JP5195582B2 - Thermosetting insulating resin composition, and insulating film with support, prepreg, laminate and multilayer printed wiring board using the same - Google Patents
Thermosetting insulating resin composition, and insulating film with support, prepreg, laminate and multilayer printed wiring board using the same Download PDFInfo
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- JP5195582B2 JP5195582B2 JP2009082884A JP2009082884A JP5195582B2 JP 5195582 B2 JP5195582 B2 JP 5195582B2 JP 2009082884 A JP2009082884 A JP 2009082884A JP 2009082884 A JP2009082884 A JP 2009082884A JP 5195582 B2 JP5195582 B2 JP 5195582B2
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- insulating resin
- resin composition
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- compound
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- 239000011342 resin composition Substances 0.000 title claims description 57
- 229920001187 thermosetting polymer Polymers 0.000 title claims description 29
- -1 N-substituted maleimide group Chemical group 0.000 claims description 79
- 229920005989 resin Polymers 0.000 claims description 45
- 239000011347 resin Substances 0.000 claims description 45
- 229920000647 polyepoxide Polymers 0.000 claims description 44
- 239000003822 epoxy resin Substances 0.000 claims description 42
- 239000003795 chemical substances by application Substances 0.000 claims description 41
- 150000001875 compounds Chemical class 0.000 claims description 38
- 230000002378 acidificating effect Effects 0.000 claims description 25
- 125000001424 substituent group Chemical group 0.000 claims description 25
- 239000003960 organic solvent Substances 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 229910052698 phosphorus Inorganic materials 0.000 claims description 18
- 239000011574 phosphorus Substances 0.000 claims description 16
- 239000011256 inorganic filler Substances 0.000 claims description 14
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- 229910052717 sulfur Inorganic materials 0.000 claims description 14
- 125000004434 sulfur atom Chemical group 0.000 claims description 14
- 230000003014 reinforcing effect Effects 0.000 claims description 9
- 239000000835 fiber Substances 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 125000000732 arylene group Chemical group 0.000 claims description 4
- 125000004104 aryloxy group Chemical group 0.000 claims description 4
- 125000003700 epoxy group Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 58
- 238000000034 method Methods 0.000 description 38
- 239000002245 particle Substances 0.000 description 30
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 28
- 238000004519 manufacturing process Methods 0.000 description 28
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 20
- 229920001971 elastomer Polymers 0.000 description 18
- 239000000758 substrate Substances 0.000 description 17
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 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 14
- 239000000243 solution Substances 0.000 description 14
- 239000005060 rubber Substances 0.000 description 13
- 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 12
- 239000004020 conductor Substances 0.000 description 12
- 229910052802 copper Inorganic materials 0.000 description 12
- 239000010949 copper Substances 0.000 description 12
- 238000010992 reflux Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 11
- 229920003986 novolac Polymers 0.000 description 11
- 229910000679 solder Inorganic materials 0.000 description 11
- 239000002966 varnish Substances 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 10
- 239000011521 glass Substances 0.000 description 10
- 230000009477 glass transition Effects 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 9
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 8
- 229920000459 Nitrile rubber Polymers 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000004305 biphenyl Chemical group 0.000 description 8
- 235000010290 biphenyl Nutrition 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-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
- 238000001035 drying Methods 0.000 description 8
- 230000001965 increasing effect Effects 0.000 description 8
- 238000010030 laminating Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000007747 plating Methods 0.000 description 8
- 238000007788 roughening Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 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 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
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 6
- 230000001681 protective effect Effects 0.000 description 6
- 125000001174 sulfone group Chemical group 0.000 description 6
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 229920001721 polyimide Polymers 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-UHFFFAOYSA-N 0.000 description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- 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 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 4
- 239000004642 Polyimide Substances 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- 239000011354 acetal resin 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
- 239000011258 core-shell material Substances 0.000 description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 125000001624 naphthyl group Chemical group 0.000 description 4
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920006324 polyoxymethylene Polymers 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- QQOWHRYOXYEMTL-UHFFFAOYSA-N triazin-4-amine Chemical compound N=C1C=CN=NN1 QQOWHRYOXYEMTL-UHFFFAOYSA-N 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 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 3
- 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 3
- 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 3
- 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 3
- 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 3
- 229920002799 BoPET Polymers 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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-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
- 238000000576 coating method Methods 0.000 description 3
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- 150000002460 imidazoles Chemical class 0.000 description 3
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- 238000003475 lamination Methods 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
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- 150000003457 sulfones Chemical class 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- 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
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-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
- JYLNVJYYQQXNEK-UHFFFAOYSA-N 3-amino-2-(4-chlorophenyl)-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(CN)C1=CC=C(Cl)C=C1 JYLNVJYYQQXNEK-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
- 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 2
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
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- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
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- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
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- 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
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- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OSNIIMCBVLBNGS-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-2-(dimethylamino)propan-1-one Chemical compound CN(C)C(C)C(=O)C1=CC=C2OCOC2=C1 OSNIIMCBVLBNGS-UHFFFAOYSA-N 0.000 description 1
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- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
- Epoxy Resins (AREA)
Description
本発明は、ガラス転移温度が高くて耐熱性に優れ、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支持体付絶縁フィルム、プリプレグ、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 having a high glass transition temperature, excellent heat resistance, and low thermal expansion, and an insulating film with a support, a prepreg, a laminate and a multilayer printed wiring board using the same. .
近年、電子機器の小型化、軽量化、多機能化が一段と進み、これに伴い、ＬＳＩやチップ部品等の高集積化が進みその形態も多ピン化、小型化へと急速に変化している。このため多層プリント配線板は、電子部品の実装密度を向上するために、微細配線化の開発が進められている。
これらの要求に合致する多層プリント配線板の製造方法として、ビルドアップ方式があり、軽量化や小型化、微細化に適した手法として主流になりつつある。
In recent years, electronic devices have become smaller, lighter, and more functional, and along with this, higher integration of LSIs and chip components has progressed, and the form has rapidly changed to multi-pin and miniaturization. . For this reason, in order to improve the mounting density of electronic components, the development of micro wiring has been advanced for multilayer printed wiring boards.
As a method for producing a multilayer printed wiring board meeting these requirements, there is a build-up method, which is becoming mainstream as a method suitable for weight reduction, miniaturization, and miniaturization.
また、環境意識の高まりから燃焼時に有害な物質を発生する可能性がある材料は電子部品も含めて規制する動きが活発になっている。従来の多層プリント配線板には、難燃化のためにブロム化合物が使用されてきたが、燃焼時に有害な物質を発生する可能性があるので、近い将来にこのブロム化合物使用できなくなるものと予想される。
電子部品を多層プリント配線板に接続するために一般的に用いられるはんだも鉛を有さない鉛フリーはんだが実用化されつつある。この鉛フリーはんだは、従来の共晶はんだよりも使用温度が約２０〜３０℃高くなることから従来にも増して材料には高い耐熱性が必要になっている。
In addition, there is an active movement to regulate materials including electronic parts that may generate harmful substances during combustion due to increased environmental awareness. Bromine compounds have been used in conventional multilayer printed wiring boards to make them flame retardant. However, since they may generate harmful substances during combustion, it is expected that they will not be used in the near future. Is done.
Lead-free solder that does not contain lead is also being put into practical use as a solder generally used for connecting electronic components to a multilayer printed wiring board. This lead-free solder has a higher use temperature than conventional eutectic solder by about 20 to 30 ° C. Therefore, the material is required to have higher heat resistance than ever before.
さらに、前記ビルドアップ構造の多層プリント配線板において、高密度化をするために層数の増加と共に、ビア部分のフィルド化、スタック化が進んでいる。しかしながら、多層プリント配線板の薄型化のためにガラスクロスを含まない絶縁樹脂層は、熱膨脹率が大きい傾向を示すため、フィルド化、スタック化したビアの銅との熱膨張率の差が、接続信頼性に大きく影響し，信頼性の懸念材料になっている。このようなことから、絶縁樹脂層には熱膨脹率の小さい材料が要求されるようになってきた。 Furthermore, in the multilayer printed wiring board having the build-up structure, in order to increase the density, the number of layers is increased and the via portion is filled and stacked. However, insulation resin layers that do not contain glass cloth tend to have a large coefficient of thermal expansion for the purpose of reducing the thickness of multilayer printed wiring boards, so the difference in coefficient of thermal expansion with copper in filled and stacked vias It greatly affects reliability and is a concern for reliability. For this reason, a material having a low coefficient of thermal expansion has been required for the insulating resin layer.
絶縁樹脂層において熱膨脹率を小さくするには、一般に熱膨脹率の小さい無機フィラーを多量に充填し、絶縁層全体の熱膨張率を低下させる方法が用いられてきた（例えば、特許文献１参照）。しかし、このような方法では、流動性の低下や、絶縁信頼性の低下など、多くの問題が発生し易い。
また、樹脂の選択又は改良により、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あるが（特許文献２参照）、充填材を８０〜９２．５容量％配合している。また、配線板用の樹脂組成物の低熱膨張率化は、従来、架橋密度を高め、ガラス転移温度（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４参照）。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必要があるが、一定以上分子鎖を短くすることは反応性や樹脂強度等の点から困難である。
In order to reduce the thermal expansion coefficient in the insulating resin layer, generally, a method of filling a large amount of an inorganic filler having a small thermal expansion coefficient and reducing the thermal expansion coefficient of the entire insulating layer has been used (for example, see Patent Document 1). However, such a method tends to cause many problems such as a decrease in fluidity and a decrease in insulation reliability.
In addition, attempts have been made to achieve low thermal expansion by selecting or improving the resin. For example, as an example of an epoxy resin having an aromatic ring, there is a resin composition for low thermal expansion pressure molding using an epoxy resin having a bifunctional naphthalene skeleton or a biphenyl skeleton (see Patent Document 2). 80 to 92.5% by volume. Moreover, conventionally, a method for reducing the thermal expansion coefficient of a resin composition for a wiring board is generally a method in which the thermal expansion coefficient is reduced by increasing the crosslinking density and increasing the glass transition temperature (Tg) (Patent Document 3 and 4). However, increasing the crosslink density requires shortening the molecular chain between the functional groups, but shortening the molecular chain beyond a certain level is difficult in terms of reactivity and resin strength.
さらに、耐熱性、低熱膨張に有用であると考えられるイミド骨格の導入も試みられており、例えば、イミド基を有する芳香族ジアミンとエポキシ樹脂を用いたビルトアップ用熱硬化性組成物が提案されている（特許文献５参照）。しかし、低分子ポリイミド化合物をエポキシ樹脂の硬化剤として用いた場合、その殆どがエポキシ樹脂の特性と変わらない場合が多い。 Furthermore, introduction of an imide skeleton, which is considered to be useful for heat resistance and low thermal expansion, has been attempted. For example, a thermosetting composition for build-up using an aromatic diamine having an imide group and an epoxy resin has been proposed. (See Patent Document 5). However, when a low molecular weight polyimide compound is used as a curing agent for an epoxy resin, most of them are not different from the characteristics of the epoxy resin in many cases.
