JP2012229363A - Thermosetting resin composition and prepreg, laminate board and circuit board using the same - Google Patents
Thermosetting resin composition and prepreg, laminate board and circuit board using the same Download PDFInfo
- Publication number
- JP2012229363A JP2012229363A JP2011099681A JP2011099681A JP2012229363A JP 2012229363 A JP2012229363 A JP 2012229363A JP 2011099681 A JP2011099681 A JP 2011099681A JP 2011099681 A JP2011099681 A JP 2011099681A JP 2012229363 A JP2012229363 A JP 2012229363A
- Authority
- JP
- Japan
- Prior art keywords
- group
- resin composition
- compound
- general formula
- maleimide
- 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.)
- Granted
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 34
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 30
- -1 maleimide compound Chemical class 0.000 claims abstract description 74
- 239000003822 epoxy resin Substances 0.000 claims abstract description 27
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 27
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- KTLIMPGQZDZPSB-UHFFFAOYSA-N diethylphosphinic acid Chemical compound CCP(O)(=O)CC KTLIMPGQZDZPSB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 10
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical class NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 4
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 claims abstract description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims abstract description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- 229920005989 resin Polymers 0.000 claims description 18
- 239000011347 resin Substances 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 125000001931 aliphatic group Chemical group 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 125000005843 halogen group Chemical group 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 239000011888 foil Substances 0.000 claims description 6
- 230000003014 reinforcing effect Effects 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 125000001118 alkylidene group Chemical group 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 125000001033 ether group Chemical group 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 3
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 3
- 239000000203 mixture Substances 0.000 abstract description 6
- 229910052736 halogen Inorganic materials 0.000 abstract description 5
- 150000002367 halogens Chemical class 0.000 abstract description 5
- 239000003063 flame retardant Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 11
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 8
- 229920003986 novolac Polymers 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical class N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 6
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-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
- 239000004305 biphenyl Substances 0.000 description 5
- 235000010290 biphenyl Nutrition 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000011256 inorganic filler Substances 0.000 description 5
- 229910003475 inorganic filler Inorganic materials 0.000 description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 4
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 4
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 4
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 4
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 4
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 4
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 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
- 230000007613 environmental effect Effects 0.000 description 4
- 239000011810 insulating material Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 3
- 229940018563 3-aminophenol Drugs 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229920006026 co-polymeric resin Polymers 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical class C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 239000012796 inorganic flame retardant Substances 0.000 description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 3
- 239000000347 magnesium hydroxide Substances 0.000 description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- XOJRVZIYCCJCRD-UHFFFAOYSA-N 1-[4-[4-(2,5-dioxopyrrol-1-yl)phenoxy]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1OC1=CC=C(N2C(C=CC2=O)=O)C=C1 XOJRVZIYCCJCRD-UHFFFAOYSA-N 0.000 description 2
- GUIACFHOZIQGKX-UHFFFAOYSA-N 1-[4-[4-(2,5-dioxopyrrol-1-yl)phenyl]sulfonylphenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=C(S(=O)(=O)C=2C=CC(=CC=2)N2C(C=CC2=O)=O)C=C1 GUIACFHOZIQGKX-UHFFFAOYSA-N 0.000 description 2
- 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
- XFDUHJPVQKIXHO-UHFFFAOYSA-N 3-aminobenzoic acid Chemical compound NC1=CC=CC(C(O)=O)=C1 XFDUHJPVQKIXHO-UHFFFAOYSA-N 0.000 description 2
- PDCMTKJRBAZZHL-UHFFFAOYSA-N 5-aminobenzene-1,3-diol Chemical compound NC1=CC(O)=CC(O)=C1 PDCMTKJRBAZZHL-UHFFFAOYSA-N 0.000 description 2
- ZXLYUNPVVODNRE-UHFFFAOYSA-N 6-ethenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=C)=N1 ZXLYUNPVVODNRE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 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
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000005456 alcohol based solvent Substances 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- XSAOTYCWGCRGCP-UHFFFAOYSA-K aluminum;diethylphosphinate Chemical compound [Al+3].CCP([O-])(=O)CC.CCP([O-])(=O)CC.CCP([O-])(=O)CC XSAOTYCWGCRGCP-UHFFFAOYSA-K 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
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 238000005553 drilling Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 239000004210 ether based solvent Substances 0.000 description 2
- 239000006081 fluorescent whitening agent Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000005453 ketone based solvent Substances 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
- 239000012766 organic filler Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical class NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 1
- QYOJZFBQEAZNEW-UHFFFAOYSA-N 1-(2-methylphenyl)pyrrole-2,5-dione Chemical compound CC1=CC=CC=C1N1C(=O)C=CC1=O QYOJZFBQEAZNEW-UHFFFAOYSA-N 0.000 description 1
- XAZPKEBWNIUCKF-UHFFFAOYSA-N 1-[4-[4-[2-[4-[4-(2,5-dioxopyrrol-1-yl)phenoxy]phenyl]propan-2-yl]phenoxy]phenyl]pyrrole-2,5-dione Chemical compound C=1C=C(OC=2C=CC(=CC=2)N2C(C=CC2=O)=O)C=CC=1C(C)(C)C(C=C1)=CC=C1OC(C=C1)=CC=C1N1C(=O)C=CC1=O XAZPKEBWNIUCKF-UHFFFAOYSA-N 0.000 description 1
- HHVCCCZZVQMAMT-UHFFFAOYSA-N 1-hydroxy-3-phenylpyrrole-2,5-dione Chemical compound O=C1N(O)C(=O)C=C1C1=CC=CC=C1 HHVCCCZZVQMAMT-UHFFFAOYSA-N 0.000 description 1
- SEULWJSKCVACTH-UHFFFAOYSA-N 1-phenylimidazole Chemical compound C1=NC=CN1C1=CC=CC=C1 SEULWJSKCVACTH-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- ZMCHBSMFKQYNKA-UHFFFAOYSA-N 2-aminobenzenesulfonic acid Chemical compound NC1=CC=CC=C1S(O)(=O)=O ZMCHBSMFKQYNKA-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- MOSSLXZUUKTULI-UHFFFAOYSA-N 3-[3-(2,5-dioxopyrrol-3-yl)-4-methylphenyl]pyrrole-2,5-dione Chemical compound CC1=CC=C(C=2C(NC(=O)C=2)=O)C=C1C1=CC(=O)NC1=O MOSSLXZUUKTULI-UHFFFAOYSA-N 0.000 description 1
- ZAJAQTYSTDTMCU-UHFFFAOYSA-N 3-aminobenzenesulfonic acid Chemical compound NC1=CC=CC(S(O)(=O)=O)=C1 ZAJAQTYSTDTMCU-UHFFFAOYSA-N 0.000 description 1
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 1
- KBZFDRWPMZESDI-UHFFFAOYSA-N 5-aminobenzene-1,3-dicarboxylic acid Chemical compound NC1=CC(C(O)=O)=CC(C(O)=O)=C1 KBZFDRWPMZESDI-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- NOHQTLHHNIKWBA-UHFFFAOYSA-N [SiH4].NC(=O)N Chemical compound [SiH4].NC(=O)N NOHQTLHHNIKWBA-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- NJYZCEFQAIUHSD-UHFFFAOYSA-N acetoguanamine Chemical compound CC1=NC(N)=NC(N)=N1 NJYZCEFQAIUHSD-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229940024548 aluminum oxide Drugs 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine powder Natural products NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 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
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920006122 polyamide resin 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
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229950000244 sulfanilic acid Drugs 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 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
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Images
Abstract
Description
本発明は電子部品等に好適に用いられる熱硬化性樹脂組成物に関し、詳しくはハロゲンフリーであり、かつ比誘電率および誘電正接のバラツキの小さい熱硬化性樹脂組成物並びにこれを用いたプリプレグ、積層板及び配線板に関する。 The present invention relates to a thermosetting resin composition suitably used for electronic parts and the like, and more specifically, is a halogen-free thermosetting resin composition having a small variation in relative dielectric constant and dielectric loss tangent, and a prepreg using the same. The present invention relates to a laminated board and a wiring board.
