JP6476599B2 - Thermosetting resin composition, and prepreg, laminate and printed wiring board using the same - Google Patents
Thermosetting resin composition, and prepreg, laminate and printed wiring board using the same Download PDFInfo
- Publication number
- JP6476599B2 JP6476599B2 JP2014118860A JP2014118860A JP6476599B2 JP 6476599 B2 JP6476599 B2 JP 6476599B2 JP 2014118860 A JP2014118860 A JP 2014118860A JP 2014118860 A JP2014118860 A JP 2014118860A JP 6476599 B2 JP6476599 B2 JP 6476599B2
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- JP
- Japan
- Prior art keywords
- bis
- compound
- prepreg
- amino
- epoxy resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000011342 resin composition Substances 0.000 title claims description 36
- 229920001187 thermosetting polymer Polymers 0.000 title claims description 31
- -1 maleimide compound Chemical class 0.000 claims description 65
- 239000003822 epoxy resin Substances 0.000 claims description 33
- 229920000647 polyepoxide Polymers 0.000 claims description 33
- 125000003277 amino group Chemical group 0.000 claims description 20
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 14
- 239000011256 inorganic filler Substances 0.000 claims description 14
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 14
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 238000010030 laminating Methods 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 34
- 229920005989 resin Polymers 0.000 description 30
- 239000011347 resin Substances 0.000 description 30
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 14
- 239000004065 semiconductor Substances 0.000 description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 12
- 239000011521 glass Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 238000000465 moulding Methods 0.000 description 12
- 239000000377 silicon dioxide Substances 0.000 description 12
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 11
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 10
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000002966 varnish Substances 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 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 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 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 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000011889 copper foil Substances 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 229920003192 poly(bis maleimide) Polymers 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 4
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 4
- 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 4
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 3
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 3
- 229940018563 3-aminophenol Drugs 0.000 description 3
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 3
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 3
- 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 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 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
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000011810 insulating material Substances 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- ZGDMDBHLKNQPSD-UHFFFAOYSA-N 2-amino-5-(4-amino-3-hydroxyphenyl)phenol Chemical compound C1=C(O)C(N)=CC=C1C1=CC=C(N)C(O)=C1 ZGDMDBHLKNQPSD-UHFFFAOYSA-N 0.000 description 2
- 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 2
- HUWXDEQWWKGHRV-UHFFFAOYSA-N 3,3'-Dichlorobenzidine Chemical group C1=C(Cl)C(N)=CC=C1C1=CC=C(N)C(Cl)=C1 HUWXDEQWWKGHRV-UHFFFAOYSA-N 0.000 description 2
- XFDUHJPVQKIXHO-UHFFFAOYSA-N 3-aminobenzoic acid Chemical compound NC1=CC=CC(C(O)=O)=C1 XFDUHJPVQKIXHO-UHFFFAOYSA-N 0.000 description 2
- WECDUOXQLAIPQW-UHFFFAOYSA-N 4,4'-Methylene bis(2-methylaniline) Chemical compound C1=C(N)C(C)=CC(CC=2C=C(C)C(N)=CC=2)=C1 WECDUOXQLAIPQW-UHFFFAOYSA-N 0.000 description 2
- KHYXYOGWAIYVBD-UHFFFAOYSA-N 4-(4-propylphenoxy)aniline Chemical compound C1=CC(CCC)=CC=C1OC1=CC=C(N)C=C1 KHYXYOGWAIYVBD-UHFFFAOYSA-N 0.000 description 2
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 description 2
- HYDATEKARGDBKU-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]phenoxy]aniline Chemical group C1=CC(N)=CC=C1OC1=CC=C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 HYDATEKARGDBKU-UHFFFAOYSA-N 0.000 description 2
- 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 2
- PDCMTKJRBAZZHL-UHFFFAOYSA-N 5-aminobenzene-1,3-diol Chemical compound NC1=CC(O)=CC(O)=C1 PDCMTKJRBAZZHL-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004697 Polyetherimide Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000005456 alcohol based solvent Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229960004050 aminobenzoic acid Drugs 0.000 description 2
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 2
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 239000011362 coarse particle Substances 0.000 description 2
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- 238000009826 distribution Methods 0.000 description 2
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- 239000011888 foil Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 239000005453 ketone based solvent Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229940018564 m-phenylenediamine Drugs 0.000 description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 2
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- 238000012360 testing method Methods 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LRMDXTVKVHKWEK-UHFFFAOYSA-N 1,2-diaminoanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=C(N)C(N)=CC=C3C(=O)C2=C1 LRMDXTVKVHKWEK-UHFFFAOYSA-N 0.000 description 1
- FQYTUPYMTLWOOF-UHFFFAOYSA-N 1,3,4,6-tetramethylcyclohex-4-ene-1,3-diamine Chemical compound CC1C=C(C)C(C)(N)CC1(C)N FQYTUPYMTLWOOF-UHFFFAOYSA-N 0.000 description 1
- YTCGLFCOUJIOQH-UHFFFAOYSA-N 1,3,4-oxadiazole-2,5-diamine Chemical compound NC1=NN=C(N)O1 YTCGLFCOUJIOQH-UHFFFAOYSA-N 0.000 description 1
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical class NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 1
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- PUKLCKVOVCZYKF-UHFFFAOYSA-N 1-[2-(2,5-dioxopyrrol-1-yl)ethyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1CCN1C(=O)C=CC1=O PUKLCKVOVCZYKF-UHFFFAOYSA-N 0.000 description 1
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- QBSMHWVGUPQNJJ-UHFFFAOYSA-N 4-[4-(4-aminophenyl)phenyl]aniline Chemical compound C1=CC(N)=CC=C1C1=CC=C(C=2C=CC(N)=CC=2)C=C1 QBSMHWVGUPQNJJ-UHFFFAOYSA-N 0.000 description 1
- WZQMIRRWFURQIS-UHFFFAOYSA-N 4-[4-(4-phenoxyphenoxy)phenoxy]aniline Chemical compound NC1=CC=C(OC2=CC=C(OC3=CC=C(OC4=CC=CC=C4)C=C3)C=C2)C=C1 WZQMIRRWFURQIS-UHFFFAOYSA-N 0.000 description 1
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 1
- WDTRNCFZFQIWLM-UHFFFAOYSA-N 4-benzylaniline Chemical compound C1=CC(N)=CC=C1CC1=CC=CC=C1 WDTRNCFZFQIWLM-UHFFFAOYSA-N 0.000 description 1
- QYSWOQHLIDKEOL-UHFFFAOYSA-N 5,6-diamino-2-sulfanylidene-1h-pyrimidin-4-one Chemical compound NC=1NC(=S)NC(=O)C=1N QYSWOQHLIDKEOL-UHFFFAOYSA-N 0.000 description 1
- IIEKUGPEYLGWQQ-UHFFFAOYSA-N 5-[4-(4-amino-2-methylpentyl)phenyl]-4-methylpentan-2-amine Chemical compound CC(N)CC(C)CC1=CC=C(CC(C)CC(C)N)C=C1 IIEKUGPEYLGWQQ-UHFFFAOYSA-N 0.000 description 1
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- KBZFDRWPMZESDI-UHFFFAOYSA-N 5-aminobenzene-1,3-dicarboxylic acid Chemical compound NC1=CC(C(O)=O)=CC(C(O)=O)=C1 KBZFDRWPMZESDI-UHFFFAOYSA-N 0.000 description 1
- MBRGOFWKNLPACT-UHFFFAOYSA-N 5-methylnonane-1,9-diamine Chemical compound NCCCCC(C)CCCCN MBRGOFWKNLPACT-UHFFFAOYSA-N 0.000 description 1
- ZXLYUNPVVODNRE-UHFFFAOYSA-N 6-ethenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=C)=N1 ZXLYUNPVVODNRE-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
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- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
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- NINVTLPETSFOLR-UHFFFAOYSA-N NC1=CC=C(C=C1)C1=C(C=CC=2C3=CC=C(C=C3CC12)S(=O)(=O)O)S(=O)(=O)O Chemical compound NC1=CC=C(C=C1)C1=C(C=CC=2C3=CC=C(C=C3CC12)S(=O)(=O)O)S(=O)(=O)O NINVTLPETSFOLR-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
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- 239000003054 catalyst Substances 0.000 description 1
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- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- UCXUKTLCVSGCNR-UHFFFAOYSA-N diethylsilane Chemical compound CC[SiH2]CC UCXUKTLCVSGCNR-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
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- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- AXQWPCXWEZQIJV-UHFFFAOYSA-N n-methyl-5-[2-[4-(methylamino)pentyl]phenyl]pentan-2-amine Chemical compound CNC(C)CCCC1=CC=CC=C1CCCC(C)NC AXQWPCXWEZQIJV-UHFFFAOYSA-N 0.000 description 1
- OKBVMLGZPNDWJK-UHFFFAOYSA-N naphthalene-1,4-diamine Chemical compound C1=CC=C2C(N)=CC=C(N)C2=C1 OKBVMLGZPNDWJK-UHFFFAOYSA-N 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- GOGZBMRXLADNEV-UHFFFAOYSA-N naphthalene-2,6-diamine Chemical compound C1=C(N)C=CC2=CC(N)=CC=C21 GOGZBMRXLADNEV-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920002627 poly(phosphazenes) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- MIROPXUFDXCYLG-UHFFFAOYSA-N pyridine-2,5-diamine Chemical compound NC1=CC=C(N)N=C1 MIROPXUFDXCYLG-UHFFFAOYSA-N 0.000 description 1
- VHNQIURBCCNWDN-UHFFFAOYSA-N pyridine-2,6-diamine Chemical compound NC1=CC=CC(N)=N1 VHNQIURBCCNWDN-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
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- 150000003335 secondary amines Chemical class 0.000 description 1
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- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
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- LTURHSAEWJPFAA-UHFFFAOYSA-N sulfuric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OS(O)(=O)=O.NC1=NC(N)=NC(N)=N1 LTURHSAEWJPFAA-UHFFFAOYSA-N 0.000 description 1
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- 150000003512 tertiary amines Chemical class 0.000 description 1
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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- 230000001988 toxicity Effects 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
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- 150000003672 ureas Chemical class 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 0.000 description 1
Description
本発明は、熱硬化性樹脂組成物、並びにこれを用いたプリプレグ、積層板及びプリント配線板に関する。 The present invention relates to a thermosetting resin composition, and a prepreg, laminate and printed wiring board using the same.