本発明の目的は、以上のような状況から、ガラス転移温度が高くて耐熱性に優れ、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支持体付絶縁フィルム、プリプレグ、積層板及び多層プリント配線板を提供することである。 An object of the present invention is to provide a thermosetting insulating resin composition having a high glass transition temperature, excellent heat resistance, and low thermal expansion, as well as an insulating film with a support and a prepreg using the same. It is to provide a laminated board and a multilayer printed wiring board.
本発明は、上記の課題を解決するために鋭意研究した結果、多層プリント配線板用絶縁樹脂組成物として、分子主鎖中に硫黄原子を有するジアミン化合物とマレイミド化合物及びモノアミン化合物を有機溶媒中で反応させて得られた酸性置換基及びＮ−置換マレイミド基を有する硬化剤と、エポキシ樹脂及びリン化合物を含有する樹脂組成物を使用することにより、ガラス転移温度が高くて耐熱性に優れ、かつ低熱膨張性である硬化性絶縁樹脂組成物が得られ、多層プリント配線板などに好適に使用できることを見出し、本発明を完成した。 As a result of diligent research to solve the above problems, the present invention, as an insulating resin composition for multilayer printed wiring boards, comprises a diamine compound having a sulfur atom in the molecular main chain, a maleimide compound, and a monoamine compound in an organic solvent. By using a curing agent having an acidic substituent and an N-substituted maleimide group obtained by the reaction, and a resin composition containing an epoxy resin and a phosphorus compound, the glass transition temperature is high and the heat resistance is excellent, and A curable insulating resin composition having low thermal expansion was obtained, and it was found that it could be suitably used for multilayer printed wiring boards and the like, and the present invention was completed.
すなわち、本発明は、以下の熱硬化性絶縁樹脂組成物、並びにこれを用いた支持体付絶縁フィルム、プリプレグ、積層板及びプリント配線板を提供するものである。
１．下記の(ａ)、（ｂ）及び（ｃ）を有機溶媒中で反応させて得られる、分子主鎖中に硫黄原子を有し、酸性置換基及びＮ−置換マレイミド基を有する硬化剤（Ａ）、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（Ｂ）及び難燃性を付与するリン化合物（Ｃ）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）分子主鎖中に硫黄原子を有するジアミン化合物、
（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．前記（ａ）の化合物が下式（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の熱硬化性絶縁樹脂組成物。
That is, the present invention provides the following thermosetting insulating resin composition, and an insulating film with a support, a prepreg, a laminate and a printed wiring board using the same.
1. Curing agent (A) obtained by reacting the following (a), (b) and (c) in an organic solvent, having a sulfur atom in the molecular main chain, and having an acidic substituent and an N-substituted maleimide group ) A thermosetting insulating resin composition comprising an epoxy resin (B) having at least two epoxy groups in one molecule and a phosphorus compound (C) imparting flame retardancy.
(A) a diamine compound having a sulfur atom in the molecular main chain,
(B) a maleimide compound having at least two N-substituted maleimide groups in the molecular structure;
(C) Monoamine compound The thermosetting insulating resin composition according to 1 above, wherein the compound (a) is a compound represented by the following formula (I) or the following formula (II), or diaminodimethyldibenzothiophenesulfone.
（式中、Ｒ1及びＲ2は各々独立に、ハロゲン原子、炭素数１〜３のアルキル基、水酸基、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ル基などで置換されてもよい。ｘ、ｙは各々独立に０〜４の整数であり、ｐ、ｑは０または１である。Ａは−Ｓ−、−ＳＯ2−、−Ｓ−Ｓ−から選ばれる硫黄原子含有基である。） (In the formula, R 1 and R 2 each independently represent a halogen atom, an alkyl group having 1 to 3 carbon atoms, a hydroxyl group, a carboxy group, or a sulfonic acid group. M represents an alkoxylene 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. It may be substituted with an alkyl group, etc. x and y are each independently an integer of 0 to 4, and p and q are 0 or 1. A is —S—, —SO 2 —, —S—S. A sulfur atom-containing group selected from-.
３．さらに、エポキシ樹脂の硬化剤及び／又は硬化促進剤（Ｄ）を含有する上記１又は２の熱硬化性絶縁樹脂組成物。
４．さらに、化学粗化可能な化合物（Ｅ）を含有する上記１〜３のいずれかの熱硬化性絶縁樹脂組成物。
５．固形分換算の（Ａ）〜(Ｄ)成分の合計量１００質量部に対し、１０〜５０質量部の無機充填材（Ｆ）を含有する上記１〜４のいずれかの熱硬化性絶縁樹脂組成物。
６．上記１〜５のいずれかの熱硬化性絶縁樹脂組成物の半硬化状態のフィルムが支持体表面に形成されていることを特徴とする支持体付絶縁フィルム。
７．上記１〜５のいずれかの熱硬化性絶縁樹脂組成物が繊維シート状補強基材中に含侵されていることを特徴とするプリプレグ。
８．絶縁樹脂層が、（１）上記１〜５のいずれかの熱硬化性絶縁樹脂組成物、（２）上記６の支持体付絶縁フィルム、（３）上記７のプリプレグの何れかを用いて形成されたものであることを特徴とする多層プリント配線板。
９． 上記８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。
3. Furthermore, the said 1 or 2 thermosetting insulating resin composition containing the hardening | curing agent and / or hardening accelerator (D) of an epoxy resin.
4). Furthermore, the thermosetting insulating resin composition in any one of said 1-3 containing the compound (E) which can be chemically roughened.
5. The thermosetting insulating resin composition according to any one of 1 to 4 above, containing 10 to 50 parts by mass of the inorganic filler (F) with respect to 100 parts by mass of the total amount of the components (A) to (D) in terms of solid content. object.
6). A semi-cured film of the thermosetting insulating resin composition according to any one of 1 to 5 above is formed on a support surface.
7). A prepreg characterized in that the thermosetting insulating resin composition of any one of 1 to 5 is impregnated in a fiber sheet-like reinforcing base material.
8). An insulating resin layer is formed using any one of (1) the thermosetting insulating resin composition according to any one of 1 to 5 above, (2) the insulating film with support according to 6 above, and (3) the prepreg according to 7 above. A multilayer printed wiring board characterized by being made.
9. A multilayer printed wiring board produced by using the laminated board of 8 above.
本発明の熱硬化性絶縁樹脂組成物は、上記のように、分子主鎖中に硫黄原子を有し、酸性置換基及び不飽和Ｎ−置換マレイミド基を有する化合物を含む硬化剤（Ａ）、エポキシ樹脂（Ｂ）及び難燃性を付与するリン化合物（Ｃ）を含有することにより、特にガラス転移温度（Ｔｇ）が高いので耐熱性に優れ、且つ低熱膨張性を有し、優れた銅箔ピール強度を示す絶縁樹脂層を形成することができ、該熱硬化性絶縁樹脂組成物及びこれを用いた支持体付絶縁フィルム、プリプレグより製造される積層板及び多層プリント配線板は、はんだ耐熱性、銅付き耐熱性（Ｔ−２８８）、耐湿性及び難燃性の全てにバランスが取れて高信頼性を有し、電子部品等に好適な製品が得られる。 As described above, the thermosetting insulating resin composition of the present invention has a sulfur atom in the molecular main chain, and includes a curing agent (A) containing a compound having an acidic substituent and an unsaturated N-substituted maleimide group, By including the epoxy resin (B) and the phosphorus compound (C) that imparts flame retardancy, the glass transition temperature (Tg) is particularly high, so it has excellent heat resistance and low thermal expansion, and an excellent copper foil An insulating resin layer exhibiting peel strength can be formed. The thermosetting insulating resin composition, an insulating film with a support using the same, a laminated board manufactured from a prepreg, and a multilayer printed wiring board have solder heat resistance. Moreover, the heat resistance with copper (T-288), the moisture resistance and the flame retardance are all balanced and highly reliable, and a product suitable for an electronic component or the like can be obtained.
以下、本発明について詳細に説明する。
本発明に係る熱硬化性絶縁樹脂組成物（以下、単に絶縁樹脂組成物とも云う）は、酸性置換基及びＮ−置換マレイミド基を有する硬化剤（Ａ）、エポキシ樹脂（Ｂ）及びリン化合物（Ｃ）、さらに、所望により、エポキシ樹脂の硬化剤及び／又は硬化促進剤（Ｄ）、化学粗化可能な化合物（Ｅ）及び無機充填剤（Ｆ）を含有するものである。
Hereinafter, the present invention will be described in detail.
The thermosetting insulating resin composition according to the present invention (hereinafter also simply referred to as an insulating resin composition) includes a curing agent (A) having an acidic substituent and an N-substituted maleimide group, an epoxy resin (B), and a phosphorus compound ( C), and optionally, a curing agent and / or a curing accelerator (D) of an epoxy resin, a compound (E) that can be chemically roughened, and an inorganic filler (F).
先ず、本発明に用いられる硬化剤（Ａ）には、下記の（ａ）、（ｂ）、及び（ｃ）の化合物を有機溶媒中で必要により加熱・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、分子主鎖中に硫黄原子を有し、酸性置換基及び不飽和Ｎ−置換マレイミド基を有する化合物が使用される。
（ａ）分子主鎖中に硫黄原子を有するジアミン化合物、
（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
なお、（ａ）、（ｂ）、及び（ｃ）の化合物の少なくとも一つに酸性置換基を含有する化合物を使用する。
First, the curing agent (A) used in the present invention is obtained by stirring and reacting the following compounds (a), (b), and (c) in an organic solvent, if necessary, while heating and keeping warm. A compound having a sulfur atom in the molecular main chain and having an acidic substituent and an unsaturated N-substituted maleimide group is used.
(A) a diamine compound having a sulfur atom in the molecular main chain,
(B) a maleimide compound having at least two N-substituted maleimide groups in the molecular structure;
(C) Monoamine compound In addition, the compound containing an acidic substituent is used for at least one of the compounds of (a), (b), and (c).
上記（ａ）の化合物は、分子骨格中に−Ｓ−、−ＳＯ2−、または−Ｓ−Ｓ−、の硫黄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、ハロゲン原子、炭素数１〜３のアルキル基、水酸基、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ル基などで置換されてもよい。ｘ、ｙは各々独立に０〜４の整数であり、ｐ、ｑは０または１である。Ａは−Ｓ−、−ＳＯ2−、−Ｓ−Ｓ−から選ばれる硫黄原子含有基である。
ここで、炭素数１〜５のアルコキシレン基としては、メトキシレン基、エトキシレン基などが挙げられる。炭素数６〜１４のアリーレン基としてはフェニレン基、ナフチレン基が挙げられる。炭素数６〜１４のアリール基としては、フェニル基、ナフチル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 a sulfur atom of —S—, —SO 2 —, or —S—S— 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 halogen atom, an alkyl group having 1 to 3 carbon atoms, a hydroxyl group, a carboxy group, or a sulfonic acid group. M represents an alkoxylene group having 1 to 5 carbon atoms or an arylene 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 0 to 4, and p and q are 0 or 1. A is a sulfur atom-containing group selected from —S—, —SO 2 —, and —S—S—.