熱硬化性樹脂は、その特有な架橋構造が高い耐熱性や寸法安定性を発現するため、電子部品等の高い信頼性を要求される分野において広く使われているが、特に銅張積層板や層間絶縁材料においては、近年の高密度化への要求から、微細配線形成のための高い銅箔接着性やドリル又は打ち抜きにより穴あけ等の加工をする際の加工性も必要とされている。 Thermosetting resins are widely used in fields that require high reliability, such as electronic parts, because their unique cross-linked structure exhibits high heat resistance and dimensional stability. In the interlayer insulating material, due to the recent demand for higher density, high copper foil adhesion for forming fine wiring and workability when performing drilling or punching by drilling or the like are also required.
近年、環境意識の高まりとともに、電子機器及び電子部品についても環境への配慮が不可欠となっている。電子部品をはじめとするプラスチック製品全般に用いられているハロゲン系難燃剤は、最も代表的な臭素系難燃剤であるデカブロモジフェニルオキサイドが焼却時に有毒な臭素化ジベンゾダイオキシンとフランを生成させることが報告されて以来、その安全性が疑われている。環境問題への配慮の点から、従来のハロゲンを含む臭素系難燃剤を使用しないハロゲンフリー製品の導入が進められている（例えば、特許文献1参照）。 In recent years, environmental awareness has become indispensable for electronic devices and electronic components as environmental awareness increases. Halogen-based flame retardants used in plastic products, including electronic parts, can produce toxic brominated dibenzodioxins and furans when incinerated, the most typical brominated flame retardant, decabromodiphenyl oxide. Since being reported, its safety has been suspected. In consideration of environmental issues, the introduction of halogen-free products that do not use conventional brominated flame retardants containing halogen has been promoted (see, for example, Patent Document 1).
ハロゲン系化合物を含まずに難燃性を付与するには、通常、比較的多量の無機充填材とリン含有難燃剤を併用して添加する方法が使われている。ここに用いられる無機充填材としては、水酸化アルミニウムが選択されることが多い。また、同様に鉛を含まない鉛フリーはんだの導入も進んでおり、従来よりも高温で行われる鉛フリーはんだプロセスに対応するため、配線板材料には高耐熱性や低熱膨張性が要求されている。 In order to impart flame retardancy without containing a halogen compound, a method of adding a relatively large amount of an inorganic filler and a phosphorus-containing flame retardant in combination is generally used. Aluminum hydroxide is often selected as the inorganic filler used here. Similarly, lead-free solders that do not contain lead are also being introduced, and high heat resistance and low thermal expansion are required for wiring board materials in order to support lead-free solder processes that are performed at higher temperatures than before. Yes.
近年では、大量のデータを高速で処理するために、コンピュータや情報機器端末等で、信号の高周波化が進んでいる。用いる周波数が高くなるにつれて、電気信号の転送損失が大きくなる。そのため、信号回路の特性インピーダンスのバラツキを抑える必要がある。信号回路の特性インピーダンスのバラツキを抑えるためには、絶縁層厚さのバラツキ、信号回路幅のバラツキおよび絶縁材料の比誘電率のバラツキの3つの要素を小さくすることが必要となる。 In recent years, in order to process a large amount of data at high speed, the frequency of signals has been increased in computers and information equipment terminals. As the frequency used increases, the transfer loss of electrical signals increases. Therefore, it is necessary to suppress variations in characteristic impedance of the signal circuit. In order to suppress variations in the characteristic impedance of the signal circuit, it is necessary to reduce the three factors of variation in the insulating layer thickness, variation in the signal circuit width, and variation in the relative dielectric constant of the insulating material.
フィラーに誘電体セラミックス材料を用いて、絶縁層の誘電特性を高誘電率かつ低誘電損失など使用目的に応じて調整できるという事例が開示されている(例えば、特許文献２参照)。しかしながら、これらは絶縁層の誘電特性(比誘電率および誘電正接)のバラツキを低減するものではない。
また、金属箔接着性、耐熱性、耐湿性、難燃性および誘電特性の全てにおいてバランスのとれた樹脂組成物として、ホスフィン酸の金属塩、マレイミド化合物、グアナミン化合物およびエポキシ樹脂を含有する化合物が知られているが（例えば、特許文献３参照）、誘電特性については更なる改善が求められている。
An example is disclosed in which a dielectric ceramic material is used for the filler, and the dielectric characteristics of the insulating layer can be adjusted according to the purpose of use, such as high dielectric constant and low dielectric loss (see, for example, Patent Document 2). However, these do not reduce variations in dielectric characteristics (relative permittivity and dielectric loss tangent) of the insulating layer.
In addition, as a resin composition balanced in all of metal foil adhesion, heat resistance, moisture resistance, flame retardancy and dielectric properties, compounds containing metal salts of phosphinic acid, maleimide compounds, guanamine compounds and epoxy resins are included. Although known (for example, refer to Patent Document 3), further improvement is required for the dielectric characteristics.
本発明の目的は、こうした現状に鑑み、ハロゲンフリーであり、かつ比誘電率および誘電正接のバラツキの小さい熱硬化性樹脂組成物並びにこれを用いたプリプレグ、積層板及び配線板を提供することである。 In view of the current situation, an object of the present invention is to provide a thermosetting resin composition that is halogen-free and has small variations in relative permittivity and dielectric loss tangent, and a prepreg, laminate, and wiring board using the same. is there.
本発明者らは、前記目的を達成するために鋭意研究を重ねた結果、微粒化したジエチルホスフィン酸のアルミニウム塩とマレイミド化合物、硬化剤およびエポキシ樹脂からなる樹脂組成物が上記目的に沿うものであることを見出した。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 achieve the above object, the present inventors have found that a resin composition comprising a finely divided aluminum salt of diethylphosphinic acid, a maleimide compound, a curing agent and an epoxy resin meets the above object. I found out. 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、積層板及び配線板を提供するものである。
１．下記一般式（１）で示される構造を有し、平均粒径が０．５〜３μｍであるジエチルホスフィン酸のアルミニウム塩（Ａ）、分子中にＮ−置換マレイミド基を有するマレイミド化合物（Ｂ）、下記一般式（２）で示す６−置換グアナミン化合物又はジシアンジアミドからなる硬化剤（Ｃ）および、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（Ｄ）を含有することを特徴とする熱硬化性樹脂組成物。
That is, the present invention provides the following thermosetting resin composition, prepreg, laminate and wiring board.
1. An aluminum salt of diethylphosphinic acid (A) having a structure represented by the following general formula (1) and having an average particle diameter of 0.5 to 3 μm, and a maleimide compound (B) having an N-substituted maleimide group in the molecule A curing agent (C) composed of a 6-substituted guanamine compound or dicyandiamide represented by the following general formula (2), and an epoxy resin (D) having at least two epoxy groups in one molecule. Thermosetting resin composition.
２．分子中にＮ−置換マレイミド基を有するマレイミド化合物（Ｂ）が、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）と、下記一般式（３）に示す酸性置換基を有するアミン化合物（ｂ−２）を反応させて得られた不飽和マレイミド基を有する化合物である上記１の熱硬化性樹脂組成物。 2. The maleimide compound (B) having an N-substituted maleimide group in the molecule and the maleimide compound (b-1) having at least two N-substituted maleimide groups in one molecule and the acidity represented by the following general formula (3) Said 1 thermosetting resin composition which is a compound which has the unsaturated maleimide group obtained by making the amine compound (b-2) which has a substituent react.
３．分子中にＮ−置換マレイミド基を有するマレイミド化合物（Ｂ）が、下記一般式（４）又は一般式（５）で示される化合物を含む上記１又は２の熱硬化性樹脂組成物。
４．硬化剤（Ｃ）が、ジシアンジアミドである上記１〜３のいずれかの熱硬化性樹脂組成物。
５．上記１〜４のいずれかの樹脂組成物がシート状補強基材中に含侵又は塗工された後、Ｂステージ化されていることを特徴とするプリプレグ。
６．絶縁樹脂層が、上記１〜４のいずれかの樹脂組成物又は上記５のプリプレグを用いて形成されたものであることを特徴とする積層板。
７．上記６の積層板における絶縁樹脂層の片面又は両面に配置された金属箔を回路加工して得られたものであることを特徴とする配線板。
4). The thermosetting resin composition according to any one of the above 1 to 3, wherein the curing agent (C) is dicyandiamide.
