JP2010043253A - Thermosetting insulating resin composition, and prepreg, film with resin, laminate and multilayer printed wiring board using the same - Google Patents
Thermosetting insulating resin composition, and prepreg, film with resin, laminate and multilayer printed wiring board using the same Download PDFInfo
- Publication number
- JP2010043253A JP2010043253A JP2009166977A JP2009166977A JP2010043253A JP 2010043253 A JP2010043253 A JP 2010043253A JP 2009166977 A JP2009166977 A JP 2009166977A JP 2009166977 A JP2009166977 A JP 2009166977A JP 2010043253 A JP2010043253 A JP 2010043253A
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- Japan
- Prior art keywords
- compound
- resin composition
- group
- insulating resin
- thermosetting insulating
- Prior art date
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- Granted
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- -1 and prepreg Substances 0.000 title claims abstract description 91
- 239000011342 resin composition Substances 0.000 title claims abstract description 65
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 65
- 229920005989 resin Polymers 0.000 title claims abstract description 56
- 239000011347 resin Substances 0.000 title claims abstract description 56
- 150000001875 compounds Chemical class 0.000 claims abstract description 95
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 49
- 239000003822 epoxy resin Substances 0.000 claims abstract description 46
- 125000004434 sulfur atom Chemical group 0.000 claims abstract description 13
- 239000011256 inorganic filler Substances 0.000 claims abstract description 11
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 30
- 125000001424 substituent group Chemical group 0.000 claims description 23
- 230000002378 acidificating effect Effects 0.000 claims description 22
- 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 claims description 13
- 125000005843 halogen group Chemical group 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 10
- 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 claims description 8
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-UHFFFAOYSA-N 0.000 claims description 7
- UTDAGHZGKXPRQI-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(S(=O)(=O)C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 UTDAGHZGKXPRQI-UHFFFAOYSA-N 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000000732 arylene group Chemical group 0.000 claims description 6
- 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 claims description 5
- 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 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 5
- 125000004104 aryloxy group Chemical group 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 4
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000001118 alkylidene group Chemical group 0.000 claims description 2
- 125000001033 ether group Chemical group 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 claims description 2
- 230000009477 glass transition Effects 0.000 abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 30
- 238000004519 manufacturing process Methods 0.000 description 28
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 23
- 238000011156 evaluation Methods 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 19
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 18
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 16
- 238000000034 method Methods 0.000 description 16
- 239000011889 copper foil Substances 0.000 description 15
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 15
- 229910052802 copper Inorganic materials 0.000 description 14
- 239000010949 copper Substances 0.000 description 14
- 229920003986 novolac Polymers 0.000 description 14
- 238000010992 reflux Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 12
- 239000000758 substrate Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 229910000679 solder Inorganic materials 0.000 description 11
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 239000004305 biphenyl Chemical group 0.000 description 9
- 235000010290 biphenyl Nutrition 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 9
- 229920003192 poly(bis maleimide) Polymers 0.000 description 9
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 8
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 8
- 238000005530 etching Methods 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 7
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 125000001174 sulfone group Chemical group 0.000 description 6
- 239000002966 varnish Substances 0.000 description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-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
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- MERLDGDYUMSLAY-UHFFFAOYSA-N 4-[(4-aminophenyl)disulfanyl]aniline Chemical compound C1=CC(N)=CC=C1SSC1=CC=C(N)C=C1 MERLDGDYUMSLAY-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 4
- 229930003836 cresol Natural products 0.000 description 4
- 239000011810 insulating material Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 150000003457 sulfones Chemical class 0.000 description 4
- QQOWHRYOXYEMTL-UHFFFAOYSA-N triazin-4-amine Chemical compound N=C1C=CN=NN1 QQOWHRYOXYEMTL-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 150000002460 imidazoles Chemical class 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 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 2
- MPLHZTWRCINWPX-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]disulfanyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1SSC1=CC=C(N2C(C=CC2=O)=O)C=C1 MPLHZTWRCINWPX-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- JFEXPVDGVLNUSC-UHFFFAOYSA-N 3-(3-aminophenyl)sulfanylaniline Chemical compound NC1=CC=CC(SC=2C=C(N)C=CC=2)=C1 JFEXPVDGVLNUSC-UHFFFAOYSA-N 0.000 description 2
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 2
- WCXGOVYROJJXHA-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(=CC=2)S(=O)(=O)C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 WCXGOVYROJJXHA-UHFFFAOYSA-N 0.000 description 2
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 2
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- 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
- 239000004593 Epoxy Substances 0.000 description 2
- OJGMBLNIHDZDGS-UHFFFAOYSA-N N-Ethylaniline Chemical compound CCNC1=CC=CC=C1 OJGMBLNIHDZDGS-UHFFFAOYSA-N 0.000 description 2
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- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 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
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 229960004050 aminobenzoic acid Drugs 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
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- PUKLCKVOVCZYKF-UHFFFAOYSA-N 1-[2-(2,5-dioxopyrrol-1-yl)ethyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1CCN1C(=O)C=CC1=O PUKLCKVOVCZYKF-UHFFFAOYSA-N 0.000 description 1
- LTGTVRSJQNJRCS-UHFFFAOYSA-N 1-[3-[1-[3-(2,5-dioxopyrrol-1-yl)phenoxy]-4-phenylcyclohexa-2,4-dien-1-yl]oxyphenyl]pyrrole-2,5-dione Chemical group O=C1C=CC(=O)N1C1=CC=CC(OC2(C=CC(=CC2)C=2C=CC=CC=2)OC=2C=C(C=CC=2)N2C(C=CC2=O)=O)=C1 LTGTVRSJQNJRCS-UHFFFAOYSA-N 0.000 description 1
- MBNMVPPPCZKPIJ-UHFFFAOYSA-N 1-[3-[3-[3-(2,5-dioxopyrrol-1-yl)phenoxy]phenoxy]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(OC=2C=C(OC=3C=C(C=CC=3)N3C(C=CC3=O)=O)C=CC=2)=C1 MBNMVPPPCZKPIJ-UHFFFAOYSA-N 0.000 description 1
- BYXJCAQAONKDLQ-UHFFFAOYSA-N 1-[3-[4-[2-[4-[3-(2,5-dioxopyrrol-1-yl)phenoxy]phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]phenoxy]phenyl]pyrrole-2,5-dione Chemical compound C=1C=C(OC=2C=C(C=CC=2)N2C(C=CC2=O)=O)C=CC=1C(C(F)(F)F)(C(F)(F)F)C(C=C1)=CC=C1OC(C=1)=CC=CC=1N1C(=O)C=CC1=O BYXJCAQAONKDLQ-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Production Of Multi-Layered Print Wiring Board (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
Description
本発明は、特定の製造法によって得られる硬化剤を使用する熱硬化性絶縁樹脂組成物、並びにこれを用いたプリプレグ、樹脂付フィルム、積層板、及び多層プリント配線板に関する。 The present invention relates to a thermosetting insulating resin composition using a curing agent obtained by a specific production method, and a prepreg, a film with a resin, a laminate, and a multilayer printed wiring board using the same.
近年の電子機器の小型化・高性能化の流れに伴い、プリント配線板では配線ピッチが狭小化した高密度の配線が要求されている。高密度配線に対応する半導体の実装方法としては、従来のワイヤボンディング方式に代わり、フリップチップ接続方式が広く用いられている。
フリップチップ接続方式は、ワイヤに替えて、はんだボールにより配線板と半導体とを接続させる方法である。互いに向き合わせにした配線板と半導体との間にはんだボールを配置させ、全体に加熱して、はんだをリフロー（溶融接続）させて、配線板と半導体を接続させて実装している。
この方法では、はんだリフロー時に３００℃近い熱が配線板などにかかる。この際、従来の樹脂組成物を材料として形成された配線板では、配線板が熱収縮して、配線板と半導体を接続するはんだボールに大きな応力が発生し、配線の接続不良を起こす場合があった。
With the recent trend toward miniaturization and high performance of electronic devices, printed wiring boards are required to have high-density wiring with narrowed wiring pitch. As a semiconductor mounting method corresponding to high-density wiring, a flip chip connection method is widely used instead of the conventional wire bonding method.
The flip chip connection method is a method in which a wiring board and a semiconductor are connected by solder balls instead of wires. Solder balls are arranged between the wiring board and the semiconductor that face each other, and the whole is heated to reflow (melt connection) the solder, and the wiring board and the semiconductor are connected and mounted.
In this method, heat close to 300 ° C. is applied to the wiring board or the like during solder reflow. At this time, in the wiring board formed using the conventional resin composition as the material, the wiring board may be thermally contracted, and a large stress is generated in the solder ball connecting the wiring board and the semiconductor, which may cause poor connection of the wiring. there were.
また、これら配線板に用いられる樹脂部材は難燃性が求められることが多い。従来この難燃性を付与するため、エポキシ樹脂においては臭素化エポキシなどのハロゲン系難燃剤を用いることが一般的であった。しかし、ハロゲン含有化合物はダイオキシン発生の原因となるおそれがあることから、昨今の環境問題の深刻化とともに、ハロゲン系難燃剤を使用することが回避されるようになり、広く産業界にハロゲンフリーの難燃化システムが求められるようになった。このような時代の要求によってリン系難燃剤が脚光を浴び、リン酸エステルや赤リンが検討されたが、これらの従来のリン系難燃剤は加水分解しやすく樹脂との反応に乏しいため、はんだへの耐熱性が低下、ガラス転移温度の低下といった問題があった。
上述の状況の背景としては、エポキシ樹脂を主剤とした樹脂組成物とガラス織布とを硬化・一体成形したものが一般的であるところ、エポキシ樹脂は、絶縁性や耐熱性、コストなどのバランスに優れるが、熱膨張率が大きいため、シリカなどの無機充填材を添加して熱膨張を抑制するのが一般的である（特許文献１）。無機充填材を高い割合で充填することにより、さらなる低熱膨張化を図ることも可能であるが、充填量を増やすことは、吸湿による絶縁信頼性の低下や樹脂−配線層の密着不足、プレス成形不良を起こすことが知られている。そのため、多層配線板における用途では、無機充填材の高充填には限界がある。
In addition, the resin member used for these wiring boards is often required to have flame retardancy. Conventionally, in order to impart this flame retardancy, it has been common to use halogen-based flame retardants such as brominated epoxy in epoxy resins. However, since halogen-containing compounds may cause dioxins, the use of halogen-based flame retardants has been avoided along with the recent serious environmental problems. A flame retardant system is now required. Phosphorus flame retardants have attracted attention due to the demands of these times, and phosphoric acid esters and red phosphorus have been studied. However, these conventional phosphorus flame retardants are easily hydrolyzed and have poor reaction with resins, so solder There have been problems such as a decrease in heat resistance and a decrease in glass transition temperature.
As a background of the above situation, a resin composition mainly composed of an epoxy resin and a glass woven fabric are generally cured and integrally molded. Epoxy resin has a balance of insulation, heat resistance, cost, etc. However, since the coefficient of thermal expansion is large, an inorganic filler such as silica is generally added to suppress thermal expansion (Patent Document 1). It is possible to further reduce the thermal expansion by filling the inorganic filler at a high rate, but increasing the filling amount reduces the insulation reliability due to moisture absorption, insufficient adhesion of the resin-wiring layer, press molding It is known to cause defects. For this reason, there is a limit to the high filling of inorganic fillers in applications in multilayer wiring boards.
また、樹脂の選択或いは改良により、低熱膨張を達成することが試みられている。例えば、芳香環を有するエポキシ樹脂の公知例としては、２官能のナフタレン骨格、あるいは
ビフェニル骨格を有するエポキシ樹脂を用いた低熱膨張性加圧成形用樹脂組成物が提案されている（特許文献２）が、充填材を８０〜９２．５容量％配合している。しかし、充填量を増やすことは、吸湿による絶縁信頼性の低下や樹脂−配線層の密着不足、プレス成形不良を起こすことが知られている。そのため、多層配線板における用途では、無機充填材の高充填には限界がある。
従来、配線板用の樹脂組成物の低熱膨張率化は架橋密度を高め、Ｔｇを高くして熱膨張率を低減する方法が一般的である（特許文献３、及び４）。しかしながら、架橋密度を高めることは官能基間の分子鎖を短くすることであるが、一定以上分子鎖を短くすることは反応性や樹脂強度などの点で不可能である。このため、架橋密度を高める手法での低熱膨張率化は限界となっていた。
In addition, attempts have been made to achieve low thermal expansion by selecting or improving the resin. For example, as a well-known example of an epoxy resin having an aromatic ring, a low thermal expansion pressure molding resin composition using an epoxy resin having a bifunctional naphthalene skeleton or a biphenyl skeleton has been proposed (Patent Document 2). However, 80-92.5 volume% of fillers are mix | blended. However, increasing the filling amount is known to cause a decrease in insulation reliability due to moisture absorption, insufficient adhesion between the resin and the wiring layer, and poor press molding. For this reason, there is a limit to the high filling of inorganic fillers in applications in multilayer wiring boards.