Here, as a C1-C5 alkoxylene group, a methoxylene group, an ethoxylene group, etc. are mentioned. Examples of the arylene group having 6 to 14 carbon atoms include a phenylene group and a naphthylene group. Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group and a naphthyl 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、良好な反応性や耐熱性を有するビス（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）スルフィドが特に好ましい。
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-aminophenoxypheny ) Such as diphenyl sulfone can be mentioned.
Among these, bis (4-aminophenyl) sulfone, bis (3-aminophenyl) sulfone, bis (4-aminophenyl) sulfide, bis (3-aminophenyl) sulfide having good reactivity and heat resistance, 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 More preferred are bis (4-aminophenyl) sulfone, bis (4-aminophenyl) sulfide, 4,4′-dithiodianiline, and bis [4- (4-aminophenoxy) phenyl] sulfone having expandability, and to the solvent. From the solubility point of bis (4-aminophenyl) sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, 4,4′-di Ojianirin, bis (4-aminophenyl) sulfide are especially preferred.
本発明に使用される（ｂ）の化合物である、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、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。 The maleimide compound having at least two unsaturated N-substituted maleimide groups in the molecular structure, which is the compound (b) used in the present invention, is, for example, N, N′-ethylenebismaleimide, 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-maleimidopheny ) 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) pheny Ru] ethane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] propane, 2,2-bis [4- (4-maleimidophenoxy) 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, '-Bis (4-maleimidophenyl) disulfide, bis (4-maleimidophenyl) disulfide, bis [4- (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-di Tylbenzyl] benzene, 1,4-bis [4- (3-maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 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, polyphenylmethanemaleimide, and the like. These maleimide compounds may be used alone or in combination of two or more. It can have.
これらの中で、反応率が高く、より高耐熱性化できるビス（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。 Among these, bis (4-maleimidophenyl) methane, bis (4-maleimidophenyl) sulfone, bis (4-maleimidophenyl) sulfide, bis (4-maleimidophenyl) with high reaction rate and higher heat resistance Disulfide, N, N ′-(1,3-phenylene) bismaleimide, 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane are preferred, and bis (4-maleimidophenyl) methane is preferred because it is inexpensive. N, N ′-(1,3-phenylene) bismaleimide is more preferable, and bis (4-maleimidophenyl) methane is particularly preferable 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、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。
The monoamine compound, which is the compound (c) used in the present invention, is a monoamine compound having an acidic substituent when the component (a) or (b) does not have an acidic substituent in the molecular structure; To do. 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-) aminophenol is 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等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、シクロヘキサノン等のケトン系溶剤、酢酸エチルエステルやγ−ブチロラクトン等のエステル系溶剤、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、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原子含有溶剤、ジメチルスルホキシド等の硫黄原子含有溶剤等が挙げられ、１種又は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 in this reaction is not particularly limited, but alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, and ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Ester solvents such as ethyl acetate and γ-butyrolactone, ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene, mesitylene, nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, Examples include sulfur atom-containing solvents such as dimethyl sulfoxide, and one or two or more of them can be used in combination. 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）成分の総和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。
有機溶剤の配合量を２５〜１０００質量部とすることで、溶解性が不足しり、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 components (a), (b) and (c).
By setting the blending amount of the organic solvent to 25 to 1000 parts by mass, the solubility is insufficient and a long time is not required for synthesis.
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等があげられ、１種又は２種以上を混合して使用できる。
触媒の添加量は、（ｂ）のビス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 bismaleimide compound (b) and the monoamine compound (c).
分子主鎖中に硫黄原子を有し、酸性置換基及び不飽和Ｎ−置換マレイミド基を有する硬化剤（Ａ）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（ポリスチレンン換算）で測定される。 The weight average molecular weight of the curing agent (A) having a sulfur atom in the molecular main chain and having an acidic substituent and an unsaturated N-substituted maleimide group is 400 to 3500 from the viewpoint of solubility and mechanical strength. preferable. The weight average molecular weight in the present invention is measured by gel permeation chromatography (GPC) method (polystyrene conversion) using tetrahydrofuran as an eluent.
次に、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(Ｂ)は、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であれば特に限定されず、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等が挙げられ、１種又は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等が好ましく、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。
難燃性を付与するリン化合物（Ｃ）は、例えば、リン含有エポキシ樹脂、リン含有フェノール樹脂、フェノキシホスファゼン化合物、縮合型リン酸エステル化合物、ジホスフィン酸塩等が挙げられる。特にこれらを併用することが有効である。
Next, the epoxy resin (B) having at least two epoxy groups in one molecule is not particularly limited as long as it is an epoxy resin having at least two epoxy groups in one molecule. Bisphenol F, biphenyl, novolak, polyfunctional phenol, naphthalene, alicyclic and alcoholic glycidyl ethers, glycidyl amines and glycidyl ester types, etc. Can be used. Specifically, in terms of dielectric properties, heat resistance, moisture resistance and copper foil adhesion, bisphenol F type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene ring-containing epoxy resin, anthracene type epoxy resin, biphenyl type epoxy resin, 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 type from the viewpoint of good low thermal expansion and high glass transition temperature An epoxy resin, a biphenyl aralkyl type epoxy resin, and a phenol novolac type epoxy resin are more preferable.
Examples of the phosphorus compound (C) that imparts flame retardancy include a phosphorus-containing epoxy resin, a phosphorus-containing phenol resin, a phenoxyphosphazene compound, a condensed phosphate ester compound, and a diphosphinate. It is particularly effective to use these in combination.
本発明の硬化性絶縁樹脂組成物には、硬化剤（Ａ）以外にも任意にエポキシ樹脂硬化剤及び／又は硬化促進剤（Ｄ）を併用することができる。
エポキシ樹脂硬化剤としては、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等の酸無水物、ジシアンジアミド等のアミン化合物、フェノールノボラック、クレゾールノボラック、アミノトリアジンノボラック樹脂等のフェノール化合物等が挙げられる。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は１種又は２種以上を混合して使用できる。
また、硬化促進剤としては、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。
In addition to the curing agent (A), an epoxy resin curing agent and / or a curing accelerator (D) can be optionally used in the curable insulating resin composition of the present invention.
The epoxy resin curing agent is not particularly limited as long as it has a curing action of epoxy resin, but examples include acid anhydrides such as maleic anhydride and maleic anhydride copolymers, amine compounds such as dicyandiamide, Examples thereof include phenol compounds such as phenol novolac, cresol novolac, and aminotriazine novolac 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 as an optional component can be used alone or in combination of two or more.
Examples of the curing accelerator include imidazoles and derivatives thereof, tertiary amines and quaternary ammonium salts.
本発明の硬化性絶縁樹脂組成物は、固形分換算の（Ａ）〜（Ｄ）成分の合計量１００質量部として、次のようにすることが好ましい。
（Ａ）成分は２０〜９５質量部とすることが好ましく、４０〜９０質量部とすることがより好ましい。（Ｂ）成分は５〜８０質量部とすることが好ましく、５〜６０質量部とすることがより好ましい。（Ｄ）成分は０〜５０質量部とすることが好ましく、０〜３０質量部とすることがより好ましい。
The curable insulating resin composition of the present invention is preferably as follows as the total amount of 100 parts by mass of the components (A) to (D) in terms of solid content.
(A) It is preferable to set it as 20-95 mass parts, and it is more preferable to set it as 40-90 mass parts. (B) It is preferable to set it as 5-80 mass parts, and it is more preferable to set it as 5-60 mass parts. (D) It is preferable to set it as 0-50 mass parts, and it is more preferable to set it as 0-30 mass parts.
本発明の硬化性絶縁樹脂組成物における（Ｃ）成分は、（Ａ）〜（Ｄ）成分の合計量１００質量部当り、リン原子含有率が０．１〜３質量部であることが好ましく、０．２〜３．０質量部であることがより好ましく、０．５〜３．０質量部が特に好ましい。リン原子含有率が低いと難燃性が不足するため、（Ａ）成分の含有量を高くすることで窒素原子含有率を高くし、難燃性を付与する必要がある。
（Ａ）〜（Ｄ）成分の含有量を上記の範囲とすることで、本発明の特徴である、低熱膨張で耐熱性が高く、難燃性や吸湿性などでバランスが取れ、高信頼性を有する多層プリント配線板用の熱硬化性絶縁樹脂組成物が得られる。
The component (C) in the curable insulating resin composition of the present invention preferably has a phosphorus atom content of 0.1 to 3 parts by mass per 100 parts by mass of the total amount of the components (A) to (D). More preferably, it is 0.2-3.0 mass parts, and 0.5-3.0 mass parts is especially preferable. When the phosphorus atom content is low, the flame retardancy is insufficient, so it is necessary to increase the nitrogen atom content by increasing the content of the component (A) and to impart flame retardancy.
By setting the content of the components (A) to (D) within the above range, the characteristics of the present invention are low thermal expansion, high heat resistance, good balance between flame retardancy and hygroscopicity, and high reliability. A thermosetting insulating resin composition for multilayer printed wiring boards having the following is obtained.
本発明の熱硬化性絶縁樹脂組成物は、メッキ密着性の観点から、化学粗化可能な化合物（Ｅ）をさらに含有することが好ましい。化学粗化可能な化合物（Ｅ）は、デスミア処理によって、後述する絶縁層表面に微細な粗化形状が形成される化合物であれば特に問わないが、架橋ゴム粒子、ポリビニルアセタール樹脂が好ましく、最も好ましくは、架橋ゴム粒子である。 The thermosetting insulating resin composition of the present invention preferably further contains a chemical roughening compound (E) from the viewpoint of plating adhesion. The chemical roughening compound (E) is not particularly limited as long as it is a compound that forms a fine roughened shape on the surface of the insulating layer, which will be described later, by desmear treatment, but crosslinked rubber particles and polyvinyl acetal resins are preferred, Preferably, it is a crosslinked rubber particle.
上記の架橋ゴム粒子としては、コアシェル型ゴム粒子、架橋アクリロニトリルブタジエンゴム粒子、架橋スチレンブタジエンゴム粒子、アクリルゴム粒子などが挙げられる。コアシェル型ゴム粒子は、コア層とシェル層とを有するゴム粒子であり、例えば、外層のシェル層がガラス状ポリマーで構成され、内層のコア層がゴム状ポリマーで構成される２層構造、または外層のシェル層がガラス状ポリマーで構成され、中間層がゴム状ポリマーで構成され、コア層がガラス状ポリマーで構成される３層構造のものなどが挙げられる。ガラス層は、例えば、メタクリル酸メチルの重合物などで構成され、ゴム状ポリマー層は、例えば、ブチルアクリレート重合物（ブチルゴム）などで構成される。
コアシェル型ゴム粒子の具体例としては、スタフィロイドＡＣ３８３２、ＡＣ３８１６Ｎ〔以上、商品名、ガンツ化成（株）製〕、メタブレンＫＷ−４４２６〔商品名、三菱レイヨン（株）製〕、ＥＸＬ−２６５５〔商品名：ローム・アンド・ハース（株）製〕等が挙げられる。架橋アクリロニトリルブタジエンゴム（ＮＢＲ）粒子の具体例としては、ＸＥＲ−９１〔平均粒径０．５μｍ、ＪＳＲ（株）製〕などが挙げられる。架橋スチレンブタジエンゴム（ＳＢＲ）粒子の具体例としては、ＸＳＫ−５００〔平均粒径０．５μｍ、ＪＳＲ（株）製〕が挙げられる。アクリルゴム粒子の具体例としては、メタブレンＷ３００Ａ（平均粒径０．１μｍ）、Ｗ４５０Ａ（平均粒径０．２μｍ）〔以上、三菱レイヨン（株）製〕を挙げることができる。架橋ゴム粒子は、単独でも、２種以上を組み合せて用いてもよい。
Examples of the crosslinked rubber particles include core-shell type rubber particles, crosslinked acrylonitrile butadiene rubber particles, crosslinked styrene butadiene rubber particles, and acrylic rubber particles. The core-shell type rubber particles are rubber particles having a core layer and a shell layer. For example, a two-layer structure in which an outer shell layer is formed of a glassy polymer and an inner core layer is formed of a rubbery polymer, or Examples include a three-layer structure in which the outer shell layer is made of a glassy polymer, the intermediate layer is made of a rubbery polymer, and the core layer is made of a glassy polymer. The glass layer is made of, for example, a polymer of methyl methacrylate, and the rubbery polymer layer is made of, for example, a butyl acrylate polymer (butyl rubber).