5. A prepreg characterized in that the resin composition according to any one of 1 to 4 is impregnated or coated in a sheet-like reinforcing base material and then B-staged.
6). A laminated board, wherein the insulating resin layer is formed using any one of the resin compositions 1 to 4 or 5 prepregs.
7). A wiring board obtained by subjecting a metal foil arranged on one or both sides of an insulating resin layer in the laminated board of 6 to a circuit process.
本発明の熱硬化性樹脂組成物は、ハロゲンフリーであり、かつ比誘電率および誘電正接のバラツキの小さい特性を有しており、大量のデータを高速で処理するコンピュータや情報機器端末等に用いられる電子機器の配線板の絶縁樹脂として好適に用いられる。 The thermosetting resin composition of the present invention is halogen-free and has characteristics with small variations in relative permittivity and dielectric loss tangent, and is used for computers and information equipment terminals that process a large amount of data at high speed. It is suitably used as an insulating resin for wiring boards of electronic devices.
以下、本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、下記一般式（１）で示される構造を有し、平均粒径が０．５〜３μｍであるジエチルホスフィン酸のアルミニウム塩（Ａ）、分子中にＮ−置換マレイミド基を有するマレイミド化合物（Ｂ）、硬化剤（Ｃ）および、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（Ｄ）を含有することを特徴とするものである。
Hereinafter, the present invention will be described in detail.
The thermosetting resin composition of the present invention has a structure represented by the following general formula (1), an aluminum salt of diethylphosphinic acid (A) having an average particle diameter of 0.5 to 3 μm, and N in the molecule. -A maleimide compound (B) having a substituted maleimide group, a curing agent (C), and an epoxy resin (D) having at least two epoxy groups in one molecule.
先ず、（Ａ）成分のジエチルホスフィン酸のアルミニウム塩は、一般式（１）で示される構造を有し、平均粒径が０．５〜３μｍである粒子状難燃剤である。このような２置換ホスフィン酸の金属塩は特開２００１−２６８６号に記載の方法により製造され、商業的にドイツ・クラリアント社から入手できる平均粒径が３〜５μｍのものを粉砕することによって得ることができる。
本発明の熱硬化性樹脂組成物は、この２置換ホスフィン酸の金属塩を必須成分とすることにより、優れた難燃性、低誘電特性及び耐熱耐湿性を付与することができる。すなわち、ジエチルホスフィン酸のアルミニウム塩を使用することで、化合物中のリン含有量を多くすることができる。また、平均粒径が０．５〜３μｍの微粒化したジエチルホスフィン酸のアルミニウム塩を使うことで、材料の電気特性（比誘電率及び誘電正接）のバラツキを低減することができる。
First, the aluminum salt of diethylphosphinic acid as component (A) is a particulate flame retardant having a structure represented by the general formula (1) and an average particle size of 0.5 to 3 μm. Such a metal salt of disubstituted phosphinic acid is produced by the method described in JP-A No. 2001-2686, and is obtained by pulverizing one having an average particle diameter of 3 to 5 μm commercially available from Clariant, Germany. be able to.
The thermosetting resin composition of the present invention can impart excellent flame retardancy, low dielectric properties, and heat and humidity resistance by using the metal salt of the disubstituted phosphinic acid as an essential component. That is, the phosphorus content in the compound can be increased by using an aluminum salt of diethylphosphinic acid. Further, by using a finely divided aluminum salt of diethylphosphinic acid having an average particle diameter of 0.5 to 3 μm, it is possible to reduce variation in electrical characteristics (relative permittivity and dielectric loss tangent) of the material.
（Ｂ）成分の分子中にＮ−置換マレイミド基を有するマレイミド化合物としては、１分子中に1個のＮ−置換マレイミド基を有するマレイミド化合物として、Ｎ−フェニルマレイミドおよびＮ−ヒドロキシフェニルマレイミドが挙げられるが、１分子中に２個のＮ−置換マレイミド基を有するマレイミド化合物が好ましい。
１分子中に２個のＮ−置換マレイミド基を有するマレイミド化合物としては、例えば、ビス（４−マレイミドフェニル）メタン、ポリ（マレイミドフェニル）メタン、ビス（４−マレイミドフェニル）エーテル、ビス（４−マレイミドフェニル）スルホン、３,３−ジメチル−５,５−ジエチル−４,４−ジフェニルメタンビスマレイミド、４−メチル−１,３−フェニレンビスマレイミド、ｍ−フェニレンビスマレイミド、２，２−ビス[４−（４−マレイミドフェノキシ）フェニル]プロパン等が挙げられる。
これらの中で、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、ｍ−フェニレンビスマレイミド及びビス（４−マレイミドフェニル）スルホンが好ましく、安価である点から、ｍ−フェニレンビスマレイミド及びビス（４−マレイミドフェニル）メタンがより好ましく、溶剤への溶解性の点からビス（４−マレイミドフェニル）メタンが特に好ましい。
Examples of the maleimide compound having an N-substituted maleimide group in the component (B) molecule include N-phenylmaleimide and N-hydroxyphenylmaleimide as maleimide compounds having one N-substituted maleimide group in one molecule. However, maleimide compounds having two N-substituted maleimide groups in one molecule are preferred.
Examples of maleimide compounds having two N-substituted maleimide groups in one molecule include bis (4-maleimidophenyl) methane, poly (maleimidophenyl) methane, bis (4-maleimidophenyl) ether, and bis (4- Maleimidophenyl) sulfone, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, 4-methyl-1,3-phenylenebismaleimide, m-phenylenebismaleimide, 2,2-bis [4 -(4-maleimidophenoxy) phenyl] propane and the like.
Among these, bis (4-maleimidophenyl) methane, m-phenylenebismaleimide, and bis (4-maleimidophenyl) sulfone, which have a high reaction rate and can have higher heat resistance, are preferable, and m- Phenylene bismaleimide and bis (4-maleimidophenyl) methane are more preferred, and bis (4-maleimidophenyl) methane is particularly preferred from the viewpoint of solubility in a solvent.
また、（Ｂ）成分として、上記の如き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）と、下記一般式（３）に示す酸性置換基を有するアミン化合物（ｂ−２）を反応させて製造された酸性置換基と不飽和マレイミド基を有する化合物が好適に用いられる。
一般式（３）に示すアミン化合物（ｂ−２）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、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、ｐ−アミノ安息香酸、ｍ−アミノ安息香酸及び３，５−ジヒドロキシアニリンが好ましく、耐熱性の点からｏ−アミノフェノール、ｍ−アミノフェノール及びｐ−アミノフェノールがより好ましく、誘電特性の点からｐ−アミノフェノールが特に好ましい。 Examples of the amine compound (b-2) represented by the general formula (3) include m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, and o-aminobenzoic acid. Acid, o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, 3,5-dicarboxyaniline, and the like. Among these, solubility and M-aminophenol, p-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid and 3,5-dihydroxyaniline are preferable from the viewpoint of the yield of synthesis, and o-aminophenol, m- Aminophenol and p-aminophenol are more preferred, and p-aminophenol is particularly preferred from the viewpoint of dielectric properties.
この反応では有機溶媒を用いることが好ましく、使用される有機溶媒は特に制限はないが、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媒、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶媒、テトラヒドロフラン等のエーテル系溶媒、トルエン、キシレン、メシチレン等の芳香族系溶媒、ジメチルホルムアミド、ジメチルアセトアミド、Ｎ−メチルピロリドン等の窒素原子含有溶媒、ジメチルスルホキシド等の硫黄原子含有溶媒等が挙げられ、これらの１種又は２種以上を混合して使用できる。 In this reaction, an organic solvent is preferably used, and the organic solvent to be used is not particularly limited. For example, alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, acetone, methyl ethyl ketone, Ketone solvents such as methyl isobutyl ketone and cyclohexanone, ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene and mesitylene, nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, dimethyl sulfoxide, etc. These sulfur atom-containing solvents can be used, and one or more of these can be mixed and used.
これらの有機溶媒中で、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及びメチルセロソルブが好ましく、低毒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がより好ましく、揮発性が高くプリプレグの製造時に残溶媒として残りにくいプロピレングリコールモノメチルエーテルが特に好ましい。 Among these organic solvents, cyclohexanone, propylene glycol monomethyl ether and methyl cellosolve are preferable from the viewpoint of solubility, cyclohexanone and propylene glycol monomethyl ether are more preferable from the viewpoint of low toxicity, and high volatility as a residual solvent at the time of production of the prepreg. Propylene glycol monomethyl ether which is difficult to remain is particularly preferable.
有機溶媒の使用量は、マレイミド化合物（ｂ−１）とアミン化合物（ｂ−２）の総和１００質量部当たり、１０〜１０００質量部とすることが好ましく、１００〜５００質量部とすることがより好ましく、２００〜５００質量部とすることが特に好ましい。
有機溶媒の使用量を１０質量部以上とすることにより溶解性が十分となり、１０００質量部以下とすることにより、反応時間が長すぎることがなくなる。
The amount of the organic solvent used is preferably 10 to 1000 parts by mass, more preferably 100 to 500 parts by mass, per 100 parts by mass of the total of the maleimide compound (b-1) and the amine compound (b-2). Preferably, it is particularly preferably 200 to 500 parts by mass.
When the amount of the organic solvent used is 10 parts by mass or more, the solubility becomes sufficient, and when it is 1000 parts by mass or less, the reaction time is not too long.
マレイミド化合物（ｂ−１）とアミン化合物（ｂ−２）の使用量は、マレイミド化合物のマレイミド基当量とアミン化合物の−ＮＨ2基換算の当量との当量比が次式：
１．０＜（マレイミド基当量）／（−ＮＨ2基換算の当量）≦１０．０
に示す範囲であることが好ましく、該当量比が２．０〜１０．０の範囲であることが更に好ましい。該当量比を上記範囲内とすることにより、溶剤への溶解性が不足したり、ゲル化を起こしたり、熱硬化性樹脂の耐熱性が低下することがない。
また、反応温度は５０〜２００℃、反応時間は０．１〜１０時間の範囲であることが好ましく、１００〜１６０℃、１〜８時間の範囲であることがより好ましい。
The amount of the maleimide compound (b-1) and the amine compound (b-2) used is such that the equivalent ratio of the maleimide group equivalent of the maleimide compound and the equivalent of the amine compound in terms of —NH 2 group is represented by the following formula:
1.0 <(maleimide group equivalent) / (-NH 2 group equivalent) ≦ 10.0
It is preferable that it is the range shown to, and it is still more preferable that the applicable amount ratio is the range of 2.0-10.0. By setting the corresponding ratio within the above range, the solubility in the solvent is not insufficient, gelation occurs, and the heat resistance of the thermosetting resin does not decrease.
The reaction temperature is preferably 50 to 200 ° C. and the reaction time is preferably in the range of 0.1 to 10 hours, more preferably in the range of 100 to 160 ° C. and 1 to 8 hours.
なお、この反応には、必要に応じて反応触媒を使用することができる。反応触媒の例としては、例えば、トリエチルアミン、ピリジン、トリブチルアミン等のアミン類、メチルイミダゾール、フェニルイミダゾール等のイミダゾール類、トリフェニルホスフィン等の有機リン系化合物が挙げられ、１種又は２種以上を混合して使用できる。 In this reaction, a reaction catalyst can be used as necessary. Examples of the reaction catalyst include, for example, amines such as triethylamine, pyridine, and tributylamine, imidazoles such as methylimidazole and phenylimidazole, and organophosphorus compounds such as triphenylphosphine. Can be mixed and used.
この反応により、例えば、マレイミド化合物（ｂ−１）としてビス（４−マレイミドフェニル）系化合物を用い、アミン化合物（ｂ−２）と反応させることにより、下記一般式（４）又は一般式（５）に示す酸性置換基と不飽和マレイミド基を有する化合物が合成される。 By this reaction, for example, by using a bis (4-maleimidophenyl) compound as the maleimide compound (b-1) and reacting with the amine compound (b-2), the following general formula (4) or general formula (5) A compound having an acidic substituent and an unsaturated maleimide group shown in FIG.
（Ｃ）成分は、下記の一般式（２）で示す６−置換グアナミン化合物又はジシアンジアミドである。一般式（２）に示す６−置換グアナミン化合物としては、例えばベンゾグアナミンと称される２，４‐ジアミノ−６−フェニル−ｓ−トリアジン、アセトグアナミンと称される２，４−ジアミノ−６−メチル−ｓ−トリアジン、２，４−ジアミノ−６−ビニル−ｓ−トリアジン等が挙げられ、これらの中で、反応率が高く、より高耐熱性化及び低誘電率化できるベンゾグアナミン及び２，４−ジアミノ−６−ビニル−ｓ−トリアジンがより好ましく、安価であることや溶媒への溶解性の点からベンゾグアナミンが特に好ましい。また、ワニスの保存安定性に優れ、高耐熱性化及び低誘電率化でき、安価である点からジシアンジアミドも特に好ましい。一般式（２）に示す６−置換グアナミン化合物及びジシアンジアミドを併用しても構わない。 The component (C) is a 6-substituted guanamine compound or dicyandiamide represented by the following general formula (2). Examples of the 6-substituted guanamine compound represented by the general formula (2) include 2,4-diamino-6-phenyl-s-triazine called benzoguanamine and 2,4-diamino-6-methyl called acetoguanamine. -S-triazine, 2,4-diamino-6-vinyl-s-triazine, and the like. Among these, benzoguanamine and 2,4-, which have a high reaction rate and can achieve higher heat resistance and lower dielectric constant. Diamino-6-vinyl-s-triazine is more preferable, and benzoguanamine is particularly preferable from the viewpoint of low cost and solubility in a solvent. Further, dicyandiamide is particularly preferable because it is excellent in storage stability of varnish, can have high heat resistance and low dielectric constant, and is inexpensive. A 6-substituted guanamine compound represented by the general formula (2) and dicyandiamide may be used in combination.
（Ｄ）成分は、１分子中に２個以上のエポキシ基を有するエポキシ樹脂であれば特に限定されず、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。
これらの中で、誘電特性、耐熱性、耐湿性及び金属箔接着性の点からビスフェノールF型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、ナフタレン環含有エポキシ樹脂、ビフェニル型エポキシ樹脂、ビフェニルアラルキル型エポキシ樹脂、フェノールノボラック型エポキシ樹脂及びクレゾールノボラック型エポキシ樹脂が好ましく、誘電特性や高いガラス転移温度を有する点からジシクロペンタジエン型エポキシ樹脂、ビフェニルアラルキル型エポキシ樹脂、ビフェニル型エポキシ樹脂及びフェノールノボラック型エポキシ樹脂がより好ましく、耐湿耐熱性の点からフェノールノボラック型エポキシ樹脂及びジシクロペンタジエン型エポキシ樹脂が特に好ましい。
The component (D) is not particularly limited as long as it is an epoxy resin having two or more epoxy groups in one molecule. For example, bisphenol A, bisphenol F, biphenyl, novolac, polyfunctional phenol, naphthalene Examples thereof include glycidyl ethers, glycidyl ethers, glycidyl amines, and glycidyl esters such as alicyclic, alicyclic, and alcohols, and one kind or a mixture of two or more kinds can be used.
Among these, bisphenol F type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene ring-containing epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin in terms of dielectric properties, heat resistance, moisture resistance and metal foil adhesion Phenol novolac type epoxy resin and cresol novolac type epoxy resin are preferable, and dicyclopentadiene type epoxy resin, biphenyl aralkyl type epoxy resin, biphenyl type epoxy resin and phenol novolac type epoxy resin are preferable because they have dielectric properties and high glass transition temperature. More preferred are phenol novolac type epoxy resins and dicyclopentadiene type epoxy resins from the viewpoint of moisture and heat resistance.
