好ましく、１００〜１６０℃であることがより好ましい。また、反応時間は０．１〜１０時間であることが好ましく、１〜８時間であることがより好ましい。
この反応には、任意に反応触媒を使用することができる。反応触媒は特に制限されないが、例えば、トリエチルアミン、ピリジン、トリブチルアミン等のアミン類；メチルイミダゾール、フェニルイミダゾール等のイミダゾール類；トリフェニルホスフィン等のリン系触媒などが挙げられ、これらは単独で又は２種以上を混合して使用できる。
The reaction temperature between the (b-1) maleimide compound and the (b-2) amino compound is preferably 50 to 200 ° C, and more preferably 100 to 160 ° C. Moreover, it is preferable that reaction time is 0.1 to 10 hours, and it is more preferable that it is 1 to 8 hours.
A reaction catalyst can be optionally used for this reaction. The reaction catalyst is not particularly limited, and examples thereof include amines such as triethylamine, pyridine, and tributylamine; imidazoles such as methylimidazole and phenylimidazole; and phosphorus-based catalysts such as triphenylphosphine. A mixture of seeds or more can be used.
（ｂ−１）マレイミド化合物と（ｂ−２）アミノ化合物とを反応して得られる（Ｂ）成分としては、例えば、下記一般式（３）で表される酸性置換基と不飽和マレイミド基とを有する化合物及び下記一般式（４）で表される酸性置換基と不飽和マレイミド基を有する化合物から選ばれる１種以上が挙げられる。 As the component (B) obtained by reacting the (b-1) maleimide compound and the (b-2) amino compound, for example, an acidic substituent represented by the following general formula (3), an unsaturated maleimide group, And at least one selected from compounds having an acidic substituent represented by the following general formula (4) and an unsaturated maleimide group.
一般式（３）中、Ｒ５、Ｒ６、ｘ及びｙは一般式（２）と同じものを示し、Ｒ７は各々独立に、水素原子、炭素数１〜５の脂肪族炭化水素基又はハロゲン原子を示す。 In General Formula (3), R 5 , R 6 , x, and y are the same as those in General Formula (2), and R 7 is independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or Indicates a halogen atom.
一般式（４）中、Ｒ５、Ｒ６、ｘ及びｙは一般式（２）と同じものを示し、Ｒ８及びＲ９は各々独立に、水素原子、炭素数１〜５の脂肪族炭化水素基又はハロゲン原子を示し、Ａはアルキレン基、アルキリデン基、エーテル基、スルフォニル基又は下記式（５）で表される２価の基を示す。 In the general formula (4), R 5 , R 6 , x and y are the same as those in the general formula (2), and R 8 and R 9 are each independently a hydrogen atom, an aliphatic carbon atom having 1 to 5 carbon atoms. A hydrogen group or a halogen atom is shown, and A represents an alkylene group, an alkylidene group, an ether group, a sulfonyl group, or a divalent group represented by the following formula (5).
＜（Ｃ）硬化剤＞
（Ｃ）硬化剤としては、本発明の熱硬化性樹脂組成物中に含まれる熱硬化性樹脂を硬化できるものであれば、特に制限なく用いることができ、耐熱性、誘電特性、成形性及び難燃性の観点からは、（ｃ−１）下記一般式（６）で表される６−置換グアナミン化合物又はジシアンジアミドが好ましい。
<(C) Curing agent>
(C) As the curing agent, any curing agent can be used as long as it can cure the thermosetting resin contained in the thermosetting resin composition of the present invention, and the heat resistance, dielectric properties, moldability and From the viewpoint of flame retardancy, (c-1) a 6-substituted guanamine compound or dicyandiamide represented by the following general formula (6) is preferable.
一般式（６）中、Ｒ１０はフェニル基、メチル基、ブチル基、アリル基、メトキシ基又はベンジルオキシ基を示す。 In the general formula (6), R 10 represents a phenyl group, a methyl group, a butyl group, an allyl group, a methoxy group or a benzyloxy group.
一般式（６）で表される６−置換グアナミン化合物としては、例えば、ベンゾグアナミンと称される２，４−ジアミノ−６−フェニル−ｓ−トリアジン、アセトグアナミンと称される２，４−ジアミノ−６−メチル−ｓ−トリアジン、２，４−ジアミノ−６−ビニル−ｓ−トリアジンが挙げられる。これらの中でも、反応率が高く、より高耐熱性化及び低誘電率化できる点から、ベンゾグアナミン及び２，４−ジアミノ−６−ビニル−ｓ−トリアジンが好ましく、安価であること及び溶媒への溶解性の点から、ベンゾグアナミンがより好ましい。また、ワニスの保存安定性に優れ、高耐熱性化及び低誘電率化でき、安価である点から、ジシアンジアミドが特に好ましい。また、一般式（６）で表される６−置換グアナミン化合物とジシアンジアミドとを併用してもよい。
これらの（ｃ−１）成分は、単独で又は２種類以上を組み合わせて使用することができる。
Examples of the 6-substituted guanamine compound represented by the general formula (6) include 2,4-diamino-6-phenyl-s-triazine called benzoguanamine and 2,4-diamino-named acetoguanamine. Examples include 6-methyl-s-triazine and 2,4-diamino-6-vinyl-s-triazine. Among these, benzoguanamine and 2,4-diamino-6-vinyl-s-triazine are preferred because they have a high reaction rate and can achieve higher heat resistance and lower dielectric constant, and are inexpensive and soluble in solvents. From the viewpoint of sex, benzoguanamine is more preferable. Further, dicyandiamide is particularly preferable from the viewpoints of excellent storage stability of varnish, high heat resistance and low dielectric constant, and low cost. Further, the 6-substituted guanamine compound represented by the general formula (6) and dicyandiamide may be used in combination.