Specific examples of the core-shell type rubber particles include Staphyloid AC3832, AC3816N [above, trade name, manufactured by Gantz Kasei Co., Ltd.], Metabrene KW-4426 [trade name, manufactured by Mitsubishi Rayon Co., Ltd.], EXL-2655 [Product Name: manufactured by Rohm and Haas Co., Ltd.). Specific examples of the crosslinked acrylonitrile butadiene rubber (NBR) particles include XER-91 [average particle diameter of 0.5 μm, manufactured by JSR Corporation]. Specific examples of the crosslinked styrene butadiene rubber (SBR) particles include XSK-500 [average particle size 0.5 μm, manufactured by JSR Corporation]. Specific examples of the acrylic rubber particles include methabrene W300A (average particle size 0.1 μm), W450A (average particle size 0.2 μm) [manufactured by Mitsubishi Rayon Co., Ltd.]. The crosslinked rubber particles may be used alone or in combination of two or more.
配合する架橋ゴム粒子の平均粒径は、好ましくは０．００５〜１μｍの範囲であり、より好ましくは０．２〜０．６μｍの範囲である。本発明で使用される架橋ゴム粒子の平均粒径は、動的光散乱法を用いて測定することができる。例えば、適当な有機溶剤に架橋ゴム粒子を超音波などにより均一に分散させ、濃厚系粒径アナライザー〔ＦＰＡＲ−１０００；大塚電子（株）製〕を用いて、架橋ゴム粒子の粒度分布を質量基準で作成し、そのメディアン径を平均粒径とすることで測定することができる。 The average particle size of the crosslinked rubber particles to be blended is preferably in the range of 0.005 to 1 μm, more preferably in the range of 0.2 to 0.6 μm. The average particle diameter of the crosslinked rubber particles used in the present invention can be measured using a dynamic light scattering method. For example, the cross-linked rubber particles are uniformly dispersed in an appropriate organic solvent by ultrasonic waves, etc., and the particle size distribution of the cross-linked rubber particles is mass-based using a concentrated particle size analyzer [FPAR-1000; manufactured by Otsuka Electronics Co., Ltd.] And the median diameter can be measured as the average particle diameter.
ポリビニルアセタール樹脂としては、その種類、水酸基量、アセチル基量は特に限定されないが、重合度は１０００〜２５００のものが好ましい。この範囲にあると、はんだ耐熱性が確保でき、また、ワニスの粘度、取り扱い性も良好である。ここでポリビニルアセタール樹脂の数平均重合度は、たとえば、その原料であるポリ酢酸ビニルの数平均分子量（ゲルパーミエーションクロマトグラフィによる標準ポリスチレンの検量線を用いて測定する）から決定することができる。また、カルボン酸変性品などを用いることもできる。 As a polyvinyl acetal resin, the kind, the amount of hydroxyl groups, and the amount of acetyl groups are not particularly limited, but those having a polymerization degree of 1000 to 2500 are preferable. Within this range, solder heat resistance can be secured, and the viscosity and handling properties of the varnish are good. Here, the number average degree of polymerization of the polyvinyl acetal resin can be determined, for example, from the number average molecular weight of polyvinyl acetate as a raw material (measured using a standard polystyrene calibration curve by gel permeation chromatography). Moreover, a carboxylic acid modified product etc. can also be used.
ポリビニルアセタール樹脂は、例えば、積水化学工業（株）製の商品名、エスレックＢＸ−１、ＢＸ−２、ＢＸ−５、ＢＸ−５５、ＢＸ−７、ＢＨ−３、ＢＨ−Ｓ、ＫＳ−３Ｚ、ＫＳ−５、ＫＳ−５Ｚ、ＫＳ−８、ＫＳ−２３Ｚ、電気化学工業（株）製の商品名、電化ブチラール４０００−２、５０００Ａ、６０００Ｃ、６０００ＥＰ等を使用することができる。これらの樹脂は単独で、または２種類以上混合して用いることもできる。 Polyvinyl acetal resin is, for example, trade name, S-REC BX-1, BX-2, BX-5, BX-55, BX-7, BH-3, BH-S, KS-3Z manufactured by Sekisui Chemical Co., Ltd. KS-5, KS-5Z, KS-8, KS-23Z, trade names manufactured by Denki Kagaku Kogyo Co., Ltd., and electrified butyral 4000-2, 5000A, 6000C, 6000EP, and the like can be used. These resins can be used alone or in admixture of two or more.
化学粗化可能な化合物（Ｅ）の含有量は、固形分換算の（Ａ）〜（Ｄ）成分の合計量１００質量部に対し、０．５〜５質量部であることが好ましく、より好ましくは、最も好ましくは０．５〜２質量部である。化学粗化可能な化合物の含有量を０．５質量部以上とすることにより、絶縁樹脂層と導体層の接着強度が高くなり、５質量部以下とすることにより、配線間の絶縁信頼性が不十分になることがない。 The content of the chemical roughening compound (E) is preferably 0.5 to 5 parts by mass, more preferably 100 parts by mass of the total amount of components (A) to (D) in terms of solid content. Is most preferably 0.5 to 2 parts by mass. By setting the content of the compound capable of chemical roughening to 0.5 parts by mass or more, the adhesive strength between the insulating resin layer and the conductor layer is increased, and by setting the content to 5 parts by mass or less, the insulation reliability between wirings is increased. It will not be insufficient.
本発明の絶縁樹脂組成物では、絶縁樹脂層の熱膨張率を低下させるために無機充填材（Ｆ）を含有させることが好ましい。無機充填材（Ｆ）の例としては、シリカ、マイカ、タルク、ガラス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、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、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、水酸化アルミニウムがより好ましい。また、下層配線層を埋めこむために、多層プリント配線板用の接着フィルムには、高い流動性が求められる。よって、無機充填材は球状であることが、流動性の観点から望ましい。 In the insulating resin composition of the present invention, it is preferable to contain an inorganic filler (F) in order to reduce the thermal expansion coefficient of the insulating resin layer. 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 of low thermal expansion. Moreover, in order to embed a lower wiring layer, the adhesive film for multilayer printed wiring boards is required to have high fluidity. Therefore, it is desirable from the viewpoint of fluidity that the inorganic filler is spherical.
無機充填材（Ｅ）の含有量は、固形分換算の（Ａ）〜（Ｄ）成分の合計量１００質量部に対し、１０〜５０質量部であることが好ましく、より好ましくは、２５〜４５質量部である。無機充填材を１０質量部以上とすることにより硬化後の絶縁樹脂層の熱膨張率が小さくなる。また、配合量が５０質量部以下とすることにより、絶縁樹脂層がもろくなり、温度サイクル試験などでクラックが発生することがない。
これらの無機充填材は、分散性を高める目的でカップリング剤で処理することができ、ニーダー、ボールミル、ビーズミル、３本ロール等既知の混練方法により無機充填材を分散できる。
無機充填材の平均粒径は、配線の微細化が進むことを考慮すると、１μｍ以下が望ましく、０．５μｍ以下がより好ましい。１μｍ以上の無機充填材は、後述するデスミア工程後の表面凹凸を大きくするために、エッチング残りが発生し、絶縁性を不十分にするおそれがある。
It is preferable that content of an inorganic filler (E) is 10-50 mass parts with respect to 100 mass parts of total amounts of (A)-(D) component of solid content conversion, More preferably, it is 25-45. Part by mass. By setting the inorganic filler to 10 parts by mass or more, the thermal expansion coefficient of the cured insulating resin layer is reduced. Further, when the blending amount is 50 parts by mass or less, the insulating resin layer becomes brittle and cracks do not occur in a temperature cycle test or the like.
These inorganic fillers can be treated with a coupling agent for the purpose of enhancing dispersibility, and the inorganic filler can be dispersed by a known kneading method such as a kneader, ball mill, bead mill, or three rolls.
The average particle diameter of the inorganic filler is preferably 1 μm or less, more preferably 0.5 μm or less, considering that the miniaturization of wiring is advanced. An inorganic filler having a size of 1 μm or more may cause an etching residue to increase surface unevenness after a desmear process, which will be described later.
さらに、本発明の絶縁樹脂組成物には、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、充填剤等の併用ができる。
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等が挙げられる。
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等が挙げられる。
難燃剤の例としては、臭素や塩素を含有する含ハロゲン系難燃剤、三酸化アンチモン、水酸化アルミニウム及び水酸化マグネシウム等の無機物の難燃剤等が挙げられる。
充填剤の例としては、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等の有機物粉末等が挙げられる。
Furthermore, in the insulating resin composition of the present invention, any known thermoplastic resin, elastomer, flame retardant, filler, etc. can be used in combination as long as the effects of the present invention are not impaired.
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 flame retardant include halogen-containing flame retardants containing bromine and chlorine, inorganic flame retardants such as antimony trioxide, aluminum hydroxide, and magnesium hydroxide.
Examples of the filler include organic powders such as silicone powder, polytetrafluoroethylene, polyethylene, polypropylene, polystyrene, and polyphenylene ether.
本発明の絶縁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等の添加も可能であり、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等の紫外線吸収剤、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やシランカップリング剤等の密着性向上剤等が挙げられる。 Arbitrary addition of an ultraviolet absorber, an antioxidant, a photopolymerization initiator, a fluorescent brightening agent, an adhesion improver and the like is also possible with respect to the insulating resin composition of the present invention, and is not particularly limited. 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.
なお、本発明の支持体付絶縁フィルム及びプリプレグに用いられる絶縁樹脂組成物には、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。該有機溶剤は特に限定されないが、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等が挙げられ、１種又は２種以上を混合して使用できる。 In the insulating resin composition used for the insulating film with support and the prepreg of the present invention, an organic solvent can be arbitrarily used as a diluting 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, aromatic solvents such as toluene, xylene, and mesitylene. Examples of the solvent include one type or a mixture of two or more types.