近年、電子機器の小型化及び薄型化に伴い、電子機器に内蔵される半導体パッケージにも小型化及び薄型化が望まれている。半導体パッケージとは半導体パッケージ用配線板に半導体素子が搭載されたものを指す。薄型化された半導体パッケージでは、半導体パッケージ用配線板に半導体素子を実装するとき及び半導体パッケージを電子機器に搭載する組立時において、半導体パッケージ用配線板と半導体素子との熱膨張係数の差に起因した反りが大きな課題となっている。このため、半導体パッケージ用配線板向けの、低熱膨張性と高弾性を兼ね備えた材料が求められている。 In recent years, with the downsizing and thinning of electronic devices, there is a demand for miniaturization and thinning of semiconductor packages incorporated in electronic devices. The semiconductor package refers to a semiconductor package on which a semiconductor element is mounted. In the thinned semiconductor package, when mounting the semiconductor element on the semiconductor package wiring board and when assembling the semiconductor package mounted on the electronic device, it is caused by the difference in thermal expansion coefficient between the semiconductor package wiring board and the semiconductor element. Warping has become a major issue. For this reason, there is a demand for a material having both low thermal expansion and high elasticity for a semiconductor package wiring board.
半導体パッケージの小型化及び薄型化に伴い、半導体パッケージ用配線板等のプリント配線板に用いられる積層板には、高密度実装及び高多層化構成が適用されている。プリント配線板用積層板としては、エポキシ樹脂を主剤とした樹脂組成物とガラスクロスとを硬化して一体成形したものが一般的である。エポキシ樹脂は、絶縁性や耐熱性、コスト等のバランスに優れるが、高密度実装及び高多層化構成において生じる耐熱性向上という課題に応えるには限界があった。 With the miniaturization and thinning of semiconductor packages, high-density mounting and multi-layered configurations are applied to laminated boards used for printed wiring boards such as semiconductor package wiring boards. As a laminated board for printed wiring boards, a resin composition mainly composed of an epoxy resin and a glass cloth are cured and integrally molded. Epoxy resins have an excellent balance of insulation, heat resistance, cost, and the like, but have a limit to meet the problem of improving heat resistance that occurs in high-density mounting and multi-layered configurations.
一方、ビスマレイミド樹脂は、エポキシ樹脂に比べて耐熱性が非常に優れているため、このような高密度実装及び高多層化された積層板に広く使用することができる。しかし、ビスマレイミド樹脂は、吸湿性が高く、接着性に難点があった。さらに、エポキシ樹脂の場合１８０℃以下の温度で硬化可能であるが、ビスマレイミド樹脂を積層する場合は、２２０℃以上の温度で、硬化までに、エポキシ樹脂よりも長時間を要するため、ビスマレイミド樹脂は、生産性が悪いという欠点もあった。
特許文献１には、マレイミド化合物、酸性置換基を有するシリコーン化合物、及び熱硬化性樹脂を含有する熱硬化性樹脂組成物が低熱膨張性に優れることが開示されている。しかしながら、特許文献１のような熱硬化性樹脂組成物は、高弾性化という課題を解決するために、無機充填剤の充填率を上げると、プレス成形が困難になり、生産性や歩留まりに影響することがある。
このように、低熱膨張性と高弾性を兼ね備え、要求された生産性を満足できる熱硬化性樹脂組成物はなかった。
On the other hand, the bismaleimide resin is extremely superior in heat resistance as compared with the epoxy resin, and thus can be widely used for such high-density mounting and multi-layered laminated boards. However, the bismaleimide resin has high hygroscopicity and has a difficulty in adhesion. Further, in the case of an epoxy resin, it can be cured at a temperature of 180 ° C. or lower. However, when a bismaleimide resin is laminated, it takes a longer time than an epoxy resin to cure at a temperature of 220 ° C. or higher. Resins also have the disadvantage of poor productivity.
Patent Document 1 discloses that a thermosetting resin composition containing a maleimide compound, a silicone compound having an acidic substituent, and a thermosetting resin is excellent in low thermal expansion. However, in order to solve the problem of high elasticity, the thermosetting resin composition as in Patent Document 1 is difficult to press-mold when the filling rate of the inorganic filler is increased, which affects productivity and yield. There are things to do.
Thus, there has been no thermosetting resin composition that has both low thermal expansibility and high elasticity and can satisfy the required productivity.
本発明は、低熱膨張性に優れ、高弾性であり、そして積層板のプレス成形時の成形性に優れる熱硬化性樹脂組成物、これを用いたプリプレグ、積層板及びプリント配線板を提供することを課題とする。 The present invention provides a thermosetting resin composition that is excellent in low thermal expansion, high elasticity, and excellent in moldability during press molding of a laminate, and a prepreg, laminate, and printed wiring board using the same. Is an issue.
本発明者らは、上記の課題を解決するために鋭意研究を重ねた結果、特定のエポキシ樹脂と、１分子中に少なくとも２個のＮ−置換マレイミド基を有するマレイミド化合物と、１分子中に少なくとも１個のアミノ基を有するアミノ化合物を用いることで、無機充填剤の充填率を上げても、プレス成形時の成形性が良好な熱硬化性樹脂組成物が得られること見出し、本発明を完成するに至った。本発明は、かかる知見に基づいて完成したものである。 As a result of intensive studies to solve the above problems, the present inventors have found that a specific epoxy resin, a maleimide compound having at least two N-substituted maleimide groups in one molecule, and one molecule. By using an amino compound having at least one amino group, a thermosetting resin composition having good moldability during press molding can be obtained even when the filling rate of the inorganic filler is increased. It came to be completed. The present invention has been completed based on such findings.
すなわち、本発明は、以下の熱硬化性樹脂組成物、プリプレグ、積層板及びプリント配線板を提供する。
（１） （Ａ）１５０℃におけるＩＣＩ粘度が０．１Ｐａ・ｓ以下のエポキシ樹脂、（Ｂ）１分子中に少なくとも２個のＮ−置換マレイミド基を有するマレイミド化合物、（Ｃ）１分子中に少なくとも１個のアミノ基を有するアミノ化合物、及び（Ｄ）無機充填剤を配合してなる熱硬化性樹脂組成物。
（２） （Ｂ）１分子中に少なくとも２個のＮ−置換マレイミド基を有するマレイミド化合物が更にフェノキシ基を有する（１）に記載の熱硬化性樹脂組成物。
（３） （Ｃ）１分子中に少なくとも１個のアミノ基を有するアミノ化合物が、更に酸性置換基を有する（１）又は（２）に記載の熱硬化性樹脂組成物。
（４） （Ｃ）１分子中に少なくとも１個のアミノ基を有するアミノ化合物が、少なくとも２個のアミノ基を有する（１）〜（３）のいずれか１項に記載の熱硬化性樹脂組成物。
（５） （１）〜（４）のいずれか１項に記載の熱硬化性樹脂組成物を基材に含浸又は塗工して製造されるプリプレグ。
（６） （５）に記載のプリプレグを積層成形して得られる積層板。
（７） （６）に記載の積層板を用いて製造されるプリント配線板。
That is, the present invention provides the following thermosetting resin composition, prepreg, laminate and printed wiring board.
(1) (A) an epoxy resin having an ICI viscosity of 0.1 Pa · s or less at 150 ° C., (B) a maleimide compound having at least two N-substituted maleimide groups in one molecule, and (C) in one molecule. A thermosetting resin composition comprising an amino compound having at least one amino group and (D) an inorganic filler.
(2) (B) The thermosetting resin composition according to (1), wherein the maleimide compound having at least two N-substituted maleimide groups in one molecule further has a phenoxy group.
(3) (C) The thermosetting resin composition according to (1) or (2), wherein the amino compound having at least one amino group in one molecule further has an acidic substituent.
(4) (C) The thermosetting resin composition according to any one of (1) to (3), wherein the amino compound having at least one amino group in one molecule has at least two amino groups. object.
(5) A prepreg produced by impregnating or coating a base material with the thermosetting resin composition according to any one of (1) to (4).
(6) A laminate obtained by laminating the prepreg according to (5).
(7) A printed wiring board manufactured using the laminated board according to (6).
本発明によれば、低熱膨張性に優れ、高弾性であり、そして積層板のプレス成形時の成形性に優れる熱硬化性樹脂組成物、これを用いたプリプレグ、積層板及びプリント配線板を提供することができる。 According to the present invention, there are provided a thermosetting resin composition having excellent low thermal expansion, high elasticity, and excellent moldability during press molding of a laminate, and a prepreg, laminate and printed wiring board using the same. can do.
以下、発明について詳細に説明する。
本発明の熱硬化性樹脂組成物は、（Ａ）１５０℃におけるＩＣＩ粘度が０．１Ｐａ・ｓ以下のエポキシ樹脂（以下、（Ａ）成分と呼ぶことがある）、（Ｂ）１分子中に少なくとも２個のＮ−置換マレイミド基を有するマレイミド化合物（以下、（Ｂ）成分と呼ぶことがある）、（Ｃ）１分子中に少なくとも１個のアミノ基を有するアミノ化合物（以下、（Ｃ）成分と呼ぶことがある）、及び（Ｄ）無機充填剤（以下、（Ｄ）成分と呼ぶことがある）を配合してなる熱硬化性樹脂組成物である。
The invention will be described in detail below.
The thermosetting resin composition of the present invention comprises (A) an epoxy resin having an ICI viscosity of 0.1 Pa · s or less at 150 ° C. (hereinafter sometimes referred to as “component (A)”), and (B) in one molecule. A maleimide compound having at least two N-substituted maleimide groups (hereinafter sometimes referred to as component (B)), (C) an amino compound having at least one amino group in one molecule (hereinafter referred to as (C) And a thermosetting resin composition obtained by blending (D) an inorganic filler (hereinafter also referred to as (D) component).
本発明におけるエポキシ樹脂は、１５０℃におけるＩＣＩ粘度が０．１Ｐａ・ｓ以下であれば、特に限定されるものではなく、例えば、ナフタレン型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂等が挙げられる。 The epoxy resin in the present invention is not particularly limited as long as the ICI viscosity at 150 ° C. is 0.1 Pa · s or less. For example, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, bisphenol S type epoxy resin And bisphenol F type epoxy resin.