熱硬化性樹脂組成物中の（Ａ）〜（Ｄ）成分の含有量は、固形分換算の（Ｂ）〜（Ｄ）成分の質量の総和１００質量部中の質量として、次のようにすることが好ましい。
（Ａ）成分は１〜９８質量部とすることが好ましく、５〜７０質量部とすることがより好ましく、５〜３０質量部とすることが特に好ましい。（Ａ）成分の含有量を１質量部以上とすることにより、難燃性が向上し、また９８質量部以下とすることにより、耐熱性や接着性が低下することがない。
（Ｂ）成分は１〜９８．９質量部とすることが好ましく、２０〜９８．９質量部とすることがより好ましく、５０〜９０質量部とすることが特に好ましい。（Ｂ）成分の含有量を１質量部以上とすることにより、難燃性や接着性、誘電特性が向上し、また９８．９質量以下とすることにより耐熱性が低下することがない。
（Ｃ）成分は０．１〜５０質量部とすることが好ましく、０．５〜５０質量部とすることがより好ましく、０．５〜３０質量部とすることが特に好ましい。（Ｃ）成分の含有量を０．１質量部以上とすることにより、溶解性や誘電特性が向上し、また５０質量部以下とすることにより、難燃性が低下することがない。
（Ｄ）成分は１〜８０質量部とすることが好ましく、１０〜７０質量部とすることがより好ましく、２０〜６０質量部とすることが特に好ましい。（Ｄ）成分の含有量を１質量部以上とすることにより、耐熱性や難燃性、またプリプレグとして使用する際に成形性が向上し、また８０質量部以下とすることにより、誘電特性が低下することがない。
The content of the components (A) to (D) in the thermosetting resin composition is as follows as the mass in 100 parts by mass of the total mass of the components (B) to (D) in terms of solid content. It is preferable.
The component (A) is preferably 1 to 98 parts by mass, more preferably 5 to 70 parts by mass, and particularly preferably 5 to 30 parts by mass. When the content of the component (A) is 1 part by mass or more, flame retardancy is improved, and when it is 98 parts by mass or less, heat resistance and adhesiveness are not reduced.
Component (B) is preferably 1 to 98.9 parts by mass, more preferably 20 to 98.9 parts by mass, and particularly preferably 50 to 90 parts by mass. By setting the content of the component (B) to 1 part by mass or more, flame retardancy, adhesiveness, and dielectric properties are improved, and by setting the content to 98.9 mass or less, heat resistance is not lowered.
The component (C) is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 50 parts by mass, and particularly preferably 0.5 to 30 parts by mass. By setting the content of component (C) to 0.1 parts by mass or more, solubility and dielectric properties are improved, and by setting it to 50 parts by mass or less, flame retardancy does not decrease.
The component (D) is preferably 1 to 80 parts by mass, more preferably 10 to 70 parts by mass, and particularly preferably 20 to 60 parts by mass. When the content of the component (D) is 1 part by mass or more, heat resistance and flame retardancy are improved, and when used as a prepreg, moldability is improved. There is no decline.
本発明の熱硬化性樹脂組成物には、（Ｅ）成分として、エポキシ樹脂の硬化剤や硬化促進剤を併用してもよい。エポキシ樹脂の硬化剤の例としては、無水マレイン酸、無水マレイン酸共重合体等の酸無水物、ジアミノジフェニルメタン等のアミン化合物、フェノールノボラック、クレゾールノボラック等のフェノール化合物等が挙げられる。また、エポキシ樹脂の硬化促進剤の例としては、イミダゾール類及びその誘導体、第三級アミン類及び第四級アンモニウム塩等が挙げられる。これらの中で、耐熱性が良好となる無水マレイン酸共重合体が好ましく、低誘電率化できることからスチレンやエチレン、プロピレン、イソブチレン等の炭素原子及び水素原子から構成される重合体モノマーと無水マレイン酸の共重合樹脂がより好ましく、溶剤への溶解性や配合される樹脂との相溶性の点から、スチレンと無水マレイン酸、又はイソブチレンと無水マレイン酸の共重合樹脂が特に好ましい。
（Ｅ）成分の含有量は、固形分換算の（Ｂ）〜（Ｄ）成分の質量の総和１００質量部に対し、０〜５０質量部とすることが好ましく、５〜４０質量部とすることがより好ましく、５〜３０質量部とすることが特に好ましい。（Ｅ）成分の含有量を５０質量部以下とすることにより、成形性や接着性、難燃性が低下することがない。
In the thermosetting resin composition of the present invention, an epoxy resin curing agent or curing accelerator may be used in combination as the component (E). Examples of epoxy resin curing agents include acid anhydrides such as maleic anhydride and maleic anhydride copolymers, amine compounds such as diaminodiphenylmethane, and phenolic compounds such as phenol novolac and cresol novolac. Examples of epoxy resin curing accelerators include imidazoles and derivatives thereof, tertiary amines, and quaternary ammonium salts. Among these, a maleic anhydride copolymer with good heat resistance is preferable, and a polymer monomer composed of carbon atoms and hydrogen atoms such as styrene, ethylene, propylene, isobutylene and the like and maleic anhydride can be reduced in dielectric constant. An acid copolymer resin is more preferable, and a copolymer resin of styrene and maleic anhydride or isobutylene and maleic anhydride is particularly preferable from the viewpoint of solubility in a solvent and compatibility with a blended resin.
The content of the component (E) is preferably 0 to 50 parts by mass, and preferably 5 to 40 parts by mass with respect to 100 parts by mass of the total mass of the components (B) to (D) in terms of solid content. Is more preferable, and 5 to 30 parts by mass is particularly preferable. (E) By making content of a component into 50 mass parts or less, a moldability, adhesiveness, and a flame retardance do not fall.
本発明の熱硬化性樹脂には、（Ｆ）成分として、任意に無機充填材を含有させることができる。無機充填材の例としては、シリカ、マイカ、タルク、ガラスの短繊維又は微粉末及び中空ガラス、三酸化アンチモン、炭酸カルシウム、石英粉末、水酸化アルミニウム、水酸化マグネシウム等が挙げられ、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及び水酸化マグネシウムが好ましく、安価であることからシリカ及び水酸化アルミニウムがより好ましい。
（Ｆ）成分の含有量は、固形分換算の（Ｂ）〜（Ｄ）成分の質量の総和１００質量部に対し、０〜３００質量部とすることが好ましく、２０〜２００質量部とすることがより好ましく、２０〜１５０質量部とすることが特に好ましい。（Ｆ）成分の含有量を３００質量部以下とすることにより、成形性や接着性が低下することがない。
The thermosetting resin of the present invention can optionally contain an inorganic filler as the component (F). Examples of inorganic fillers 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. Silica, aluminum hydroxide, and magnesium hydroxide are preferable from the viewpoint of dielectric properties, heat resistance, and flame retardancy, and silica and aluminum hydroxide are more preferable because they are inexpensive.
The content of the component (F) is preferably 0 to 300 parts by mass and preferably 20 to 200 parts by mass with respect to 100 parts by mass of the total mass of the components (B) to (D) in terms of solid content. Is more preferable and it is especially preferable to set it as 20-150 mass parts. (F) By making content of a component into 300 mass parts or less, a moldability and adhesiveness do not fall.
さらに、本発明の熱硬化性樹脂組成物には、樹脂組成物として熱硬化性の性質を損なわない程度に、任意に公知の熱可塑性樹脂、エラストマー、難燃剤、有機充填材等を含有させることができる。
熱可塑性樹脂の例としては、ポリテトラフルオロエチレン、ポリエチレン、ポリプロピレン、ポリスチレン、ポリフェニレンエーテル樹脂、フェノキシ樹脂、ポリカーボネート樹脂、ポリエステル樹脂、ポリアミド樹脂、ポリイミド樹脂、キシレン樹脂、石油樹脂、シリコン樹脂などが挙げられる。
Furthermore, the thermosetting resin composition of the present invention may optionally contain a known thermoplastic resin, elastomer, flame retardant, organic filler, etc. to such an extent that the thermosetting properties of the resin composition are not impaired. Can do.
Examples of thermoplastic resins include polytetrafluoroethylene, polyethylene, polypropylene, polystyrene, polyphenylene ether resin, phenoxy resin, polycarbonate resin, polyester resin, polyamide resin, polyimide resin, xylene resin, petroleum resin, silicon resin, and the like. .
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、カルボキシ変性ポリアクリロニトリル等が挙げられる。 Examples of the elastomer include polybutadiene, polyacrylonitrile, epoxy-modified polybutadiene, maleic anhydride-modified polybutadiene, phenol-modified polybutadiene, carboxy-modified polyacrylonitrile, and the like.