本発明の絶縁樹脂組成物は、多層プリント配線板の製造において、絶縁樹脂層を形成するために好適に使用することができる。本発明の絶縁樹脂組成物は、ワニス状態で回路基板に塗布して絶縁樹脂層を形成することもできるが、工業的には一般に、支持体付絶縁フィルム、プリプレグ等のシート状積層材料の形態で用いるのが好ましい。 The insulating resin composition of the present invention can be suitably used for forming an insulating resin layer in the production of a multilayer printed wiring board. Although the insulating resin composition of the present invention can be applied to a circuit board in a varnish state to form an insulating resin layer, it is generally industrially in the form of a sheet-like laminated material such as an insulating film with a support, a prepreg, etc. Is preferably used.
本発明の支持体付絶縁フィルムは、（Ａ）、（Ｂ）及び（Ｃ）成分を配合した絶縁樹脂組成物、又は更に（Ｄ）、（Ｅ）、（Ｆ）成分を加えた該樹脂組成物を、支持体フィルムに塗布し、乾燥によってワニス中の溶剤を揮発させ、半硬化（Ｂステージ化）させて絶縁樹脂組成物層を形成したものである。ただし、この半硬化状態は、絶縁樹脂組成物を硬化する際に、絶縁樹脂層とそれを形成する回路パターン基板の接着力が確保される範囲で、また、回路パターン基板の埋めこみ性（流動性）が確保される範囲であることが望ましい。塗工方法（塗工機）としては、ダイコーター、コンマコータ、バーコータ、キスコータ、ロールコーター等が利用でき、絶縁樹脂層の厚みによって適宜使用される。乾燥方法としては、加熱、あるいは熱風吹きつけなどを用いることができる。 The insulating film with a support of the present invention is an insulating resin composition in which the components (A), (B) and (C) are blended, or the resin composition in which the components (D), (E) and (F) are further added. The product is applied to a support film, the solvent in the varnish is volatilized by drying and semi-cured (B-stage) to form an insulating resin composition layer. However, this semi-cured state is within the range where the adhesive strength between the insulating resin layer and the circuit pattern substrate forming the insulating resin layer is secured when the insulating resin composition is cured, and the embedding property (fluidity) of the circuit pattern substrate. ) Is desirable. As a coating method (coating machine), a die coater, a comma coater, a bar coater, a kiss coater, a roll coater or the like can be used, and it is appropriately used depending on the thickness of the insulating resin layer. As a drying method, heating, hot air blowing, or the like can be used.
乾燥条件は特に限定されないが、該絶縁樹脂組成物層への有機溶剤の含有量が通常の１０質量％以下、好ましくは５質量％以下となるように乾燥させる。ワニス中の有機溶剤量、有機溶剤の沸点によっても異なるが、例えば３０〜６０質量％の有機溶剤を含むワニスを５０〜１５０℃で３〜１０分程度乾燥させることにより、絶縁樹脂組成物層の半硬化状態のフィルムが形成される。乾燥条件は、予め簡単な実験により適宜、好適な乾燥条件を設定することが好ましい。 The drying conditions are not particularly limited, but the drying is performed so that the content of the organic solvent in the insulating resin composition layer is 10% by mass or less, preferably 5% by mass or less. Depending on the amount of the organic solvent in the varnish and the boiling point of the organic solvent, for example, by drying a varnish containing 30 to 60% by mass of the organic solvent at 50 to 150 ° C. for about 3 to 10 minutes, A semi-cured film is formed. It is preferable to set suitable drying conditions as appropriate by simple experiments in advance.
支持体付絶縁フィルムにおいて形成される絶縁樹脂組成物層の厚さは、通常、導体層の厚さ以上とする。回路基板が有する導体層の厚さは５〜７０μｍであることが好ましく、多層プリント配線板の軽薄短小化のために、５〜５０μｍであることがより好ましく、５〜３０μｍであることが最も好ましい。 The thickness of the insulating resin composition layer formed in the insulating film with support is usually not less than the thickness of the conductor layer. The thickness of the conductor layer included in the circuit board is preferably 5 to 70 μm, more preferably 5 to 50 μm, and most preferably 5 to 30 μm in order to reduce the thickness of the multilayer printed wiring board. .
支持体付絶縁フィルムにおける支持は、ポリエチレン、ポリプロピレン、ポリ塩化ビニル等のポリオレフィン、ポリエチレンテレフタレート（以下「ＰＥＴ」と略称することがある。）、ポリエチレンナフタレート等のポリエステル、ポリカーボネート、ポリイミドなどからなるフィルム、更には離型紙や銅箔、アルミニウム箔等の金属箔などを挙げることができる。なお、支持体及び後述する保護フィルムには、マッド処理、コロナ処理の他、離型処理が施してもよい。 Support in the insulating film with support is a film made of polyolefin such as polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes referred to as “PET”), polyester such as polyethylene naphthalate, polycarbonate, polyimide, etc. Furthermore, release paper, copper foil, metal foil such as aluminum foil, and the like can be mentioned. The support and the protective film to be described later may be subjected to a release treatment in addition to the mud treatment and the corona treatment.
支持体の厚さは特に限定されないが、１０〜１５０μｍが好ましく、より好ましくは２５〜５０μｍである。絶縁樹脂組成物層の支持体が密着していない面には、支持体に準じた保護フィルムをさらに積層することができる。保護フィルムの厚さは、特に限定されるものではないが、例えば１〜４０μｍである。保護フィルムを積層することにより、異物混入を防止することができる。
支持体付絶縁フィルムは、ロール状に巻き取って貯蔵することもできる。
Although the thickness of a support body is not specifically limited, 10-150 micrometers is preferable, More preferably, it is 25-50 micrometers. A protective film according to the support can be further laminated on the surface of the insulating resin composition layer on which the support is not in close contact. Although the thickness of a protective film is not specifically limited, For example, it is 1-40 micrometers. By laminating the protective film, foreign matter can be prevented from being mixed.
The insulating film with a support can be wound and stored in a roll shape.
本発明の支持体付絶縁フィルムを用いて積層板を形成し、多層プリント配線板を製造する方法の形態としては、例えば、支持体付絶縁フィルムを、真空ラミネーターを用いて回路基板の片面又は両面にラミネートする。回路基板に用いられる基板としては、例えば、ガラスエポキシ基板、金属基板、ポリエステル基板、ポリイミド基板、ＢＴレジン基板、熱硬化型ポリフェニレンエーテル基板等が挙げられる。なお、ここで回路基板とは、上記のような基板の片面又は両面にパターン加工された導体層（回路）が形成されたものをいう。また導体層と絶縁層とを交互に積層してなる積層板及び該積層板から製造される多層プリント配線板において、該多層プリント配線板の最外層の片面又は両面がパターン加工された導体層（回路）となっているものも、ここでいう回路基板に含まれる。なお導体層表面には、黒化処理等により予め粗化処理が施されていてもよい。 As a form of the method of forming a laminated board using the insulating film with a support of the present invention and producing a multilayer printed wiring board, for example, the insulating film with a support is used on one or both sides of a circuit board using a vacuum laminator. Laminate. Examples of the substrate used for the circuit substrate include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like. In addition, a circuit board means here that the conductor layer (circuit) patterned was formed in the one or both surfaces of the above boards. Further, in a laminated board obtained by alternately laminating conductor layers and insulating layers, and a multilayer printed wiring board manufactured from the laminated board, a conductor layer in which one or both surfaces of the outermost layer of the multilayer printed wiring board are patterned ( Circuits) are also included in the circuit board here. The surface of the conductor layer may be subjected to a roughening process in advance by a blackening process or the like.
上記ラミネートにおいて、支持体付絶縁フィルムが保護フィルムを有している場合には該保護フィルムを除去した後、必要に応じて支持体付絶縁フィルム及び回路基板をプレヒートし、支持体付絶縁フィルムを加圧及び加熱しながら回路基板に圧着する。本発明の支持体付絶縁フィルムにおいては、真空ラミネート法により減圧下で回路基板にラミネートする方法が好適に用いられる。ラミネート条件は、特に限定されるものではないが、例えば、圧着温度（ラミネート温度）を好ましくは７０〜１４０℃、圧着圧力を好ましくは０．１〜１．１ＭＰａとし、空気圧２０ｍｍＨｇ（２６．７ｈＰａ）以下の減圧下でラミネートするのが好ましい。また、ラミネートの方法は、バッチ式であってもロールでの連続式であってもよい。 In the above laminate, when the insulating film with a support has a protective film, after removing the protective film, the insulating film with a support and the circuit board are preheated as necessary, Crimp to circuit board while pressing and heating. In the insulating film with a support of the present invention, a method of laminating on a circuit board under reduced pressure by a vacuum laminating method is suitably used. Lamination conditions are not particularly limited. For example, the pressure bonding temperature (laminating temperature) is preferably 70 to 140 ° C., the pressure bonding pressure is preferably 0.1 to 1.1 MPa, and the air pressure is 20 mmHg (26.7 hPa). Lamination is preferably performed under the following reduced pressure. The laminating method may be a batch method or a continuous method using a roll.
支持体付絶縁フィルムを回路基板にラミネートした後、室温付近に冷却してから、支持を剥離する場合は剥離し、熱硬化することにより回路基板に絶縁樹脂層を形成することができる。熱硬化の条件は、絶縁樹脂組成物中の樹脂成分の種類、含有量などに応じて適宜選択すればよいが、好ましくは１５０℃〜２２０℃で２０分〜１８０分、より好ましくは１６０℃〜２００℃で３０〜１２０分の範囲で選択される。 After laminating the insulating film with the support on the circuit board, the support is peeled off after cooling to near room temperature, and the insulating resin layer can be formed on the circuit board by peeling and thermosetting. The thermosetting conditions may be appropriately selected according to the type and content of the resin component in the insulating resin composition, but are preferably 150 ° C. to 220 ° C. for 20 minutes to 180 minutes, more preferably 160 ° C. to It is selected in the range of 30 to 120 minutes at 200 ° C.
絶縁樹脂層を形成した後、硬化前に支持を剥離しなかった場合は、ここで剥離する。次いで必要により、回路基板上に形成された絶縁樹脂層に穴開けを行ってビアホール、スルーホールを形成する。穴あけは、例えば、ドリル、レーザー、プラズマ等の公知の方法により、また必要によりこれらの方法を組み合わせて行うことができるが、炭酸ガスレーザー、ＹＡＧレーザー等のレーザーによる穴あけが最も一般的な方法である。 If the support is not peeled off after the insulating resin layer is formed, it is peeled off here. Next, if necessary, holes are formed in the insulating resin layer formed on the circuit board to form via holes and through holes. Drilling can be performed, for example, by a known method such as drilling, laser, or plasma, or by combining these methods as necessary. However, drilling by a laser such as a carbon dioxide gas laser or a YAG laser is the most common method. is there.