本発明の（Ａ）成分としては市販品を用いてもよい。市販品としては、例えば、ナフタレン型エポキシ樹脂として、ＤＩＣ株式会社製、商品名：ＥＸＡ−７３１１−Ｇ４（１５０℃におけるＩＣＩ粘度：０．０５Ｐａ・ｓ）、ジシクロペンタジエン型エポキシ樹脂として、ＤＩＣ株式会社製、商品名：ＨＰ−７２００Ｌ（１５０℃におけるＩＣＩ粘度：０．０３Ｐａ・ｓ）、ジシクロペンタジエン型エポキシ樹脂として、ＤＩＣ株式会社製、商品名：ＨＰ−７２００（１５０℃におけるＩＣＩ粘度：０．０６Ｐａ・ｓ）、ナフタレン型エポキシ樹脂として、ＤＩＣ株式会社製、商品名：ＨＰ−５０００Ｌ、ＨＰ−５０００（１５０℃におけるＩＣＩ粘度：０．０６Ｐａ・ｓ）、ビスフェノールＦ型エポキシ樹脂として、ＤＩＣ株式会社製、商品名：ＥＸＡ−１５１４（１５０℃におけるＩＣＩ粘度：０．０８Ｐａ・ｓ）、ビスフェノールＦ型エポキシ樹脂として、新日鉄住金化学株式会社製、商品名：ＹＳＬＶ−７０ＸＹ（１５０℃におけるＩＣＩ粘度：０．０１Ｐａ・ｓ）等が挙げられる。
本発明におけるＩＣＩ粘度は、ＩＣＩ粘度計として知られる高せん断速度を測定するもので、コーンプレート粘度計（Ｍ．Ｓ．Ｔ Ｅｎｇｉｎｅｅｒｉｎｇ製、装置名：ＩＣＩ ＣＯＮＥ ＡＮＤ ＰＬＡＴＥ ＶＩＳＣＯ ＭＥＴＥＲ）で測定される粘度である。
A commercially available product may be used as the component (A) of the present invention. Commercially available products include, for example, naphthalene type epoxy resin, manufactured by DIC Corporation, trade name: EXA-731-G4 (ICI viscosity at 150 ° C .: 0.05 Pa · s), dicyclopentadiene type epoxy resin, DIC stock Product name: HP-7200L (ICI viscosity at 150 ° C .: 0.03 Pa · s), dicyclopentadiene type epoxy resin, product name: HP-7200 (ICI viscosity at 150 ° C .: 0 .06 Pa · s), naphthalene type epoxy resin, manufactured by DIC Corporation, trade names: HP-5000L, HP-5000 (ICI viscosity at 150 ° C .: 0.06 Pa · s), bisphenol F type epoxy resin, DIC stock Product name: EXA-1514 (ICI viscosity at 150 ° C : 0.08 Pa · s), as bisphenol F type epoxy resin, Nippon Steel Sumitomo Metal Chemical Co., Ltd., trade name: ICI viscosity at YSLV-70XY (150 ℃: 0.01Pa · s), and the like.
The ICI viscosity in the present invention measures a high shear rate known as an ICI viscometer, and is measured with a cone plate viscometer (manufactured by MS Engineering, apparatus name: ICI CONE AND PLATE VISCO METER). It is.
本発明における（Ｂ）成分は、Ｎ−置換マレイミド基を１分子中に少なくとも２個有していれば、特に限定されるものではなく、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（例えば、大和化成株式会社製、商品名：ＢＭＩ−２３００）等が挙げられる。これらは１種を用いても、２種以上を併用してもよい。
これらの中でも、有機溶媒への溶解性の点から、１分子中に少なくとも２個のＮ−置換マレイミド基を有し、更にフェノキシ基を有するマレイミド化合物が好ましい。このようなマレイミド化合物としては、例えば、２，２−ビス［４−（４−マレイミドフェノキシ）フェニル］プロパン等が挙げられる。
（Ｂ）成分の使用量は、（Ａ）成分１００質量部に対して３０〜５００質量部が好ましく、７５〜２００質量部がより好ましい。３０質量部以上とすることにより耐薬品性が向上し、５００質量部以下とすることにより耐熱性が向上する。
The component (B) in the present invention is not particularly limited as long as it has at least two N-substituted maleimide groups in one molecule. For example, N, N′-ethylene bismaleimide, N, N '-Hexamethylene bismaleimide, N, N'-(1,3-phenylene) bismaleimide, N, N '-[1,3- (2-methylphenylene)] bismaleimide, N, N'-[1, 3- (4-methylphenylene)] bismaleimide, N, N ′-(1,4-phenylene) bismaleimide, bis (4-maleimidophenyl) methane, bis (3-methyl-4-maleimidophenyl) methane, 3 , 3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, bis (4-maleimidophenyl) ether, bis (4-maleimidophenyl) sulfone, bis (4-ma Imidophenyl) sulfide, bis (4-maleimidophenyl) ketone, bis (4-maleimidocyclohexyl) methane, 1,4-bis (4-maleimidophenyl) cyclohexane, 1,4-bis (maleimidomethyl) cyclohexane, 1,4 -Bis (maleimidomethyl) benzene, 1,3-bis (4-maleimidophenoxy) benzene, 1,3-bis (3-maleimidophenoxy) benzene, bis [4- (3-maleimidophenoxy) phenyl] methane, bis [ 4- (4-maleimidophenoxy) phenyl] methane, 1,1-bis [4- (3-maleimidophenoxy) phenyl] ethane, 1,1-bis [4- (4-maleimidophenoxy) phenyl] ethane, 1, 2-bis [4- (3-maleimidophenoxy) phenyl] ethane, 1,2 Bis [4- (4-maleimidophenoxy) phenyl] ethane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] propane, 2,2-bis [4- (4-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-hexafluoro Propane, 4,4-bis (3-maleimidophenoxy) biphenyl, 4,4-bis (4-maleimidophenoxy) biphenyl, bis [4- (3-maleimidophenoxy) Cis) phenyl] ketone, bis [4- (4-maleimidophenoxy) phenyl] ketone, 2,2′-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-dimethylbenzyl] 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 (for example, trade name: BMI-2300, manufactured by Daiwa Kasei Co., Ltd.), and the like. These may be used alone or in combination of two or more.
Among these, a maleimide compound having at least two N-substituted maleimide groups in one molecule and further having a phenoxy group is preferable from the viewpoint of solubility in an organic solvent. Examples of such maleimide compounds include 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane.
(B) As for the usage-amount of a component, 30-500 mass parts is preferable with respect to 100 mass parts of (A) component, and 75-200 mass parts is more preferable. Chemical resistance improves by setting it as 30 mass parts or more, and heat resistance improves by setting it as 500 mass parts or less.
本発明における（Ｃ）成分は、１個以上のアミノ基を有する化合物で特に限定されるものではないが、１分子中に少なくとも１個のアミノ基を有するアミノ化合物としては、更に酸性置換基を有するものや、少なくとも２個のアミノ基を有するものが好ましく、これらを併用することが特に好ましい。
１分子中に少なくとも１個のアミノ基を有するアミノ化合物であり、更に酸性置換基を有する化合物としては、例えば、ｍ−アミノフェノール、ｐ−アミノフェノール、ｏ−アミノフェノール、ｐ−アミノ安息香酸、ｍ−アミノ安息香酸、ｏ−アミノ安息香酸、ｏ−アミノベンゼンスルホン酸、ｍ−アミノベンゼンスルホン酸、ｐ−アミノベンゼンスルホン酸、３，５−ジヒドロキシアニリン、３，５−ジカルボキシアニリン等が挙げられる。
これらの中で、溶解性や合成の収率の点から、ｍ−アミノフェノール、ｐ−アミノフェノール、ｏ−アミノフェノール、ｐ−アミノ安息香酸、ｍ−アミノ安息香酸、及び３，５−ジヒドロキシアニリンが好ましい。また、耐熱性の点から、ｍ−アミノフェノール及びｐ−アミノフェノールがより好ましい。さらに、低熱膨張性の点から、ｐ−アミノフェノールが特に好ましい。
１分子中に少なくとも２個のアミノ基を有するアミノ化合物としては、例えば、ｍ−フェニレンジアミン、ｐ−フェニレンジアミン、４，６−ジメチル−ｍ−フェニレンジアミン、２，５−ジメチル−ｐ−フェニレンジアミン、２，３，５，６−テトラメチル−ｐ−フェニレンジアミン、２，４−ジアミノメシチレン、ｍ−キシレン−２，５−ジアミン、ｍ−キシリレンジアミン、ｐ−キシリレンジアミン、２，４−ジアミノトルエン、２，５−ジアミノトルエン、２，４−ビス（アミノ−ｔ−ブチル）トルエン、２，４−ジアミノキシレン、２，４−ジアミノピリジン、２，６−ジアミノピリジン、２，５−ジアミノピリジン、２，４−ジアミノデュレン、４，５−ジアミノ−６−ヒドロキシ−２−メルカプトピリミジン、３−ビス（３−アミノベンジル）ベンゼン、４−ビス（４−アミノベンジル）ベンゼン、１，４−ビス（４−アミノフェニル）ベンゼン、１，３−ビス（３−アミノフェノキシ）ベンゼン、１，３−ビス（４−アミノフェノキシ）ベンゼン、１，４−ビス（４−アミノフェノキシ）ベンゼン、３−ビス（３−（３−アミノフェノキシ）フェノキシ）ベンゼン、４−ビス（４−（４−アミノフェノキシ）フェノキシ）ベンゼン、３−ビス（３−（３−（３−アミノフェノキシ）フェノキシ）フェノキシ）ベンゼン、４−ビス（４−（４−（４−アミノフェノキシ）フェノキシ）フェノキシ）ベンゼン、３−ビス（α，α−ジメチル−３−アミノベンジル）ベンゼン、１，４−ビス（α，α−ジメチル−３−アミノベンジル）ベンゼン、３−ビス（α，α−ジメチル−４−アミノベンジル）ベンゼン、ビス（４−メチルアミノペンチル）ベンゼン、ｐ−ビス（２−メチル−４−アミノペンチル）ベンゼン、１，４−ビス（３−アミノプロピルジメチルシリル）ベンゼン、ビス［（４−アミノフェニル）−２−プロピル］１，４−ベンゼン、２，５−ジアミノベンゼンスルホン酸、３，３’−ジアミノジフェニルメタン、４，４’−ジアミノジフェニルメタン、３，３’−ジメチル−４，４’−ジアミノジフェニルメタン、３，３’，５，５’−テトラメチル−４，４’−ジアミノジフェニルメタン、３，３’−ジエチル−４，４’−ジアミノジフェニルメタン、３，３’−ジメチル、５，５’−ジエチル−４，４’−ジアミノジフェニルメタン、４，４’−メチレン−ビス（２−クロロアニリン）、３，３’−ジアミノジフェニルエタン、４，４’−ジアミノジフェニルエタン、２，２’−ジアミノジフェニルプロパン、３，３’−ジアミノジフェニルプロパン、４，４’−ジアミノジフェニルプロパン、２，２’−ビス［４−（４−アミノフェノキシ）フェニル］プロパン、２，２’−ビス［４−（４−アミノフェノキシ）フェニル］ヘキサフルオロプロパン、３−（２’，４’−ジアミノフェノキシ）プロパンスルホン酸、ビス（４−アミノフェニル）ジエチルシラン、３，３’−ジアミノベンゾフェノン、４，４’−ジアミノベンゾフェノン、３，３’−ジアミノジフェニルエーテル、４，４’−ジアミノジフェニルエーテル、３，３’−ジメチル−４，４’−ジアミノジフェニルエーテル、ビス（４−アミノ−ｔ−ブチルフェニル）エ−テル、４，４’−ジアミノジフェニルエーテル−２，２’−ジスルホン酸、３，３’−ジアミノジフェニルスルホン、４，４’−ジアミノジフェニルスルホン、ビス［４−（４−アミノフェノキシ）フェニル］スルホン、ビス［４−（３−アミノフェノキシ）フェニル］スルホン、ベンジジン、２，２’−ジメチル−４，４’−ジアミノビフェニル、３，３’−ジメチル−４，４’−ジアミノビフェニル、３，３’−ジメトキシ−４，４’−ジアミノビフェニル、３，３’−ジメチル−４，４’−ジアミノビフェニル−６，６’−ジスルホン酸、２，２’，５，５’−テトラクロロ−４，４’−ジアミノビフェニル、３，３’−ジクロロ−４，４’−ジアミノビフェニル、３，３’−ジクロロ−４，４’−ジアミノビフェニル、４，４’−ビス（４−アミノフェノキシ）ビフェニル、４，４’−ジアミノジフェニルスルフィド、４，４’−ジアミノ−３，３’−ビフェニルジオール、１，５−ジアミノナフタレン、１，４−ジアミノナフタレン、２，６−ジアミノナフタレン、９，９’−ビス（４−アミノフェニル）フルオレン、９，９’−ビス（４−アミノフェニル）フルオレン−２，７−ジスルホン酸、９，９’−ビス（４−アミノフェノキシフェニル）フルオレン、ジアミノアントラキノン、３，７−ジアミノ−２，８−ジメチルジベンゾチオフェンスルホン等の芳香族アミン類、エチレンジアミン、テトラメチレンジアミン、ペンタメチレンジアミン、ヘキサメチレンジアミン、ヘプタメチレンジアミン、オクタメチレンジアミン、ノナメチレンジアミン、デカメチレンジアミン、２，５−ジメチルヘキサメチレンジアミン、３−メトキシヘキサメチレンジアミン、２，５−ジメチルヘプタメチレンジアミン、３−メチルヘプタメチレンジアミン、４，４−ジメチルヘプタメチレンジアミン、５−メチルノナメチレンジアミン、１，４−ジアミノシクロヘキサン、１，３−ビス（３−アミノプロピル）テトラメチルジシロキサン、２，５−ジアミノ−１，３，４−オキサジアゾ−ル、ビス（４−アミノシクロヘキシル）メタン等の脂肪族アミン類、メラミン、ベンゾグアナミン、アセトグアナミン、２，４−ジアミノ−６−ビニル−ｓ−トリアジン、２，４−ジアミノ−６−アリル−ｓ−トリアジン、２，４−ジアミノ−６−アクリロイルオキシエチル−ｓ−トリアジン、２，４−ジアミノ−６−メタクリロイルオキシエチル−ｓ−トリアジンのグアナミン化合物類などが挙げられる。
これらの中でも、良好な反応性や耐熱性を有する芳香族アミン類であるｍ−フェニレンジアミン、ｐ−フェニレンジアミン、１，４−ビス（４−アミノフェノキシ）ベンゼン、４，４’−ジアミノジフェニルメタン、３，３’−ジメチル−４，４’−ジアミノジフェニルメタン、３，３’−ジエチル−４，４’−ジアミノジフェニルメタン、２，２’−ビス［４−（４−アミノフェノキシ）フェニル］プロパン、４，４’−ジアミノベンゾフェノン、４，４’−ジアミノジフェニルエーテル、３，３’−ジアミノジフェニルスルホン、４，４’−ジアミノジフェニルスルホン、ビス［４−（４−アミノフェノキシ）フェニル］スルホン、ベンジジン、４，４’−ビス（４−アミノフェノキシ）ビフェニル、４，４’−ジアミノジフェニルスルフィド、４，４’−ジアミノ−３，３’−ビフェニルジオール、及びグアナミン化合物類であるベンゾグアナミンが好ましい。
これらのうち安価である点から、ｐ−フェニレンジアミン、４，４’−ジアミノジフェニルメタン、４，４’−ジアミノジフェニルエーテル、３，３’−ジアミノジフェニルスルホン、４，４’−ジアミノジフェニルスルホン、３，３’−ジメチル−４，４’−ジアミノジフェニルメタン、３，３’−ジエチル−４，４’−ジアミノジフェニルメタン、ベンゾグアナミンがより好ましい。毒性や溶剤への溶解性の点から、３，３’−ジアミノジフェニルスルホン、３，３’−ジエチル−４，４’−ジアミノジフェニルメタンが特に好ましい。
The component (C) in the present invention is not particularly limited as a compound having one or more amino groups, but as an amino compound having at least one amino group in one molecule, an acidic substituent is further added. And those having at least two amino groups are preferred, and it is particularly preferred to use these in combination.
Examples of compounds having at least one amino group in one molecule and further having an acidic substituent include m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, o-aminobenzoic acid, o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, 3,5-dicarboxyaniline, etc. It is done.
Among these, m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, and 3,5-dihydroxyaniline in terms of solubility and synthesis yield. Is preferred. Moreover, m-aminophenol and p-aminophenol are more preferable from the viewpoint of heat resistance. Furthermore, p-aminophenol is particularly preferable from the viewpoint of low thermal expansion.
Examples of the amino compound having at least two amino groups in one molecule include m-phenylenediamine, p-phenylenediamine, 4,6-dimethyl-m-phenylenediamine, and 2,5-dimethyl-p-phenylenediamine. 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4-diaminomesitylene, m-xylene-2,5-diamine, m-xylylenediamine, p-xylylenediamine, 2,4- Diaminotoluene, 2,5-diaminotoluene, 2,4-bis (amino-t-butyl) toluene, 2,4-diaminoxylene, 2,4-diaminopyridine, 2,6-diaminopyridine, 2,5-diamino Pyridine, 2,4-diaminodurene, 4,5-diamino-6-hydroxy-2-mercaptopyrimidine, 3-bis (3- Minobenzyl) benzene, 4-bis (4-aminobenzyl) benzene, 1,4-bis (4-aminophenyl) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-amino) Phenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3-bis (3- (3-aminophenoxy) phenoxy) benzene, 4-bis (4- (4-aminophenoxy) phenoxy) benzene, 3 -Bis (3- (3- (3-aminophenoxy) phenoxy) phenoxy) benzene, 4-bis (4- (4- (4-aminophenoxy) phenoxy) phenoxy) benzene, 3-bis (α, α-dimethyl) -3-aminobenzyl) benzene, 1,4-bis (α, α-dimethyl-3-aminobenzyl) benzene, 3-bis (α, α-dimethyl) 4-aminobenzyl) benzene, bis (4-methylaminopentyl) benzene, p-bis (2-methyl-4-aminopentyl) benzene, 1,4-bis (3-aminopropyldimethylsilyl) benzene, bis [( 4-aminophenyl) -2-propyl] 1,4-benzene, 2,5-diaminobenzenesulfonic acid, 3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,3′-dimethyl-4, 4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl, 5 , 5′-diethyl-4,4′-diaminodiphenylmethane, 4,4′-methylene-bis (2-chloroaniline), 3,3′-diaminodiphenyl Ethane, 4,4′-diaminodiphenylethane, 2,2′-diaminodiphenylpropane, 3,3′-diaminodiphenylpropane, 4,4′-diaminodiphenylpropane, 2,2′-bis [4- (4- Aminophenoxy) phenyl] propane, 2,2′-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 3- (2 ′, 4′-diaminophenoxy) propanesulfonic acid, bis (4-aminophenyl) ) Diethylsilane, 3,3′-diaminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,3′-dimethyl-4,4′-diaminodiphenyl ether Bis (4-amino-tert-butylphenyl) ether, 4,4′-diaminodiphenyl ether -2,2'-disulfonic acid, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) ) Phenyl] sulfone, benzidine, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diamino Biphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl-6,6′-disulfonic acid, 2,2 ′, 5,5′-tetrachloro-4,4′-diaminobiphenyl, 3,3 ′ -Dichloro-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'-diaminodiphenylsulfur Fido, 4,4′-diamino-3,3′-biphenyldiol, 1,5-diaminonaphthalene, 1,4-diaminonaphthalene, 2,6-diaminonaphthalene, 9,9′-bis (4-aminophenyl) Fluorene, 9,9′-bis (4-aminophenyl) fluorene-2,7-disulfonic acid, 9,9′-bis (4-aminophenoxyphenyl) fluorene, diaminoanthraquinone, 3,7-diamino-2,8 -Aromatic amines such as dimethyldibenzothiophene sulfone, ethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, 2,5-dimethylhexamethylenediamine 3-methoxyhexamethylene di Min, 2,5-dimethylheptamethylenediamine, 3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 5-methylnonamethylenediamine, 1,4-diaminocyclohexane, 1,3-bis (3-amino Propyl) tetramethyldisiloxane, 2,5-diamino-1,3,4-oxadiazol, aliphatic amines such as bis (4-aminocyclohexyl) methane, melamine, benzoguanamine, acetoguanamine, 2,4-diamino -6-vinyl-s-triazine, 2,4-diamino-6-allyl-s-triazine, 2,4-diamino-6-acryloyloxyethyl-s-triazine, 2,4-diamino-6-methacryloyloxyethyl Examples include guanamine compounds of -s-triazine.
Among these, m-phenylenediamine, p-phenylenediamine, 1,4-bis (4-aminophenoxy) benzene, 4,4′-diaminodiphenylmethane, which are aromatic amines having good reactivity and heat resistance, 3,3′-dimethyl-4,4′-diaminodiphenylmethane, 3,3′-diethyl-4,4′-diaminodiphenylmethane, 2,2′-bis [4- (4-aminophenoxy) phenyl] propane, 4 , 4′-diaminobenzophenone, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, benzidine, 4 , 4′-bis (4-aminophenoxy) biphenyl, 4,4′-diaminodiphenyl sulfide, 4,4′- Diamino-3,3′-biphenyldiol and benzoguanamine which is a guanamine compound are preferable.
Among these, p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfone, 3, More preferred are 3′-dimethyl-4,4′-diaminodiphenylmethane, 3,3′-diethyl-4,4′-diaminodiphenylmethane, and benzoguanamine. From the viewpoint of toxicity and solubility in a solvent, 3,3′-diaminodiphenyl sulfone and 3,3′-diethyl-4,4′-diaminodiphenylmethane are particularly preferable.
上記の（Ｃ）成分は、１種を用いても、２種以上を併用してもよい。ここで、（Ｃ）成分の使用量は、−ＮＨ2基当量の総和と、（Ｂ）成分のＣ＝Ｃ基当量との関係が、次式に示す範囲になることが好ましい。
０．１≦〔Ｃ＝Ｃ基当量〕／〔−ＮＨ2基当量の総和〕≦１０．０
さらに好ましくは、この関係が次式に示す範囲になることである。
１．０≦〔Ｃ＝Ｃ基当量〕／〔−ＮＨ2基当量の総和〕≦９．０
特に好ましくは、この関係が次式に示す範囲になることである。
２．０≦〔Ｃ＝Ｃ基当量〕／〔−ＮＨ2基当量の総和〕≦８．０
該当量比を０．１以上とすることにより、熱硬化性樹脂組成物のゲル化が抑制される傾向にあり、熱硬化性樹脂組成物の良好な耐熱性が得られる。また、該当量比を１０．０以下とすることにより、（Ｃ）成分の有機溶剤への溶解性の低下が抑制される傾向にあり、熱硬化性樹脂組成物の良好な耐熱性が得られる。
Said (C) component may use 1 type, or may use 2 or more types together. Here, the amount of component (C), 2 group and the sum of the equivalents of -NH, the relationship between the C = C group equivalent of the component (B), it is preferable that the range shown in the following equation.
0.1 ≦ [C = C group equivalent] / [-NH 2 group equivalent] ≦ 10.0
More preferably, this relationship is within the range shown in the following equation.
1.0 ≦ [C = C group equivalent] / [total of —NH 2 group equivalent] ≦ 9.0
Particularly preferably, this relationship is within the range shown in the following equation.
2.0 ≦ [C = C group equivalent] / [total of —NH 2 group equivalent] ≦ 8.0
When the amount ratio is 0.1 or more, gelation of the thermosetting resin composition tends to be suppressed, and good heat resistance of the thermosetting resin composition is obtained. In addition, by setting the corresponding amount ratio to 10.0 or less, a decrease in solubility of the component (C) in the organic solvent tends to be suppressed, and good heat resistance of the thermosetting resin composition can be obtained. .
本発明の熱硬化性樹脂組成物では、（Ｂ）成分と（Ｃ）成分とを、必要により反応させてもよい。当該反応で得られる、アミノ基、イミド基及びＮ−置換マレイミド基を有する化合物を、本発明の熱硬化性樹脂組成物に配合させてもよい。
この反応の際の（Ｂ）成分の使用量は、上記式を満たす範囲であることが好ましい。
また、反応条件は特に限定されるものではなく、当該反応温度は７０〜２００℃とすることが好ましく、反応時間は０．５〜１０時間とすることが好ましい。
In the thermosetting resin composition of the present invention, the component (B) and the component (C) may be reacted as necessary. You may make the thermosetting resin composition of this invention mix | blend the compound which has an amino group, an imide group, and N-substituted maleimide group obtained by the said reaction.
The amount of component (B) used in this reaction is preferably in the range satisfying the above formula.
Moreover, reaction conditions are not specifically limited, It is preferable that the said reaction temperature shall be 70-200 degreeC, and it is preferable that reaction time shall be 0.5 to 10 hours.
以上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などが挙げられる。これらは１種を用いても、２種以上を併用してもよい。
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、及びジメチルアセトアミドが好ましく、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、及びジメチルアセトアミドが特に好ましい。
The organic solvent used in the above reaction is not particularly limited, but for example, alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Ketone solvents, ester solvents such as ethyl acetate and γ-butyrolactone, ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene and mesitylene, nitrogen atoms such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone Examples thereof include a solvent containing a sulfur atom-containing solvent such as dimethyl sulfoxide. These may be used alone or in combination of two or more.
Among these, cyclohexanone, propylene glycol monomethyl ether, methyl cellosolve, γ-butyrolactone, and dimethylacetamide are preferable from the viewpoint of solubility, and have low toxicity and high volatility, so that they do not remain as residual solvents when producing prepregs. To cyclohexanone, propylene glycol monomethyl ether, and dimethylacetamide are particularly preferred.
有機溶媒の使用量は、溶解性と反応時間の観点から、（Ｂ）成分と（Ｃ）成分との合計量１００質量部に対して、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。
また、上記反応には、必要により反応触媒を使用することができる。反応触媒としては、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挙げられる。これらは１種を用いても、２種以上を併用してもよい。
From the viewpoint of solubility and reaction time, the organic solvent is preferably used in an amount of 25 to 1000 parts by mass with respect to 100 parts by mass of the total amount of the component (B) and the component (C). It is more preferable to use a mass part.
In the above reaction, a reaction catalyst can be used as necessary. The reaction catalyst is not particularly limited, and examples thereof include amines such as triethylamine, pyridine, and tributylamine, imidazoles such as methylimidazole and phenylimidazole, and phosphorus-based catalysts such as triphenylphosphine. These may be used alone or in combination of two or more.
（Ｄ）無機充填剤としては、例えば、シリカ、アルミナ、タルク、マイカ、カオリン、水酸化アルミニウム、ベーマイト、水酸化マグネシウム、ホウ酸亜鉛、スズ酸亜鉛、酸化亜鉛、酸化チタン、窒化ホウ素、炭酸カルシウム、硫酸バリウム、ホウ酸アルミニウム、チタン酸カリウム、ＥガラスやＴガラス、Ｄガラス等のガラス粉や中空ガラスビーズなどが挙げられる。これらは１種を用いても、２種以上を併用してもよい。
（Ｄ）無機充填剤としては、誘電特性、耐熱性、低熱膨張性の点からシリカが特に好ましい。シリカとしては、例えば、湿式法で製造され含水率の高い沈降シリカと、乾式法で製造され結合水等をほとんど含まない乾式法シリカが挙げられる。乾式法シリカとしてはさらに、製造法の違いにより破砕シリカ、フュームドシリカ、溶融球状シリカが挙げられる。これらの中で、低熱膨張性及び樹脂に充填した際の高流動性から溶融球状シリカが好ましい。
（Ｄ）無機充填剤として溶融球状シリカを用いる場合、その平均粒子径は０．１〜１０μｍであることが好ましく、０．３〜８μｍであることがより好ましい。該溶融球状シリカの平均粒子径を０．１μｍ以上にすることで、樹脂に高充填した際の流動性を良好に保つことができ、さらに１０μｍ以下にすることで、粗大粒子の混入確率を減らし粗大粒子起因の不良の発生を抑えることができる。ここで、平均粒子径とは、粒子の全体積を１００％として粒子径による累積度数分布曲線を求めたとき、体積５０％に相当する点の粒子径であり、レーザ回折散乱法を用いた粒度分布測定装置等で測定することができる。また、異なる粒径のシリカを組み合わせて充填することで、さらなる充填化が可能となり、流動性を維持したまま充填率の向上が可能となる。
（Ｄ）無機充填剤の配合量は、固形分換算の（Ａ）〜（Ｃ）成分の総和１００質量部当たり１０〜３００質量部であることが好ましく、５０〜２５０質量部であることがより好ましい。無機充填剤の含有量を樹脂成分の総和１００質量部当たり１０〜３００質量部にすることで、樹脂組成物の成形性と低熱膨張性を良好に保つことができる。
(D) Examples of inorganic fillers include silica, alumina, talc, mica, kaolin, aluminum hydroxide, boehmite, magnesium hydroxide, zinc borate, zinc stannate, zinc oxide, titanium oxide, boron nitride, and calcium carbonate. , Barium sulfate, aluminum borate, potassium titanate, glass powder such as E glass, T glass, D glass, and hollow glass beads. These may be used alone or in combination of two or more.
(D) As the inorganic filler, silica is particularly preferable in terms of dielectric properties, heat resistance, and low thermal expansion. Examples of the silica include precipitated silica produced by a wet method and having a high water content, and dry method silica produced by a dry method and containing almost no bound water or the like. Examples of the dry process silica further include crushed silica, fumed silica, and fused spherical silica depending on the production method. Among these, fused spherical silica is preferable because of its low thermal expansion and high fluidity when filled in a resin.
(D) When using fused spherical silica as the inorganic filler, the average particle size is preferably 0.1 to 10 μm, and more preferably 0.3 to 8 μm. By setting the average particle diameter of the fused spherical silica to 0.1 μm or more, the fluidity when the resin is highly filled can be kept good, and by setting it to 10 μm or less, the mixing probability of coarse particles is reduced. Generation of defects due to coarse particles can be suppressed. Here, the average particle diameter is a particle diameter at a point corresponding to a volume of 50% when the cumulative frequency distribution curve by the particle diameter is obtained with the total volume of the particles being 100%, and the particle size using the laser diffraction scattering method. It can be measured with a distribution measuring device or the like. Further, by combining and packing silica having different particle diameters, further filling is possible, and the filling rate can be improved while maintaining fluidity.
(D) The blending amount of the inorganic filler is preferably 10 to 300 parts by mass and more preferably 50 to 250 parts by mass per 100 parts by mass of the total of components (A) to (C) in terms of solid content. preferable. By making content of an inorganic filler into 10-300 mass parts per 100 mass parts of sum total of a resin component, the moldability and low thermal expansibility of a resin composition can be kept favorable.
本発明の熱硬化性樹脂組成物には、硬化促進剤を配合してもよい。硬化促進剤としては、例えば、イミダゾール類及びその誘導体、有機リン系化合物、第二級アミン類、第三級アミン類、並びに第四級アンモニウム塩等が挙げられる。これらは１種を用いても、２種以上を併用してもよい。 You may mix | blend a hardening accelerator with the thermosetting resin composition of this invention. Examples of the curing accelerator include imidazoles and derivatives thereof, organic phosphorus compounds, secondary amines, tertiary amines, and quaternary ammonium salts. These may be used alone or in combination of two or more.
本発明の熱硬化性樹脂組成物には、その他の成分として、例えば、熱可塑性樹脂、エラストマー、有機充填材、難燃剤、紫外線吸収剤、酸化防止剤、光重合開始剤、蛍光増白剤、接着性向上剤等を配合してもよい。
熱可塑性樹脂の例としては、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、ポリアミドイミド樹脂、ポリイミド樹脂、キシレン樹脂、ポリフェニレンスルフィド樹脂、ポリエーテルイミド樹脂、ポリエーテルエーテルケトン樹脂、ポリエーテルイミド樹脂、シリコーン樹脂、テトラフルオロエチレ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、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アクリロニトリル等が挙げられる。
有機充填材の例としては、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、シリコーン樹脂、テトラフルオロエチレン樹脂等よりなる樹脂フィラー、アクリル酸エステル系樹脂、メタクリル酸エステル系樹脂、共役ジエン系樹脂等よりなるゴム状態のコア層と、アクリル酸エステル系樹脂、メタクリル酸エステル系樹脂、芳香族ビニル系樹脂、シアン化ビニル系樹脂よりなるガラス状態のシェル層を持つコアシェル構造の樹脂フィラー等が挙げられる。
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、トリフェニルホスフェート、トリクレジルホスフェート、トリスジクロロプロピルホスフェート、リン酸エステル系化合物、赤リン等のリン系難燃剤、スルファミン酸グアニジン、硫酸メラミン、ポリリン酸メラミン、メラミンシアヌレート等の窒素系難燃剤、シクロホスファゼン、ポリホスファゼン等のホスファゼン系難燃剤、三酸化アンチモン等の無機系難燃剤などが挙げられる。
紫外線吸収剤の例としてはベンゾトリアゾール系紫外線吸収剤、酸化防止剤の例としてはヒンダードフェノール系やヒンダードアミン系酸化防止剤、光重合開始剤の例としてはベンゾフェノン類、ベンジルケタール類、チオキサントン系の光重合開始剤、蛍光増白剤の例としてはスチルベン誘導体の蛍光増白剤、接着性向上剤の例としては尿素シラン等の尿素化合物やシラン系、チタネート系、アルミネート系等のカップリング剤が挙げられる。
In the thermosetting resin composition of the present invention, as other components, for example, a thermoplastic resin, an elastomer, an organic filler, a flame retardant, an ultraviolet absorber, an antioxidant, a photopolymerization initiator, a fluorescent whitening agent, You may mix | blend an adhesive improvement agent etc.
Examples of thermoplastic resins include polyethylene, polypropylene, polystyrene, polyphenylene ether resin, phenoxy resin, polycarbonate resin, polyester resin, polyamide resin, polyamideimide resin, polyimide resin, xylene resin, polyphenylene sulfide resin, polyetherimide resin, poly Examples include ether ether ketone resins, polyether imide resins, silicone resins, and tetrafluoroethylene resins.
Examples of the elastomer include polybutadiene, acrylonitrile, epoxy-modified polybutadiene, maleic anhydride-modified polybutadiene, phenol-modified polybutadiene, and carboxy-modified acrylonitrile.
Examples of organic fillers include resin fillers made of polyethylene, polypropylene, polystyrene, polyphenylene ether resins, silicone resins, tetrafluoroethylene resins, acrylic ester resins, methacrylic ester resins, conjugated diene resins, etc. Examples thereof include a resin filler having a core-shell structure having a rubbery core layer and a glassy shell layer made of an acrylic ester resin, a methacrylic ester resin, an aromatic vinyl resin, or a vinyl cyanide resin.
Examples of flame retardants include halogen-containing flame retardants containing bromine and chlorine, triphenyl phosphate, tricresyl phosphate, trisdichloropropyl phosphate, phosphoric ester compounds, phosphorous flame retardants such as red phosphorus, sulfamic acid Nitrogen flame retardants such as guanidine, melamine sulfate, melamine polyphosphate and melamine cyanurate, phosphazene flame retardants such as cyclophosphazene and polyphosphazene, and inorganic flame retardants such as antimony trioxide.
Examples of UV absorbers include benzotriazole UV absorbers, examples of antioxidants include hindered phenols and hindered amines, and examples of photopolymerization initiators include benzophenones, benzyl ketals, and thioxanthones. Examples of photopolymerization initiators and fluorescent brighteners include fluorescent brighteners of stilbene derivatives, and examples of adhesion improvers include urea compounds such as urea silane and silane, titanate, and aluminate coupling agents. Is mentioned.
また、無機充填剤を配合する際に、無機充填剤をシラン系、チタネート系等のカップリング剤、シリコーンオリゴマー等の表面処理剤で前処理、あるいはインテグラルブレンド処理することも好ましい。 In addition, when blending the inorganic filler, it is also preferable that the inorganic filler is pretreated with a silane-based or titanate-based coupling agent, or a surface treatment agent such as a silicone oligomer, or an integral blend treatment.
本発明の熱硬化性樹脂組成物は、通常、希釈溶媒として有機溶媒を使用し、各成分が有機溶媒中に溶解又は分散されたワニスの状態で使用される。該有機溶媒は特に制限されないが、例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶媒、メチルセロソルブ等のアルコール系溶媒、テトラヒドロフランなどのエーテル系溶媒、トルエン、キシレン、メシチレンなどの芳香族系溶媒が挙げられる。これらは１種を用いても、２種以上を併用してもよい。 The thermosetting resin composition of the present invention is usually used in the state of a varnish in which an organic solvent is used as a diluting solvent and each component is dissolved or dispersed in the organic 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. And system solvents. These may be used alone or in combination of two or more.
最終的に得られるワニス中の樹脂組成物は、ワニス全体の４０〜９０質量％であることが好ましく、５０〜８０質量％であることがより好ましい。ワニス中の樹脂組成物の含有量を４０〜９０質量％にすることで、塗工性を良好に保ち、適切な樹脂組成物付着量のプリプレグを得ることができる It is preferable that the resin composition in the varnish finally obtained is 40 to 90 mass% of the whole varnish, and it is more preferable that it is 50 to 80 mass%. By setting the content of the resin composition in the varnish to 40 to 90% by mass, it is possible to maintain good coating properties and obtain a prepreg having an appropriate resin composition adhesion amount.
本発明のプリプレグは、本発明の熱硬化性樹脂組成物を、基材に含浸又は塗工して製造されるものである。すなわち、本発明の熱硬化性樹脂組成物を、基材に含浸又は、吹付け、押出し等の方法で塗工した後、加熱等により半硬化の状態（Ｂステージ状態）にして本発明のプリプレグを製造することができる。以下、本発明のプリプレグについて詳述する。 The prepreg of the present invention is produced by impregnating or coating the base material with the thermosetting resin composition of the present invention. That is, after the thermosetting resin composition of the present invention is applied to a substrate by a method such as impregnation, spraying or extrusion, it is made into a semi-cured state (B stage state) by heating or the like, and then the prepreg of the present invention. Can be manufactured. Hereinafter, the prepreg of the present invention will be described in detail.
本発明のプリプレグに用いられる基材として、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などが挙げられる。
これらの基材は、例えば、織布、不織布、ロービンク、チョップドストランドマット及びサーフェシングマット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る。これらは、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のものを使用することができ、シランカップリング剤等で表面処理したもの又は機械的に開繊処理を施したものが、耐熱性や耐湿性、加工性の面から好適である。
該基材に対する樹脂組成物の付着量が、乾燥後のプリプレグの樹脂含有率で、２０〜９０質量％となるように、基材に含浸又は塗工した後、通常、１００〜２００℃の温度で１〜３０分加熱乾燥し、半硬化の状態（Ｂステージ状態）にすることで、本発明のプリプレグを製造することができる。
As the base material used in the prepreg of the present invention, known materials used for various types of laminates for electrical insulating materials can be used. Examples of the material include inorganic fibers such as E glass, D glass, S glass and Q glass, organic fibers such as polyimide, polyester and tetrafluoroethylene, and mixtures thereof.
These base materials have shapes such as woven fabric, non-woven fabric, robink, chopped strand mat, and surfacing mat, and the material and shape are selected depending on the intended use and performance of the molded product. These can be used alone or in combination of two or more kinds of materials and shapes.
The thickness of the substrate is not particularly limited. For example, a substrate having a thickness of about 0.03 to 0.5 mm can be used, and the substrate is surface-treated with a silane coupling agent or the like, or mechanically opened. Is suitable from the viewpoints of heat resistance, moisture resistance and processability.
After impregnating or coating the base material so that the amount of the resin composition attached to the base material is 20 to 90% by mass in terms of the resin content of the prepreg after drying, the temperature is usually 100 to 200 ° C. The prepreg of the present invention can be produced by heating and drying for 1 to 30 minutes to obtain a semi-cured state (B stage state).
本発明の積層板は、本発明のプリプレグを積層成形して得られるものである。例えば、前述のプリプレグを、１〜２０枚重ね、その片面又は両面に銅及びアルミニウム等の金属箔を配置した構成で積層成形することにより積層板を製造することができる。金属箔は、電気絶縁材料用積層板で用いるものであれば特に制限されない。また、成形条件は、例えば、電気絶縁材料用積層板及び多層板の手法が適用でき、例えば多段プレス、多段真空プレス、連続成形、オートクレーブ成形機等を使用し、温度１００〜２５０℃、圧力０．２〜１０ＭＰａ、昇温速度１〜１０℃／分、加熱時間０．１〜５時間の範囲で成形することができる。また、本発明のプリプレグと内層用配線板とを組合せ、積層成形して、多層板を製造することもできる。 The laminate of the present invention is obtained by laminating the prepreg of the present invention. For example, a laminated board can be manufactured by laminating 1-20 sheets of the prepregs described above and laminating them with a structure in which a metal foil such as copper and aluminum is disposed on one or both sides thereof. The metal foil is not particularly limited as long as it is used for the laminate for an electrical insulating material. The molding conditions may be, for example, a laminated plate for an electrical insulating material and a multilayer plate. For example, a multistage press, a multistage vacuum press, continuous molding, an autoclave molding machine or the like is used, and the temperature is 100 to 250 ° C. and the pressure is 0. It can be molded in a range of 2 to 10 MPa, a temperature increase rate of 1 to 10 ° C./min, and a heating time of 0.1 to 5 hours. Further, the prepreg of the present invention and the inner layer wiring board can be combined and laminated to produce a multilayer board.
本発明のプリント配線板は、本発明の積層板を用いて製造されるものである。例えば、本発明の積層板の導体層を通常のエッチング法によって配線加工し、前述のプリプレグを介して配線加工した積層板を複数積層し、加熱プレス加工することによって一括して多層化した後、ドリル加工又はレーザ加工によるスルーホール又はブラインドビアホールの形成と、メッキ又は導電性ペーストによる層間配線の形成を経て多層プリント配線板を製造することができる。 The printed wiring board of the present invention is manufactured using the laminated board of the present invention. For example, the conductor layer of the laminate of the present invention is subjected to wiring processing by a normal etching method, a plurality of laminates processed by wiring through the above-described prepreg are laminated, and then multilayered by heating press processing, A multilayer printed wiring board can be manufactured through formation of through holes or blind via holes by drilling or laser processing, and formation of interlayer wiring by plating or conductive paste.
次に、下記の実施例により本発明をさらに詳しく説明するが、これらの実施例は本発明を制限するものではない。 Next, the present invention will be described in more detail with reference to the following examples, but these examples do not limit the present invention.
実施例において使用した各成分は、以下の通りである。
（Ａ）１５０℃におけるＩＣＩ粘度が０．１Ｐａ・ｓ以下のエポキシ樹脂
Ａ−１：ナフタレン型エポキシ樹脂〔ＤＩＣ株式会社製、商品名：ＥＸＡ−７３１１−Ｇ４〕、１５０℃におけるＩＣＩ粘度：０．０５Ｐａ・ｓ
Ａ−２：ビスフェノールＦ型エポキシ樹脂〔新日鉄住金化学株式会社製、商品名：ＹＳＬＶ−７０ＸＹ〕、１５０℃におけるＩＣＩ粘度：０．０１Ｐａ・ｓ
Each component used in the examples is as follows.
(A) Epoxy resin having an ICI viscosity at 150 ° C. of 0.1 Pa · s or less A-1: Naphthalene type epoxy resin [manufactured by DIC Corporation, trade name: EXA-7311-G4], ICI viscosity at 150 ° C .: 0. 05Pa · s
A-2: Bisphenol F type epoxy resin [manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name: YSLV-70XY], ICI viscosity at 150 ° C .: 0.01 Pa · s
（Ｂ）１分子中に少なくとも２個のＮ−置換マレイミド基を有するマレイミド化合物
Ｂ−１：２，２−ビス［（４−（４−マレイミドフェノキシ）フェニル）］プロパン〔大和化成工業株式会社製；商品名ＢＭＩ−４０００〕
(B) Maleimide compound having at least two N-substituted maleimide groups in one molecule B-1: 2,2-bis [(4- (4-maleimidophenoxy) phenyl)] propane [manufactured by Daiwa Kasei Kogyo Co., Ltd. ; Brand name BMI-4000]
（Ｃ）１分子中に少なくとも１個のアミノ基を有するアミン化合物
Ｃ−１：ｐ−アミノフェノール〔関東化学株式会社製〕
Ｃ−２：３，３’−ジエチル−４，４’−ジアミノジフェニルメタン〔日本化薬株式会社製；商品名：ＫＡＹＡＨＡＲＤ Ａ−Ａ〕
(C) Amine compound having at least one amino group in one molecule C-1: p-aminophenol [manufactured by Kanto Chemical Co., Inc.]
C-2: 3,3′-diethyl-4,4′-diaminodiphenylmethane [manufactured by Nippon Kayaku Co., Ltd .; trade name: KAYAHARD AA]
（Ｄ）無機充填剤
Ｄ−１：シリカ：ＳＯ−Ｇ１（商品名、株式会社アドマテックス製）７００ｇを、７ｇのＫＢＭ−９０３（商品名、信越化学工業株式会社製）を加えた３００ｇのメチルイソブチルケトン溶液に攪拌しながら加え、メチルイソブチルケトンのシリカ分散液を作製した。
(D) Inorganic filler D-1: Silica: SO-G1 (trade name, manufactured by Admatex Co., Ltd.) 700 g and 7 g of KBM-903 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) 300 g of methyl It was added to the isobutyl ketone solution while stirring to prepare a silica dispersion of methyl isobutyl ketone.
（Ｅ）硬化促進剤
Ｅ−１：イソシアネートマスクイミダゾール〔第一工業製薬株式会社製〕
(E) Curing accelerator E-1: Isocyanate mask imidazole [Daiichi Kogyo Seiyaku Co., Ltd.]
（Ｆ）１５０℃におけるＩＣＩ粘度が０．１Ｐａ・ｓを超えるエポキシ樹脂
Ｆ−１：α−ナフトール／クレゾールノボラック型エポキシ樹脂〔日本化薬株式会社製、商品名：ＮＣ−７０００Ｌ〕、１５０℃におけるＩＣＩ粘度：０．２５Ｐａ・ｓ
(F) Epoxy resin with ICI viscosity at 150 ° C. exceeding 0.1 Pa · s F-1: α-naphthol / cresol novolac type epoxy resin [manufactured by Nippon Kayaku Co., Ltd., trade name: NC-7000L], at 150 ° C. ICI viscosity: 0.25 Pa · s
実施例１
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器２リットルの反応容器に、ｐ−アミノフェノール（Ｃ−１成分）１５．６ｇと、３，３’−ジエチル−４，４’−ジアミノジフェニルメタン（Ｃ−２成分）４９．４ｇと、２，２−ビス［（４−（４−マレイミドフェノキシ）フェニル）］プロパン（Ｂ−１成分）７０８．４ｇ及びプロピレングリコールモノメチルエーテル（有機溶媒）１１６０．０ｇを入れ、１１５℃で４時間反応させた後、固形分６０質量％になるまで濃縮した。その後、ナフタレン型エポキシ樹脂（Ａ−１成分）１７３ｇ、メチルイソブチルケトンのシリカ分散液（Ｄ−１成分）２２５．５ｇ、イソシアネートマスクイミダゾール（Ｅ−１成分）０．３ｇを２時間混合して樹脂分６５質量％のワニスを作製した。次に、上記ワニスを厚さ０．１ｍｍのＳガラスクロスに含浸し、１６０℃で３分３０秒加熱乾燥して樹脂含有量４７質量％のプリプレグを得た。このプリプレグを２枚重ね、１２μｍの電解銅箔を上下に配置し、圧力２．５ＭＰａ、成形温度２４０℃、昇温速度３℃／分、４．５℃／分、６℃／分の各条件で６０分間プレスを行って、実施例１の銅張積層板（大きさ２５０ｍｍ×２５０ｍｍ）を得た。
実施例２
Ｄ−１のメチルイソブチルケトンのシリカ分散液を３４４．９ｇに変えた以外は、実施例１と同様にして作製した。
実施例３
Ｄ−１のメチルイソブチルケトンのシリカ分散液を４１７．５ｇに変えた以外は、実施例１と同様にして作製した。
実施例４
Ａ−１成分のナフタレン型エポキシ樹脂をＡ−２成分のビスフェノールＦ型エポキシ樹脂１７３ｇに変えた以外は、実施例１と同様にして作製した。
実施例５
Ｄ−１のメチルイソブチルケトンのシリカ分散液を３４４．９ｇに変えた以外は、実施例４と同様にして作製した。
実施例６
Ｄ−１のメチルイソブチルケトンのシリカ分散液を４１７．５ｇに変えた以外は、実施例４と同様にして作製した。
Example 1
A 2 liter reaction vessel equipped with a thermometer, a stirrer, a moisture meter with a reflux condenser, and a 2 liter reaction vessel, 15.6 g of p-aminophenol (C-1 component) and 3,3′-diethyl -4,4'-diaminodiphenylmethane (C-2 component) 49.4 g, 2,2-bis [(4- (4-maleimidophenoxy) phenyl)] propane (B-1 component) 708.4 g and propylene glycol 1160.0 g of monomethyl ether (organic solvent) was added, reacted at 115 ° C. for 4 hours, and then concentrated to a solid content of 60% by mass. Then, 173 g of naphthalene type epoxy resin (A-1 component), 225.5 g of silica dispersion of methyl isobutyl ketone (D-1 component), and 0.3 g of isocyanate mask imidazole (E-1 component) were mixed for 2 hours. A varnish of 65% by weight was prepared. Next, an S glass cloth having a thickness of 0.1 mm was impregnated with the varnish and dried by heating at 160 ° C. for 3 minutes and 30 seconds to obtain a prepreg having a resin content of 47 mass%. Two sheets of this prepreg are stacked, and 12 μm electrolytic copper foils are arranged at the top and bottom, pressure 2.5 MPa, molding temperature 240 ° C., heating rate 3 ° C./min, 4.5 ° C./min, 6 ° C./min. Was pressed for 60 minutes to obtain a copper-clad laminate (size 250 mm × 250 mm) of Example 1.
Example 2
It was produced in the same manner as in Example 1 except that the silica dispersion of methyl isobutyl ketone D-1 was changed to 344.9 g.
Example 3
It was produced in the same manner as in Example 1 except that the silica dispersion of methyl isobutyl ketone D-1 was changed to 417.5 g.
Example 4
It was produced in the same manner as in Example 1 except that the A-1 component naphthalene type epoxy resin was changed to 173 g of the A-2 component bisphenol F type epoxy resin.
Example 5
It was produced in the same manner as in Example 4 except that the silica dispersion of methyl isobutyl ketone D-1 was changed to 344.9 g.
Example 6
It was produced in the same manner as in Example 4 except that the silica dispersion of methyl isobutyl ketone D-1 was changed to 417.5 g.
比較例１
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器２リットルの反応容器に、ｐ−アミノフェノール（Ｃ−１成分）１５．６ｇと、３，３’−ジエチル−４，４’−ジアミノジフェニルメタン（Ｃ−２成分）４９．４ｇと、２，２−ビス［（４−（４−マレイミドフェノキシ）フェニル）］プロパン（Ｂ−１成分）７０８．４ｇ及びプロピレングリコールモノメチルエーテル（有機溶媒）１１６０．０ｇを入れ、１１５℃で４時間反応させた後、固形分６０質量％になるまで濃縮した。その後、α−ナフトール／クレゾールノボラック型エポキシ樹脂（Ｆ−１成分）１７３ｇ、メチルイソブチルケトンのシリカ分散液（Ｄ−１成分）２２５．５ｇ、イソシアネートマスクイミダゾール（Ｅ−１成分）０．３ｇを２時間混合して樹脂分６５質量％のワニスを作製した。次に、上記ワニスを厚さ０．１ｍｍのＳガラスクロスに含浸塗工し、１６０℃で３分３０秒加熱乾燥して樹脂含有量４７質量％のプリプレグを得た。このプリプレグを２枚重ね、１２μｍの電解銅箔を上下に配置し、圧力２．５ＭＰａ、成形温度２４０℃、昇温速度３℃／分、４．５℃／分、６℃／分の各条件で６０分間プレスを行って、比較例１の銅張積層板（大きさ２５０ｍｍ×２５０ｍｍ）を得た。
比較例２
Ｄ−１のメチルイソブチルケトンのシリカ分散液を３４４．９ｇに変えた以外は、比較例１と同様にして作製した。
比較例３
Ｄ−１のメチルイソブチルケトンのシリカ分散液を４１７．５ｇに変えた以外は、比較例１と同様にして作製した。
Comparative Example 1
A 2 liter reaction vessel equipped with a thermometer, a stirrer, a moisture meter with a reflux condenser, and a 2 liter reaction vessel, 15.6 g of p-aminophenol (C-1 component) and 3,3′-diethyl -4,4'-diaminodiphenylmethane (C-2 component) 49.4 g, 2,2-bis [(4- (4-maleimidophenoxy) phenyl)] propane (B-1 component) 708.4 g and propylene glycol 1160.0 g of monomethyl ether (organic solvent) was added, reacted at 115 ° C. for 4 hours, and then concentrated to a solid content of 60% by mass. Then, 173 g of α-naphthol / cresol novolak type epoxy resin (F-1 component), 225.5 g of silica dispersion of methyl isobutyl ketone (D-1 component), and 0.3 g of isocyanate mask imidazole (E-1 component) were added. By mixing for a time, a varnish with a resin content of 65% by mass was produced. Next, the varnish was impregnated and applied to an S glass cloth having a thickness of 0.1 mm and dried by heating at 160 ° C. for 3 minutes and 30 seconds to obtain a prepreg having a resin content of 47 mass%. Two sheets of this prepreg are stacked, and 12 μm electrolytic copper foils are arranged at the top and bottom, pressure 2.5 MPa, molding temperature 240 ° C., heating rate 3 ° C./min, 4.5 ° C./min, 6 ° C./min. Was pressed for 60 minutes to obtain a copper clad laminate (size 250 mm × 250 mm) of Comparative Example 1.
Comparative Example 2
It was produced in the same manner as in Comparative Example 1 except that the silica dispersion of methyl isobutyl ketone D-1 was changed to 344.9 g.
Comparative Example 3
It was produced in the same manner as Comparative Example 1 except that the silica dispersion of methyl isobutyl ketone D-1 was changed to 417.5 g.
実施例１〜６、及び比較例１〜３で得られた銅張り積層板を以下の方法で評価した。第１表に評価結果を示す。
（１）熱膨張率の測定
成形温度２４０℃、昇温速度６℃／分で成形した銅張積層板を銅エッチング液に浸漬することにより銅箔を取り除いた５ｍｍ角の評価基板を作製し、ＴＭＡ試験装置（ＴＡ Ｉｎｓｔｒｕｍｅｎｔｓ製、ＴＭＡＱ４００ＥＭ）を用いて圧縮法で熱機械分析をおこなった。評価基板を前記装置にＸ方向に装着後、昇温速度１０℃／分の測定条件にて連続して２回測定した。２回目の測定における３０℃から１００℃までの平均熱膨張率を算出し、これを熱膨張率の値とした。熱膨張率が５．８ｐｐｍ／℃以下であれば、実用上許容できる。
（２）曲げ弾性率の測定
成形温度２４０℃、昇温速度６℃／分で成形した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２５×４０ｍｍ角の評価基板を作製し、曲げ弾性率試験装置（株式会社オリエンテック製、５トンテンシロン）を用いて、クロスヘッド速度１ｍｍ／分スパン間距離２０ｍｍで測定した。
（３）成形性の確認
成形温度２４０℃、昇温速度３℃／分、４．５℃／分、６℃／分で得られた銅張積層板（大きさ２５０ｍｍ×２５０ｍｍ）の成形性を確認し、成形温度限界を観察した。また、成形性の確認法は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き、中心部分と端から１０ｍｍの部分の厚みの差で評価し、その差が０．０５ｍｍ以下のとき成形できているとした。成形できた場合には○、できない場合には×とした。
The copper-clad laminates obtained in Examples 1 to 6 and Comparative Examples 1 to 3 were evaluated by the following methods. Table 1 shows the evaluation results.
(1) Measurement of coefficient of thermal expansion A 5 mm square evaluation board was prepared by removing a copper foil by immersing a copper-clad laminate molded at a molding temperature of 240 ° C. and a heating rate of 6 ° C./min in a copper etching solution, Thermomechanical analysis was performed by a compression method using a TMA test apparatus (TA Instruments, TMAQ400EM). After mounting the evaluation substrate on the apparatus in the X direction, the measurement substrate was measured twice continuously under the measurement conditions of a temperature increase rate of 10 ° C./min. The average coefficient of thermal expansion from 30 ° C. to 100 ° C. in the second measurement was calculated and used as the value of the coefficient of thermal expansion. A thermal expansion coefficient of 5.8 ppm / ° C. or lower is acceptable in practice.
(2) Measurement of flexural modulus A 25 × 40 mm square evaluation board is produced by removing the copper foil by immersing a copper-clad laminate molded at a molding temperature of 240 ° C. and a heating rate of 6 ° C./min in a copper etching solution. Then, using a flexural modulus test apparatus (Orientec Co., Ltd., 5 ton tensilon), the crosshead speed was 1 mm / min and the span distance was 20 mm.
(3) Confirmation of formability The moldability of a copper clad laminate (size: 250 mm × 250 mm) obtained at a molding temperature of 240 ° C., a heating rate of 3 ° C./min, 4.5 ° C./min, and 6 ° C./min. Confirmed and observed the molding temperature limit. Moreover, the moldability confirmation method removes copper foil by immersing a copper clad laminated board in a copper etching solution, and evaluates by the difference in thickness between a central portion and a portion 10 mm from the end, and the difference is 0.05 mm or less. It was sometimes molded. When it was able to be molded, it was marked as ◯, and when it could not be marked as x.
実施例１と４、比較例１の比較から、本発明に係る熱硬化性樹脂組成物によれば、熱膨張率、曲げ弾性率を維持しながら成形性を向上できることがわかる。また、実施例２，３，５，及び６のように、（Ｄ）無機充填剤の充填率を増やしても、昇温速度４．５℃／分以上であれば、十分な成形性が得られることがわかる。以上のことから、本発明に係る熱硬化性樹脂組成物によれば、成形低熱膨張性と高弾性を兼ね備え、要求される生産性に応えることができる。 From the comparison of Examples 1 and 4 and Comparative Example 1, it can be seen that the thermosetting resin composition according to the present invention can improve the moldability while maintaining the thermal expansion coefficient and the flexural modulus. Further, as in Examples 2, 3, 5, and 6, even if the filling rate of (D) inorganic filler is increased, sufficient moldability can be obtained as long as the heating rate is 4.5 ° C./min or more. I understand that From the above, the thermosetting resin composition according to the present invention has both molded low thermal expansion and high elasticity, and can meet the required productivity.
本発明に係る熱硬化性樹脂組成物を基材に含浸、又は塗工して得たプリプレグ、及び該プリプレグを積層成形することにより製造した積層板、及び該積層板を用いて製造されたプリント配線板は、低熱膨張性に優れ、高弾性であり、そしてプレス成形性が良好なことから、高集積化された電子機器用プリント配線板に有用である。 A prepreg obtained by impregnating or coating a base material with the thermosetting resin composition according to the present invention, a laminate produced by laminating the prepreg, and a print produced using the laminate The wiring board is useful for highly integrated printed wiring boards for electronic devices because of its excellent low thermal expansion, high elasticity, and good press moldability.
Claims (7)
前記（Ａ）１５０℃におけるＩＣＩ粘度が０．１Ｐａ・ｓ以下のエポキシ樹脂が、ナフタレン型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂又はビスフェノールＦ型エポキシ樹脂であり、
前記（Ｃ）成分がアミノ基を有するシリコーン化合物以外のアミノ化合物であり、
前記（Ｂ）成分の配合量が、前記（Ａ）成分１００質量部に対して７５〜５００質量部であり、前記（Ｄ）成分の配合量が（Ａ）〜（Ｃ）成分の総和１００質量部当たり１０〜３００質量部である、プリプレグ。 (A) Epoxy resin having an ICI viscosity at 150 ° C. of 0.1 Pa · s or less, (B) a maleimide compound having at least two N-substituted maleimide groups in one molecule, and (C) at least one in one molecule A prepreg comprising a thermosetting resin composition comprising an amino compound having an amino group of (D) and an inorganic filler (D),
Wherein (A) 150 ICI viscosity at ℃ following 0.1 Pa · s epoxy resin, a naphthalene type epoxy resin, bisphenol S type epoxy resin or bisphenol F type epoxy resin,
The component (C) is an amino compound other than a silicone compound having an amino group,
The blending amount of the component (B) is 75 to 500 parts by mass with respect to 100 parts by mass of the component (A), and the blending amount of the component (D) is 100 masses of the sum of the components (A) to (C). is 10-300 parts by weight per part, the prepreg.
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