難燃剤の例としては、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、ホスファゼン、赤リン等のリン系難燃剤、三酸化アンチモン、水酸化アルミニウム、水酸化マグネシウム等の無機物の難燃剤等が挙げられる。これらの難燃剤の中で、非ハロゲン難燃剤であるリン系難燃剤、無機物の難燃剤等が環境上から好ましい。また、リン系難燃剤と水酸化アルミニウムなどの無機物の難燃剤を併用して用いることが、安価であり、難燃性、耐熱性等の他特性との両立の点から好ましい。 Examples of flame retardants include halogen-containing flame retardants containing bromine and chlorine, triphenyl phosphate, tricresyl phosphate, trisdichloropropyl phosphate, phosphazenes, red phosphorus and other phosphorus flame retardants, antimony trioxide, hydroxylation Examples include inorganic flame retardants such as aluminum and magnesium hydroxide. Among these flame retardants, phosphorus-based flame retardants that are non-halogen flame retardants, inorganic flame retardants, and the like are preferable from the environmental viewpoint. In addition, it is preferable to use a phosphorus-based flame retardant in combination with an inorganic flame retardant such as aluminum hydroxide from the viewpoint of compatibility with other characteristics such as flame retardancy and heat resistance.
有機充填材の例としては、シリコーンパウダー、ポリテトラフルオロエチレン、ポリエチレン、ポリプロピレン、ポリスチレン、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。 Examples of the organic filler include organic powders such as silicone powder, polytetrafluoroethylene, polyethylene, polypropylene, polystyrene, and polyphenylene ether.
また、本発明の熱硬化性樹脂組成物において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。該有機溶剤は特に制限されないが、例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶剤、メチルセロソルブ等のアルコール系溶剤、テトラヒドロフランなどのエーテル系溶剤、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。 Moreover, an organic solvent can be arbitrarily used as a dilution solvent in the thermosetting resin composition of the present invention. 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.
更に、該熱硬化性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を含有させることも可能であり、特に制限されないが、例えば、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、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。 Further, the thermosetting resin composition can optionally contain an ultraviolet absorber, an antioxidant, a photopolymerization initiator, a fluorescent whitening agent, an adhesion improver, and the like, but is not particularly limited. UV absorbers such as benzotriazoles, antioxidants such as hindered phenols and styrenated phenols, photopolymerization initiators such as benzophenones, benzyl ketals, thioxanthones, and fluorescent whitening agents such as stilbene derivatives And urea compounds such as urea silane, and adhesion improvers such as silane coupling agents.
本発明のプリプレグは、本発明の熱硬化性樹脂組成物を、シート状補強基材に含浸又は塗工した後、Ｂステージ化してなるものである。すなわち、本発明の熱硬化性樹脂組成物を、シート状補強基材に含浸又は塗工した後、加熱等により半硬化（Ｂステージ化）させて本発明のプリプレグを製造する。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 formed by impregnating or coating the thermosetting resin composition of the present invention on a sheet-like reinforcing base material, and then forming a B-stage. That is, after impregnating or coating the thermosetting resin composition of the present invention on a sheet-like reinforcing base material, it is semi-cured (B-staged) by heating or the like to produce the prepreg of the present invention. Hereinafter, the prepreg of the present invention will be described in detail.
本発明のプリプレグに用いられるシート状補強基材には、各種の電気絶縁材料用積層板に用いられている周知のものが使用できる。その材質の例としては、Ｅガラス、Ｄガラス、Ｓガラス及びＱガラス等の無機物の繊維、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物の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。
シート状補強基材の厚さは、特に制限されないが、例えば、約０．０３〜０．５ｍｍのものを使用することができ、シランカップリング剤等で表面処理したもの又は機械的に開繊処理を施したものが、耐熱性や耐湿性、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（Ｂステージ化）させて、本発明のプリプレグを得ることができる。
As the sheet-like reinforcing base material used for the prepreg of the present invention, known materials used for various types of laminates for electrical insulating materials can be used. Examples of the material include inorganic fibers such as E glass, D glass, S glass, and Q glass, organic fibers such as polyimide, polyester, and polytetrafluoroethylene, and mixtures thereof. These base materials have, 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 sheet-like reinforcing substrate is not particularly limited, but for example, a sheet having a thickness of about 0.03 to 0.5 mm can be used, and the surface treated with a silane coupling agent or the like or mechanically opened. What gave the process is suitable from the surface of heat resistance, moisture resistance, or workability.
After impregnating or coating the base material so that the amount of the resin composition attached to the base material is 20 to 90% by mass in terms of the resin content of the prepreg after drying, the temperature is usually 100 to 200 ° C. Can be heated and dried for 1 to 30 minutes and semi-cured (B-stage) to obtain the prepreg of the present invention.
本発明の積層板は、絶縁樹脂層が本発明の樹脂組成物又はプリプレグを用いて形成されたものである。プリプレグを用いる場合には、本発明のプリプレグを、例えば、１〜２０枚重ね、その片面又は両面に銅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が得られる。成形条件は、例えば、電気絶縁材料用積層板及び多層板手法が適用でき、例えば多段プレス、多段真空プレス、連続成形、オートクレーブ成形機等を使用し、温度１００〜２５０℃、圧力０．２〜１０ＭＰa、加熱時間０．１〜５時間の範囲で成形することができる。また、本発明のプリプレグと内層用配線板を組み合わせ、積層成形して、多層板を製造することもできる。
本発明の配線板は、積層板における絶縁樹脂層の片面又は両面に配置された金属箔を回路加工して得られたものであり、上述の積層板に一般的な回路加工を施して得ることができる。
In the laminate of the present invention, the insulating resin layer is formed using the resin composition or prepreg of the present invention. When using a prepreg, a laminated board is obtained by carrying out the lamination | stacking shaping | molding of the prepreg of this invention, for example by the structure which piled 1-20 sheets, and has arrange | positioned metal foil, such as copper and aluminum, on the single side | surface or both surfaces. As the molding conditions, for example, a laminate for electric insulating material and a multilayer board method can be applied. For example, a multistage press, a multistage vacuum press, continuous molding, an autoclave molding machine, etc. are used, and a temperature is 100 to 250 ° C., a pressure is 0.2 to It can be molded in the range of 10 MPa and heating time of 0.1 to 5 hours. In addition, the prepreg of the present invention and the inner layer wiring board can be combined and laminated to produce a multilayer board.
The wiring board of the present invention is obtained by subjecting a metal foil disposed on one or both sides of an insulating resin layer in a laminate to circuit processing, and is obtained by subjecting the above-mentioned laminate to general circuit processing. Can do.
次に、下記の実施例により本発明を更に詳しく説明するが、これらの実施例は本発明を制限するものではない。
なお、以下の実施例で得られた銅張積層板は、以下の方法で性能を測定・評価した。
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.
The copper clad laminate obtained in the following examples was measured and evaluated for performance by the following method.
（１）比誘電率及び誘電正接の測定
ヒューレットパッカード製ネットワークアナライザ（８７２２Ｃ）を用い、トリプレート構造直線線路共振器法により１〜１０ＧＨｚにおける銅張積層板の比誘電率及び誘電正接の測定を実施した。試験片サイズは２００ｍｍ×５０ｍｍ×厚さ０．８ｍｍで、１枚のＭＣＬ片面の中心にエッチングにより幅１．０ｍｍの直線線路(ライン長さ２００ｍｍ)を形成し,裏面は全面に銅を残しグランド層とした。もう1枚は片面を全面エッチングし、裏面はグランド層とした。ついで２枚のＭＣＬグランド層を外側にして重ね合わせストリップ線路とした。測定は２５℃で行った。
（２）ＪＭＰによる測定データ解析
ＪＭＰ（統計解析ソフトウェア）を用いて比誘電率及び誘電正接測定データの解析を行った。
(1) Measurement of relative dielectric constant and dielectric loss tangent Using a Hewlett Packard network analyzer (8722C), measurement of relative dielectric constant and dielectric loss tangent of copper-clad laminate at 1-10 GHz is performed by the triplate structure linear line resonator method. did. The test piece size is 200mm x 50mm x thickness 0.8mm. A straight line (line length 200mm) with a width of 1.0mm is formed by etching at the center of one MCL single side, and copper is left on the entire surface, leaving copper on the entire surface. Layered. The other was etched on one side and the back side was a ground layer. Next, two MCL ground layers were placed outside to form a strip line. The measurement was performed at 25 ° C.