次いで、乾式メッキ又は湿式メッキにより絶縁樹脂層上に導体層を形成する。乾式メッキとしては、蒸着、スパッタリング、イオンプレーティング等の公知の方法を使用することができる。湿式メッキの場合は、まず、硬化した絶縁樹脂層の表面を、過マンガン酸塩（過マンガン酸カリウム、過マンガン酸ナトリウム等）、重クロム酸塩、オゾン、過酸化水素／硫酸、硝酸等の酸化剤で粗化処理し、凸凹のアンカーを形成する。酸化剤としては、特に過マンガン酸カリウム、過マンガン酸ナトリウム等の水酸化ナトリウム水溶液（アルカリ性過マンガン酸水溶液）が好ましく用いられる。次いで、無電解メッキと電解メッキとを組み合わせた方法で導体層を形成する。また導体層とは逆パターンのメッキレジストを形成し、無電解メッキのみで導体層を形成することもできる。その後のパターン形成の方法として、例えば、公知のサブトラクティブ法、セミアディティブ法などを用いることができる。 Next, a conductor layer is formed on the insulating resin layer by dry plating or wet plating. As the dry plating, a known method such as vapor deposition, sputtering, or ion plating can be used. In the case of wet plating, first, the surface of the cured insulating resin layer is made of permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid, etc. Roughening treatment is performed with an oxidizing agent to form uneven anchors. As the oxidizing agent, an aqueous sodium hydroxide solution (alkaline permanganate aqueous solution) such as potassium permanganate and sodium permanganate is particularly preferably used. Next, a conductor layer is formed by a method combining electroless plating and electrolytic plating. Alternatively, a plating resist having a pattern opposite to that of the conductor layer can be formed, and the conductor layer can be formed only by electroless plating. As a subsequent pattern formation method, for example, a known subtractive method or semi-additive method can be used.
本発明のプリプレグは、絶縁樹脂組成物が繊維シート状補強基材に含浸されているものであり、本発明の絶縁樹脂組成物を繊維シート状補強基材にホットメルト法又はソルベント法により含浸した後、加熱してＢステージ化することによる製造される。 The prepreg of the present invention is a fiber sheet-like reinforcing base impregnated with an insulating resin composition, and the fiber sheet-like reinforcing base is impregnated with a hot melt method or a solvent method. After that, it is manufactured by heating to B stage.
繊維シート状補強基材としては、例えば、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ガラス及びＱガラス等の無機物繊維、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等の有機繊維、並びにそれらの混合物等が挙げられる。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等の形状を有するが、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、耐熱性や耐湿性、加工性の面から好適である。 As the fiber sheet reinforcing substrate, for example, known materials used for various types of laminated sheets 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, for example, shapes such as woven fabric, non-woven fabric, robink, 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 base material 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 mechanically subjected to a fiber opening treatment. However, it is suitable from the aspects of heat resistance, moisture resistance, and workability.
上記のホットメルト法は、樹脂を有機溶剤に溶解することなく、該樹脂との剥離性の良い塗工紙に一旦コーティングし、それをシート状補強基材にラミネートする、あるいは樹脂を、有機溶剤に溶解することなく、ダイコーターによりシート状補強基材に直接塗工するなどして、プリプレグを製造する方法である。またソルベント法は、支持体付絶縁フィルムと同様にして樹脂を有機溶剤に溶解して樹脂ワニスを調製し、このワニスにシート状補強基材を浸漬し、樹脂ワニスをシート状補強基材に含浸させ、その後乾燥させる方法である。 The above hot-melt method is a method in which the resin is once coated on a coated paper having good releasability from the resin without dissolving the resin in the organic solvent, and then laminated on the sheet-like reinforcing substrate, or the resin is added to the organic solvent. In this method, the prepreg is produced by, for example, coating directly on a sheet-like reinforcing substrate with a die coater without being dissolved in the substrate. In the solvent method, the resin is dissolved in an organic solvent in the same manner as the insulating film with a support to prepare a resin varnish, the sheet-like reinforcing base material is immersed in the varnish, and the sheet-like reinforcing base material is impregnated with the resin varnish. And then drying.
次に、上記のようにして製造したプリプレグを用いて多層プリント配線板を製造する方法として、例えば、回路基板に本発明のプリプレグを１枚あるいは必要により数枚重ね、離型フィルムを介して金属プレートで挟み、加圧・加熱条件下でプレス積層する。加圧・加熱条件は、好ましくは、圧力が０．５〜４ＭＰａ、温度が１２０〜２００℃で２０〜１００分である。また支持体付絶縁フィルムと同様に、プリプレグを真空ラミネート法により回路基板にラミネートした後、加熱硬化することも可能である。得られた積層板は、その後、上記で記載した方法と同様にして、硬化したプリプレグ表面を粗化した後、導体層をメッキにより形成して多層プリント配線板を製造することができる。 Next, as a method for producing a multilayer printed wiring board using the prepreg produced as described above, for example, one or more of the prepregs of the present invention are stacked on a circuit board, and a metal is disposed through a release film. It is sandwiched between plates and press laminated under pressure and heating conditions. The pressurizing / heating conditions are preferably a pressure of 0.5 to 4 MPa and a temperature of 120 to 200 ° C. for 20 to 100 minutes. Similarly to the insulating film with support, the prepreg can be laminated on a circuit board by a vacuum laminating method and then cured by heating. The obtained laminate can then be used to produce a multilayer printed wiring board by roughening the cured prepreg surface in the same manner as described above, and then forming a conductor layer by plating.
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、各実施例及び比較例で得られた支持体付絶縁フィルムの絶縁樹脂層と銅張積層板は、以下の方法により性能を測定・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.
In addition, the performance of the insulating resin layer and the copper-clad laminate of the insulating film with support obtained in each Example and Comparative Example was measured and evaluated by the following method.
（１）ガラス転移温度（Ｔｇ）及び熱膨張率
支持体付絶縁フィルムの絶縁樹脂層を、銅箔〔Ｆ３−ＷＳ−１８、商品名、古河サーキットフォイル（株）社製〕に向かい合わせてラミネートし、ＰＥＴフィルムを剥離し、１８０℃で９０分間硬化した。その後、銅箔を全面エッチングして、硬化後の絶縁樹脂層の熱膨張係数を評価する試料を作製した。
得られたシート状の硬化物を、長さ２０ｍｍ、幅３ｍｍに切断し、ＴＭＡ試験装置（デュポン社製、ＴＭＡ２９４０）を用いて、昇温速度１０℃／分、測定長１５ｍｍ、加重５ｇ、引張加重法で連続して２回測定した。２回目の測定におけるガラス転移温度（Ｔｇ）、３０〜１２０℃までの平均線熱膨張率を算出した。
(1) Laminate the insulating resin layer of the insulating film with a glass transition temperature (Tg) and a coefficient of thermal expansion support facing a copper foil [F3-WS-18, trade name, manufactured by Furukawa Circuit Foil Co., Ltd.] The PET film was peeled off and cured at 180 ° C. for 90 minutes. Thereafter, the entire surface of the copper foil was etched to prepare a sample for evaluating the thermal expansion coefficient of the cured insulating resin layer.
The obtained sheet-like cured product was cut into a length of 20 mm and a width of 3 mm, and using a TMA test apparatus (manufactured by DuPont, TMA2940), the heating rate was 10 ° C./min, the measurement length was 15 mm, the load was 5 g, and the tension was The measurement was performed twice in succession by the weight method. The glass transition temperature (Tg) in the second measurement and the average linear thermal expansion coefficient from 30 to 120 ° C. were calculated.
（２）銅箔接着性（銅箔ピール強度）
ガラス布基材エポキシ樹脂両面銅張積層板〔日立化成工業（株）製、商品名：ＭＣＬ−Ｅ−６７９Ｆ、銅箔厚さ：１２μｍ〕の両面をメック（株）製「ＣＺ８１００」（商品名）を用いて粗化処理を行った。
支持体付絶縁フィルムを、上記で粗化処理を行った回路基板の両面にラミネートした。ラミネートは３０秒間減圧して気圧を１３ｈＰａ以下とし、その後３０秒間、圧力０．５ＭＰａでプレスすることにより行った。
ラミネートされた支持体付絶縁フィルムからＰＥＴフィルムを剥離し、１８０℃、６０分の硬化条件で絶縁樹脂組成物層を硬化して、絶縁樹脂層を形成した。
次いで、積層板をデスミア処理液に浸漬することによって、絶縁樹脂層表面に微細な凹凸を形成した。セミアディティブ工法によるメッキを行い、積層板を銅エッチング液に浸漬することにより３ｍｍ幅のメッキ銅箔を形成して評価基板を作製し、オートグラフ（島津製作所製ＡＧ−１００Ｃ）を用いてピール強度を測定した。
(2) Copper foil adhesion (copper foil peel strength)
“CZ8100” (trade name) manufactured by MEC Co., Ltd. on both sides of a glass cloth base epoxy resin double-sided copper-clad laminate [manufactured by Hitachi Chemical Co., Ltd., trade name: MCL-E-679F, copper foil thickness: 12 μm] ) Was used for roughening treatment.
The insulating film with a support was laminated on both surfaces of the circuit board that had been roughened as described above. Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressing at a pressure of 0.5 MPa for 30 seconds.
The PET film was peeled from the laminated insulating film with a support, and the insulating resin composition layer was cured under curing conditions at 180 ° C. for 60 minutes to form an insulating resin layer.
Next, fine irregularities were formed on the surface of the insulating resin layer by immersing the laminate in a desmear treatment liquid. A semi-additive method is used for plating, and the laminated board is immersed in a copper etching solution to form a 3 mm-wide plated copper foil to produce an evaluation board. The peel strength is obtained using an autograph (AG-100C manufactured by Shimadzu Corporation). Was measured.
（３）はんだ耐熱性
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、平山製作所（株）製プレッシャー・クッカー試験装置を用いて、１２１℃、０．２ＭＰａ（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。
(3) Solder heat resistance A 5 cm square evaluation board from which the copper foil has been removed by immersing a copper clad laminate in a copper etching solution is prepared and 121 ° C. using a pressure cooker test apparatus manufactured by Hirayama Seisakusho. After performing pressure-cooker treatment for up to 4 hours under the condition of 0.2 MPa (2 atm), the test substrate is immersed in a solder bath at a temperature of 288 ° C. for 20 seconds, and then the solder heat resistance is evaluated by observing the appearance. did.
（４）銅付き耐熱性（Ｔ−２８８）
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、圧縮法により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。
(4) Heat resistance with copper (T-288)
An evaluation board of 5 mm square was produced from a copper clad laminate, and evaluation was performed by measuring the time until the evaluation board swells at 288 ° C. by a compression method using a TMA test apparatus (manufactured by DuPont, TMA2940). .
（５）吸湿性（吸水率）
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、平山製作所（株）製プレッシャー・クッカー試験装置を用いて、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。
(5) Hygroscopicity (water absorption rate)
A copper-clad laminate was immersed in a copper etching solution to produce an evaluation substrate from which the copper foil was removed, and pressure was applied for up to 4 hours under the conditions of 121 ° C. and 2 atm using a pressure cooker test apparatus manufactured by Hirayama Seisakusho. -After the cooker treatment, the water absorption rate of the evaluation substrate was measured.
（６）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。
(6) 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, and tested for UL94. Evaluation was made according to the method (Method V).