These (c-1) components can be used individually or in combination of 2 or more types.
さらに、本発明の熱硬化性樹脂組成物は、（Ｃ）硬化剤として（ｃ−２）エポキシ樹脂の硬化剤を含有していてもよい。
（ｃ−２）エポキシ樹脂の硬化剤としては、無水マレイン酸、無水マレイン酸共重合体等の酸無水物；ジアミノジフェニルメタン等のアミン化合物；フェノールノボラック、クレゾールノボラック等のフェノール化合物などが挙げられる。
これらの中でも、耐熱性が良好となる点から、無水マレイン酸共重合体が好ましく、低誘電率化できる点から、スチレン、エチレン、プロピレン、イソブチレン等の炭素原子及び水素原子から構成される重合体モノマーと無水マレイン酸の共重合樹脂がより好ましく、溶剤への溶解性及び配合される樹脂との相溶性の点から、スチレンと無水マレイン酸との共重合樹脂、又はイソブチレンと無水マレイン酸との共重合樹脂が更に好ましい。
Furthermore, the thermosetting resin composition of this invention may contain the hardening | curing agent of the (c-2) epoxy resin as (C) hardening | curing agent.
(C-2) Examples of epoxy resin curing agents include acid anhydrides such as maleic anhydride and maleic anhydride copolymers; amine compounds such as diaminodiphenylmethane; phenol compounds such as phenol novolac and cresol novolac.
Among these, a maleic anhydride copolymer is preferred from the viewpoint of good heat resistance, and a polymer composed of carbon atoms and hydrogen atoms such as styrene, ethylene, propylene, isobutylene, etc., from the viewpoint of low dielectric constant. A copolymer resin of monomer and maleic anhydride is more preferable. From the viewpoint of solubility in a solvent and compatibility with a resin to be blended, a copolymer resin of styrene and maleic anhydride, or isobutylene and maleic anhydride. More preferred are copolymer resins.
＜（Ｄ）１分子中に２個以上のエポキシ基を有するエポキシ樹脂＞
（Ｄ）成分としては、１分子中に２個以上のエポキシ基を有するエポキシ樹脂であれば、特に制限なく用いることができ、例えば、ビスフェノールＡ系、ビスフェノールＦ系、ビフェニル系、ノボラック系、多官能フェノール系、ナフタレン系、脂環式系及びアルコール系等のグリシジルエーテル、グリシジルアミン系並びにグリシジルエステル系が挙げられ、これらは単独で又は２種以上を混合して使用することができる。
これらの中でも、誘電特性、耐熱性、耐湿性及び銅箔接着性の点から、ビスフェノールＦ型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、ナフタレン環含有エポキシ樹脂、ビフェニル型エポキシ樹脂、ビフェニルアラルキル型エポキシ樹脂、フェノールノボラック型エポキシ樹脂及びクレゾールノボラック型エポキシ樹脂が好ましく、誘電特性及び高いガラス転移温度を有する点から、ジシクロペンタジエン型エポキシ樹脂、ビフェニルアラルキル型エポキシ樹脂、ビフェニル型エポキシ樹脂及びフェノールノボラック型エポキシ樹脂がより好ましく、耐湿耐熱性の点から、クレゾールノボラック型エポキシ樹脂及びジシクロペンタジエン型エポキシ樹脂が更に好ましい。
<(D) Epoxy resin having two or more epoxy groups in one molecule>
As the component (D), any epoxy resin having two or more epoxy groups in one molecule can be used without particular limitation. For example, bisphenol A, bisphenol F, biphenyl, novolac, Examples thereof include glycidyl ethers such as functional phenols, naphthalenes, alicyclics, and alcohols, glycidylamines, and glycidyl esters, and these can be used alone or in admixture of two or more.
Among these, bisphenol F type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene ring-containing epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin in terms of dielectric properties, heat resistance, moisture resistance and copper foil adhesion Phenol novolac type epoxy resin and cresol novolac type epoxy resin are preferable, and from the viewpoint of having dielectric properties and high glass transition temperature, dicyclopentadiene type epoxy resin, biphenyl aralkyl type epoxy resin, biphenyl type epoxy resin and phenol novolak type epoxy resin Are more preferable, and a cresol novolac type epoxy resin and a dicyclopentadiene type epoxy resin are more preferable from the viewpoint of moisture and heat resistance.
本発明の熱硬化性樹脂組成物中の（Ａ）成分の含有量は、固形分換算の（Ｂ）〜（Ｄ）成分の総和１００質量部に対して、０．１〜５０質量部とすることが好ましく、０．２〜３０質量部とすることがより好ましく、０．５〜２０質量部とすることが更に好ましく、０．７〜１５質量部とすることが特に好ましい。（Ａ）成分の含有量を０．１質量部以上とすることにより、低い比誘電率及び低い誘電正接を得られ、また５０質量部以下とすることにより、成形性が低下することがない。
ここで、本明細書において、「固形分換算」とは、有機溶剤等の揮発性成分を除いた不揮発分のみを基準とすることを意味する。つまり、固形分換算１００質量部とは、不揮発分１００質量部相当を意味する。
Content of (A) component in the thermosetting resin composition of this invention shall be 0.1-50 mass parts with respect to 100 mass parts of total of (B)-(D) component of solid content conversion. It is preferably 0.2 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, and particularly preferably 0.7 to 15 parts by mass. By setting the content of the component (A) to 0.1 parts by mass or more, a low relative dielectric constant and a low dielectric loss tangent can be obtained, and by setting it to 50 parts by mass or less, moldability does not deteriorate.
Here, in this specification, “in terms of solid content” means that only non-volatile content excluding volatile components such as organic solvents is used as a reference. That is, 100 mass parts in terms of solid content means equivalent to 100 mass parts of nonvolatile content.