(2) Measurement data analysis by JMP The dielectric constant and dielectric loss tangent measurement data were analyzed using JMP (statistical analysis software).
製造例１：ジエチルホスフィン酸アルミニウム塩微粒品（Ａ−１）の製造
クラリアント（株）製のジエチルホスフィン酸アルミニウム塩（ＤＥＰＡＬ）を粉砕して平均粒径１．５μｍの塩微粒品を製造した。
Production Example 1: Production of Aluminum Diethylphosphinate Fine Salt Product (A-1) Diethylphosphinic acid aluminum salt (DEPAL) manufactured by Clariant Co., Ltd. was pulverized to produce a salt fine product having an average particle size of 1.5 μm.
製造例２：マレイミド化合物（Ｂ−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−マレイミドフェニル）エーテル：１０００ｇ、ｐ−アミノフェノール：８０ｇ及びＮ，Ｎ−ジメチルアセトアミド：８５０ｇを入れ[（マレイミド基当量）/（−ＮＨ2基換算の当量）＝４．０]、１００℃で２時間反応させてマレイミド化合物（Ｂ−１）の溶液を得た。
Production Example 2: Production of maleimide compound (B-1) Bis (4-maleimidophenyl) ether was added to a reaction vessel having a volume of 2 liters capable of being heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. : 1000 g, p-aminophenol: 80 g and N, N-dimethylacetamide: 850 g [(maleimide group equivalent) / (-NH 2 group equivalent) = 4.0] and reacted at 100 ° C. for 2 hours. A solution of the maleimide compound (B-1) was obtained.
実施例１〜２、比較例１〜２
希釈溶剤にメチルエチルケトンを使用し、下記成分を第１表に示す配合割合（質量部）で混合して樹脂分４５質量％の均一なワニスを製造した。
（Ａ）成分：ジエチルホスフィン酸のアルミニウム塩
Ａ−１：製造例１による微粒化品
ＤＥＰＡＬ〔クラリアント（株）製、平均粒径４μｍ〕
（Ｂ）成分：製造例２で得られたマレイミド化合物（Ｂ−１）
（Ｃ）成分：ジシアンジアミド［関東化学（株）製］
（Ｄ）成分（エポキシ樹脂）
Ｄ−１：フェノールノボラック型エポキシ樹脂［大日本インキ化学工業（株）製、商品名Ｎ−６９５］
Ｄ−２：ジシクロペンタジエン型エポキシ樹脂［大日本インキ化学工業（株）製、商品名：ＨＰ−７２００Ｈ］、
（Ｅ）成分（エポキシ樹脂硬化剤）：スチレンと無水マレイン酸の共重合樹脂［サートマー（株）製、商品名：ＳＭＡ−ＥＦ−４０］
（Ｆ）成分（無機充填材）：オリゴマ処理溶融シリカ［アドマテック（株）製、商品名：ＳＣ２０５０−ＫＣ］
なお、リン酸エステル系難燃剤［大八化学社製、商品名：ＰＸ−２００］を併用した。
Examples 1-2 and Comparative Examples 1-2
Methyl ethyl ketone was used as a diluent solvent, and the following components were mixed at a blending ratio (parts by mass) shown in Table 1 to produce a uniform varnish having a resin content of 45% by mass.
(A) Component: Aluminum salt of diethylphosphinic acid A-1: Atomized product according to Production Example 1 DEPAL [manufactured by Clariant Co., Ltd., average particle size 4 μm]
(B) Component: Maleimide compound (B-1) obtained in Production Example 2
Component (C): Dicyandiamide [manufactured by Kanto Chemical Co., Inc.]
Component (D) (epoxy resin)
D-1: Phenol novolac type epoxy resin [Dainippon Ink Chemical Co., Ltd., trade name N-695]
D-2: Dicyclopentadiene type epoxy resin [Dainippon Ink Chemical Co., Ltd., trade name: HP-7200H],
Component (E) (epoxy resin curing agent): copolymer resin of styrene and maleic anhydride [manufactured by Sartomer Co., Ltd., trade name: SMA-EF-40]
Component (F) (inorganic filler): Oligomer-treated fused silica [manufactured by Admatech Co., Ltd., trade name: SC2050-KC]
A phosphate ester flame retardant [manufactured by Daihachi Chemical Co., Ltd., trade name: PX-200] was used in combination.
作製したワニスを厚さ０．１ｍｍのガラスクロス（旭シュエベール株式会社製、商品名：＃２１１６）に含浸後、１６０℃で５分間加熱、乾燥して樹脂分４５質量％のプリプレグを得た。このプリプレグを８枚重ね、１８μｍの電解銅箔を上下に配置し、圧力４．０ＭＰａ、温度１８５℃で６０分間プレスを行って、銅張積層板を得た。
得られた銅張積層板を用いて、比誘電率及び誘電正接を測定、評価した。ＪＭＰ統計ソフトで誘電特性（比誘電率及び誘電正接）のバラツキを評価した。その評価結果を第１表及び第１図（実施例）、第２図(比較例)に示す。Ｒ２乗の値が１に近いほどバラツキが小さいと判定される。
The prepared varnish was impregnated into a 0.1 mm thick glass cloth (trade name: # 2116, manufactured by Asahi Shweer Co., Ltd.), heated and dried at 160 ° C. for 5 minutes to obtain a prepreg having a resin content of 45 mass%. Eight prepregs were stacked, 18 μm electrolytic copper foils were placed one above the other, and pressed at a pressure of 4.0 MPa and a temperature of 185 ° C. for 60 minutes to obtain a copper clad laminate.
Using the obtained copper-clad laminate, the relative dielectric constant and dielectric loss tangent were measured and evaluated. JMP statistical software was used to evaluate variations in dielectric properties (relative dielectric constant and dielectric loss tangent). The evaluation results are shown in Table 1, FIG. 1 (Example), and FIG. 2 (Comparative Example). It is determined that the closer the value of R square is to 1, the smaller the variation.
第１表及び第１図、第２図から明らかなように、本発明の実施例では、粒子径の小さいジエチルホスフィン酸のアルミニウム塩を使用することで、比誘電率および誘電正接のバラツキが小さくことが分かる。 As is apparent from Table 1 and FIGS. 1 and 2, in the examples of the present invention, the use of an aluminum salt of diethylphosphinic acid having a small particle diameter reduces variations in relative permittivity and dielectric loss tangent. I understand that.
本発明の熱硬化性樹脂組成物は、ハロゲンフリーであり、かつ比誘電率および誘電正接のバラツキの小さい特性を有しており、大量のデータを高速で処理するコンピュータや情報機器端末等の用いられる電子機器の配線板に好適に用いられる。 The thermosetting resin composition of the present invention is halogen-free and has a characteristic with small variations in relative permittivity and dielectric loss tangent, and is used in computers and information equipment terminals that process a large amount of data at high speed. It is suitably used for a wiring board of an electronic device.