製造例１：硬化剤（Ａ−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：２６．４０ｇ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：４８４．５０gと、p−アミノ安息香酸：２９．１０ｇ、及びジメチルアセトアミド：３６０．００gを入れ、１４０℃で５時間反応させて分子主鎖中にスルホン基を有し、酸性置換基と不飽和Ｎ−置換マレイミド基を有する硬化剤（Ａ−１）の溶液を得た。
Production Example 1: Production of Curing Agent (A-1) Bis (4-aminophenyl) sulfone 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. : 26.40 g, 2,2′-bis [4- (4-maleimidophenoxy) phenyl] propane: 484.50 g, p-aminobenzoic acid: 29.10 g, and dimethylacetamide: 360.00 g The reaction was carried out at 140 ° C. for 5 hours to obtain a solution of a curing agent (A-1) having a sulfone group in the molecular main chain and having an acidic substituent and an unsaturated N-substituted maleimide group.
製造例２：硬化剤の製造（Ａ−２）
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：４０．２０ｇと、ビス（４−マレイミドフェニル）メタン：４６４．４０gと、p−アミノフェノール：３５．４０ｇ、及びジメチルアセトアミド：３６０．００gを入れ、１００℃で４時間反応させて分子主鎖中にスルホン基を有し、酸性置換基と不飽和Ｎ−置換マレイミド基を有する硬化剤（Ａ−２）の溶液を得た。
Production Example 2: Production of curing agent (A-2)
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 meter with a reflux condenser, bis (4-aminophenyl) sulfone: 40.20 g and bis (4-maleimidophenyl) Methane: 464.40 g, p-aminophenol: 35.40 g, and dimethylacetamide: 360.00 g were added and reacted at 100 ° C. for 4 hours to have a sulfone group in the molecular main chain. A solution of a curing agent (A-2) having a saturated N-substituted maleimide group was obtained.
製造例３：硬化剤（Ａ−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：４３．４０ｇと、４−メチル−１，３−フェニレンビスマレイミド：４５２．９０gと、p−アミノフェノール：４３．７０ｇ、及びジメチルアセトアミド：３６０．００gを入れ、１００℃で２時間反応させて分子主鎖中にスルフィド基を有し、酸性置換基と不飽和Ｎ−置換マレイミド基を有する硬化剤（Ａ−３）の溶液を得た。
Production Example 3: Production of Curing Agent (A-3) Bis (4-aminophenyl) sulfide was added to a reaction vessel with 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. : 43.40 g, 4-methyl-1,3-phenylenebismaleimide: 452.90 g, p-aminophenol: 43.70 g, and dimethylacetamide: 360.00 g, and reacted at 100 ° C. for 2 hours. A solution of a curing agent (A-3) having a sulfide group in the molecular main chain and having an acidic substituent and an unsaturated N-substituted maleimide group was obtained.
製造例４：硬化剤（Ａ−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：４４．８０ｇ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：４７２．６０gと、p−アミノフェノール：２２．６０ｇ、及びプロピレングリコールモノメチルエーテル：３６０．００gを入れ、還流温度で２時間反応させて分子主鎖中にスルホン基を有し、酸性置換基と不飽和Ｎ−置換マレイミド基を有する硬化剤（Ａ−４）の溶液を得た。
Production Example 4: Production of curing agent (A-4) Bis [4- (4-amino) was added to a reaction vessel with 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. Phenoxy) phenyl] sulfone: 44.80 g, 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane: 472.60 g, p-aminophenol: 22.60 g, and propylene glycol monomethyl ether: 360 0.000 g was added and reacted at reflux temperature for 2 hours to obtain a solution of a curing agent (A-4) having a sulfone group in the molecular main chain and having an acidic substituent and an unsaturated N-substituted maleimide group.
製造例５：硬化剤（Ａ−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：６６．３０ｇと、ポリフェニルメタンマレイミド：４４０．３０gと、p−アミノフェノール：３３．４０ｇ、及びプロピレングリコールモノメチルエーテル：３６０．００gを入れ、還流温度で２時間反応させて分子主鎖中にスルホン基を有し、酸性置換基と不飽和Ｎ−置換マレイミド基を有する硬化剤（Ａ−５）の溶液を得た。
Production Example 5 Production of Curing Agent (A-5) 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 meter with a reflux condenser, bis [4- (4-amino] Phenoxy) phenyl] sulfone: 66.30 g, polyphenylmethanemaleimide: 440.30 g, p-aminophenol: 33.40 g, and propylene glycol monomethyl ether: 360.00 g were allowed to react at reflux temperature for 2 hours. A solution of a curing agent (A-5) having a sulfone group in the molecular main chain and having an acidic substituent and an unsaturated N-substituted maleimide group was obtained.
製造例６：硬化剤（Ａ−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：７９．４０ｇと、ビス（４−マレイミドフェニル）スルホン：４２０．５０gと、p−アミノフェノール：４０．１０ｇ、及びプロピレングリコールモノメチルエーテル：３６０．００gを入れ、還流温度で２時間反応させて分子主鎖中にスルホン基を有し、酸性置換基と不飽和Ｎ−置換マレイミド基を有する硬化剤（Ａ−６）の溶液を得た。
Production Example 6: Production of curing agent (A-6) A reaction vessel with 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, was charged with bis [4- (4-amino]. Phenoxy) phenyl] sulfone: 79.40 g, bis (4-maleimidophenyl) sulfone: 420.50 g, p-aminophenol: 40.10 g, and propylene glycol monomethyl ether: 360.00 g were added at reflux temperature. It was made to react for a time and the solution of the hardening | curing agent (A-6) which has a sulfone group in a molecular principal chain and has an acidic substituent and unsaturated N-substituted maleimide group was obtained.
製造例７：硬化剤（Ａ−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、o‐トリジンスルホン：４４．１０ｇと、ビス（４−マレイミドフェニル）メタン：４６０．８０gと、p−アミノフェノール：３５．１０ｇ、及びジメチルアセトアミド：３６０．００gを入れ、１００℃で２時間反応させて分子主鎖中にスルホン基とビフェニル骨格を有し、酸性置換基と不飽和Ｎ−置換マレイミド基を有する硬化剤（Ａ−７）の溶液を得た。
Production Example 7: Production of curing agent (A-7) In a reaction vessel with 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, o-tolidine sulfone: 44.10 g Bis (4-maleimidophenyl) methane: 460.80 g, p-aminophenol: 35.10 g, and dimethylacetamide: 360.00 g, and reacted at 100 ° C. for 2 hours to give a sulfone group in the molecular main chain. And a solution of a curing agent (A-7) having a biphenyl skeleton and having an acidic substituent and an unsaturated N-substituted maleimide group.
比較製造例１：硬化剤（Ａ−８）の製造
特公昭６３−３４８９９号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：３５８．００gとｍ−アミノフェノール：５４．５０ｇ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不飽和Ｎ−置換マレイミド基を有する硬化剤（Ａ−８）の粉末を得た。
Comparative Production Example 1: Production of Curing Agent (A-8) With reference to the example of JP-B 63-34899, a 1 liter kneader equipped with a steam heating device was charged with bis (4-maleimidophenyl) methane: 358. 0.000 g and m-aminophenol: 54.50 g, heated and kneaded at 135 to 140 ° C. for 15 minutes, cooled, pulverized, and a curing agent having an acidic substituent and an unsaturated N-substituted maleimide group (A-8 ) Was obtained.
比較製造例２：硬化剤（Ａ−９）の製造
特公平６−８３４２号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：３５８．００gとｍ−アミノ安息香酸：６８．５０ｇ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不飽和Ｎ−置換マレイミド基を有する硬化剤（Ａ−９）の粉末を得た。
Comparative production example 2: Production of curing agent (A-9) With reference to the example of JP-B-6-8342, a kneader having a volume of 1 liter equipped with a steam heating device, bis (4-maleimidophenyl) methane: 358 0.000 g and m-aminobenzoic acid: 68.50 g, heated and kneaded at 135 to 140 ° C. for 15 minutes, cooled and pulverized to have a curing agent having an acidic substituent and an unsaturated N-substituted maleimide group (A- The powder of 9) was obtained.
比較製造例３：硬化剤（Ａ−１０）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：３２．６０ｇと、ビス（４−マレイミドフェニル）メタン：４７１．５０gと、p−アミノフェノール：３５．９０ｇ、及びジメチルアセトアミド：３６０．００gを入れ、１００℃で２時間反応させ、酸性置換基と不飽和Ｎ−置換マレイミド基を有する硬化剤（Ａ−１０）の溶液を得た。
Comparative Production Example 3: Production of Curing Agent (A-10) In a reaction vessel with a thermometer, a stirrer, a reflux condenser and a heatable and coolable volume of 2 liters, diaminodiphenylmethane: 32.60 g and bis (4 -Maleimidophenyl) Methane: 471.50 g, p-aminophenol: 35.90 g, and dimethylacetamide: 360.00 g were added and reacted at 100 ° C. for 2 hours to convert acidic substituents and unsaturated N-substituted maleimide groups. A solution of the curing agent (A-10) was obtained.
比較製造例４：硬化剤（Ａ−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、２，２'−ビス[４−（４−アミノフェノキシ）フェニル]プロパン：６３．４０ｇと、ビス（４−マレイミドフェニル）メタン：４７１．２０gと、p−アミノフェノール：３３．７０ｇ、及びジメチルアセトアミド：３６０．００gを入れ、１００℃で２時間反応させ、酸性置換基と不飽和Ｎ−置換マレイミド基を有する硬化剤（Ａ−１１）の溶液を得た。
Comparative Production Example 4: Production of Curing Agent (A-11) 2,2′-bis [4- (4) was added to a 2 liter reaction vessel with a thermometer, a stirrer, a reflux condenser and a heatable and coolable volume. -Aminophenoxy) phenyl] propane: 63.40 g, bis (4-maleimidophenyl) methane: 471.20 g, p-aminophenol: 33.70 g, and dimethylacetamide: 360.00 g. It was made to react for the time and the solution of the hardening | curing agent (A-11) which has an acidic substituent and an unsaturated N-substituted maleimide group was obtained.
実施例１〜９、比較例１〜６
希釈溶剤にメチルエチルケトンを使用して、下記成分を第１表〜第３表に示す配合割合（質量部）で混合して樹脂分６５質量％の均一な絶縁樹脂組成物ワニスを作製した。
すなわち、
（１）酸性置換基と不飽和Ｎ−置換マレイミド基を有する化合物Ａとして、実施例１〜９では製造例１〜７で得られた硬化剤を使用した。また、比較例１〜６では製造例８〜１１で得られた酸性置換基と不飽和Ｎ−置換マレイミド基を有する硬化剤を使用した。
（２）エポキシ樹脂（Ｂ）として、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〕、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〕を使用した。
（３）難燃性を付与するリン化合物（Ｃ）として、リン含有エポキシ樹脂〔東都化成（株）製、商品名：エポトートＺＸ−１５４８−３、リン含有量３質量％〕、リン含有フェノール樹脂〔三光化学（株）製、商品名：ＨＣＡ−ＨＱ、リン含有量９．６質量％〕、縮合型リン酸エステル化合物〔第八化学工業（株）、商品名：ＰＸ−２００、リン含有量９質量％〕、ジアルキルホスフィン酸アルミニウム塩〔クラリアント（株）製、商品名：ＯＰ−９３０、リン含有量２３．５質量％〕を使用した。
（４）（Ｄ）成分のエポキシ樹脂硬化剤として、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〕、ベンゾグアナミン〔日本触媒（株）製〕、ジシアンジアミド〔大栄化学工業（株）製〕を使用した。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〕を使用した。
（５）化学粗化可能な化合物（Ｅ）として、架橋アクリロニトリルブタジエンゴム（ＮＢＲ）粒子：ＸＥＲ−９１〔ＪＳＲ（株）製〕、コアシェル型ゴム粒子：スタフィロイドＡＣ３８３２〔商品名、ガンツ化成（株）製〕を使用した。
（６）無機充填材（Ｆ）として、溶融シリカ〔アドマテック（株）製、商品名：ＳＣ２０５０−ＫＣ〕、水酸化アルミニウム〔昭和電工（株）製、商品名：ＨＰ−３６０〕を使用した。
Examples 1-9, Comparative Examples 1-6
Using methyl ethyl ketone as a diluent solvent, the following components were mixed at the blending ratios (parts by mass) shown in Tables 1 to 3 to prepare a uniform insulating resin composition varnish having a resin content of 65% by mass.
That is,
(1) As compound A having an acidic substituent and an unsaturated N-substituted maleimide group, Examples 1 to 9 used the curing agents obtained in Production Examples 1 to 7. Moreover, in the comparative examples 1-6, the hardening | curing agent which has the acidic substituent obtained by manufacture examples 8-11 and the unsaturated N-substituted maleimide group was used.
(2) As epoxy resin (B), 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 [manufactured by Japan Epoxy Resin Co., Ltd., trade name: YX-4000], Anthracene type epoxy resin [manufactured by Japan Epoxy Resin Co., Ltd., trade name: YX-8800] was used.
(3) Phosphorus-containing epoxy resin [manufactured by Toto Kasei Co., Ltd., trade name: Epototo ZX-1548-3, phosphorus content 3% by mass], phosphorus-containing phenol resin as phosphorus compound (C) imparting flame retardancy [Manufactured by Sanko Chemical Co., Ltd., trade name: HCA-HQ, phosphorus content 9.6 mass%], condensed phosphate ester compound [Eighth Chemical Industry Co., Ltd., trade name: PX-200, phosphorus content 9 mass%], dialkylphosphinic acid aluminum salt [manufactured by Clariant Co., Ltd., trade name: OP-930, phosphorus content 23.5 mass%].
(4) As an epoxy resin curing agent of component (D), aminotriazine novolak resin [Dainippon Ink Chemical Co., Ltd., trade name: LA-3018], benzoguanamine [manufactured by Nippon Shokubai Co., Ltd.], dicyandiamide [Daiei] Chemical Industry Co., Ltd.] was used. As a curing accelerator, an imidazole derivative [Daiichi Kogyo Seiyaku Co., Ltd., trade name: G8009L] was used.
(5) Cross-linked acrylonitrile butadiene rubber (NBR) particles: XER-91 [manufactured by JSR Co., Ltd.], core-shell type rubber particles: Staphyloid AC3832 [trade name, Gantz Kasei Co., Ltd.] )] Was used.
(6) As the inorganic filler (F), fused silica [manufactured by Admatech Co., Ltd., trade name: SC2050-KC], aluminum hydroxide [manufactured by Showa Denko KK, trade name: HP-360] was used.
次に、絶縁樹脂組成物ワニスをポリエチレンテレフタレートフィルム（厚さ３８μｍ、以下ＰＥＴフィルムと称す）上に、乾燥後の絶縁樹脂組成物層の厚みが４０μｍとなるようにダイコーターにて均一に塗布し、８０〜１３０℃で６分間乾燥した。次いで、絶縁樹脂組成物層の表面に厚さ１５μｍのポリプロピレンフィルムを貼り合わせながらロール状に巻き取った。得られたロール状のフィルムを幅５０７ｍｍにスリット（ｓｌｉｔ）し、５０７×３３６ｍｍサイズのシート状の支持体付絶縁フィルムを製造した。
また、絶縁樹脂組成物ワニスを厚さ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２．５ＭＰａ、温度１８５℃で９０分間プレスを行って、銅張積層板を得た。
このようにして作製した支持体付絶縁フィルムの絶縁樹脂層及び銅張積層板について、前記の方法によりにより性能を測定・評価した。結果を第１表〜第３表に示す。
Next, the insulating resin composition varnish was uniformly coated on a polyethylene terephthalate film (thickness 38 μm, hereinafter referred to as PET film) with a die coater so that the thickness of the insulating resin composition layer after drying was 40 μm. , And dried at 80 to 130 ° C. for 6 minutes. Subsequently, it wound up in roll shape, bonding the 15-micrometer-thick polypropylene film on the surface of the insulating resin composition layer. The obtained roll-shaped film was slit to a width of 507 mm to produce a sheet-like insulating film with a support having a size of 507 × 336 mm.
Moreover, the insulating resin composition 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 2.5 MPa and a temperature of 185 ° C. for 90 minutes to obtain a copper clad laminate.
With respect to the insulating resin layer and the copper-clad laminate of the insulating film with support thus produced, the performance was measured and evaluated by the method described above. The results are shown in Tables 1 to 3.
第１表〜第２表から明らかなように、本発明に係る実施例の絶縁樹脂組成物では、ガラス転移温度（Ｔｇ）が２４０℃以上であり、熱膨張率が２４〜３２ｐｐｍ/℃と低熱膨張性を有し、はんだ耐熱性、難燃性、銅箔ピール強度、銅付き耐熱性（Ｔ−２８８）、耐湿性の全てにバランスが取れており、信頼性が高い。
一方、第３表から明らかなように、比較例の絶縁樹脂組成物では、ガラス転移温度（Ｔｇ）が２００℃以下であり、熱膨張率が４３〜５２ｐｐｍ/℃と大きい。また、銅箔ピール強度、はんだ耐熱性、銅付き耐熱性（Ｔ−２８８）、耐湿性、難燃性のいずれかの特性に劣っており、信頼性が低くなる。
As is apparent from Tables 1 and 2, the insulating resin compositions of the examples according to the present invention have a glass transition temperature (Tg) of 240 ° C. or higher and a coefficient of thermal expansion of 24 to 32 ppm / ° C. and low heat. It has expansibility, is balanced with all of solder heat resistance, flame retardancy, copper foil peel strength, heat resistance with copper (T-288), and moisture resistance, and has high reliability.
On the other hand, as is apparent from Table 3, the insulating resin composition of the comparative example has a glass transition temperature (Tg) of 200 ° C. or lower and a coefficient of thermal expansion as high as 43 to 52 ppm / ° C. Moreover, it is inferior to any of the characteristics of copper foil peel strength, solder heat resistance, heat resistance with copper (T-288), moisture resistance, and flame retardancy, resulting in low reliability.
Claims (9)
（ａ）分子主鎖中に硫黄原子を有するジアミン化合物、
（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 Curing agent (A) obtained by reacting the following (a), (b) and (c) in an organic solvent, having a sulfur atom in the molecular main chain, and having an acidic substituent and an N-substituted maleimide group ) A thermosetting insulating resin composition comprising an epoxy resin (B) having at least two epoxy groups in one molecule and a phosphorus compound (C) imparting flame retardancy.
(A) a diamine compound having a sulfur atom in the molecular main chain,
(B) a maleimide compound having at least two N-substituted maleimide groups in the molecular structure;
(C) Monoamine compound
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009082884A JP5195582B2 (en) | 2009-03-30 | 2009-03-30 | Thermosetting insulating resin composition, and insulating film with support, prepreg, laminate and multilayer printed wiring board using the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009082884A JP5195582B2 (en) | 2009-03-30 | 2009-03-30 | Thermosetting insulating resin composition, and insulating film with support, prepreg, laminate and multilayer printed wiring board using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2010235690A JP2010235690A (en) | 2010-10-21 |
| JP5195582B2 true JP5195582B2 (en) | 2013-05-08 |
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| JP5407679B2 (en) * | 2009-09-04 | 2014-02-05 | 日立化成株式会社 | Thermosetting insulating resin composition, and insulating film with support, prepreg, laminate and multilayer printed wiring board using the same |
| JP5407678B2 (en) * | 2009-09-04 | 2014-02-05 | 日立化成株式会社 | Thermosetting insulating resin composition, and insulating film with support, prepreg, laminate and multilayer printed wiring board using the same |
| JP5540611B2 (en) * | 2009-09-04 | 2014-07-02 | 日立化成株式会社 | Thermosetting insulating resin composition, and insulating film with support, prepreg, laminate and printed wiring board using the same |
| JP5740940B2 (en) * | 2010-11-30 | 2015-07-01 | 味の素株式会社 | Method for producing metal-clad laminate |
| JP5914988B2 (en) * | 2011-05-27 | 2016-05-11 | 日立化成株式会社 | Prepreg, laminate and printed wiring board using thermosetting resin composition |
| KR101788738B1 (en) * | 2012-08-30 | 2017-10-20 | 삼성전기주식회사 | Insulating film and manufacturing method for insulating film |
| JP6172520B2 (en) * | 2013-10-31 | 2017-08-02 | パナソニックＩｐマネジメント株式会社 | Resin composition, prepreg, metal-clad laminate, and printed wiring board |
| US9708468B2 (en) | 2013-10-31 | 2017-07-18 | Panasonic Intellectual Property Management Co., Ltd. | Thermosetting resin composition, prepreg, metal clad laminate plate, and printed wiring board |
| JP6443657B2 (en) * | 2014-07-04 | 2018-12-26 | 日立化成株式会社 | Thermosetting insulating resin composition, and insulating film with support, prepreg, laminate and multilayer printed wiring board using the same |
| JP2016034996A (en) * | 2014-08-01 | 2016-03-17 | 日本化薬株式会社 | Epoxy resin composition, prepreg, metal-clad laminate and printed wiring board |
| WO2019225482A1 (en) * | 2018-05-21 | 2019-11-28 | 日立化成株式会社 | Resin varnish, prepreg, laminate, printed wiring board, and semiconductor package |
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| JPS5334895A (en) * | 1976-09-14 | 1978-03-31 | Hitachi Ltd | Heat resistant and flame retardant resin composition |
| JPH02209965A (en) * | 1989-02-10 | 1990-08-21 | Mitsui Toatsu Chem Inc | Resin composition for sealing semiconductor |
| JPH10298269A (en) * | 1997-04-24 | 1998-11-10 | Sumitomo Bakelite Co Ltd | Flame-retardant resin composition |
| JP5499544B2 (en) * | 2008-07-15 | 2014-05-21 | 日立化成株式会社 | Thermosetting insulating resin composition, and prepreg, film with resin, laminated board, and multilayer printed wiring board using the same |
| JP5149917B2 (en) * | 2009-03-27 | 2013-02-20 | 日立化成工業株式会社 | Thermosetting resin composition, and prepreg, laminate and multilayer printed wiring board using the same |
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