本発明の熱硬化性樹脂組成物中の（Ｂ）〜（Ｄ）成分の含有量は、次の範囲とすることが好ましい。
（Ｂ）成分の含有量は、固形分換算の（Ｂ）〜（Ｄ）成分の総和１００質量部に対して、１〜９８．９質量部とすることが好ましく、２０〜８５質量部とすることがより好ましく、４０〜７５質量部とすることが更に好ましい。（Ｂ）成分の含有量を１質量部以上とすることにより、難燃性、接着性及び誘電特性が向上し、また９８．９質量以下とすることにより耐熱性が低下することがない。
（Ｃ）成分の含有量は、固形分換算の（Ｂ）〜（Ｄ）成分の総和１００質量部に対して、０．１〜５０質量部とすることが好ましく、０．５〜５０質量部とすることがより好ましく、０．５〜３０質量部とすることが更に好ましい。（Ｃ）成分の含有量を０．１質量部以上とすることにより、溶解性及び誘電特性が向上し、また５０質量部以下とすることにより、難燃性が低下することがない。
（Ｃ−１）成分の含有量は、固形分換算の（Ｂ）〜（Ｄ）成分の総和１００質量部に対して、０．１〜３０質量部とすることが好ましく、０．５〜２０質量部とすることがより好ましく、０．５〜１０質量部とすることが更に好ましい。（Ｃ−１）成分の含有量を０．１質量部以上とすることにより、溶解性及び誘電特性が向上し、また５０質量部以下とすることにより、難燃性が低下することがない。
（Ｃ−２）成分の含有量は、固形分換算の（Ｂ）〜（Ｄ）成分の総和１００質量部に対して、０〜４０質量部とすることが好ましく、５〜３０質量部とすることがより好ましく、５〜２０質量部とすることが更に好ましい。（Ｃ−２）成分を用いることで、優れた耐熱性及び誘電特性が得られる傾向にあり、（Ｃ−２）成分の含有量を４０質量部以下とすることにより、成形性、接着性及び難燃性が低下することがない。
（Ｄ）成分の含有量は、固形分換算の（Ｂ）〜（Ｄ）成分の総和１００質量部に対して、０．５〜８０質量部とすることが好ましく、１０〜６０質量部とすることがより好ましく、２０〜４０質量部とすることが更に好ましい。（Ｄ）成分の含有量を０．５質量部以上とすることにより、耐熱性、難燃性、またプリプレグとして使用する際に成形性が向上し、また８０質量部以下とすることにより、誘電特性が低下することがない。
It is preferable to make content of (B)-(D) component in the thermosetting resin composition of this invention into the following range.
The content of the component (B) is preferably 1 to 98.9 parts by mass and preferably 20 to 85 parts by mass with respect to 100 parts by mass of the total of the components (B) to (D) in terms of solid content. It is more preferable, and it is still more preferable to set it as 40-75 mass parts. By setting the content of the component (B) to 1 part by mass or more, flame retardancy, adhesion and dielectric properties are improved, and by setting the content to 98.9 parts by mass or less, heat resistance does not decrease.
The content of the component (C) is preferably 0.1 to 50 parts by mass, and 0.5 to 50 parts by mass with respect to 100 parts by mass of the sum of the components (B) to (D) in terms of solid content. More preferably, it is more preferable to set it as 0.5-30 mass parts. By setting the content of component (C) to 0.1 parts by mass or more, solubility and dielectric properties are improved, and by setting it to 50 parts by mass or less, flame retardancy does not decrease.
The content of the component (C-1) is preferably 0.1 to 30 parts by mass, and 0.5 to 20 parts per 100 parts by mass of the total of the components (B) to (D) in terms of solid content. It is more preferable to set it as a mass part, and it is still more preferable to set it as 0.5-10 mass parts. By setting the content of the component (C-1) to 0.1 parts by mass or more, solubility and dielectric properties are improved, and by setting the content to 50 parts by mass or less, flame retardancy does not decrease.
The content of the component (C-2) is preferably 0 to 40 parts by mass, and 5 to 30 parts by mass with respect to 100 parts by mass of the total of the components (B) to (D) in terms of solid content. More preferably, it is more preferable to set it as 5-20 mass parts. By using the component (C-2), excellent heat resistance and dielectric properties tend to be obtained. By controlling the content of the component (C-2) to 40 parts by mass or less, moldability, adhesiveness, and Flame retardancy does not decrease.
The content of the component (D) is preferably 0.5 to 80 parts by mass, and preferably 10 to 60 parts by mass with respect to 100 parts by mass of the total of the components (B) to (D) in terms of solid content. It is more preferable and it is still more preferable to set it as 20-40 mass parts. By setting the content of component (D) to 0.5 parts by mass or more, heat resistance, flame retardancy, and moldability when used as a prepreg are improved, and by setting it to 80 parts by mass or less, dielectric The characteristic does not deteriorate.
＜（Ｅ）エポキシ樹脂の硬化促進剤＞
本発明の熱硬化性樹脂組成物には、（Ｅ）成分として、エポキシ樹脂の硬化促進剤を含有させることができる。
エポキシ樹脂の硬化促進剤の例としては、イミダゾール類及びその誘導体、第三級アミン類及び第四級アンモニウム塩等が挙げられる。
<(E) Epoxy resin curing accelerator>
The thermosetting resin composition of the present invention may contain an epoxy resin curing accelerator as the component (E).
Examples of epoxy resin curing accelerators include imidazoles and derivatives thereof, tertiary amines and quaternary ammonium salts.
＜（Ｆ）無機充填材＞
本発明の熱硬化性樹脂組成物には、任意に（Ｆ）無機充填材を含有させることができる。（Ｆ）無機充填材としては、シリカ、マイカ、タルク、ガラスの短繊維又は微粉末及び中空ガラス、三酸化アンチモン、炭酸カルシウム、石英粉末、水酸化アルミニウム、水酸化マグネシウム等が挙げられる。これらの中でも、誘電特性、耐熱性及び難燃性の点から、シリカ、水酸化アルミニウム及び水酸化マグネシウムが好ましく、安価であることから、シリカ及び水酸化アルミニウムがより好ましい。
<(F) Inorganic filler>
The (F) inorganic filler can be arbitrarily contained in the thermosetting resin composition of the present invention. Examples of the inorganic filler (F) include silica, mica, talc, short glass fiber or fine powder and hollow glass, antimony trioxide, calcium carbonate, quartz powder, aluminum hydroxide, magnesium hydroxide and the like. Among these, silica, aluminum hydroxide, and magnesium hydroxide are preferable from the viewpoint of dielectric properties, heat resistance, and flame retardancy, and silica and aluminum hydroxide are more preferable because they are inexpensive.
本発明の熱硬化性樹脂組成物中の（Ｆ）無機充填材の含有量は、固形分換算の（Ｂ）〜（Ｄ）成分の総和１００質量部に対して、０〜３００質量部とすることが好ましく、２０〜２００質量部とすることがより好ましく、２０〜１５０質量部とすることが更に好ましい。（Ｆ）無機充填材を用いることで、熱膨張率を低減できる傾向にあり、（Ｆ）成分の含有量を３００質量部以下とすることにより、成形性及び接着性が低下することがない。 The content of the inorganic filler (F) in the thermosetting resin composition of the present invention is 0 to 300 parts by mass with respect to 100 parts by mass of the total of components (B) to (D) in terms of solid content. It is preferably 20 to 200 parts by mass, more preferably 20 to 150 parts by mass. (F) By using an inorganic filler, the coefficient of thermal expansion tends to be reduced. By making the content of the component (F) 300 parts by mass or less, moldability and adhesiveness are not lowered.
＜その他の成分＞
さらに、本発明の熱硬化性樹脂組成物には、本発明の効果を阻害しない範囲で、任意に公知の熱可塑性樹脂、エラストマー、難燃剤、有機充填材等を含有させることができる。
<Other ingredients>
Furthermore, the thermosetting resin composition of the present invention can optionally contain known thermoplastic resins, elastomers, flame retardants, organic fillers and the like as long as the effects of the present invention are not impaired.
熱可塑性樹脂としては、ポリテトラフルオロエチレン、ポリエチレン、ポリプロピレン、ポリスチレン、（Ａ）成分以外のポリフェニレンエーテル樹脂、フェノキシ樹脂、ポリカーボネート樹脂、ポリエステル樹脂、ポリアミド樹脂、ポリイミド樹脂、キシレン樹脂、石油樹脂、シリコン樹脂等が挙げられる。 Thermoplastic resins include polytetrafluoroethylene, polyethylene, polypropylene, polystyrene, polyphenylene ether resin other than component (A), phenoxy resin, polycarbonate resin, polyester resin, polyamide resin, polyimide resin, xylene resin, petroleum resin, silicone resin Etc.
エラストマーとしては、ポリブタジエン、ポリアクリロニトリル、エポキシ変性ポリブタジエン、無水マレイン酸変性ポリブタジエン、フェノール変性ポリブタジエン、カルボキシ変性ポリアクリロニトリル等が挙げられる。 Examples of the elastomer include polybutadiene, polyacrylonitrile, epoxy-modified polybutadiene, maleic anhydride-modified polybutadiene, phenol-modified polybutadiene, carboxy-modified polyacrylonitrile, and the like.
難燃剤としては、トリフェニルホスフェート、トリクレジルホスフェート、トリスジクロロプロピルホスフェート、ホスファゼン、赤リン等のリン系難燃剤；三酸化アンチモン、水酸化アルミニウム、水酸化マグネシウム等の無機物の難燃剤などが挙げられる。これらの中でも、環境負荷低減の点から、リン系難燃剤、無機物の難燃剤が好ましい。また、経済性、難燃性、耐熱性等の両立の点から、リン系難燃剤と水酸化アルミニウム等の無機物の難燃剤とを併用することが好ましい。 Examples of the flame retardant include phosphorus-based flame retardants such as triphenyl phosphate, tricresyl phosphate, trisdichloropropyl phosphate, phosphazene, and red phosphorus; inorganic flame retardants such as antimony trioxide, aluminum hydroxide, and magnesium hydroxide. It is done. Among these, a phosphorus flame retardant and an inorganic flame retardant are preferable from the viewpoint of reducing environmental burden. Moreover, it is preferable to use together a phosphorus type flame retardant and inorganic flame retardants, such as aluminum hydroxide, from the viewpoint of economical efficiency, flame retardancy, heat resistance, and the like.
有機充填材としては、シリコーンパウダー、ポリテトラフルオロエチレン、ポリエチレン、ポリプロピレン、ポリスチレン、（Ａ）成分以外のポリフェニレンエーテル等の有機物粉末が挙げられる。 Examples of the organic filler include organic powders such as silicone powder, polytetrafluoroethylene, polyethylene, polypropylene, polystyrene, and polyphenylene ether other than the component (A).
また、本発明の熱硬化性樹脂組成物は、希釈溶剤として有機溶剤を任意に使用することができる。有機溶剤としては、特に制限されないが、例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶剤；メチルセロソルブ等のアルコール系溶剤；テトラヒドロフラン等のエーテル系溶剤；トルエン、キシレン、メシチレン等の芳香族系溶剤などが挙げられ、これらは単独で又は２種以上を混合して使用できる。 Moreover, the thermosetting resin composition of this invention can use arbitrarily an organic solvent as a dilution solvent. The organic solvent is not particularly limited. For example, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohol solvents such as methyl cellosolve; ether solvents such as tetrahydrofuran; aromatics such as toluene, xylene, and mesitylene A group solvent etc. are mentioned, These can be used individually or in mixture of 2 or more types.
さらに、本発明の熱硬化性樹脂組成物は、本発明の効果を阻害しない範囲で、ベンゾトリアゾール系等の紫外線吸収剤、ヒンダードフェノール系、スチレン化フェノール等の酸化防止剤、ベンゾフェノン類、ベンジルケタール類、チオキサントン系等の光重合開始剤、スチルベン誘導体等の蛍光増白剤、尿素シラン等の尿素化合物、シランカップリング剤等の密着性向上剤などを含有させることができる。 Further, the thermosetting resin composition of the present invention is not limited to the effects of the present invention, but includes ultraviolet absorbers such as benzotriazoles, antioxidants such as hindered phenols and styrenated phenols, benzophenones, benzyl Ketals, photopolymerization initiators such as thioxanthones, fluorescent brighteners such as stilbene derivatives, urea compounds such as urea silane, adhesion improvers such as silane coupling agents, and the like can be included.
［プリプレグ］
本発明のプリプレグは、上記本発明の熱硬化性樹脂組成物を、基材に含浸又は塗工し、加熱乾燥して得られるものである。
すなわち、本発明の熱硬化性樹脂組成物を、基材に含浸又は塗工した後、加熱乾燥し、半硬化（Ｂステージ化）させて本発明のプリプレグを製造するこができる。
以下、本発明のプリプレグについて詳述する。
[Prepreg]
The prepreg of the present invention is obtained by impregnating or coating the above-mentioned thermosetting resin composition of the present invention on a substrate, followed by heating and drying.
That is, after impregnating or coating the base material with the thermosetting resin composition of the present invention, it is heat-dried and semi-cured (B-stage) to produce the prepreg of the present invention.
Hereinafter, the prepreg of the present invention will be described in detail.
本発明のプリプレグに用いられる基材には、各種の電気絶縁材料用積層板に用いられている周知のものが使用できる。
その材質の例としては、Ｅガラス、Ｄガラス、Ｓガラス、Ｑガラス等の無機物の繊維；ポリイミド、ポリエステル、ポリテトラフルオロエチレン等の有機物の繊維並びにそれらの混合物が挙げられる。
これらの基材は、例えば、織布、不織布、ロービンク、チョップドストランドマット及びサーフェシングマットの形状を有する。これらの材質及び形状は、目的とする成形物の用途及び性能により選択され、必要により、単独又は２種類以上の材質及び形状を組み合わせることができる。
基材の厚さは、特に制限されないが、例えば、約０．０３〜０．５ｍｍのものを使用することができ、シランカップリング剤等で表面処理したもの又は機械的に開繊処理を施したものが、耐熱性、耐湿性及び加工性の面から好適である。
該基材に対する樹脂組成物の付着量が、乾燥後のプリプレグの樹脂含有率で、２０〜９０質量％となるように、基材に含浸又は塗工した後、通常、１００〜２００℃の温度で１〜３０分加熱乾燥し、半硬化（Ｂステージ化）させて、本発明のプリプレグを得ることができる。
As the base material used for the prepreg of the present invention, known materials used for various types of laminates for electrical insulating materials can be used.
Examples of the material include inorganic fibers such as E glass, D glass, S glass, and Q glass; organic fibers such as polyimide, polyester, and polytetrafluoroethylene, and mixtures thereof.
These base materials have the shape of a woven fabric, a nonwoven fabric, a robink, a chopped strand mat, and a surfacing mat, for example. These materials and shapes are selected depending on the intended use and performance of the molded article, and if necessary, two or more kinds of materials and shapes can be combined.
The thickness of the substrate is not particularly limited. For example, a substrate having a thickness of about 0.03 to 0.5 mm can be used, and the substrate is surface-treated with a silane coupling agent or the like, or mechanically opened. Is suitable from the viewpoints of heat resistance, moisture resistance and processability.
After impregnating or coating the base material so that the amount of the resin composition attached to the base material is 20 to 90% by mass in terms of the resin content of the prepreg after drying, the temperature is usually 100 to 200 ° C. Can be heated and dried for 1 to 30 minutes and semi-cured (B-stage) to obtain the prepreg of the present invention.
［積層板］
本発明の積層板は、上記本発明のプリプレグを用いてなる積層板である。
すなわち、本発明の積層板は、上記本発明のプリプレグを積層成形して得られるものであり、本発明のプリプレグを、例えば、１〜２０枚重ね、その片面又は両面に銅箔を配置した構成で積層成形したものである。成形条件は、例えば、電気絶縁材料用積層板及び多層板手法が適用でき、例えば、多段プレス、多段真空プレス、連続成形、オートクレーブ成形機を使用し、温度１００〜２５０℃、圧力０．２〜１０ＭＰａ、加熱時間０．１〜５時間の範囲で成形することができる。また、本発明のプリプレグと内層用配線板を組み合わせ、積層成形して、多層板を製造することもできる。
[Laminated board]
The laminated board of this invention is a laminated board formed using the said prepreg of this invention.
That is, the laminated board of the present invention is obtained by laminating the above-described prepreg of the present invention. For example, 1 to 20 prepregs of the present invention are stacked, and a copper foil is arranged on one or both sides thereof. Is formed by lamination. As the molding conditions, for example, a laminate for electrical insulating material and a multilayer board method can be applied. For example, a multistage press, a multistage vacuum press, continuous molding, an autoclave molding machine is used, and a temperature is 100 to 250 ° C., a pressure is 0.2 to It can be molded in a range of 10 MPa and a heating time of 0.1 to 5 hours. In addition, the prepreg of the present invention and the inner layer wiring board can be combined and laminated to produce a multilayer board.
［プリント配線板］
本発明のプリント配線板は、上記本発明の積層板を回路加工してなるものである。
例えば、本発明の積層板の導体層を通常のエッチング法によって配線加工し回路基板を得ることができる。そして、前述のプリプレグを介して配線加工した積層板を複数積層し、加熱プレス加工することによって一括して多層化する。その後、ドリル加工、レーザー加工によるスルーホール又はブラインドビアホールの形成と、メッキ又は導電性ペーストによる層間配線の形成を経てプリント配線板を製造することができる。
[Printed wiring board]
The printed wiring board of the present invention is obtained by subjecting the laminated board of the present invention to circuit processing.
For example, the circuit board can be obtained by wiring the conductor layer of the laminated board of the present invention by a normal etching method. Then, a plurality of laminated boards processed by wiring through the above-described prepreg are laminated and subjected to hot press processing to be multi-layered at once. Thereafter, a printed wiring board can be manufactured through formation of a through hole or blind via hole by drilling or laser processing and formation of an interlayer wiring by plating or conductive paste.
次に、下記の実施例により本発明を更に詳しく説明するが、これらの実施例は本発明を制限するものではない。 Next, the present invention will be described in more detail with reference to the following examples, but these examples do not limit the present invention.
重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により、標準ポリスチレンを用いた検量線から換算した。検量線は、標準ポリスチレン：Ｓｔａｎｄａｒｄ Ｐｏｌｙｓｔｙｒｅｎｅ（ＰＳｔＱｕｉｃｋ Ｅ，Ｆ［東ソー株式会社製、商品名］）を用いて３次式で近似した。ＧＰＣの条件は、以下に示す。
装置：ＨＬＣ−８３２０ＧＰＣ［東ソー株式会社製、商品名］
カラム：本カラム：ＴＳｋｇｅｌ ＳｕｐｅｒＨＺ２０００＋３０００（４．６×１５０ｍｍ）［東ソー株式会社製、商品名］
ガードカラム：ＴＳＫｇｕａｒｄｃｏｌｕｍｎ ＳｕｐｅｒＨＺ−Ｌ（４．６×２０ｍｍ）［東ソー株式会社製、商品名］
溶離液：テトラヒドロフラン
試料濃度：５ｍｇ／１．５ｍｌ
注入量：１０μｌ
流量：０．３５ｍｌ／分
The weight average molecular weight was converted from a calibration curve using standard polystyrene by gel permeation chromatography (GPC). The calibration curve was approximated by a cubic equation using standard polystyrene: Standard Polystyrene (PStQuick E, F [trade name, manufactured by Tosoh Corporation]). The GPC conditions are shown below.
Device: HLC-8320GPC [trade name, manufactured by Tosoh Corporation]
Column: This column: TSkgel SuperHZ2000 + 3000 (4.6 × 150 mm) [trade name, manufactured by Tosoh Corporation]
Guard column: TSK guard column Super HZ-L (4.6 × 20 mm) [trade name, manufactured by Tosoh Corporation]
Eluent: Tetrahydrofuran Sample concentration: 5 mg / 1.5 ml
Injection volume: 10 μl
Flow rate: 0.35 ml / min
また、以下の実施例で得られた銅張積層板は、以下の方法で性能を測定及び評価した。 Moreover, the copper clad laminated board obtained by the following example measured and evaluated the performance with the following method.
（１）ガラス転移温度（Ｔｇ）の測定
銅張積層板を銅エッチング液に浸漬することにより銅箔を取り除いた５ｍｍ×５ｍｍの評価基板を作製し、ＴＭＡ試験装置（デュポン社製、商品名：ＴＭＡ２９４０）を用いて、圧縮法で熱機械分析をおこなった。評価基板を前記装置にＺ方向に装着後、荷重５ｇ、昇温速度１０℃／分の測定条件にて連続して２回測定した。２回目の測定における熱膨張曲線の異なる接線の交点で示されるＴｇを求めた。
（２）銅付耐熱性（Ｔ−２８８）の評価
銅張積層板から５ｍｍ×５ｍｍの評価基板を作製し、ＩＰＣ ＴＭ６５０で定められた試験法に準じて、ＴＭＡ試験装置（デュポン社製、商品名：ＴＭＡ２９４０）を用い、２８８℃で評価基板の膨れが発生するまでの時間を測定することにより評価した。
（３）誘電特性（比誘電率及び誘電正接）
得られた銅張積層板を用いてネットワークアナライザ（ヒューレットパッカード社製、商品名：８７２２Ｃ）で、トリプレート構造直線線路共振器法により１ＧＨｚにおける銅張積層板の比誘電率及び誘電正接の測定を実施した。試験片サイズは厚さ０．８ｍｍ×縦２００ｍｍ×横５０ｍｍで、１枚の銅張積層板の片面の中心にエッチングにより幅１．０ｍｍの直線線路（ライン長さ２００ｍｍ）を形成し、裏面は全面に銅を残しグランド層とした。もう１枚は片面を全面エッチングし、裏面はグランド層とした。次いで、２枚の銅張積層板のグランド層を外側にして重ね合わせストリップ線路とした。測定は２５℃で行った。
（４）難燃性の評価
銅張積層板を銅エッチング液に浸漬することにより銅箔を取り除いた評価基板から、長さ１２７ｍｍ、幅１２．７ｍｍに切り出した試験片を作製し、ＵＬ９４の試験法（Ｖ法）に準じて評価した。
（５）エッチング後の基材外観（成形性）の評価
銅張積層板を銅エッチング液に浸漬することにより銅箔を取り除いた５０ｃｍ×５０ｃｍの評価基板を作製し、１０倍の拡大鏡を用いて、ボイド（空隙）、異物、凝集物、分離の有無の評価を行った。評価結果は、以下のように分類した。
「異常なし」：ボイド（空隙）、異物、凝集物、分離がいずれも確認されなかったことを意味する。
「ボイド」：ボイド（空隙）が確認されたことを意味する。
「樹脂分離」：樹脂中の充填材が均一分散を保てなくなった状態が確認されたことを意味する。
「かすれ」：ボイドが密集し、かすれた外観が確認されたことを意味する。
(1) Measurement of glass transition temperature (Tg) A 5 mm × 5 mm evaluation board from which a copper foil was removed by immersing a copper clad laminate in a copper etching solution was prepared, and a TMA test apparatus (manufactured by DuPont, trade name: Thermomechanical analysis was performed by compression method using TMA2940). After mounting the evaluation substrate on the apparatus in the Z direction, the measurement substrate was measured twice continuously under the measurement conditions of a load of 5 g and a heating rate of 10 ° C./min. The Tg indicated by the intersection of tangents with different thermal expansion curves in the second measurement was determined.
(2) Evaluation of heat resistance with copper (T-288) An evaluation board of 5 mm × 5 mm was produced from a copper clad laminate, and a TMA test apparatus (manufactured by DuPont, manufactured by the company) according to the test method defined by IPC TM650 Name: TMA2940), and evaluation was performed by measuring the time until swelling of the evaluation substrate occurred at 288 ° C.
(3) Dielectric properties (dielectric constant and dielectric loss tangent)
Using the obtained copper-clad laminate, the relative dielectric constant and dielectric loss tangent of the copper-clad laminate at 1 GHz are measured with a network analyzer (trade name: 8722C, manufactured by Hewlett-Packard Co.) using the triplate structure linear line resonator method. Carried out. The test piece size is 0.8mm thick x 200mm long x 50mm wide, and a straight line (line length 200mm) with a width of 1.0mm is formed by etching at the center of one side of one copper clad laminate. Copper was left on the entire surface to form a ground layer. In the other sheet, one surface was etched entirely, and the back surface was a ground layer. Next, a strip line was formed with the ground layers of the two copper-clad laminates on the outside. The measurement was performed at 25 ° C.
(4) Flame Retardancy Evaluation A test piece cut out to 127 mm in length and 12.7 mm in width was prepared from an evaluation board from which a copper foil was removed by immersing a copper-clad laminate in a copper etching solution. Evaluation was made according to the method (Method V).
(5) Evaluation of substrate appearance (formability) after etching A 50 cm × 50 cm evaluation board from which copper foil was removed by immersing a copper clad laminate in a copper etching solution was used, and a 10 × magnifier was used. The presence or absence of voids (voids), foreign matters, aggregates, and separation was evaluated. The evaluation results were classified as follows.
“No abnormality” means that no voids (voids), foreign matters, aggregates, or separation were confirmed.
“Void”: Means that a void has been confirmed.
“Resin separation”: means that it was confirmed that the filler in the resin could not maintain uniform dispersion.
“Haze”: Means that voids are dense and a haze appearance is confirmed.
（製造例１：（Ｂ−１）マレイミド化合物の製造）
温度計、撹拌装置、還流冷却管付き水分定量器の付いた加熱及び冷却可能な容積２リットルの反応容器に、ビス（４−マレイミドフェニル）エーテルを１０００ｇ、ｐ−アミノフェノールを８０ｇ、Ｎ，Ｎ−ジメチルアセトアミドを８５０ｇ入れ［（マレイミド基当量）／（−ＮＨ２基換算の当量）＝８．０］、１００℃で２時間反応させて（Ｂ−１）マレイミド化合物の溶液を得た。
(Production Example 1: (B-1) Production of maleimide compound)
In a reaction vessel with a volume of 2 liters that can be heated and cooled equipped with a thermometer, a stirrer, and a moisture quantifier with a reflux condenser, 1000 g of bis (4-maleimidophenyl) ether, 80 g of p-aminophenol, N, N -850 g of dimethylacetamide was added [(maleimide group equivalent) / (-NH 2 group equivalent) = 8.0] and reacted at 100 ° C for 2 hours to obtain a solution of (B-1) maleimide compound.
（実施例１）
（Ａ）成分として、（Ａ−１）ポリフェニレンエーテル樹脂（ＳＡＢＩＣジャパン合同会社製、重量平均分子量が２４００）、（Ｂ）成分として、製造例１で得られた（Ｂ−１）マレイミド化合物、（Ｃ−１）成分として、ジシアンジアミド（関東化学株式会社製）、（Ｃ−２）成分として、スチレンと無水マレイン酸の共重合樹脂（サートマー社製、商品名：ＳＭＡ−ＥＦ−４０）、（Ｄ）成分として、（Ｄ−１）クレゾールノボラック型エポキシ樹脂（ＤＩＣ株式会社製、商品名：Ｎ−６９５）及び（Ｄ−２）ジシクロペンタジエン型エポキシ樹脂（ＤＩＣ株式会社製、商品名：ＨＰ−７２００Ｈ）、（Ｆ）成分として、オリゴマ処理溶融シリカ（株式会社アドマテックス製、商品名：ＳＣ２０５０−ＫＣ）、難燃剤として、リン酸エステル（大八化学工業株式会社製、商品名：ＰＸ−２００）、希釈溶剤にメチルエチルケトンを使用して、表１に示す配合割合（質量部）で混合して、固形分６３質量％の均一なワニスを得た。
作製したワニスを厚さ０．１ｍｍのＥガラスクロスに含浸後、１６０℃で５分間加熱、乾燥して熱硬化性樹脂組成物を固形分換算で４５質量％含有するプリプレグを得た。
このプリプレグを８枚重ね、厚さ１８μｍの電解銅箔を上下に配置し、圧力４．０ＭＰａ、温度１８５℃で６０分間プレスを行って、銅張積層板を得た。
Example 1
As component (A), (B-1) maleimide compound obtained in Production Example 1 as component (A-1) (A-1) polyphenylene ether resin (manufactured by SABIC Japan LLC, weight average molecular weight is 2400), (B) component, C-1) As component, dicyandiamide (manufactured by Kanto Chemical Co., Ltd.), and as component (C-2), copolymer resin of styrene and maleic anhydride (manufactured by Sartomer, trade name: SMA-EF-40), (D ) As components, (D-1) cresol novolac type epoxy resin (manufactured by DIC Corporation, trade name: N-695) and (D-2) dicyclopentadiene type epoxy resin (manufactured by DIC Corporation, trade name: HP- 7200H), as component (F), oligomer-treated fused silica (manufactured by Admatechs Co., Ltd., trade name: SC2050-KC), as a flame retardant, phosphoric acid ester (Made by Daihachi Chemical Industry Co., Ltd., trade name: PX-200), using methyl ethyl ketone as a diluent solvent, mixing at a blending ratio (parts by mass) shown in Table 1, and having a solid content of 63% by mass A varnish was obtained.
The prepared varnish was impregnated into an E glass cloth having a thickness of 0.1 mm, and then heated and dried at 160 ° C. for 5 minutes to obtain a prepreg containing 45% by mass of the thermosetting resin composition in terms of solid content.
Eight prepregs were stacked and 18 μm-thick electrolytic copper foils were placed one above the other and pressed at a pressure of 4.0 MPa and a temperature of 185 ° C. for 60 minutes to obtain a copper-clad laminate.
（実施例２〜４、比較例１〜５）
実施例１において、原料組成を表１に示す組成に変更した以外は、実施例１と同様にして、銅張積層板を得た。
(Examples 2-4, Comparative Examples 1-5)
In Example 1, the copper clad laminated board was obtained like Example 1 except having changed the raw material composition into the composition shown in Table 1.
実施例１〜４及び比較例１〜５で得られた銅張積層板の評価結果を表１に示す。 Table 1 shows the evaluation results of the copper clad laminates obtained in Examples 1 to 4 and Comparative Examples 1 to 5.
表１から明らかなように、本発明の実施例では、重量平均分子量が２０００〜１７０００の（Ａ）ポリフェニレンエーテル樹脂を使用することで、比較例よりも耐熱性、誘電特性、成形性及び難燃性が高度に両立した積層板を得ることができた。 As is apparent from Table 1, in the examples of the present invention, by using (A) polyphenylene ether resin having a weight average molecular weight of 2000 to 17000, heat resistance, dielectric properties, moldability and flame retardancy are improved as compared with Comparative Examples. A laminate with high compatibility was obtained.
Claims (9)
（一般式（１）中、Ｒ１〜Ｒ４は各々独立に、水素原子、ハロゲン原子又は炭素数１〜６のアルキル基を示す。） (A) The thermosetting resin composition according to claim 1, wherein the polyphenylene ether resin has a structural unit represented by the following general formula (1).
(In general formula (1), R < 1 > -R < 4 > shows a hydrogen atom, a halogen atom, or a C1-C6 alkyl group each independently.)
（一般式（２）中、Ｒ５は各々独立に、水酸基、カルボキシ基及びスルホン酸基から選ばれる酸性置換基を示し、Ｒ６は各々独立に、水素原子、炭素数１〜５の脂肪族炭化水素基又はハロゲン原子を示し、ｘは１〜５の整数、ｙは０〜４の整数で、かつｘとｙの和は５である。） (B) a maleimide compound having an N-substituted maleimide group in the molecule is (b-1) a maleimide compound having at least two N-substituted maleimide groups in one molecule; and (b-2) the following general formula ( The thermosetting resin composition according to any one of claims 1 to 3, which is a compound having an unsaturated maleimide group obtained by reacting with an amine compound having an acidic substituent represented by 2). .
(In General Formula (2), each R 5 independently represents an acidic substituent selected from a hydroxyl group, a carboxy group, and a sulfonic acid group, and each R 6 independently represents a hydrogen atom or an aliphatic group having 1 to 5 carbon atoms. A hydrocarbon group or a halogen atom, x is an integer of 1 to 5, y is an integer of 0 to 4, and the sum of x and y is 5.
（一般式（３）中、Ｒ５、Ｒ６、ｘ及びｙは一般式（２）と同じものを示し、Ｒ７は各々独立に、水素原子、炭素数１〜５の脂肪族炭化水素基又はハロゲン原子を示す。）
（一般式（４）中、Ｒ５、Ｒ６、ｘ及びｙは一般式（２）と同じものを示し、Ｒ８及びＲ９は各々独立に、水素原子、炭素数１〜５の脂肪族炭化水素基又はハロゲン原子を示し、Ａはアルキレン基、アルキリデン基、エーテル基、スルフォニル基又は下記式（５）で表される２価の基を示す。）
(In General Formula (3), R 5 , R 6 , x and y are the same as those in General Formula (2), and R 7 is independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. Or a halogen atom.)
(In General Formula (4), R 5 , R 6 , x and y are the same as those in General Formula (2), and R 8 and R 9 are each independently a hydrogen atom, an aliphatic group having 1 to 5 carbon atoms. A hydrocarbon group or a halogen atom, and A represents an alkylene group, an alkylidene group, an ether group, a sulfonyl group, or a divalent group represented by the following formula (5).
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