Conventionally, a method for reducing the thermal expansion coefficient of a resin composition for a wiring board is generally a method of increasing the crosslinking density and increasing the Tg to reduce the thermal expansion coefficient (Patent Documents 3 and 4). However, increasing the crosslink density is to shorten the molecular chain between the functional groups, but it is impossible to shorten the molecular chain beyond a certain point in terms of reactivity and resin strength. For this reason, the low thermal expansion coefficient by the method of increasing the crosslinking density has been a limit.
一方、低熱熱膨張の樹脂としてはポリイミドが広く知られているが、成形に高温を要する、コストが高い、といった問題がある。また、フィルム状の形態であるため、フレキシブル基板用の材料として適している反面、剛性を必要とする多層配線板用途には適さなかった。また、ビスマレイミド化合物は、誘電特性、難燃性、耐熱性に優れる樹脂であるが、エポキシ樹脂との硬化反応性を有さない公知のビスマレイミド化合物は、エポキシ硬化系の熱硬化性絶縁樹脂にそのまま使用した場合、耐熱性が不足する問題があった。この問題点を解決するために、具体的には、有機溶媒を使用せずに加熱混練によりビスマレイミド化合物とアミノフェノールとの付加物を製造し使用する熱硬化性絶縁樹脂に関する発明が開示されている（特許文献５、及び６）が、ビスマレイミド化合物とアミノフェノールとの付加物の収率が低く、これらを銅張積層板や層間絶縁材料として使用すると、耐熱性や加工性などが不足となる。更に、有機溶媒を使用せずに製造されるビスマレイミド化合物とアミノ安息香酸の付加物やベンゾグアナミンホルムアルデヒド縮合物などを使用する熱硬化性絶縁樹脂に関する発明が開示されている（特許文献７）が、熱分解温度が低く、近年要求される鉛フリーはんだへの耐熱性や銅付き耐熱性に不足する。 On the other hand, polyimide is widely known as a low thermal expansion resin, but there are problems such as high temperature required for molding and high cost. Moreover, since it is a film-like form, it is suitable as a material for a flexible substrate, but it is not suitable for a multilayer wiring board application requiring rigidity. The bismaleimide compound is a resin having excellent dielectric properties, flame retardancy, and heat resistance, but a known bismaleimide compound having no curing reactivity with an epoxy resin is an epoxy curable thermosetting insulating resin. When used as is, the heat resistance is insufficient. In order to solve this problem, specifically, an invention relating to a thermosetting insulating resin in which an adduct of a bismaleimide compound and aminophenol is produced and used by heating and kneading without using an organic solvent is disclosed. (Patent Documents 5 and 6), however, the yield of the adduct of bismaleimide compound and aminophenol is low, and when these are used as a copper clad laminate or an interlayer insulating material, heat resistance and workability are insufficient. Become. Furthermore, an invention relating to a thermosetting insulating resin using an adduct of a bismaleimide compound and an aminobenzoic acid produced without using an organic solvent or a benzoguanamine formaldehyde condensate is disclosed (Patent Document 7). The thermal decomposition temperature is low and the heat resistance to lead-free solder and the heat resistance with copper are insufficient in recent years.
本発明は、ガラス転移温度（Ｔｇ）が高く、耐熱性に優れ、かつ低熱膨張性である熱硬化性絶縁樹脂組成物、並びにこれを用いたプリプレグ、樹脂付フィルム、積層板、及び多層プリント配線板を提供することを目的とする。 The present invention relates to a thermosetting insulating resin composition having a high glass transition temperature (Tg), excellent heat resistance, and low thermal expansion, and a prepreg, a resin-coated film, a laminate, and a multilayer printed wiring using the same. The purpose is to provide a board.
本発明は、上記の課題を解決するために、鋭意研究が行われた結果、発明が完成されたものであって、以下を要旨とするものである。
１．下記の(ａ)、（ｂ）、及び（ｃ）の化合物を反応させて得られる、分子骨格中にＳ原子を有する化合物（１）を含有することを特徴とする熱硬化性絶縁樹脂組成物。
（ａ）分子骨格中にＳ原子を有する芳香族ジアミン化合物
（ｂ）分子構造中に少なくとも２個のＮ−置換マレイミド基を有するマレイミド化合物
（ｃ）モノアミン化合物
２．化合物（１）が、(ａ)、（ｂ）、及び（ｃ）の化合物を有機溶媒中で反応させて得られる化合物である上記１の熱硬化性絶縁樹脂組成物。
３．化合物（１）が、分子骨格中に酸性置換基、及び置換マレイミド基を有する化合物である上記１又は２の熱硬化性絶縁樹脂組成物。
４．前記（ａ）の芳香族ジアミン化合物が下式（Ｉ）もしくは下式（II）で表される化合物、またはジアミノジメチルジベンゾチオフェンスルホンである上記１〜３のいずれかの熱硬化性絶縁樹脂組成物。
In order to solve the above-mentioned problems, the present invention has been completed as a result of intensive studies and has the following gist.
1. A thermosetting insulating resin composition comprising a compound (1) having an S atom in a molecular skeleton obtained by reacting the following compounds (a), (b), and (c): .
(A) an aromatic diamine compound having an S atom in the molecular skeleton (b) a maleimide compound having at least two N-substituted maleimide groups in the molecular structure (c) a monoamine compound The thermosetting insulating resin composition according to 1 above, wherein the compound (1) is a compound obtained by reacting the compounds (a), (b), and (c) in an organic solvent.
3. The thermosetting insulating resin composition according to 1 or 2 above, wherein the compound (1) is a compound having an acidic substituent and a substituted maleimide group in the molecular skeleton.
4). The thermosetting insulating resin composition according to any one of 1 to 3 above, wherein the aromatic diamine compound (a) is a compound represented by the following formula (I) or (II), or diaminodimethyldibenzothiophenesulfone: .
（式中、Ｒ1及びＲ2は各々独立に水素原子、ハロゲン原子、炭素数１〜３のアルキル基、カルボキシル基、またはスルホン酸基を示す。Ｍは炭素数１〜５のオキサアルキレン基、または炭素数６〜１４のアリーレン基を示す。Ｂはアミノ基を有する炭素数６〜１４のアリール基、またはアリールオキシ基を示し、これらは、さらにハロゲン原子や、炭素数１〜３のハロゲン化アルキレン基で置換されてもよい。ｘ、ｙは各々独立に１〜４の整数であり、ｐ、ｑは０または１である。Ａは−Ｓ−、−ＳＯ2−、−Ｓ−Ｓ−から選ばれるＳ原子含有基である。） (In the formula, R 1 and R 2 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, a carboxyl group, or a sulfonic acid group. M is an oxaalkylene group having 1 to 5 carbon atoms, Or an arylene group having 6 to 14 carbon atoms, and B represents an aryl group having 6 to 14 carbon atoms or an aryloxy group having an amino group, which further includes a halogen atom or a halogenated group having 1 to 3 carbon atoms. X and y are each independently an integer of 1 to 4, and p and q are 0 or 1. A is —S—, —SO 2 —, —S—S—. S atom-containing group selected from
５．前記（ｂ）のマレイミド化合物が下式（III）で表される化合物である上記１〜４のいずれかの熱硬化性絶縁樹脂組成物。
６．前記（ｃ）のモノアミン化合物が、酸性置換基を有する化合物である上記１〜５のいずれかの熱硬化性絶縁樹脂組成物。
７．前記（ｃ）のモノアミン化合物が、下式（IV）で表される化合物である上記６の熱硬化性絶縁樹脂組成物。
7). The thermosetting insulating resin composition according to 6 above, wherein the monoamine compound (c) is a compound represented by the following formula (IV):
８．下式（V）で示される化合物を含有する上記１〜７のいずれかの熱硬化性絶縁樹脂組成物。
９．下式（VI）で示される化合物を含有する上記１〜８のいずれかの熱硬化性絶縁樹脂組成物。
１０．下式（VII）で示される化合物を含有する上記１〜９のいずれかの熱硬化性絶縁樹脂組成物。
１１．（ａ）の芳香族ジアミン化合物が、２，２−ビス（４−アミノフェニル）スルホン、ビス（４−アミノフェニル）スルフィド、ビス[４−（４−アミノフェノキシ）フェニル]スルホン、および４，４’−ジチオジアニリンから選ばれる少なくとも１種である上記１〜１０のいずれかの熱硬化性絶縁樹脂組成物。
１２．（ｂ）のマレイミド化合物が、２，２−ビス[４−（４−マレイミドフェノキシ）フェニル]プロパン、ビス（４−マレイミドフェニル）メタン、４−メチル−１，３−フェニレンビスマレイミド、ポリフェニルメタンマレイミド、およびビス（４−マレイミドフェニル）スルホンから選ばれる少なくとも１種である上記１〜１１のいずれかの熱硬化性絶縁樹脂組成物。
11. The aromatic diamine compound of (a) is 2,2-bis (4-aminophenyl) sulfone, bis (4-aminophenyl) sulfide, bis [4- (4-aminophenoxy) phenyl] sulfone, and 4,4 The thermosetting insulating resin composition according to any one of 1 to 10 above, which is at least one selected from '-dithiodianiline.
12 The maleimide compound (b) is 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, bis (4-maleimidophenyl) methane, 4-methyl-1,3-phenylenebismaleimide, polyphenylmethane The thermosetting insulating resin composition according to any one of 1 to 11, which is at least one selected from maleimide and bis (4-maleimidophenyl) sulfone.
１３．さらに、エポキシ樹脂（２）を含有する上記１〜１２のいずれかの熱硬化性絶縁樹脂組成物。
１４．エポキシ樹脂（２）が少なくとも２個のエポキシ基を含有する化合物である上記１３の熱硬化性絶縁樹脂組成物。
１５．さらに、前記エポキシ樹脂の硬化剤（３）を含有する上記１〜１４のいずれかの熱硬化性絶縁樹脂組成物。
１６．さらに、無機充填材（４）を含有する上記１〜１５のいずれかの熱硬化性絶縁樹脂組成物。
13. Furthermore, the thermosetting insulating resin composition in any one of said 1-12 containing an epoxy resin (2).
14 14. The thermosetting insulating resin composition as described in 13 above, wherein the epoxy resin (2) is a compound containing at least two epoxy groups.
15. Furthermore, the thermosetting insulating resin composition in any one of said 1-14 containing the hardening | curing agent (3) of the said epoxy resin.
16. Furthermore, the thermosetting insulating resin composition in any one of said 1-15 containing an inorganic filler (4).
１７．上記１〜１６のいずれかの熱硬化性絶縁樹脂組成物を用いてなることを特徴とするプリプレグ。
１８．上記１〜１６のいずれかの熱硬化性絶縁樹脂組成物を用いてなることを特徴とする樹脂付フィルム。
１９．上記１７のプリプレグを用いて積層成形されてなることを特徴とする積層板。
２０．上記１９の積層板を用いて製造されてなることを特徴とする多層プリント配線板。
17. A prepreg comprising the thermosetting insulating resin composition according to any one of 1 to 16 above.
18. A film with a resin comprising the thermosetting insulating resin composition according to any one of 1 to 16 above.
19. A laminate comprising the 17 prepregs and formed by lamination.
20. A multilayer printed wiring board produced by using the above 19 laminated board.
本発明は、ガラス転移温度（Ｔｇ）が高く、耐熱性に優れ、かつ低熱膨張性である熱硬化性絶縁樹脂組成物、並びにこれを用いたプリプレグ、樹脂付フィルム、積層板、及び多層プリント配線板を提供することができる。 The present invention relates to a thermosetting insulating resin composition having a high glass transition temperature (Tg), excellent heat resistance, and low thermal expansion, and a prepreg, a resin-coated film, a laminate, and a multilayer printed wiring using the same. Board can be provided.
以下、本発明について詳細に説明する。
本発明の熱硬化性絶縁樹脂組成物に用いられる化合物（１）は、下記の（ａ）、（ｂ）、及び（ｃ）の化合物を、必要により有機溶媒中で加熱・保温しながら攪拌し、反応させて得られる化合物であって、分子骨格中にＳ原子を有する化合物である。
（ａ）分子骨格中にＳ原子を有する芳香族ジアミン化合物
（ｂ）分子構造中に少なくとも２個のＮ−置換マレイミド基を有するマレイミド化合物
（ｃ）モノアミン化合物
Hereinafter, the present invention will be described in detail.
The compound (1) used in the thermosetting insulating resin composition of the present invention is prepared by stirring the following compounds (a), (b), and (c) while heating and keeping heat in an organic solvent as necessary. , A compound obtained by reaction, and having an S atom in the molecular skeleton.
(A) aromatic diamine compound having S atom in molecular skeleton (b) maleimide compound having at least two N-substituted maleimide groups in molecular structure (c) monoamine compound
上記（ａ）の化合物は、分子骨格中に−Ｓ−、−ＳＯ2−、または−Ｓ−Ｓ−、のＳ原子を有する芳香族ジアミン化合物である。このような芳香族ジアミン化合物であれば、任意のものを使用することができるが、一例としては、前記式（Ｉ）もしくは前記式（II）で表される化合物が挙げられる。
各式中、Ｒ1及びＲ2は各々独立に水素原子、ハロゲン原子、炭素数１〜３のアルキル基、カルボキシ基、またはスルホン酸基を示す。Ｍは炭素数１〜５のアルコキシ基、または炭素数６〜１４のアリール基を示す。Ｂはアミノ基を有する炭素数６〜１４のアリール基、またはアリールオキシ基を示し、これらは、さらにハロゲン原子や、炭素数１〜３のハロゲン化アルキル基などで置換されてもよい。ｘ、ｙは各々独立に１〜４の整数であり、ｐ、ｑは０または１である。Ａは−Ｓ−、−ＳＯ2−、−Ｓ−Ｓ−から選ばれるＳ原子含有基である。
ここで、炭素数１〜５のアルコキシ基としては、メトキシ基、エトキシ基などが挙げられる。炭素数６〜１４のアリール基としては、フェニル基、ナフト基などが挙げられる。炭素数６〜１４のアリールオキシ基としては、フェノキシ基、ナフトキシ基などが挙げられる。
The compound (a) is an aromatic diamine compound having an S atom of -S-, -SO 2- , or -SS- in the molecular skeleton. Any compound can be used as long as it is such an aromatic diamine compound, and examples thereof include compounds represented by the formula (I) or the formula (II).
In each formula, R 1 and R 2 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, a carboxy group, or a sulfonic acid group. M represents an alkoxy group having 1 to 5 carbon atoms or an aryl group having 6 to 14 carbon atoms. B represents an aryl group having 6 to 14 carbon atoms having an amino group, or an aryloxy group, and these may be further substituted with a halogen atom or a halogenated alkyl group having 1 to 3 carbon atoms. x and y are each independently an integer of 1 to 4, and p and q are 0 or 1. A is -S -, - SO 2 -, - an S atom-containing group selected from S-S-.
Here, examples of the alkoxy group having 1 to 5 carbon atoms include a methoxy group and an ethoxy group. Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group and a naphtho group. Examples of the aryloxy group having 6 to 14 carbon atoms include a phenoxy group and a naphthoxy group.
前記式（Ｉ）で示される具体的な化合物としては、例えば、ビス（３−アミノフェニル）スルホン、ビス（４−アミノフェニル）スルホン、２，２'−ジアミノジフェニルスルフィド、ビス（４−アミノフェニル）スルフィド、ビス（３−アミノフェニル）スルフィド、ビス（２，３，５，６）−テトラフルオロ−４−アミノフェニル）スルフィド、２，２'−ジチオジアニリン、３，３'−ジチオジアニリン、４，４'−ジチオジアニリンなどを挙げることができる。
一方、前記式（II）で示される具体的な化合物としては、例えば、４，４'−ビス（４−アミノ−２−トリフルオロメチルフェノキシ）ジフェニルスルホン、４，４'−ビス（３−アミノ−５−トリフルオロメチルフェノキシ）ジフェニルスルホン、ビス[４−（３−アミノフェノキシ）フェニル]スルホン、ビス[４−（４−アミノフェノキシ）フェニル]スルホン、２，２'−ビス［４−｛２−（４−アミノフェノキシ）エトキシ｝フェニル］スルホン、３，３'−ジスルホン酸−ビス｛４−（３−アミノフェノキシ）−フェニル｝スルホン、３，３'，５，５'−テトラメチル−ビス｛４−（４−アミノフェノキシ）フェニル｝スルホン、４，４'−ビス（６−アミノナフトキシ）ジフェニルスルホン、４，４'−ビス（３−アミノフェノキシフェニル）ジフェニルスルホンなどを挙げることができる。
これらの中で、ビス（４−アミノフェニル）スルホン、ビス（４−アミノフェニル）スルフィド、ビス[４−（４−アミノフェノキシ）フェニル]スルホン、および４，４’−ジチオジアニリンが好ましい。
Specific examples of the compound represented by the formula (I) include bis (3-aminophenyl) sulfone, bis (4-aminophenyl) sulfone, 2,2′-diaminodiphenyl sulfide, and bis (4-aminophenyl). ) Sulfide, bis (3-aminophenyl) sulfide, bis (2,3,5,6) -tetrafluoro-4-aminophenyl) sulfide, 2,2′-dithiodianiline, 3,3′-dithiodianiline 4,4′-dithiodianiline and the like.
On the other hand, specific compounds represented by the formula (II) include, for example, 4,4′-bis (4-amino-2-trifluoromethylphenoxy) diphenylsulfone, 4,4′-bis (3-amino). -5-trifluoromethylphenoxy) diphenylsulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2'-bis [4- {2 -(4-Aminophenoxy) ethoxy} phenyl] sulfone, 3,3′-disulfonic acid-bis {4- (3-aminophenoxy) -phenyl} sulfone, 3,3 ′, 5,5′-tetramethyl-bis {4- (4-aminophenoxy) phenyl} sulfone, 4,4′-bis (6-aminonaphthoxy) diphenylsulfone, 4,4′-bis (3-aminophenoxyphenyl) Such as diphenyl sulfone can be mentioned.
Of these, bis (4-aminophenyl) sulfone, bis (4-aminophenyl) sulfide, bis [4- (4-aminophenoxy) phenyl] sulfone, and 4,4′-dithiodianiline are preferred.
なお、良好な反応性や耐熱性を有する点から、ビス（４−アミノフェニル）スルホン、ビス（３−アミノフェニル）スルホン、ビス（４−アミノフェニル）スルフィド、ビス（３−アミノフェニル）スルフィド、４，４'−ジチオジアニリン、３，３'−ジチオジアニリン、ビス[４−（４−アミノフェノキシ）フェニル]スルホン、ビス[４−（３−アミノフェノキシ）フェニル]スルホンが好ましく、更に低熱膨張性を有する点から、ビス（４−アミノフェニル）スルホン、ビス（４−アミノフェニル）スルフィド、４，４'−ジチオジアニリン、ビス[４−（４−アミノフェノキシ）フェニル]スルホンがより好ましく、溶剤への溶解性の点から、ビス（４−アミノフェニル）スルホン、ビス[４−（４−アミノフェノキシ）フェニル]スルホン、４，４'−ジチオジアニリン、ビス（４−アミノフェニル）スルフィドが好ましい。 From the point of having good reactivity and heat resistance, bis (4-aminophenyl) sulfone, bis (3-aminophenyl) sulfone, bis (4-aminophenyl) sulfide, bis (3-aminophenyl) sulfide, Preferred are 4,4′-dithiodianiline, 3,3′-dithiodianiline, bis [4- (4-aminophenoxy) phenyl] sulfone, and bis [4- (3-aminophenoxy) phenyl] sulfone, and further lower heat From the viewpoint of swelling, bis (4-aminophenyl) sulfone, bis (4-aminophenyl) sulfide, 4,4′-dithiodianiline, and bis [4- (4-aminophenoxy) phenyl] sulfone are more preferable. From the viewpoint of solubility in solvents, bis (4-aminophenyl) sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, 4 4'dithio dianiline, bis (4-aminophenyl) sulfide are preferable.
本発明に使用される（ｂ）の化合物は、分子構造中に少なくとも２個の不飽和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、任意のものを使用することができるが、一例としては、前記の式（III）で表される化合物が挙げられる。
（ｂ）の化合物としては、例えば、Ｎ，Ｎ'−エチレンビスマレイミド、Ｎ，Ｎ'−ヘキサメチレンビスマレイミド、Ｎ，Ｎ'−(１，３−フェニレン）ビスマレイミド、Ｎ，Ｎ'−[１，３−(２−メチルフェニレン)]ビスマレイミド、Ｎ，Ｎ'−[１，３−(４−メチルフェニレン)]ビスマレイミド、Ｎ，Ｎ'−(１，４−フェニレン）ビスマレイミド、ビス(４−マレイミドフェニル）メタン、ビス(３−メチル−４−マレイミドフェニル）メタン、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、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、ビス(４−マレイミドフェニル）スルフィド、ビス(４−マレイミドフェニル）ケトン、ビス(４−マレイミドシクロヘキシル）メタン、１，４−ビス(４−マレイミドフェニル）シクロヘキサン、１，４−ビス（マレイミドメチル）シクロヘキサン、１，４−ビス（マレイミドメチル）ベンゼン、１，３−ビス(４−マレイミドフェノキシ）ベンゼン、１，３-ビス(３−マレイミドフェノキシ）ベンゼン、ビス[４−(３−マレイミドフェノキシ）フェニル]メタン、ビス[４−(４−マレイミドフェノキシ）フェニル]メタン、１，１−ビス[４−(３−マレイミドフェノキシ）フェニル]エタン、１，１−ビス[４−(４−マレイミドフェノキシ）フェニル]エタン、１，２−ビス[４−(３−マレイミドフェノキシ）フェニル]エタン、１，２−ビス[４−(４−マレイミドフェノキシ）フェニル]エタン、２，２-ビス[４−(３−マレイミドフェノキシ）フェニル]プロパン、２，２−ビス[４−(４−マレイミドフェノキシ）フェニル]プロパン、２，２−ビス[４−(３−マレイミドフェノキシ）フェニル]ブタン、２，２−ビス[４−(４−マレイミドフェノキシ）フェニル]ブタン、２，２−ビス[４−(３−マレイミドフェノキシ）フェニル]−１，１，１，３，３，３−ヘキサフルオロプロパン、２，２−ビス[４−(４−マレイミドフェノキシ）フェニル] −１，１，１，３，３，３−ヘキサフルオロプロパン、４，４−ビス(３−マレイミドフェノキシ）ビフェニル、４，４−ビス(４−マレイミドフェノキシ）ビフェニル、ビス[４−(３−マレイミドフェノキシ）フェニル]ケトン、ビス[４−(４−マレイミドフェノキシ)フェニル]ケトン、２，２'−ビス（４−マレイミドフェニル）ジスルフィド、ビス（４−マレイミドフェニル）ジスルフィド、ビス[４−(３−マレイミドフェノキシ）フェニル]スルフィド、ビス[４−(４−マレイミドフェノキシ）フェニル]スルフィド、ビス[４−(３−マレイミドフェノキシ）フェニル]スルホキシド、ビス[４−(４−マレイミドフェノキシ）フェニル]スルホキシド、ビス[４−(３−マレイミドフェノキシ）フェニル]スルホン、ビス[４−(４−マレイミドフェノキシ）フェニル]スルホン、ビス[４−(３−マレイミドフェノキシ）フェニル]エーテル、ビス[４−(４−マレイミドフェノキシ）フェニル]エーテル、１，４−ビス[４−(４−マレイミドフェノキシ)−α，α−ジメチルベンジル]ベンゼン、１，３−ビス[４−(４−マレイミドフェノキシ)−α，α−ジメチルベンジル]ベンゼン、１，４−ビス[４−(３−マレイミドフェノキシ)−α，α−ジメチルベンジル]ベンゼン、１，３−ビス[４−(３−マレイミドフェノキシ)−α，α−ジメチルベンジル]ベンゼン、１，４−ビス[４−(４−マレイミドフェノキシ)−３，５−ジメチル−α，α−ジメチルベンジル]ベンゼン、１，３−ビス[４−(４−マレイミドフェノキシ)−３，５−ジメチル−α，α−ジメチルベンジル]ベンゼン、１，４−ビス[４−(３−マレイミドフェノキシ)−３，５−ジメチル−α，α−ジメチルベンジル]ベンゼン、１，３−ビス[４−(３−マレイミドフェノキシ)−３，５−ジメチル−α，α−ジメチルベンジル]ベンゼン、４−メチル−１，３−フェニレンビスマレイミド、ポリフェニルメタンマレイミドなどが挙げられ、これらのマレイミド化合物は、単独で用いても２種類以上を混合して用いてもよい。
これらの中で、２，２−ビス[４−（４−マレイミドフェノキシ）フェニル]プロパン、ビス（４−マレイミドフェニル）メタン、４−メチル−１，３−フェニレンビスマレイミド、ポリフェニルメタンマレイミド、およびビス（４−マレイミドフェニル）スルホンが好ましい。
なお、反応率が高く、より高耐熱性化できる点からは、ビス（４−マレイミドフェニル）メタン、ビス（４−マレイミドフェニル）スルホン、ビス(４−マレイミドフェニル)スルフィド、ビス（４−マレイミドフェニル）ジスルフィド、Ｎ，Ｎ'−(１，３−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）プロパンが好ましく、安価である点からビス（４−マレイミドフェニル）メタン、Ｎ，Ｎ'−(１，３−フェニレン)ビスマレイミドがより好ましく、溶剤への溶解性の点から、ビス（４−マレイミドフェニル）メタンが特に好ましい。
As the compound (b) used in the present invention, any maleimide compound having at least two unsaturated N-substituted maleimide groups in the molecular structure can be used. And compounds represented by the above formula (III).
Examples of the compound (b) include N, N′-ethylene bismaleimide, N, N′-hexamethylene bismaleimide, N, N ′-(1,3-phenylene) bismaleimide, N, N ′-[ 1,3- (2-methylphenylene)] bismaleimide, N, N ′-[1,3- (4-methylphenylene)] bismaleimide, N, N ′-(1,4-phenylene) bismaleimide, bis (4-maleimidophenyl) methane, bis (3-methyl-4-maleimidophenyl) methane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, bis (4-maleimidophenyl) ether, Bis (4-maleimidophenyl) sulfone, bis (4-maleimidophenyl) sulfide, bis (4-maleimidophenyl) ketone, bis (4-maleimidocyclohexyl) methane, 1 4-bis (4-maleimidophenyl) cyclohexane, 1,4-bis (maleimidomethyl) cyclohexane, 1,4-bis (maleimidomethyl) benzene, 1,3-bis (4-maleimidophenoxy) benzene, 1,3- Bis (3-maleimidophenoxy) benzene, bis [4- (3-maleimidophenoxy) phenyl] methane, bis [4- (4-maleimidophenoxy) phenyl] methane, 1,1-bis [4- (3-maleimidophenoxy) ) Phenyl] ethane, 1,1-bis [4- (4-maleimidophenoxy) phenyl] ethane, 1,2-bis [4- (3-maleimidophenoxy) phenyl] ethane, 1,2-bis [4- ( 4-maleimidophenoxy) phenyl] ethane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] propane, 2,2-bis [4- (4-male Imidophenoxy) phenyl] propane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] butane, 2,2-bis [4- (4-maleimidophenoxy) phenyl] butane, 2,2-bis [4 -(3-maleimidophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-maleimidophenoxy) phenyl] -1,1,1,3 , 3,3-hexafluoropropane, 4,4-bis (3-maleimidophenoxy) biphenyl, 4,4-bis (4-maleimidophenoxy) biphenyl, bis [4- (3-maleimidophenoxy) phenyl] ketone, bis [4- (4-maleimidophenoxy) phenyl] ketone, 2,2′-bis (4-maleimidophenyl) disulfide, bis (4-maleimidophenyl) disulfide, bis [ -(3-maleimidophenoxy) phenyl] sulfide, bis [4- (4-maleimidophenoxy) phenyl] sulfide, bis [4- (3-maleimidophenoxy) phenyl] sulfoxide, bis [4- (4-maleimidophenoxy) phenyl ] Sulfoxide, bis [4- (3-maleimidophenoxy) phenyl] sulfone, bis [4- (4-maleimidophenoxy) phenyl] sulfone, bis [4- (3-maleimidophenoxy) phenyl] ether, bis [4- ( 4-maleimidophenoxy) phenyl] ether, 1,4-bis [4- (4-maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-maleimidophenoxy) -α, α-dimethylbenzyl] benze 1,3-bis [4- (3-maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (4-maleimidophenoxy) -3,5-dimethyl-α, α- Dimethylbenzyl] benzene, 1,3-bis [4- (4-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-maleimidophenoxy)- 3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (3-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 4-methyl-1 , 3-phenylene bismaleimide, polyphenylmethane maleimide and the like. These maleimide compounds may be used alone or in combination of two or more.
Among these, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, bis (4-maleimidophenyl) methane, 4-methyl-1,3-phenylenebismaleimide, polyphenylmethanemaleimide, and Bis (4-maleimidophenyl) sulfone is preferred.
From the point of high reaction rate and higher heat resistance, bis (4-maleimidophenyl) methane, bis (4-maleimidophenyl) sulfone, bis (4-maleimidophenyl) sulfide, bis (4-maleimidophenyl) ) Disulfide, N, N ′-(1,3-phenylene) bismaleimide, 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane are preferred, and bis (4-maleimidophenyl) is inexpensive. Methane and N, N ′-(1,3-phenylene) bismaleimide are more preferred, and bis (4-maleimidophenyl) methane is particularly preferred from the viewpoint of solubility in a solvent.
本発明に使用される（ｃ）の化合物である、モノアミン化合物としては、酸性置換基を有するモノアミン化合物が好ましく、前記の式（IV）で表される化合物が更に好ましい。なお、前記（ａ）または（ｂ）成分が分子構造中に酸性置換基を有しない場合は、酸性置換基を有するモノアミン化合物とすることが好ましい。
このようなモノアミン化合物としては、例えば、（ｏ‐，ｍ‐，ｐ‐）（この表記はo-、ｍ-またはｐ−を表す。）アミノフェノール、（ｏ‐，ｍ‐，ｐ‐）アミノ安息香酸、（ｏ‐，ｍ‐，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などが挙げられるが、低熱膨張性や溶解性の点から、（ｏ‐，ｍ‐，ｐ‐）アミノフェノールが特に好ましい。
一方、前記（ａ）または（ｂ）の化合物が分子構造中に酸性置換基を有する場合は、モノアミン化合物としては、特に酸性置換基を有していても、有していなくても良く、たとえば、アニリン、（ｏ‐，ｍ‐，ｐ‐）メチルアニリン、（ｏ‐，ｍ‐，ｐ‐）エチルアニリン、（ｏ‐，ｍ‐，ｐ‐）ビニルアニリン、（ｏ‐，ｍ‐，ｐ‐）アリルアニリンなどのモノアミン化合物を使用することもできる。
As the monoamine compound (c) used in the present invention, a monoamine compound having an acidic substituent is preferable, and a compound represented by the above formula (IV) is more preferable. In addition, when the said (a) or (b) component does not have an acidic substituent in molecular structure, it is preferable to set it as the monoamine compound which has an acidic substituent.
Examples of such monoamine compounds include (o-, m-, p-) (this notation represents o-, m-, or p-) aminophenol, (o-, m-, p-) amino. Benzoic acid, (o-, m-, p-) aminobenzenesulfonic acid, 3,5-dihydroxyaniline, 3,5-dicarboxyaniline and the like can be mentioned. From the viewpoint of low thermal expansion and solubility, (o -, M-, p-) aminophenols are particularly preferred.
On the other hand, when the compound (a) or (b) has an acidic substituent in the molecular structure, the monoamine compound may or may not have an acidic substituent. Aniline, (o-, m-, p-) methylaniline, (o-, m-, p-) ethylaniline, (o-, m-, p-) vinylaniline, (o-, m-, p -) Monoamine compounds such as allylaniline can also be used.
以上の（ａ）、（ｂ）、及び（ｃ）の化合物を有機溶媒中で反応させる際、反応温度は７０〜２００℃であることが好ましく、７０〜１６０℃であることがさらに好ましい。
反応時間は０．１〜１０時間であることが好ましく、１〜６時間であることがさらに好ましい。
ここで、（ａ）の芳香族ジアミン化合物と（ｃ）の酸性置換基を有する場合のモノアミン化合物の使用量は、−ＮＨ2基当量の総和と、（ｂ）のマレイミド化合物のＣ＝Ｃ基当量との関係が、
０．１≦〔Ｃ＝Ｃ基当量〕／〔−ＮＨ2基当量の総和〕≦１０．０
に示す範囲になることが好ましい。より好ましくは、この関係が、
１．０≦〔Ｃ＝Ｃ基当量〕／〔−ＮＨ2基当量の総和〕≦９．０、特に好ましくは、
２．０≦〔Ｃ＝Ｃ基当量〕／〔−ＮＨ2基当量の総和〕≦８．０
の範囲とする。
該当量比を０．１以上とすることによりゲル化及び耐熱性が低下することがなく、又、１０．０以下とすることにより有機溶剤への溶解性、接着性、及び耐熱性が低下することがない。
When the above compounds (a), (b), and (c) are reacted in an organic solvent, the reaction temperature is preferably 70 to 200 ° C, and more preferably 70 to 160 ° C.
The reaction time is preferably 0.1 to 10 hours, and more preferably 1 to 6 hours.
Here, when the aromatic amine diamine compound (a) and the acidic substituent (c) are used, the amount of the monoamine compound used is the sum of the —NH 2 group equivalents and the C═C group of the maleimide compound (b). The relationship with the equivalent is
0.1 ≦ [C = C group equivalent] / [-NH 2 group equivalent] ≦ 10.0
It is preferable to be in the range shown in. More preferably, this relationship is
1.0 ≦ [C = C group equivalent] / [total of —NH 2 group equivalent] ≦ 9.0, particularly preferably
2.0 ≦ [C = C group equivalent] / [total of —NH 2 group equivalent] ≦ 8.0
The range.
When the amount ratio is 0.1 or more, gelation and heat resistance do not decrease, and when it is 10.0 or less, solubility in organic solvents, adhesiveness, and heat resistance decrease. There is nothing.
この反応で必要に応じて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、ブタノール、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などのアルコール系溶剤、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノンなどのケトン系溶剤、酢酸エチルエステルや、γ−ブチロラクトンなどのエステル系溶剤、テトラヒドロフランなどのエーテル系溶剤、トルエン、キシレン、メシチレンなどの芳香族系溶剤、ジメチルホルムアミド、ジメチルアセトアミド、Ｎ−メチルピロリドンなどのＮ原子含有溶剤、ジメチルスルホキシドなどのＳ原子を有し、含有溶剤などが挙げられ、１種または２種以上を混合して使用できる。これらの中で、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、メチルセロソルブ、γ−ブチロラクトンが好ましく、低毒性であることや揮発性が高くプリプレグの製造時に残溶剤として残りにくい点から、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、ジメチルアセトアミドが特に好ましい。 The organic solvent used as necessary in this reaction is not particularly limited, but alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Ketone solvents, ester solvents such as ethyl acetate and γ-butyrolactone, ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene, mesitylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. An N atom-containing solvent, an S atom such as dimethyl sulfoxide, and the like are included, and one kind or a mixture of two or more kinds can be used. Among these, cyclohexanone, propylene glycol monomethyl ether, methyl cellosolve, and γ-butyrolactone are preferable from the viewpoint of solubility, cyclohexanone, which has low toxicity and high volatility and does not easily remain as a residual solvent during prepreg production. Propylene glycol monomethyl ether and dimethylacetamide are particularly preferred.
有機溶媒の使用量は、（ａ）、（ｂ）、及び（ｃ）の化合物の総和１００質量部当たり、２５〜１０００質量部とすることが好ましく、４０〜７００質量部とすることがより好ましい。有機溶剤の配合量が２５〜１０００質量部とすることで、溶解性が不足したり、合成に長時間を要することがない。 The amount of the organic solvent used is preferably 25 to 1000 parts by mass, more preferably 40 to 700 parts by mass per 100 parts by mass of the sum of the compounds of (a), (b), and (c). . When the blending amount of the organic solvent is 25 to 1000 parts by mass, the solubility is not insufficient and the synthesis does not take a long time.
また、この反応には任意に反応触媒を使用することができる。このような反応触媒の例としては、特に限定されないが、トリエチルアミン、ピリジン、トリブチルアミンなどのアミン類、メチルイミダゾール、フェニルイミダゾールなどのイミダゾール類、トリフェニルホスフィンなどのリン系触媒などがあげられ、１種または２種以上を混合して使用できる。
触媒の添加量は、（ｂ）のマレイミド化合物と（ｃ）のモノアミン化合物との合計質量に対して、０．００１〜５質量％が好ましい。
Moreover, a reaction catalyst can be arbitrarily used for this reaction. Examples of such reaction catalysts include, but are not limited to, amines such as triethylamine, pyridine, and tributylamine, imidazoles such as methylimidazole and phenylimidazole, and phosphorus-based catalysts such as triphenylphosphine. A seed or a mixture of two or more can be used.
The addition amount of the catalyst is preferably 0.001 to 5% by mass with respect to the total mass of the maleimide compound (b) and the monoamine compound (c).
化合物（１）の重量平均分子量は、溶解性や機械強度の観点から４００〜３５００であるのが好ましい。なお本発明における重量平均分子量は、溶離液としてテトラヒドロフランを用いたゲルパーミエーションクロマトグラフィー（ＧＰＣ）法（ポリスチレン換算）で測定される。
なお、（ｂ）のマレイミド化合物と（ｃ）のモノアミン化合物が反応して前記の式（Ｖ）で示される化合物が得られ、（ａ）の芳香族ジアミン化合物と（ｂ）のマレイミド化合物が反応して前記の式（ＶI）又は前記の式（ＶII）で示される化合物が得られる。
本発明の熱硬化性絶縁樹脂組成物には前記の式（Ｖ）、式（ＶI）および式（ＶII）で示される化合物を含有することが好ましい。
The weight average molecular weight of the compound (1) is preferably 400 to 3500 from the viewpoints of solubility and mechanical strength. The weight average molecular weight in the present invention is measured by gel permeation chromatography (GPC) method (polystyrene conversion) using tetrahydrofuran as an eluent.
The maleimide compound (b) and the monoamine compound (c) react to obtain the compound represented by the formula (V), and the aromatic diamine compound (a) and the maleimide compound (b) react. Thus, the compound represented by the formula (VI) or the formula (VII) is obtained.
The thermosetting insulating resin composition of the present invention preferably contains a compound represented by the above formula (V), formula (VI) and formula (VII).
本発明の熱硬化性絶縁樹脂組成物には、樹脂成分としてエポキシ樹脂（２）を含有することが好ましい。エポキシ樹脂（２）は、１分子中に少なくとも以上の２個のエポキシ基を有するエポキシ樹脂が好ましく、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などのグリシジルエーテル系、グリシジルアミン系、並びにグリシジルエステル系などが挙げられ、１種または２種以上を混合して使用することができる。具体的には、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、アントラセン型エポキシ樹脂、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などが好ましく、良好な低熱膨張性や高いガラス転移温度を有する点から、ナフタレン環含有エポキシ樹脂、アントラセン型エポキシ樹脂、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、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い。 The thermosetting insulating resin composition of the present invention preferably contains an epoxy resin (2) as a resin component. The epoxy resin (2) is preferably an epoxy resin having at least two epoxy groups in one molecule. For example, bisphenol A, bisphenol F, biphenyl, novolac, polyfunctional phenol, naphthalene, Examples thereof include alicyclic and alcohol-based glycidyl ethers, glycidylamines, glycidyl esters, and the like, which can be used alone or in combination. Specifically, bisphenol F type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene ring-containing epoxy resin, anthracene type epoxy resin, biphenyl type epoxy resin in terms of dielectric properties, heat resistance, moisture resistance, and copper foil adhesion , Biphenyl aralkyl type epoxy resin, phenol novolac type epoxy resin, cresol novolak type epoxy resin, etc. are preferable, and naphthalene ring-containing epoxy resin, anthracene type epoxy resin, biphenyl from the point of having good low thermal expansion property and high glass transition temperature Type epoxy resin, biphenyl aralkyl type epoxy resin, and phenol novolac type epoxy resin are more preferable.
本発明に係る熱硬化性絶縁樹脂には、以上のように(１)及び（２）成分に加えて、エポキシ樹脂の硬化剤（３）を併用することができる。そのようなエポキシ樹脂の硬化剤としては、エポキシ樹脂の硬化作用があれば特に限定されるものではないが、例としては、無水マレイン酸、無水マレイン酸共重合体などの酸無水物、ジシアンジアミドなどのアミン化合物、フェノールノボラック、クレゾールノボラック、アミノトリアジンノボラック樹脂などのフェノール化合物などが挙げられる。これらの中で、硬化性と低熱膨張性の観点からジシアンジアミド、クレゾールノボラック、アミノトリアジンノボラックが好ましく、難燃性や接着性が向上することからジシアンジアミド、アミノトリアジンノボラック樹脂が特に好ましい。上記の、任意成分としてのエポキシ樹脂の硬化剤（３）は１種または２種以上を混合して使用できる。 In addition to the components (1) and (2), the epoxy resin curing agent (3) can be used in combination with the thermosetting insulating resin according to the present invention. The epoxy resin curing agent is not particularly limited as long as the epoxy resin has a curing action, but examples include acid anhydrides such as maleic anhydride and maleic anhydride copolymers, and dicyandiamide. And phenol compounds such as phenol novolak, cresol novolak, and aminotriazine novolak resin. Among these, dicyandiamide, cresol novolak, and aminotriazine novolak are preferable from the viewpoints of curability and low thermal expansion, and dicyandiamide and aminotriazine novolak resin are particularly preferable because flame retardancy and adhesion are improved. The epoxy resin curing agent (3) as an optional component may be used alone or in combination of two or more.
本発明に係る樹脂組成物においては、さらに硬化促進剤を含むことができる。このような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などが挙げられる。 The resin composition according to the present invention can further contain a curing accelerator. Examples of such curing accelerators include imidazoles and derivatives thereof, tertiary amines and quaternary ammonium salts.
本発明に係る熱硬化性絶縁樹脂組成物は、固形分換算の該成分（１）、（２）、（３）の総和１００質量部当たり、該成分（１）の使用量は２０〜９５質量部、より好ましくは４０〜９０質量部、成分（２）の使用量は５〜８０質量部、より好ましくは１０〜６０質量部、および成分（３）の使用量は０〜５０質量部、より好ましくは５〜３０質量部とすることが望ましい。
成分（１）、（２）および（３）の配合量を上記の範囲とすることで、本発明の熱硬化性絶縁樹脂組成物の難燃性、耐熱性、接着性、及び誘電特性が良好に発揮される。
The thermosetting insulating resin composition according to the present invention is used in an amount of 20 to 95 mass per 100 mass parts of the total of the components (1), (2) and (3) in terms of solid content. Parts, more preferably 40 to 90 parts by weight, the amount of component (2) used is 5 to 80 parts by weight, more preferably 10 to 60 parts by weight, and the amount of component (3) used is 0 to 50 parts by weight. Preferably it is 5-30 mass parts.
By setting the blending amounts of the components (1), (2) and (3) within the above ranges, the flame retardant, heat resistance, adhesiveness, and dielectric properties of the thermosetting insulating resin composition of the present invention are good. To be demonstrated.
本発明に係る熱硬化性絶縁樹脂においては、さらに、無機充填材（４）を併用することができる。
このような無機充填材の例としては、シリカ、マイカ、タルク、ガラス短繊維また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、または水酸化マグネシウムなどが挙げられる。これらの中で誘電特性、耐熱性、難燃性の点からシリカ、水酸化アルミニウム、または水酸化マグネシウムが好ましく、低熱膨張性であることからシリカ、または水酸化アルミニウムがより好ましい。
固形分換算の該成分（１）、（２）、及び（３）成分の総和１００質量部に対し、該（４）成分の無機充填材の使用量は、０〜４００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、５０〜１５０質量部とすることが特に好ましい。
（４）成分の配合量が０〜４００質量部とすることで、成形性、及び接着性が良好に発揮される。
In the thermosetting insulating resin according to the present invention, an inorganic filler (4) can be used in combination.
Examples of such inorganic fillers include silica, mica, talc, short glass fiber or fine powder and hollow glass, antimony trioxide, calcium carbonate, quartz powder, aluminum hydroxide, or magnesium hydroxide. Among these, silica, aluminum hydroxide, or magnesium hydroxide is preferable from the viewpoint of dielectric properties, heat resistance, and flame retardancy, and silica or aluminum hydroxide is more preferable from the viewpoint of low thermal expansion.
The amount of the inorganic filler used in the component (4) is 0 to 400 parts by mass with respect to 100 parts by mass of the total of the components (1), (2), and (3) in terms of solid content. Preferably, it is more preferably 20 to 200 parts by mass, and particularly preferably 50 to 150 parts by mass.
(4) By making the compounding quantity of component 0-400 mass parts, a moldability and adhesiveness are exhibited favorably.
以上の他にも、本発明に係る熱硬化性絶縁樹脂組成物においては、樹脂組成物として熱硬化性の性質を損なわない程度に、任意に公知の熱可塑性樹脂、エラストマー、及び充填材などを併用することができる。
熱可塑性樹脂の例としては、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、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、石油樹脂及びシリコーン樹脂などが挙げられる。
エラストマーの例としては、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及びカルボキシ変性ポリアクリロニトリルなどが挙げられる。
充填材の例としては、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、並びにポリフェニレンエーテルなどの有機物粉末などが挙げられる。
In addition to the above, in the thermosetting insulating resin composition according to the present invention, a known thermoplastic resin, elastomer, filler, etc. are arbitrarily added to such an extent that the thermosetting property is not impaired as the resin composition. Can be used together.
Examples of the thermoplastic resin include polytetrafluoroethylene, polyethylene, polypropylene, polystyrene, polyphenylene ether resin, phenoxy resin, polycarbonate resin, polyester resin, polyamide resin, polyimide resin, xylene resin, petroleum resin, and silicone resin. .
Examples of the elastomer include polybutadiene, polyacrylonitrile, epoxy-modified polybutadiene, maleic anhydride-modified polybutadiene, phenol-modified polybutadiene, and carboxy-modified polyacrylonitrile.
Examples of the filler include organic powders such as silicone powder, polytetrafluoroethylene, polyethylene, polypropylene, polystyrene, and polyphenylene ether.
本発明に係る樹脂組成物に対して、任意に紫外線吸収剤、酸化防止剤、光重合開始剤、蛍光増白剤及び密着性向上剤などを添加することも可能であり、特に限定されない。これらの例としては、ベンゾトリアゾール系などの紫外線吸収剤、ヒンダードフェノール系やスチレン化フェノールなどの酸化防止剤、ベンゾフェノン類、ベンジルケタール類、チオキサントン系などの光重合開始剤、スチルベン誘導体などの蛍光増白剤、尿素シランなどの尿素化合物やシランカップリング剤などの密着性向上剤などが挙げられる。 An ultraviolet absorber, an antioxidant, a photopolymerization initiator, a fluorescent whitening agent, an adhesion improver, and the like can be arbitrarily added to the resin composition according to the present invention, and there is no particular limitation. Examples of these include UV absorbers such as benzotriazoles, antioxidants such as hindered phenols and styrenated phenols, photopolymerization initiators such as benzophenones, benzyl ketals, and thioxanthones, and fluorescence such as stilbene derivatives. Examples include brighteners, urea compounds such as urea silane, and adhesion improvers such as silane coupling agents.
次に、上記熱硬化性絶縁樹脂組成物を含むプリプレグ、樹脂付フィルム、積層板、及び多層プリント配線板について説明を行う。
先ず、本発明に係るプリプレグは、前記の熱硬化性絶縁樹脂組成物を用いてなり、上記熱硬化性絶縁樹脂組成物を基材に含浸または塗工した後、Ｂステージ化(半硬化)して得られるプリプレグである。すなわち、本発明に係る熱硬化性絶縁樹脂組成物を、基材に含浸または塗工した後、加熱などによりＢステージ化させてプリプレグが製造される。
Next, the prepreg containing the said thermosetting insulating resin composition, the film with resin, a laminated board, and a multilayer printed wiring board are demonstrated.
First, a prepreg according to the present invention comprises the thermosetting insulating resin composition described above. After impregnating or coating the thermosetting insulating resin composition on a substrate, it is made into a B-stage (semi-cured). It is a prepreg obtained. That is, after impregnating or applying the thermosetting insulating resin composition according to the present invention to a base material, it is B-staged by heating or the like to produce a prepreg.
本発明に係る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ものが使用できる。基材の材質としては、Ｅガラス、Ｄガラス、Ｓガラス及びＱガラスなどの無機物繊維、ポリイミド、ポリエステル及びポリテトラフルオロエチレンなどの有機繊維、並びにそれらの混合物などが挙げられる。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などの形状を有するが、材質及び形状は、目的とする成形物の用途や性能により選択され、必要により、単独または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、特に制限されず、例えば、約０．０３〜０．５ｍｍを使用することができ、シランカップリング剤などで表面処理したものまたは機械的に開繊処理を施したものが、耐熱性や耐湿性、加工性の面から好適である。
前記基材に対する樹脂組成物の付着量は、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または塗工する。その後、通常、１００〜２００℃の温度で１〜３０分加熱乾燥し、Ｂステージ化させる。
本発明に係る樹脂付フィルムは、基材に樹脂フィルム、例えばポリイミド、ポリエステル及びポリアミドなどを使用し、これに本発明に係る熱硬化性絶縁樹脂組成物を塗工した後、Ｂステージ化して製造される。
As the base material used in the prepreg according to the present invention, those used in various laminates for electrical insulating materials can be used. Examples of the material of the substrate 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, for example, woven fabric, non-woven fabric, low-ink, chopped strand mat, and surfacing mat, but the material and shape are selected depending on the intended use and performance of the molded product, and if necessary, A single material or two or more materials and shapes can be combined. The thickness of the substrate is not particularly limited, and for example, about 0.03 to 0.5 mm can be used, and the surface is treated with a silane coupling agent or the like, or is mechanically subjected to fiber opening treatment. However, it is suitable from the aspects of heat resistance, moisture resistance, and workability.
The base material is impregnated or coated so that the amount of the resin composition attached to the base material is 20 to 90% by mass based on the resin content of the prepreg after drying. Thereafter, it is usually heated and dried at a temperature of 100 to 200 ° C. for 1 to 30 minutes to form a B stage.
The film with resin according to the present invention is manufactured by using a resin film as a base material, for example, polyimide, polyester, polyamide, etc., and coating the thermosetting insulating resin composition according to the present invention on this, and then making it into a B-stage. Is done.
次に、本発明に係る積層板は、前述の本発明に係るプリプレグを積層成形して得られるものである。すなわち、本発明に係るプリプレグを、例えば、１〜２０枚重ね、その片面または両面に銅やアルミニウムなどの金属箔を配置した構成で積層成形したものである。
金属箔は、電気絶縁材料用途で用いるものであれば、特に制限されない。
成形条件は、電気絶縁材料用積層板や多層板の手法が適用でき、例えば、多段プレス、多段真空プレス、連続成形機、オートクレーブ成形機などを使用し、温度１００〜２５０℃程度、圧力２〜１００ＭＰａ程度、及び加熱時間０．１〜５時間程度の範囲で成形することができる。また、本発明に係るプリプレグと内層用配線板とを組合せ、積層成形して、多層板を製造することもできる。
Next, the laminated board according to the present invention is obtained by laminating the above-described prepreg according to the present invention. That is, for example, 1 to 20 prepregs according to the present invention are laminated and laminated and formed with a configuration in which a metal foil such as copper or aluminum is disposed on one or both sides thereof.
The metal foil is not particularly limited as long as it is used for electrical insulating material applications.
The molding conditions can be applied to a laminate for an electrical insulating material or a multilayer board, for example, using a multistage press, a multistage vacuum press, a continuous molding machine, an autoclave molding machine, etc., at a temperature of about 100 to 250 ° C., a pressure of 2 Molding can be performed in a range of about 100 MPa and a heating time of about 0.1 to 5 hours. Further, the prepreg according to the present invention and the inner layer wiring board can be combined and laminated to produce a multilayer board.
本発明に係るプリント配線板は、前記の積層板を用いて製造されるものであって、前記積層板の表面に回路を形成して製造される。すなわち、本発明に係る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、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、ドリル加工またはレーザー加工によるスルーホールまたはブラインドビアホールの形成と、メッキまたは導電性ペーストによる層間配線の形成を経て多層プリント配線板を製造することができる。 The printed wiring board which concerns on this invention is manufactured using the said laminated board, Comprising: A circuit is formed in the surface of the said laminated board, and is manufactured. That is, the conductor layer of the laminated board according to the present invention is subjected to wiring processing by a normal etching method, and a plurality of laminated boards subjected to wiring processing through the above-described prepreg are laminated and subjected to hot press processing to be multilayered at once. Thereafter, a multilayer printed wiring board can be manufactured through formation of through holes or blind via holes by drilling or laser processing, and formation of interlayer wiring by plating or conductive paste.
以上に述べたように、本発明は、特定の化合物を使用する熱硬化性絶縁樹脂、及び前記熱硬化性絶縁樹脂を用いたプリプレグ、樹脂付フィルム、積層板、及びプリント配線板であって、特に、ガラス転移温度（Ｔｇ）が高く、耐熱性に優れ、また、毒性が低く安全性や作業環境に優れる、電子部品などに好適な製品を提供することができる。 As described above, the present invention is a thermosetting insulating resin using a specific compound, and a prepreg, a film with a resin, a laminate, and a printed wiring board using the thermosetting insulating resin, In particular, a product suitable for an electronic component or the like having a high glass transition temperature (Tg), excellent heat resistance, low toxicity, and excellent safety and work environment can be provided.
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、本発明はこれらの記載に限定されるものではない。
なお、以下の実施例で得られた熱膨張率測定用樹脂板と銅張積層板は、以下の方法で性能を測定・評価した。
Next, the present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these descriptions.
The thermal expansion coefficient measuring resin plates and copper clad laminates obtained in the following examples were measured and evaluated for performance by the following methods.
（１）熱膨張率の測定
熱膨張率測定用樹脂板から５ｍｍ角の試験片を切り出し、ＴＭＡ試験装置（デュポン社製、ＴＭＡ２９４０）を用い、試験片のＴｇ未満の熱膨張特性を観察することにより評価した。
（２）銅箔接着性（銅箔ピール強度）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、３ｍｍ幅の銅箔を形成するように評価基板を作製し、オートグラフ（島津製作所製、ＡＧ−１００Ｃ）を用いて銅箔の接着性（ピール強度）を測定した。
（３）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角の評価基板を作製し、ＴＭＡ試験装置（デュポン社製、ＴＭＡ２９４０）を用い、評価基板の熱膨張特性を観察することにより評価した。
（４）はんだ耐熱性の評価
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５ｃｍ角の評価基板を作製し、プレッシャー・クッカー試験装置（平山製作所（株）製）を用いて、１２１℃、２ａｔｍの条件で４時間までプレッシャー・クッカー処理を行った後、温度２８８℃のはんだ浴に、評価基板を２０秒間浸漬した後、外観を観察することにより、はんだ耐熱性を評価した。
評価結果を以下の通り表記した。
○ 良好（ふくれなし）
× 不良（ふくれあり）
（５）銅付き耐熱性（Ｔ−２８８）の評価
銅張積層板から５ｍｍ角の評価基板を作製し、ＴＭＡ試験装置（デュポン社製、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。
（６）吸湿性（吸水率）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を作製し、プレッシャー・クッカー試験装置（平山製作所（株）製）を用いて、１２１℃、２ａｔｍの条件で４時間までプレッシャー・クッカー処理を行った後、評価基板の吸水率を測定した。
（７）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。
（８）比誘電率及び誘電正接の測定
銅張積層板を銅エッチング液に浸漬することにより、銅箔を取り除いた評価基板を作製し、比誘電率測定装置（Ｈｅｗｌｅｔ・Ｐａｃｋａｒｄ社製、製品名：ＨＰ４２９１Ｂ）を用いて、周波数１ＧＨｚでの比誘電率及び誘電正接を測定した。
(1) Measurement of thermal expansion coefficient A test piece of 5 mm square is cut out from a resin plate for measuring thermal expansion coefficient, and the thermal expansion characteristics of the test specimen less than Tg are observed using a TMA test apparatus (manufactured by DuPont, TMA2940). It was evaluated by.
(2) Evaluation of copper foil adhesion (copper foil peel strength) By immersing a copper-clad laminate in a copper etching solution, an evaluation substrate was prepared so as to form a copper foil having a width of 3 mm. The adhesiveness (peel strength) of the copper foil was measured using AG-100C).
(3) Measurement of glass transition temperature (Tg) By immersing the copper-clad laminate in a copper etching solution, a 5 mm square evaluation substrate from which the copper foil was removed was prepared, and a TMA test apparatus (manufactured by DuPont, TMA2940) was used. Used and evaluated by observing the thermal expansion characteristics of the evaluation substrate.
(4) Evaluation of solder heat resistance By immersing the copper-clad laminate in a copper etching solution, a 5 cm square evaluation board from which the copper foil has been removed is prepared, and a pressure cooker test apparatus (manufactured by Hirayama Seisakusho) is used. After using the pressure cooker treatment for up to 4 hours under the conditions of 121 ° C. and 2 atm, immersing the evaluation substrate in a solder bath at a temperature of 288 ° C. for 20 seconds, and then observing the appearance, solder heat resistance can be obtained. evaluated.
The evaluation results are shown as follows.
○ Good (no blister)
× Defect (with blisters)
(5) Evaluation of heat resistance with copper (T-288) An evaluation board of 5 mm square was prepared from a copper-clad laminate, and the evaluation board swelled at 288 ° C. using a TMA test apparatus (manufactured by DuPont, TMA2940). It was evaluated by measuring the time to do.
(6) Evaluation of hygroscopicity (water absorption rate) By immersing a copper clad laminate in a copper etching solution, an evaluation substrate from which the copper foil was removed was prepared, and a pressure cooker test apparatus (manufactured by Hirayama Seisakusho) was used. Then, after performing the pressure cooker treatment up to 4 hours under the conditions of 121 ° C. and 2 atm, the water absorption rate of the evaluation substrate was measured.
(7) Evaluation of flame retardance By immersing a copper clad laminate in a copper etching solution, a test piece cut out to a length of 127 mm and a width of 12.7 mm was prepared from the evaluation substrate from which the copper foil was removed. Evaluation was performed according to the test method (Method V).
(8) Measurement of relative dielectric constant and dielectric loss tangent A copper-clad laminate is immersed in a copper etching solution to produce an evaluation substrate from which the copper foil has been removed, and a relative dielectric constant measuring device (product name, manufactured by Hewlett Packard, product name). : HP4291B), relative permittivity and dielectric loss tangent at a frequency of 1 GHz were measured.
製造例１：化合物（１−１）の製造
温度計、攪拌装置、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−アミノフェニル）スルホン２６．４ｇと、２，２−ビス［４−（４−マレイミドフェノキシ）フェニル］プロパン４８４．５gと、p−アミノ安息香酸２９．１ｇ、及びジメチルアセトアミド３６０．０gを入れ、１４０℃で５時間反応させて、分子骨格中にスルホン基を有し、酸性置換基およびＮ−置換マレイミド基を有する化合物（１−１）含有溶液を得た。
Production Example 1: Production of Compound (1-1) Bis (4-aminophenyl) sulfone 26 was added to a reaction vessel having a volume of 2 liters capable of being heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. 4 g, 484.5 g of 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, 29.1 g of p-aminobenzoic acid and 360.0 g of dimethylacetamide were added and reacted at 140 ° C. for 5 hours. Thus, a compound (1-1) -containing solution having a sulfone group in the molecular skeleton and having an acidic substituent and an N-substituted maleimide group was obtained.
製造例２：化合物（１−２）の製造
温度計、攪拌装置、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−アミノフェニル）スルホン４０．２ｇと、ビス（４−マレイミドフェニル）メタン４６４．４gと、p−アミノフェノール３５．４ｇ、及びジメチルアセトアミド３６０．０gを入れ、１００℃で４時間反応させて、分子骨格中にスルホン基を有し、酸性置換基およびＮ−置換マレイミド基を有する化合物（１−２）含有溶液を得た。
Production Example 2: Production of Compound (1-2) Bis (4-aminophenyl) sulfone 40 was added to a reaction vessel having a volume of 2 liters capable of being heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. .2 g, 464.4 g of bis (4-maleimidophenyl) methane, 35.4 g of p-aminophenol, and 360.0 g of dimethylacetamide were reacted at 100 ° C. for 4 hours to form a sulfone group in the molecular skeleton. And a compound (1-2) -containing solution having an acidic substituent and an N-substituted maleimide group.
製造例３：化合物（１−３）の製造
温度計、攪拌装置、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−アミノフェニル）スルフィド４３．４ｇと、４−メチル−１，３−フェニレンビスマレイミド４５２．９gと、p−アミノフェノール４３．７、及びジメチルアセトアミド３６０．０gを入れ、１００℃で２時間反応させて、分子骨格中にスルフィド基を有し、酸性置換基およびＮ−置換マレイミド基を有する化合物（１−３）含有溶液を得た。
Production Example 3: Production of Compound (1-3) Bis (4-aminophenyl) sulfide 43 was placed in a reaction vessel having a volume of 2 liters capable of being heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. .4 g, 4-methyl-1,3-phenylenebismaleimide 452.9 g, p-aminophenol 43.7 and dimethylacetamide 360.0 g were added and reacted at 100 ° C. for 2 hours to form a molecular skeleton. A compound (1-3) -containing solution having a sulfide group and having an acidic substituent and an N-substituted maleimide group was obtained.
製造例４：化合物（１−４）の製造
温度計、攪拌装置、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−（４−アミノフェノキシ）フェニル]スルホン４４．８ｇと、２，２−ビス（４−（４−マレイミドフェノキシ）フェニル）プロパン４７２．６gと、p−アミノフェノール２２．６ｇ、及びプロピレングリコールモノメチルエーテル３６０．０gを入れ、還流温度で２時間反応させて、分子骨格中にスルホン基を有し、酸性置換基およびＮ−置換マレイミド基を有する化合物（１−４）含有溶液を得た。
Production Example 4: Production of Compound (1-4) Bis [4- (4-aminophenoxy) was placed in a 2 liter reaction vessel with a thermometer, a stirrer, and a water quantifier with a reflux condenser and capable of heating and cooling. ) Phenyl] sulfone 44.8 g, 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane 472.6 g, p-aminophenol 22.6 g, and propylene glycol monomethyl ether 360.0 g, Reaction was performed at reflux temperature for 2 hours to obtain a compound (1-4) -containing solution having a sulfone group in the molecular skeleton and an acidic substituent and an N-substituted maleimide group.
製造例５：化合物（１−５）の製造
温度計、攪拌装置、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−（４−アミノフェノキシ）フェニル]スルホン６６．３ｇと、ポリフェニルメタンマレイミド４４０．３gと、p−アミノフェノール３３．４ｇ、及びプロピレングリコールモノメチルエーテル３６０．０gを入れ、還流温度で２時間反応させて、分子骨格中にスルホン基を有し、酸性置換基およびＮ−置換マレイミド基を有する化合物（１−５）含有溶液を得た。
Production Example 5: Production of Compound (1-5) Bis [4- (4-aminophenoxy) was added to a reaction vessel having a volume of 2 liters that can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. ) 66.3 g of phenyl] sulfone, 440.3 g of polyphenylmethanemaleimide, 33.4 g of p-aminophenol and 360.0 g of propylene glycol monomethyl ether, and reacted for 2 hours at the reflux temperature. A compound (1-5) -containing solution having a sulfone group and having an acidic substituent and an N-substituted maleimide group was obtained.
製造例６：化合物（１−６）の製造
温度計、攪拌装置、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−（４−アミノフェノキシ）フェニル]スルホン７９．４ｇと、ビス（４−マレイミドフェニル）スルホン４２０．５gと、p−アミノフェノール４０．１ｇ、及びプロピレングリコールモノメチルエーテル３６０．０gを入れ、還流温度で２時間反応させて、分子骨格中にスルホン基を有し、酸性置換基およびＮ−置換マレイミド基を有する化合物（１−６）含有溶液を得た。
Production Example 6: Production of Compound (1-6) Bis [4- (4-aminophenoxy) was placed in a 2 liter reaction vessel with a thermometer, a stirrer, and a moisture quantifier equipped with a reflux condenser and capable of heating and cooling. ) Phenyl] sulfone 79.4 g, bis (4-maleimidophenyl) sulfone 420.5 g, p-aminophenol 40.1 g and propylene glycol monomethyl ether 360.0 g were added and reacted at reflux temperature for 2 hours. A compound (1-6) -containing solution having a sulfone group in the molecular skeleton and an acidic substituent and an N-substituted maleimide group was obtained.
製造例７：化合物（１−７）の製造
温度計、攪拌装置、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、３，７−ジアミノ−２，８−ジメチルベンゾチオフェンスルホン４４．１ｇと、ビス（４−マレイミドフェニル）メタン４６０．８gと、p−アミノフェノール３５．１ｇ、及びジメチルアセトアミド３６０．０gを入れ、１００℃で２時間反応させて、分子骨格中にスルホン基とビフェニル骨格を有し、酸性置換基およびＮ−置換マレイミド基を有する化合物（１−７）含有溶液を得た。
Production Example 7: Production of Compound (1-7) 3,7-Diamino-2,8 was placed in a reaction vessel having a volume of 2 liters capable of being heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. -44.1 g of dimethylbenzothiophene sulfone, 460.8 g of bis (4-maleimidophenyl) methane, 35.1 g of p-aminophenol, and 360.0 g of dimethylacetamide were allowed to react at 100 ° C for 2 hours. A compound (1-7) -containing solution having a sulfone group and a biphenyl skeleton in the skeleton, and having an acidic substituent and an N-substituted maleimide group was obtained.
製造例８：化合物（１−８）の製造
温度計、攪拌装置、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、４，４'−ジチオジアニリン２６．７ｇと、２，２−ビス（４−（４−マレイミドフェノキシ）フェニル）プロパン４８９．９gと、p−アミノフェノール２３．４ｇ、及びプロピレングリコールモノメチルエーテル３６０．０gを入れ、還流温度で２時間反応させて分子骨格中にジスルフィド基を有し、酸性置換基および不飽和Ｎ−置換マレイミド基を有する化合物（１−８）の溶液を得た。
Production Example 8 Production of Compound (1-8) 4,4′-dithiodianiline 26 was placed in a reaction vessel having a volume of 2 liters capable of being heated and cooled, equipped with a thermometer, a stirrer, and a moisture quantifier with a reflux condenser. 7 g, 489.9 g of 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane, 23.4 g of p-aminophenol, and 360.0 g of propylene glycol monomethyl ether were added at reflux temperature for 2 hours. Reaction was performed to obtain a solution of the compound (1-8) having a disulfide group in the molecular skeleton and an acidic substituent and an unsaturated N-substituted maleimide group.
比較製造例１：化合物（１−９）の製造
特公昭６３−３４８９９号（特許文献５）の実施例を参考にし、蒸気加熱装置を付けた容積１リットルのニーダーに、ビス（４−マレイミドフェニル）メタン３５８．０gとｍ−アミノフェノール５４．５ｇを入れ、１３５〜１４０℃で１５分間加熱混練した後、冷却し、粉砕して酸性置換基とＮ−置換マレイミド基を有する化合物（１−９）の粉末を得た。
Comparative Production Example 1: Production of Compound (1-9) With reference to the example of JP-B 63-34899 (Patent Document 5), bis (4-maleimidophenyl) was added to a 1 liter kneader equipped with a steam heating device. ) 358.0 g of methane and 54.5 g of m-aminophenol were added, and the mixture was heated and kneaded at 135 to 140 ° C. for 15 minutes, then cooled and pulverized to have a compound having an acidic substituent and an N-substituted maleimide group (1-9) ) Was obtained.
比較製造例２：化合物（１−１０）の製造
特公平６−８３４２号（特許文献７）の実施例を参考にし、蒸気加熱装置を付けた容積１リットルのニーダーに、ビス（４−マレイミドフェニル）メタン３５８．０gとｍ−アミノ安息香酸６８．５ｇを入れ、１３５〜１４０℃で１５分間加熱混練した後、冷却し、粉砕して酸性置換基とＮ−置換マレイミド基を有する化合物（１−１０）の粉末を得た。
Comparative Production Example 2: Production of Compound (1-10) With reference to the example of JP-B-6-8342 (Patent Document 7), bis (4-maleimidophenyl) was added to a 1 liter kneader equipped with a steam heating device. ) Add 358.0 g of methane and 68.5 g of m-aminobenzoic acid, heat knead at 135 to 140 ° C. for 15 minutes, cool, pulverize, and have a compound having an acidic substituent and an N-substituted maleimide group (1- 10) powder was obtained.
比較製造例３：化合物（１−１１）の製造
温度計、攪拌装置、還流冷却管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、ジアミノジフェニルメタン３２．６ｇと、ビス（４−マレイミドフェニル）メタン４７１．５gと、p−アミノフェノール３５．９ｇ、及びジメチルアセトアミド３６０．０gを入れ、１００℃で２時間反応させ、酸性置換基とＮ−置換マレイミド基を有する化合物（１−１１）含有溶液を得た。
Comparative Production Example 3: Production of Compound (1-11) In a reaction vessel with a thermometer, a stirrer, a reflux condenser and a heatable and coolable volume of 2 liters, 32.6 g of diaminodiphenylmethane and bis (4-maleimide) were prepared. Phenyl) methane (471.5 g), p-aminophenol (35.9 g) and dimethylacetamide (360.0 g) were added, reacted at 100 ° C. for 2 hours, and a compound having an acidic substituent and an N-substituted maleimide group (1-11) A containing solution was obtained.
比較製造例４：化合物（１−１２）の製造
温度計、攪拌装置、還流冷却管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、２，２'−ビス[４−（４−アミノフェノキシ）フェニル]プロパン６３．４ｇと、ビス（４−マレイミドフェニル）メタン４７１．２gと、p−アミノフェノール３３．７ｇ、及びジメチルアセトアミド３６０．０gを入れ、１００℃で２時間反応させ、酸性置換基とＮ−置換マレイミド基を有する化合物（１−１２）含有溶液を得た。
Comparative Production Example 4: Production of Compound (1-12) 2,2′-bis [4- (4-) was added to a reaction vessel having a thermometer, a stirrer, a reflux condenser and a heatable and coolable volume of 2 liters. Aminophenoxy) phenyl] propane (63.4 g), bis (4-maleimidophenyl) methane (471.2 g), p-aminophenol (33.7 g), and dimethylacetamide (360.0 g) were added and reacted at 100 ° C. for 2 hours. A compound (1-12) -containing solution having a substituent and an N-substituted maleimide group was obtained.
実施例１〜１５、比較例１〜６
先ず、実施例１〜１５は、製造例１〜８で得られた（１）成分の、分子骨格中にＳ原子を有し、酸性置換基とＮ−置換マレイミド基を有する化合物含有溶液と、（２）成分のエポキシ樹脂と、（３）成分のエポキシ樹脂の硬化剤、硬化促進剤として、イミダゾール誘導体〔第一工業製薬（株）、商品名：Ｇ８００９Ｌ〕、及び希釈溶剤にメチルエチルケトンを使用して、表１に示した配合割合（質量部）で混合して樹脂分６５質量％の均一なワニスを作製した。
Examples 1-15, Comparative Examples 1-6
First, in Examples 1 to 15, the compound-containing solution of the component (1) obtained in Production Examples 1 to 8 having an S atom in the molecular skeleton and having an acidic substituent and an N-substituted maleimide group, (2) Component epoxy resin, (3) Component epoxy resin curing agent, curing accelerator, imidazole derivative [Daiichi Kogyo Seiyaku Co., Ltd., trade name: G8009L], and methyl ethyl ketone as diluent solvent Then, a uniform varnish having a resin content of 65% by mass was prepared by mixing at a blending ratio (parts by mass) shown in Table 1.
ここで、（２）成分として使用したエポキシ樹脂は以下の通り（表１は商品名で記載）。
ビスフェノールＦ型エポキシ樹脂〔ジャパンエポキシレジン（株）製、商品名：ＥＰ８０６〕
フェノールノボラック型エポキシ樹脂〔大日本インキ化学工業（株）製、商品名、Ｎ−７７０〕
２官能ナフタレン型エポキシ樹脂〔大日本インキ化学工業（株）製、商品名、ＨＰ−４０３２Ｄ〕
ナフトールアラルキル型エポキシ樹脂〔東都化成（株）製、商品名：ＥＳＮ−１７５〕
２官能ナフタレンアラルキル型エポキシ樹脂〔東都化成（株）製、商品名：ＥＳＮ−３７５〕
ビフェニル型エポキシ樹脂〔ジャパンエポキシレジン（株）製、商品名：ＹＸ−４０００〕
ビフェニルアラルキル型エポキシ樹脂〔日本化薬（株）製、商品名：ＮＣ−３０００−Ｈ〕
アントラセン型エポキシ樹脂〔ジャパンエポキシレジン（株）製、商品名：ＹＸ−８８００〕
Here, the epoxy resin used as the component (2) is as follows (Table 1 is described by trade name).
Bisphenol F type epoxy resin [made by Japan Epoxy Resin Co., Ltd., trade name: EP806]
Phenol novolac type epoxy resin [Dainippon Ink Chemical Co., Ltd., trade name, N-770]
Bifunctional naphthalene type epoxy resin [Dainippon Ink Chemical Co., Ltd., trade name, HP-4032D]
Naphthol aralkyl-type epoxy resin [manufactured by Toto Kasei Co., Ltd., trade name: ESN-175]
Bifunctional naphthalene aralkyl type epoxy resin [manufactured by Toto Kasei Co., Ltd., trade name: ESN-375]
Biphenyl type epoxy resin [made by Japan Epoxy Resin Co., Ltd., trade name: YX-4000]
Biphenyl aralkyl type epoxy resin [made by Nippon Kayaku Co., Ltd., trade name: NC-3000-H]
Anthracene type epoxy resin [Japan Epoxy Resin Co., Ltd., trade name: YX-8800]
（３）成分として使用したエポキシ樹脂の硬化剤は以下の通り（同上）。
クレゾールノボラック樹脂〔大日本インキ化学工業（株）製、商品名：ＫＡ−１１６５〕
フェノールアラルキル樹脂〔明和化成（株）製、商品名：ＭＥＨ−７８００〕
サリチルアルデヒドノボラック樹脂〔明和化成（株）製、商品名：ＭＥＨ−７５００〕
アミノトリアジンノボラック樹脂〔大日本インキ化学工業（株）製、商品名：ＬＡ−３０１８〕
ジシアンジアミド〔大栄化学工業（株）製、ジシアンジアミド〕、
(3) The epoxy resin curing agent used as a component is as follows (same as above).
Cresol novolak resin [Dainippon Ink Chemical Co., Ltd., trade name: KA-1165]
Phenol aralkyl resin [Maywa Kasei Co., Ltd., trade name: MEH-7800]
Salicylaldehyde novolak resin [Madewa Kasei Co., Ltd., trade name: MEH-7500]
Aminotriazine novolak resin [Dainippon Ink Chemical Co., Ltd., trade name: LA-3018]
Dicyandiamide (Daiyan Chemical Industry Co., Ltd., Dicyandiamide),
また、比較例１〜６では、比較製造例１〜４で得られた化合物含有溶液を使用し、表２に示した配合割合（質量部）で混合して樹脂分６５質量％の均一なワニスを作製した。 Moreover, in Comparative Examples 1-6, the compound containing solution obtained by the comparative manufacture examples 1-4 was used, it mixed by the mixture ratio (mass part) shown in Table 2, and the uniform varnish whose resin content is 65 mass% Was made.
これらのワニスをＰＥＴフィルム上に塗工し、１６０℃で１０分間乾燥させて、半硬化状態とし、膜厚１３０±５μｍの樹脂付フィルムを作製した。樹脂付フィルムから半硬化した樹脂を採取して粉末にした。半硬化樹脂の粉末から、次の手順で樹脂板を作製した。
スペーサ及び離型シートとして、樹脂板の型として３０ｍｍ角に穴あけをしたフッ素樹脂シートを配置し、この中に樹脂粉を入れ、この上下に銅箔を配置して、１８５℃、９０分、２．５ＭＰａのプレス条件で硬化させた。その後銅箔をエッチング除去し、樹脂板はフッ素樹脂シートから剥がして、厚さ１．０ｍｍの熱膨張率測定用樹脂板を作製した。
このようにして得られた熱膨張率測定用樹脂板を用いて、熱膨張率について前記の方法で測定・評価した。評価結果を、表１と表２に示す。
These varnishes were coated on a PET film and dried at 160 ° C. for 10 minutes to obtain a semi-cured state, thereby producing a film with a resin having a film thickness of 130 ± 5 μm. A semi-cured resin was collected from the film with resin and powdered. A resin plate was prepared from the semi-cured resin powder by the following procedure.
As a spacer and a release sheet, a fluororesin sheet having a hole of 30 mm square is placed as a mold of a resin plate, resin powder is put therein, and copper foil is placed above and below this, at 185 ° C., 90 minutes, 2 Cured under 5 MPa pressing conditions. Thereafter, the copper foil was removed by etching, and the resin plate was peeled off from the fluororesin sheet to produce a resin plate for measuring a coefficient of thermal expansion having a thickness of 1.0 mm.
Using the thus obtained thermal expansion coefficient measuring resin plate, the thermal expansion coefficient was measured and evaluated by the method described above. The evaluation results are shown in Tables 1 and 2.
実施例１６〜３０、比較例７〜１２
実施例１６〜３０として、上記実施例１〜１５の樹脂配合に、さらに（４）成分の無機充填材として、水酸化アルミニウム〔昭和電工（株）製、商品名：ＨＰ−３６０〕と、溶融シリカ〔アドマテック（株）製、商品名：ＳＣ２０５０−ＫＣ〕、また希釈溶剤にメチルエチルケトンを使用して、表３に示した配合割合（質量部）で混合して、樹脂分６５ｗｔ％の均一なワニスを作製した。
一方、比較例７〜１２として、比較例１〜６の樹脂配合を用いて、表４に示した配合割合（質量部）で混合して樹脂分６５質量％の均一なワニスを作製した。
次に、上記ワニスを厚さ０．１ｍｍのＥガラスクロスに含浸塗工し、１６０℃で１０分加熱乾燥して樹脂含有量５０重量％のプリプレグを得た。次に、このプリプレグを４枚重ね、１８μｍの電解銅箔を上下に配置し、圧力２５Ｋｇ/ｃｍ2、温度１８５℃で９０分間プレスを行って、銅張積層板を得た。
このようにして得られた銅張積層板を用いて、銅箔接着性（銅箔ピール強度）、ガラス転移温度、はんだ耐熱性、吸湿性（吸水率）、難燃性、比誘電率（１ＧＨｚ）、及び誘電正接（１ＧＨｚ）について、前記の方法で測定・評価した。評価結果を表３と表４に示す。
Examples 16-30, Comparative Examples 7-12
As Examples 16 to 30, the resin blends of Examples 1 to 15 above, and as an inorganic filler of the component (4), aluminum hydroxide [manufactured by Showa Denko KK, trade name: HP-360] and melting Silica (manufactured by Admatech Co., Ltd., trade name: SC2050-KC), and methyl ethyl ketone as a diluent solvent, mixed at a blending ratio (parts by mass) shown in Table 3, and a uniform varnish with a resin content of 65 wt% Was made.
On the other hand, as Comparative Examples 7 to 12, the resin blends of Comparative Examples 1 to 6 were mixed at the blending ratio (parts by mass) shown in Table 4 to prepare uniform varnishes having a resin content of 65% by weight.
Next, the varnish was impregnated and applied to an E glass cloth having a thickness of 0.1 mm and dried by heating at 160 ° C. for 10 minutes to obtain a prepreg having a resin content of 50% by weight. Next, four prepregs were stacked, 18 μm electrolytic copper foils were placed one above the other, and pressed at a pressure of 25 kg / cm 2 and a temperature of 185 ° C. for 90 minutes to obtain a copper clad laminate.
Using the copper-clad laminate thus obtained, copper foil adhesion (copper foil peel strength), glass transition temperature, solder heat resistance, moisture absorption (water absorption), flame retardancy, relative dielectric constant (1 GHz ) And dielectric loss tangent (1 GHz) were measured and evaluated by the methods described above. The evaluation results are shown in Tables 3 and 4.
表１及び表３から、本発明に係る表1及び表３の実施例の熱硬化性絶縁樹脂組成物では、表２及び表４の比較例の熱硬化性絶縁樹脂組成物と比べて、ガラス転移温度（Ｔｇ）が高く、耐熱性が優れ、かつ低熱膨張性であることがわかる。 From Table 1 and Table 3, in the thermosetting insulating resin composition of the Example of Table 1 and Table 3 which concerns on this invention, compared with the thermosetting insulating resin composition of the comparative example of Table 2 and Table 4, it is glass. It can be seen that the transition temperature (Tg) is high, the heat resistance is excellent, and the thermal expansion is low.
Claims (20)
（ａ）分子骨格中にＳ原子を有する芳香族ジアミン化合物
（ｂ）分子構造中に少なくとも２個のＮ−置換マレイミド基を有するマレイミド化合物
（ｃ）モノアミン化合物 A thermosetting insulating resin composition comprising a compound (1) having an S atom in a molecular skeleton obtained by reacting the following compounds (a), (b), and (c): .
(A) aromatic diamine compound having S atom in molecular skeleton (b) maleimide compound having at least two N-substituted maleimide groups in molecular structure (c) monoamine compound
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010235690A (en) * | 2009-03-30 | 2010-10-21 | Hitachi Chem Co Ltd | Thermosetting insulating resin composition, and insulating film with support, prepreg, laminated board and multilayer printed wiring board using the same |
| JP2011052188A (en) * | 2009-09-04 | 2011-03-17 | Hitachi Chem Co Ltd | Thermosetting insulating resin composition and insulating film with substrate, prepreg, laminated board, and multilayer printed wiring board using the same |
| JP2011052184A (en) * | 2009-09-04 | 2011-03-17 | Hitachi Chem Co Ltd | Thermosetting insulating resin composition and insulating film with substrate using the same, prepreg, laminated board, and multilayer printed circuit board |
| JP2011052183A (en) * | 2009-09-04 | 2011-03-17 | Hitachi Chem Co Ltd | Thermosetting insulating resin composition and insulating film with substrate using the same, prepreg, laminated board, and multilayer printed circuit board |
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| JP2014019795A (en) * | 2012-07-18 | 2014-02-03 | Hitachi Chemical Co Ltd | Thermosetting resin composition, and prepreg, laminate and printed wiring board using the same |
| JP2014019796A (en) * | 2012-07-18 | 2014-02-03 | Hitachi Chemical Co Ltd | Thermosetting resin composition, and prepreg, laminate and printed wiring board using the same |
| JP2014024925A (en) * | 2012-07-25 | 2014-02-06 | Hitachi Chemical Co Ltd | Thermosetting resin composition and prepreg, laminate sheet, and print wire board using the same |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4919120B1 (en) * | 1970-12-30 | 1974-05-15 | ||
| JPS62132915A (en) * | 1985-12-04 | 1987-06-16 | Toshiba Chem Corp | Heat-resistant resin composition for molding |
| JPH01294736A (en) * | 1988-05-23 | 1989-11-28 | Mitsubishi Petrochem Co Ltd | Heat-resistant resin composition |
| JPH0297515A (en) * | 1989-08-21 | 1990-04-10 | E I Du Pont De Nemours & Co | Composition for manufacture of circuit board |
| JPH02147636A (en) * | 1988-07-21 | 1990-06-06 | Kanebo Ltd | Prepreg sheet and preparation thereof |
| JPH02272028A (en) * | 1989-04-14 | 1990-11-06 | Mitsui Toatsu Chem Inc | Thermosetting resin composition |
| JPH05170951A (en) * | 1991-12-25 | 1993-07-09 | Hitachi Chem Co Ltd | Production of polyaminobismaleimide prepreg |
| JPH08143670A (en) * | 1994-11-24 | 1996-06-04 | Showa Highpolymer Co Ltd | Heat resistant resin composition |
-
2009
- 2009-07-15 JP JP2009166977A patent/JP5499544B2/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4919120B1 (en) * | 1970-12-30 | 1974-05-15 | ||
| JPS62132915A (en) * | 1985-12-04 | 1987-06-16 | Toshiba Chem Corp | Heat-resistant resin composition for molding |
| JPH01294736A (en) * | 1988-05-23 | 1989-11-28 | Mitsubishi Petrochem Co Ltd | Heat-resistant resin composition |
| JPH02147636A (en) * | 1988-07-21 | 1990-06-06 | Kanebo Ltd | Prepreg sheet and preparation thereof |
| JPH02272028A (en) * | 1989-04-14 | 1990-11-06 | Mitsui Toatsu Chem Inc | Thermosetting resin composition |
| JPH0297515A (en) * | 1989-08-21 | 1990-04-10 | E I Du Pont De Nemours & Co | Composition for manufacture of circuit board |
| JPH05170951A (en) * | 1991-12-25 | 1993-07-09 | Hitachi Chem Co Ltd | Production of polyaminobismaleimide prepreg |
| JPH08143670A (en) * | 1994-11-24 | 1996-06-04 | Showa Highpolymer Co Ltd | Heat resistant resin composition |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010235690A (en) * | 2009-03-30 | 2010-10-21 | Hitachi Chem Co Ltd | Thermosetting insulating resin composition, and insulating film with support, prepreg, laminated board and multilayer printed wiring board using the same |
| JP2011052188A (en) * | 2009-09-04 | 2011-03-17 | Hitachi Chem Co Ltd | Thermosetting insulating resin composition and insulating film with substrate, prepreg, laminated board, and multilayer printed wiring board using the same |
| JP2011052184A (en) * | 2009-09-04 | 2011-03-17 | Hitachi Chem Co Ltd | Thermosetting insulating resin composition and insulating film with substrate using the same, prepreg, laminated board, and multilayer printed circuit board |
| JP2011052183A (en) * | 2009-09-04 | 2011-03-17 | Hitachi Chem Co Ltd | Thermosetting insulating resin composition and insulating film with substrate using the same, prepreg, laminated board, and multilayer printed circuit board |
| JP2011252949A (en) * | 2010-05-31 | 2011-12-15 | Nikon Corp | Paint for optical element, film, optical element and optical instrument |
| JP2012056994A (en) * | 2010-09-06 | 2012-03-22 | Sumitomo Bakelite Co Ltd | Prepreg, metal-clad laminate, printed wiring board, and semiconductor device |
| JP2014019795A (en) * | 2012-07-18 | 2014-02-03 | Hitachi Chemical Co Ltd | Thermosetting resin composition, and prepreg, laminate and printed wiring board using the same |
| JP2014019796A (en) * | 2012-07-18 | 2014-02-03 | Hitachi Chemical Co Ltd | Thermosetting resin composition, and prepreg, laminate and printed wiring board using the same |
| JP2014024925A (en) * | 2012-07-25 | 2014-02-06 | Hitachi Chemical Co Ltd | Thermosetting resin composition and prepreg, laminate sheet, and print wire board using the same |
| JP2015146386A (en) * | 2014-02-03 | 2015-08-13 | 住友ベークライト株式会社 | Heat conductive sheet and semiconductor device |
| US9859189B2 (en) | 2014-02-03 | 2018-01-02 | Sumitomo Bakelite Co., Ltd. | Thermally conductive sheet and semiconductor device |
| JP2021167422A (en) * | 2017-03-31 | 2021-10-21 | 昭和電工マテリアルズ株式会社 | Epoxy resin composition, epoxy resin cured product, and electronic component device |
| JP7338661B2 (en) | 2017-03-31 | 2023-09-05 | 株式会社レゾナック | Epoxy resin composition, cured epoxy resin and electronic component device |
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