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011099681A JP5772189B2 (en) | 2011-04-27 | 2011-04-27 | Thermosetting resin composition and prepreg, laminate and wiring board using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011099681A JP5772189B2 (en) | 2011-04-27 | 2011-04-27 | Thermosetting resin composition and prepreg, laminate and wiring board using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2012229363A true JP2012229363A (en) | 2012-11-22 |
| JP5772189B2 JP5772189B2 (en) | 2015-09-02 |
Family
ID=47431189
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2011099681A Active JP5772189B2 (en) | 2011-04-27 | 2011-04-27 | Thermosetting resin composition and prepreg, laminate and wiring board using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5772189B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015168744A (en) * | 2014-03-06 | 2015-09-28 | 日立化成株式会社 | Thermosetting resin composition, prepreg using the same, laminate sheet, and printed wiring board |
| KR20150137585A (en) * | 2014-05-30 | 2015-12-09 | 엘지이노텍 주식회사 | Epoxy resin composite and printed circuit board comprising the same |
| JP2016008229A (en) * | 2014-06-23 | 2016-01-18 | 日立化成株式会社 | Insulating resin composition and prepreg using the same, and laminate for printed wiring board |
| WO2016194927A1 (en) * | 2015-06-02 | 2016-12-08 | 日立化成株式会社 | Thermosetting resin composition, prepreg, laminate, and printed circuit board |
| WO2016199857A1 (en) * | 2015-06-11 | 2016-12-15 | 三菱レイヨン株式会社 | Epoxy resin composition, molded article, prepreg, fiber-reinforced composite material and structure |
| JP2018012791A (en) * | 2016-07-21 | 2018-01-25 | 日立化成株式会社 | Thermosetting resin composition, prepreg, laminate and printed wiring board |
| WO2018105070A1 (en) * | 2016-12-07 | 2018-06-14 | 日立化成株式会社 | Resin varnish, prepreg, laminate, and printed wiring board |
| WO2018105071A1 (en) * | 2016-12-07 | 2018-06-14 | 日立化成株式会社 | Thermosetting resin composition, method for producing same, prepreg, laminate, and printed wiring board |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006143844A (en) * | 2004-11-18 | 2006-06-08 | Hitachi Chem Co Ltd | Resin composition and prepreg, metal clad laminated board and printed wiring board using the same |
| JP2009155399A (en) * | 2007-12-25 | 2009-07-16 | Hitachi Chem Co Ltd | Thermosetting resin composition, and prepreg and laminate both made by using the same |
-
2011
- 2011-04-27 JP JP2011099681A patent/JP5772189B2/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006143844A (en) * | 2004-11-18 | 2006-06-08 | Hitachi Chem Co Ltd | Resin composition and prepreg, metal clad laminated board and printed wiring board using the same |
| JP2009155399A (en) * | 2007-12-25 | 2009-07-16 | Hitachi Chem Co Ltd | Thermosetting resin composition, and prepreg and laminate both made by using the same |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015168744A (en) * | 2014-03-06 | 2015-09-28 | 日立化成株式会社 | Thermosetting resin composition, prepreg using the same, laminate sheet, and printed wiring board |
| KR20150137585A (en) * | 2014-05-30 | 2015-12-09 | 엘지이노텍 주식회사 | Epoxy resin composite and printed circuit board comprising the same |
| KR102172293B1 (en) * | 2014-05-30 | 2020-10-30 | 엘지이노텍 주식회사 | Epoxy resin composite and printed circuit board comprising the same |
| JP2016008229A (en) * | 2014-06-23 | 2016-01-18 | 日立化成株式会社 | Insulating resin composition and prepreg using the same, and laminate for printed wiring board |
| WO2016194927A1 (en) * | 2015-06-02 | 2016-12-08 | 日立化成株式会社 | Thermosetting resin composition, prepreg, laminate, and printed circuit board |
| JPWO2016194927A1 (en) * | 2015-06-02 | 2018-03-22 | 日立化成株式会社 | Thermosetting resin composition, prepreg, laminate and printed wiring board |
| US10513577B2 (en) | 2015-06-11 | 2019-12-24 | Mitsubishi Chemical Corporation | Epoxy resin composition, molded article, prepreg, fiber-reinforced composite material and structure |
| WO2016199857A1 (en) * | 2015-06-11 | 2016-12-15 | 三菱レイヨン株式会社 | Epoxy resin composition, molded article, prepreg, fiber-reinforced composite material and structure |
| JPWO2016199857A1 (en) * | 2015-06-11 | 2017-06-22 | 三菱ケミカル株式会社 | Epoxy resin composition, molded article, prepreg, fiber reinforced composite material and structure |
| EP3309190A4 (en) * | 2015-06-11 | 2018-07-25 | Mitsubishi Chemical Corporation | Epoxy resin composition, molded article, prepreg, fiber-reinforced composite material and structure |
| JP2018012791A (en) * | 2016-07-21 | 2018-01-25 | 日立化成株式会社 | Thermosetting resin composition, prepreg, laminate and printed wiring board |
| WO2018105070A1 (en) * | 2016-12-07 | 2018-06-14 | 日立化成株式会社 | Resin varnish, prepreg, laminate, and printed wiring board |
| JP6402827B1 (en) * | 2016-12-07 | 2018-10-10 | 日立化成株式会社 | Thermosetting resin composition and method for producing the same, prepreg, laminate and printed wiring board |
| JPWO2018105070A1 (en) * | 2016-12-07 | 2018-12-06 | 日立化成株式会社 | Resin varnish, prepreg, laminate and printed wiring board |
| CN108401433B (en) * | 2016-12-07 | 2019-05-28 | 日立化成株式会社 | Resin varnish, prepreg, plywood and printed wiring board |
| CN108401433A (en) * | 2016-12-07 | 2018-08-14 | 日立化成株式会社 | Resin varnish, prepreg, plywood and printed wiring board |
| WO2018105071A1 (en) * | 2016-12-07 | 2018-06-14 | 日立化成株式会社 | Thermosetting resin composition, method for producing same, prepreg, laminate, and printed wiring board |
| US10940674B2 (en) | 2016-12-07 | 2021-03-09 | Showa Denko Materials Co., Ltd. | Resin varnish, prepreg, laminate, and printed wiring board |
| US11136454B2 (en) | 2016-12-07 | 2021-10-05 | Showa Denko Materials Co., Ltd. | Thermosetting resin composition and its production method, prepreg, laminate, and printed wiring board |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5772189B2 (en) | 2015-09-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10604641B2 (en) | Thermosetting resin composition and prepreg and laminate both made with the same | |
| JP5320699B2 (en) | Thermosetting resin composition, prepreg and laminate using the same | |
| JP5772189B2 (en) | Thermosetting resin composition and prepreg, laminate and wiring board using the same | |
| KR101398731B1 (en) | Thermosetting resin composition and prepreg and laminate obtained with the same | |
| JP5298462B2 (en) | Method for producing curing agent having acidic substituent and unsaturated maleimide group, thermosetting resin composition, prepreg and laminate | |
| JP5023877B2 (en) | Flame retardant resin compound, thermosetting resin composition using the same, prepreg and laminate | |
| KR20090014362A (en) | Method for producing curing agent having acidic substituent and unsaturated maleimide group, thermosetting resin composition, prepreg, and laminate | |
| JP2008133353A (en) | Thermosetting resin composition, and prepreg and laminate using the resin composition | |
| JP5266685B2 (en) | Thermosetting resin composition, prepreg and laminate using the same | |
| JP6575151B2 (en) | Thermosetting resin composition, and prepreg, laminate and printed wiring board using the same | |
| JP6311922B2 (en) | Thermosetting resin composition, prepreg using the same, laminate, and printed wiring board | |
| JP5028971B2 (en) | (Modified) Guanamine compound solution, thermosetting resin composition, and prepreg and laminate using the same | |
| JP6977241B2 (en) | Thermosetting resin composition, prepreg, laminated board and printed wiring board | |
| JP5682664B2 (en) | Thermosetting resin composition, prepreg and laminate using the same | |
| JP2013237844A (en) | Thermosetting resin composition, prepreg using the same, and laminate | |
| JP2010106149A (en) | Thermosetting resin composition and prepreg and laminate using the same | |
| JP2007138127A (en) | Phosphorus-containing guanamine resin, thermosetting resin composition using the same, and prepreg and laminated plate using the same | |
| JP5088060B2 (en) | Thermosetting resin composition, and prepreg, laminate and printed wiring board using the same | |
| JP2014012762A (en) | Prepreg using organic fiber base material and manufacturing method of the same, and laminated plate, metal foil-clad laminated plate, and wiring board using the prepreg | |
| JP2008150575A (en) | Guanamine compound-comtaining solution, thermosetting resin composition and prepreg, laminated plate, and printed wiring board using the same | |
| JP2014012759A (en) | Prepreg using organic fiber base material and manufacturing method of the same, and laminated plate, metal foil-clad laminated plate, and wiring board using the prepreg | |
| JP2012236909A (en) | Thermosetting resin composition, and prepreg, laminate and printed wiring board using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20140303 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20140619 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20140624 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20141202 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20150302 |
|
| A911 | Transfer to examiner for re-examination before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20150421 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20150602 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20150615 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 5772189 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |