JP2009024146A - Thermosetting resin composition and prepreg and laminate using the same - Google Patents
Thermosetting resin composition and prepreg and laminate using the same Download PDFInfo
- Publication number
- JP2009024146A JP2009024146A JP2007204363A JP2007204363A JP2009024146A JP 2009024146 A JP2009024146 A JP 2009024146A JP 2007204363 A JP2007204363 A JP 2007204363A JP 2007204363 A JP2007204363 A JP 2007204363A JP 2009024146 A JP2009024146 A JP 2009024146A
- Authority
- JP
- Japan
- Prior art keywords
- group
- general formula
- resin composition
- thermosetting resin
- laminate
- 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
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 45
- 239000011342 resin composition Substances 0.000 title claims abstract description 36
- -1 guanamine compound Chemical class 0.000 claims abstract description 56
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 37
- 239000003822 epoxy resin Substances 0.000 claims abstract description 33
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 33
- 229920006026 co-polymeric resin Polymers 0.000 claims abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 125000001424 substituent group Chemical group 0.000 claims abstract description 12
- 239000011888 foil Substances 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 125000005843 halogen group Chemical group 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- 230000002378 acidificating effect Effects 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- 125000001931 aliphatic group Chemical group 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 4
- 238000010030 laminating Methods 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 125000001118 alkylidene group Chemical group 0.000 claims description 3
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 125000003700 epoxy group Chemical group 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
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- 238000003825 pressing Methods 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 7
- 239000002253 acid Substances 0.000 abstract description 5
- 230000001464 adherent effect Effects 0.000 abstract 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 36
- 238000004519 manufacturing process Methods 0.000 description 29
- 229920005989 resin Polymers 0.000 description 21
- 239000011347 resin Substances 0.000 description 21
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 20
- 238000011156 evaluation Methods 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000011889 copper foil Substances 0.000 description 18
- 229910052802 copper Inorganic materials 0.000 description 17
- 239000010949 copper Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 16
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 16
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 14
- 238000010992 reflux Methods 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 229920003986 novolac Polymers 0.000 description 11
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 10
- 229910000679 solder Inorganic materials 0.000 description 10
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical class O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-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
- 239000003063 flame retardant Substances 0.000 description 8
- 230000009477 glass transition Effects 0.000 description 8
- 229940018563 3-aminophenol Drugs 0.000 description 7
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005530 etching Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 5
- 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 5
- 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 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-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
- 229930003836 cresol Natural products 0.000 description 5
- 239000011810 insulating material Substances 0.000 description 5
- 231100000053 low toxicity Toxicity 0.000 description 5
- 150000002989 phenols Chemical class 0.000 description 5
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical class NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 4
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-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
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 229960004050 aminobenzoic acid Drugs 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
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- GUIACFHOZIQGKX-UHFFFAOYSA-N 1-[4-[4-(2,5-dioxopyrrol-1-yl)phenyl]sulfonylphenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=C(S(=O)(=O)C=2C=CC(=CC=2)N2C(C=CC2=O)=O)C=C1 GUIACFHOZIQGKX-UHFFFAOYSA-N 0.000 description 3
- 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 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 3
- SXPVZPQNFIDDPP-UHFFFAOYSA-N 3-(4-hydroxyphenyl)pyrrole-2,5-dione Chemical compound C1=CC(O)=CC=C1C1=CC(=O)NC1=O SXPVZPQNFIDDPP-UHFFFAOYSA-N 0.000 description 3
- XFDUHJPVQKIXHO-UHFFFAOYSA-N 3-aminobenzoic acid Chemical compound NC1=CC=CC(C(O)=O)=C1 XFDUHJPVQKIXHO-UHFFFAOYSA-N 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 3
- 0 CI1=CC=CC(*(C(C=C2)O)C2=O)=C1 Chemical compound CI1=CC=CC(*(C(C=C2)O)C2=O)=C1 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 239000012796 inorganic flame retardant Substances 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 239000002648 laminated material 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
- 238000000465 moulding Methods 0.000 description 3
- 229920003192 poly(bis maleimide) Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 2
- 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 2
- PDCMTKJRBAZZHL-UHFFFAOYSA-N 5-aminobenzene-1,3-diol Chemical compound NC1=CC(O)=CC(O)=C1 PDCMTKJRBAZZHL-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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-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
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 239000005456 alcohol based solvent Substances 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
- 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
- 230000015572 biosynthetic process Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-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
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 239000005453 ketone based solvent Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 238000005259 measurement Methods 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
- 239000002245 particle Substances 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000004848 polyfunctional curative Substances 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
- 238000004080 punching Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 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
- 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
- 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 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
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-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
- WAXBZQUSTLNLPU-UHFFFAOYSA-N 2,5-dioxo-3-phenylpyrrole-1-carboxylic acid Chemical compound O=C1N(C(=O)O)C(=O)C=C1C1=CC=CC=C1 WAXBZQUSTLNLPU-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
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-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
- BTOVVHWKPVSLBI-UHFFFAOYSA-N 2-methylprop-1-enylbenzene Chemical compound CC(C)=CC1=CC=CC=C1 BTOVVHWKPVSLBI-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
- OUVFWIHVZPQHJF-UHFFFAOYSA-N 5-ethenyl-5-methylcyclohexa-1,3-diene Chemical compound C=CC1(C)CC=CC=C1 OUVFWIHVZPQHJF-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
- 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
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-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
- YMOONIIMQBGTDU-VOTSOKGWSA-N [(e)-2-bromoethenyl]benzene Chemical compound Br\C=C\C1=CC=CC=C1 YMOONIIMQBGTDU-VOTSOKGWSA-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
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 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
- 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
- 238000011088 calibration curve Methods 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-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
- 238000001035 drying Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- MSYLJRIXVZCQHW-UHFFFAOYSA-N formaldehyde;6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound O=C.NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 MSYLJRIXVZCQHW-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine powder Natural products NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-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
- 150000002790 naphthalenes Chemical class 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
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical class NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 229920006287 phenoxy resin Polymers 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
- 238000007747 plating Methods 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
- 238000012545 processing Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 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
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000007787 solid 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
- 150000003440 styrenes Chemical class 0.000 description 1
- 229950000244 sulfanilic acid Drugs 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 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
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 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
- 230000002087 whitening effect Effects 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Abstract
Description
本発明は、金属箔接着性、耐熱性、耐湿性、難燃性、金属付き耐熱性及び誘電特性（比誘電率、誘電正接）の全てにおいてバランスがとれ、また、毒性が低く安全性や作業環境に優れ、電子部品等に好適に用いられる熱硬化性樹脂組成物並びにこれを用いたプリプレグ及び積層板に関する。 The present invention balances all of metal foil adhesion, heat resistance, moisture resistance, flame retardancy, heat resistance with metal and dielectric properties (relative permittivity, dielectric loss tangent), and has low toxicity and safety and work. The present invention relates to a thermosetting resin composition excellent in the environment and suitably used for electronic parts and the like, and a prepreg and a laminate using the same.
熱硬化性樹脂は、その特有な架橋構造が高い耐熱性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る。
また、近年の環境問題から、鉛フリーはんだによる電子部品の搭載やハロゲンフリーによる難燃化が要求され、そのため従来のものよりも高い耐熱性及び難燃性が必要とされる。さらに、製品の安全性や作業環境の向上化のため、毒性の低い成分のみで構成され、毒性ガス等が発生しない熱硬化性樹脂組成物が望まれている。
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 adhesiveness for forming fine wiring and workability when drilling or punching is required.
Moreover, due to recent environmental problems, mounting of electronic parts using lead-free solder and flame resistance using halogen-free are required, and therefore higher heat resistance and flame resistance than conventional ones are required. Furthermore, in order to improve the safety of the product and the working environment, there is a demand for a thermosetting resin composition that is composed only of low-toxic components and does not generate toxic gases.
ビスマレイミド化合物は、誘電特性、難燃性、耐熱性に優れる熱硬化性樹脂用の硬化剤であるが、公知のビスマレイミド化合物はエポキシ樹脂との硬化反応性を有さないため、エポキシ硬化系の熱硬化性樹脂にそのまま使用した場合、耐熱性が不足する問題があった。すなわち、有機溶媒を使用せずに加熱混練によりビスマレイミド化合物とアミノフェノールの付加物を製造し使用する熱硬化性樹脂に関する事例（例えば、特許文献１、特許文献２参照）が開示されているが、ビスマレイミド化合物とアミノフェノールの付加物の収率が低く、これらを銅張積層板や層間絶縁材料として使用すると、耐熱性や加工性等が不足である。 Bismaleimide compounds are curing agents for thermosetting resins that have excellent dielectric properties, flame retardancy, and heat resistance, but since known bismaleimide compounds do not have curing reactivity with epoxy resins, epoxy curing systems When used as it is in the thermosetting resin, there is a problem that the heat resistance is insufficient. That is, although examples relating to thermosetting resins in which an adduct of a bismaleimide compound and an aminophenol is produced and used by heat-kneading without using an organic solvent (see, for example, Patent Document 1 and Patent Document 2) are disclosed. The yield of the adduct of bismaleimide compound and aminophenol is low, and when these are used as a copper clad laminate or an interlayer insulating material, heat resistance, workability and the like are insufficient.
また、熱硬化性樹脂であるメラミン樹脂やグアナミン化合物は、接着性、難燃性及び耐熱性に優れているが、有機溶剤への溶解性が不足し、毒性の高いＮ，Ｎ−ジメチルホルムアミド等の窒素原子含有有機溶剤を多量に使用しないと熱硬化性樹脂組成物の作製が困難であったり、また保存安定性が不足する問題があった。また、これらの熱硬化性樹脂を使用した銅張積層板や層間絶縁材料は、電子部品等を製造する際、めっき液等の各種薬液を汚染する問題があった。 In addition, melamine resins and guanamine compounds, which are thermosetting resins, are excellent in adhesiveness, flame retardancy, and heat resistance, but lack solubility in organic solvents and have high toxicity such as N, N-dimethylformamide. Unless a large amount of the nitrogen atom-containing organic solvent is used, it is difficult to produce a thermosetting resin composition, and storage stability is insufficient. In addition, copper clad laminates and interlayer insulating materials using these thermosetting resins have the problem of contaminating various chemicals such as plating solutions when manufacturing electronic parts and the like.
これらの問題を解決するためのものとして、メラミン樹脂やグアナミン化合物を使用した熱硬化性樹脂に関する多くの事例が知られている（例えば、特許文献３〜７参照）。
しかしながら、これらはメラミン樹脂やグアナミン化合物をホルムアルデヒド等のアルデヒド類を用いて縮合させた熱硬化性樹脂であり、有機溶剤への溶解性は改良されているものの、熱分解温度が低く、毒性の分解ガスを発生するため作業環境を悪化させたり、近年要求される鉛フリーはんだへの耐熱性や銅付き耐熱性に不足する。また微細な加工処理・配線形成において、銅箔接着性や可とう性、靭性が不足し、回路パターンが断線や剥離を生じたり、ドリルや打ち抜きにより穴あけ等の加工をする際にクラックが発生する等の不具合が生じる。
また、メチロール化グアナミン樹脂に関する事例（例えば、特許文献８参照）が開示されているが、これらも上記と同様に耐熱性や接着性、加工性等の問題がある。
さらに、有機溶媒を使用せずに製造されるビスマレイミド化合物とアミノ安息香酸の付加物、ベンゾグアナミンホルムアルデヒド縮合物等を使用する熱硬化性樹脂に関する事例（例えば、特許文献９参照）が開示されているが、熱分解温度が低く、近年要求される鉛フリーはんだへの耐熱性や銅付き耐熱性に不足する。
Many examples of thermosetting resins using melamine resins and guanamine compounds are known as solutions for solving these problems (see, for example, Patent Documents 3 to 7).
However, these are thermosetting resins obtained by condensing melamine resins and guanamine compounds with aldehydes such as formaldehyde, and although their solubility in organic solvents has been improved, the thermal decomposition temperature is low, and toxic decomposition Since it generates gas, the working environment is deteriorated, and the heat resistance to lead-free solder and the heat resistance with copper are insufficient in recent years. Also, in fine processing and wiring formation, copper foil adhesion, flexibility, and toughness are insufficient, circuit patterns are broken or peeled off, and cracks occur when drilling or punching is performed. Such problems occur.
Moreover, although the example (for example, refer patent document 8) regarding a methylolation guanamine resin is disclosed, these also have problems, such as heat resistance, adhesiveness, workability, like the above.
Furthermore, a case relating to a thermosetting resin using an adduct of a bismaleimide compound and an aminobenzoic acid produced without using an organic solvent, a benzoguanamine formaldehyde condensate, etc. (see, for example, Patent Document 9) is disclosed. However, the thermal decomposition temperature is low, and the heat resistance to lead-free solder and the heat resistance with copper are insufficient in recent years.
エポキシ樹脂を硬化剤とし、無水マレイン酸を含有する共重合樹脂を使用する樹脂組成物又は積層板の事例として、スチレンと無水マレイン酸からなる共重合樹脂等による可撓性印刷配線板（例えば、特許文献１０参照）が開示されている。また、エポキシ樹脂、芳香族ビニル化合物及び無水マレイン酸から得られる酸価が２８０以上の共重合樹脂並びにジシアンジアミドを含有するエポキシ樹脂化合物（例えば、特許文献１１参照）が開示されている。更に、ブロム化されたエポキシ樹脂、スチレンと無水マレイン酸の共重合樹脂（エポキシ樹脂硬化剤）、スチレン系化合物及び溶剤を含むプリプレグ、電気用積層板材料（例えば、特許文献１２参照）、エポキシ樹脂、芳香族ビニル化合物と無水マレイン酸の共重合樹脂、フェノール化合物を含むプリプレグ、電気用積層板材料（例えば、特許文献１３参照）、エポキシ樹脂、芳香族ビニル化合物と無水マレイン酸の共重合樹脂、フェノール化合物および、スチレン或いはスチレン低重合体を含むプリプレグ、電気用積層板材料（例えば、特許文献１４参照）、エポキシ樹脂、カルボン酸無水物型エポキシ樹脂用架橋剤、アリル網目形成化合物を含む樹脂組成物、積層板、プリント配線板（例えば、特許文献１５参照）などが開示されている。
しかし、これらはパターンの細密化、信号の高周波化等に伴ない要求されている誘電特性、高耐熱性、高耐湿性及び銅箔との高接着性等における性能が不充分である。
As an example of a resin composition or laminate using an epoxy resin as a curing agent and a copolymer resin containing maleic anhydride, a flexible printed wiring board made of a copolymer resin composed of styrene and maleic anhydride (for example, Patent Document 10) is disclosed. Further, a copolymer resin having an acid value of 280 or more obtained from an epoxy resin, an aromatic vinyl compound and maleic anhydride, and an epoxy resin compound containing dicyandiamide (for example, see Patent Document 11) are disclosed. Further, brominated epoxy resin, copolymer resin of styrene and maleic anhydride (epoxy resin curing agent), prepreg containing styrene compound and solvent, electrical laminate material (for example, see Patent Document 12), epoxy resin , A copolymer resin of an aromatic vinyl compound and maleic anhydride, a prepreg containing a phenol compound, an electrical laminate material (for example, see Patent Document 13), an epoxy resin, a copolymer resin of an aromatic vinyl compound and maleic anhydride, A resin composition containing a phenol compound and a prepreg containing styrene or a styrene low polymer, an electrical laminate material (see, for example, Patent Document 14), an epoxy resin, a crosslinking agent for a carboxylic anhydride type epoxy resin, and an allyl network-forming compound. Articles, laminated boards, printed wiring boards (for example, see Patent Document 15), etc.
However, these have insufficient performance in terms of dielectric properties, high heat resistance, high moisture resistance, and high adhesion to copper foil, which are required with fine patterning, high frequency signals, and the like.
本発明の目的は、こうした現状に鑑み、金属箔接着性、耐熱性、耐湿性、難燃性、金属付き耐熱性、比誘電率及び誘電正接の全てにおいてバランスのとれた熱硬化性樹脂組成物並びにこれを用いたプリプレグ及び積層板を提供することである。 In view of the present situation, the object of the present invention is a thermosetting resin composition balanced in all of metal foil adhesion, heat resistance, moisture resistance, flame resistance, heat resistance with metal, relative dielectric constant and dielectric loss tangent. And providing a prepreg and a laminate using the same.
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、特定の方法により製造された酸性置換基と不飽和マレイミド基を有する硬化剤（以下、単に硬化剤とも云う）、６−置換グアナミン化合物、特定のモノマー単位を含む共重合樹脂及びエポキシ樹脂を含有する熱硬化性樹脂組成物が上記目的に沿うものであり、積層板用熱硬化性樹脂組成物として有利に用いられることを見出した。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 curing agent having an acidic substituent and an unsaturated maleimide group produced by a specific method (hereinafter also simply referred to as a curing agent), 6 -A thermosetting resin composition containing a substituted guanamine compound, a copolymer resin containing a specific monomer unit, and an epoxy resin meets the above-mentioned purpose, and can be advantageously used as a thermosetting resin composition for a laminate. I found. 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、プリプレグ及び積層板を提供するものである。
１．（Ａ）（ａ−１）１分子中に少なくとも２個のＮ−置換マレイミド基を有するマレイミド化合物と（ａ−２）下記一般式（１）に示す酸性置換基を有するアミン化合物を有機溶媒中で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硬化剤、（Ｂ）下記一般式（２）に示す６−置換グアナミン化合物、（Ｃ）（ｃ−１）下記一般式（３）で示されるモノマー単位と（ｃ−２）下記一般式（４）で示されるモノマー単位を含む共重合樹脂及び(Ｄ) １分子中に少なくとも２個のエポキシ基を有するエポキシ樹脂を含有する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 and laminate.
1. (A) (a-1) A maleimide compound having at least two N-substituted maleimide groups in one molecule and (a-2) an amine compound having an acidic substituent represented by the following general formula (1) in an organic solvent (B) 6-substituted guanamine compound represented by the following general formula (2), (C) (c-1) the following general formula (3) And (c-2) a copolymer resin containing a monomer unit represented by the following general formula (4) and (D) an epoxy resin having at least two epoxy groups in one molecule. A thermosetting resin composition characterized by the above.
２．（Ａ）硬化剤が、下記一般式（５）又は下記一般式（６）で示される化合物である請求項１に記載の熱硬化性樹脂組成物。
３．上記１又は２の熱硬化性樹脂組成物を、基材に含浸又は塗工した後、Ｂステージ化して得られたプリプレグ。
４．上記３のプリプレグを積層成形して得られた積層板。
５．プリプレグの少なくとも一方に金属箔を重ねた後、加熱加圧成形して得られた金属張積層板である上記４の積層板。
3. A prepreg obtained by impregnating or coating the thermosetting resin composition according to 1 or 2 on a base material and then forming a B-stage.
4). A laminate obtained by laminating the prepreg of 3 above.
5). 4. The laminate of 4 above, which is a metal-clad laminate obtained by heating and pressing after a metal foil is laminated on at least one of the prepregs.
本発明の熱硬化性樹脂組成物は、金属箔接着性、耐熱性、耐湿性、難燃性、金属付き耐熱性、比誘電率及び誘電正接の全てにおいてバランスがとれたものであり、また、毒性が低く安全性や作業環境にも優れるものである。
このため本発明により、該熱硬化性樹脂組成物を用いて、優れた性能を有するプリプレグや積層板などを提供することができる。
The thermosetting resin composition of the present invention is balanced in all of metal foil adhesion, heat resistance, moisture resistance, flame resistance, heat resistance with metal, relative dielectric constant and dielectric loss tangent, Low toxicity and excellent safety and work environment.
Therefore, according to the present invention, it is possible to provide a prepreg or a laminate having excellent performance using the thermosetting resin composition.
以下、本発明について詳細に説明する。
先ず、本発明の熱硬化性樹脂組成物の（Ａ）成分の硬化剤は、（ａ−１）１分子中に少なくとも２個のＮ−置換マレイミド基を有するマレイミド化合物と（ａ−２）下記一般式（１）に示す酸性置換基を有するアミン化合物を有機溶媒中で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硬化剤である。
Hereinafter, the present invention will be described in detail.
First, the curing agent of the component (A) of the thermosetting resin composition of the present invention includes (a-1) a maleimide compound having at least two N-substituted maleimide groups in one molecule and (a-2) A curing agent having an acidic substituent and an unsaturated maleimide group, produced by reacting an amine compound having an acidic substituent represented by the general formula (1) in an organic solvent.
（ａ−１）１分子中に少なくとも２個のＮ−置換マレイミド基を有するマレイミド化合物としては、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、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。 (A-1) Examples of maleimide compounds having at least two N-substituted maleimide groups in one molecule include bis (4-maleimidophenyl) methane, poly (maleimidophenyl) methane, and bis (4-maleimidophenyl). Ether, 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, etc. Among them, bis (4-maleimidophenyl) methane, m-phenylenebis, which has a high reaction rate and can have higher heat resistance. Maleimide and bis (4-maleimidophenyl) sulfone are preferred and inexpensive because - phenylene bismaleimide and bis (4-maleimide phenyl) methane are more preferred, bis terms of solubility in a solvent (4-maleimide phenyl) methane are particularly preferred.
（ａ−２）一般式（１）に示すアミン化合物としては、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、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、低毒性である点からｍ−アミノフェノールが特に好ましい。 (A-2) Examples of the amine compound represented by the general formula (1) 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 preferred from the viewpoint of synthesis yield, and m-aminophenol and p- from the viewpoint of heat resistance. Aminophenol is more preferred, and m-aminophenol is particularly preferred from the viewpoint of low toxicity.
（ａ−１）のマレイミド化合物と（ａ−２）のアミン化合物の使用量比は、（ａ−１）のマレイミド化合物のマレイミド基当量と（ａ−２）のアミン化合物の−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。
The amount ratio of the maleimide compound (a-1) and the amine compound (a-2) is equivalent to the maleimide group equivalent of the maleimide compound (a-1) and —NH 2 group equivalent of the amine compound (a-2). The equivalent ratio with the equivalent of
1.0 ≦ (maleimide group equivalent) / (- equivalent of NH 2 groups in terms) ≦ 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.
この反応で使用される有機溶媒は特に制限されないが、例えばエタノール、プロパノール、ブタノール、メチルセロソルブ、ブチルセロソルブ、プロピレングリコールモノメチルエーテル等のアルコール系溶媒、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶媒、テトラヒドロフラン等のエーテル系溶媒、トルエン、キシレン、メシチレン等の芳香族系溶媒、ジメチルホルムアミド、ジメチルアセトアミド、Ｎ−メチルピロリドン等の窒素含有溶媒、ジメチルスルホキシド等の硫黄含有溶媒等が挙げられ、１種又は２種以上を混合して使用できる。
これらの有機溶媒の中で、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及びメチルセロソルブが好ましく、低毒性である点からシクロヘキサノン及びプロピレングリコールモノメチルエーテルがより好ましく、揮発性が高くプリプレグの製造時に残溶媒として残りにくい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。
有機溶媒の使用量は、（ａ−１）のアミン化合物と（ａ−２）のマレイミド化合物の総和１００質量部当たり、１０〜１０００質量部とすることが好ましく、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。
The organic solvent used in this reaction is not particularly limited, but alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, and ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. And ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene, and mesitylene, nitrogen-containing solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone, and sulfur-containing solvents such as dimethylsulfoxide. Or 2 or more types can be mixed and used.
Among these organic solvents, cyclohexanone, propylene glycol monomethyl ether and methyl cellosolve are preferable from the viewpoint of solubility, and cyclohexanone and propylene glycol monomethyl ether are more preferable from the viewpoint of low toxicity, and they are highly volatile and remain at the time of production of the prepreg. Particularly preferred is propylene glycol monomethyl ether which hardly remains as a solvent.
The amount of the organic solvent used is preferably 10 to 1000 parts by mass, preferably 100 to 500 parts by mass, per 100 parts by mass of the sum of the amine compound (a-1) and the maleimide compound (a-2). Is more preferable, and 200 to 500 parts by mass is particularly preferable.
反応温度は５０〜２００℃であることが好ましく、１００〜１６０℃であることがさらに好ましい。反応時間は０．１〜１０時間であることが好ましく、１〜８時間であることがさらに好ましい。
この反応には、必要により任意に反応触媒を使用することができる。反応触媒は特に制限されないが、例えば、トリエチルアミン、ピリジン、トリブチルアミン等のアミン類、メチルイミダゾール、フェニルイミダゾール等のイミダゾール類、トリフェニルホスフィン等のリン系触媒等が挙げられ、１種又は２種以上を混合して使用できる。
The reaction temperature is preferably 50 to 200 ° C, more preferably 100 to 160 ° C. The reaction time is preferably 0.1 to 10 hours, and more preferably 1 to 8 hours.
In this reaction, a reaction catalyst can be optionally 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. Can be used in combination.
この反応により、例えば、（ａ−１）のマレイミド化合物としてビス（４−マレイミドフェニル）化合物を用い、（ａ−２）のアミン化合物と反応させることにより、下記一般式（５）又は一般式（６）に示す酸性置換基と不飽和マレイミド基を有する硬化剤が合成される。 By this reaction, for example, by using a bis (4-maleimidophenyl) compound as the maleimide compound of (a-1) and reacting with the amine compound of (a-2), the following general formula (5) or general formula ( A curing agent having an acidic substituent and an unsaturated maleimide group shown in 6) is synthesized.
本発明の熱硬化性樹脂組成物の（Ｂ）成分は、下記の一般式（２）に示す６−置換グアナミン化合物である。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、反応の反応率が高く、より高耐熱性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、低毒性で安価である点からベンゾグアナミンが特に好ましい。 The component (B) of the thermosetting resin composition of the present invention is a 6-substituted guanamine compound 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 them, benzoguanamine and 2,4-diamino-6, which have a high reaction rate and can have higher heat resistance, are included. -Vinyl-s-triazine is more preferred, and benzoguanamine is particularly preferred from the viewpoint of low toxicity and low cost.
本発明の熱硬化性樹脂組成物の（Ｃ）成分は、（ｃ−１）下記一般式（３）で示されるモノマー単位及び（ｃ−２）下記一般式（４）で示されるモノマー単位を含む共重合樹脂である。
（ｃ−１）の一般式（３）で示されるモノマー単位は、例えば、スチレン、１−メチルスチレン、ビニルトルエン、ジメチルスチレン、クロルスチレン、ブロムスチレン等のスチレン化合物や、エチレン、プロピレン、イソブチレン等のビニル化合物から得られ、必要により２種以上のモノマーを混合して用いてもよい。
また、（ｃ−２）の一般式（４）で示されるモノマー単位は、無水マレイン酸から得られる。
（Ｃ）成分の共重合樹脂には、更に、上記のモノマー単位以外にも、各種の重合可能なモノマー単位を含有させてもよく、これら各種のモノマー単位（ｃ−３）が得られるモノマーとして、例えば、Ｎ−フェニルマレイミド、Ｎ−ヒドロキシフェニルマレイミド、Ｎ−カルボキシフェニルマレイミド、Ｎ−シクロヘキシルマレイミド等のマレイミド化合物、メチルメタクリレートやメチルアクリレート等のメタクリロイル基又はアクリロイル基を有する化合物等が挙げられ、誘電特性や難燃性の点からマレイミド化合物が好ましく、耐湿耐熱性や接着性の点からＮ−フェニルマレイミド及びＮ−ヒドロキシフェニルマレイミドがより好ましい。
Examples of the monomer unit represented by the general formula (3) in (c-1) include styrene compounds such as styrene, 1-methylstyrene, vinyltoluene, dimethylstyrene, chlorostyrene, bromostyrene, ethylene, propylene, isobutylene, and the like. It is obtained from the above vinyl compound, and if necessary, two or more monomers may be mixed and used.
Further, the monomer unit represented by the general formula (4) of (c-2) is obtained from maleic anhydride.
In addition to the above monomer units, the copolymer resin of component (C) may further contain various polymerizable monomer units. As monomers for obtaining these various monomer units (c-3), Examples thereof include maleimide compounds such as N-phenylmaleimide, N-hydroxyphenylmaleimide, N-carboxyphenylmaleimide, and N-cyclohexylmaleimide, compounds having a methacryloyl group or acryloyl group such as methyl methacrylate and methyl acrylate, and the like. A maleimide compound is preferable from the viewpoint of characteristics and flame retardancy, and N-phenylmaleimide and N-hydroxyphenylmaleimide are more preferable from the viewpoint of moisture and heat resistance and adhesiveness.
（Ｃ）成分の共重合樹脂における（ｃ−１）のモノマー単位数をｍ、（ｃ−２）のモノマー単位数をｎ、（ｃ−３）の共重合可能な成分をモノマー単位数をｒとした場合、（Ｃ）成分の共重合樹脂中のモノマー比率（ｍ／ｎ）は、誘電特性やガラス転移温度、耐湿耐熱性、接着性とのバランスを考慮すると、０．８〜１９．０が好ましく、１．０〜６．０がより好ましい。また、（ｃ−３）のモノマー単位を含有する場合のモノマー比率〔ｍ／（ｎ＋ｒ）〕は、誘電特性やガラス転移温度、耐湿耐熱性、接着性とのバランスを考慮すると、０．１〜９．０が好ましく、１．０〜６．０がより好ましい。
また、（Ｃ）成分の共重合樹脂の重量平均分子量は、耐熱性や機械強度と成型加工性とのバランスを考慮すると、１，０００〜２００，０００であることが好ましい。なお、重量平均分子量は、溶離液としてテトラヒドロフランを用いたＧＰＣにより測定し、標準ポリスチレン検量線により換算した値である。
In the copolymer resin of component (C), the number of monomer units of (c-1) is m, the number of monomer units of (c-2) is n, and the copolymerizable component of (c-3) is r In this case, the monomer ratio (m / n) in the copolymer resin of component (C) is 0.8 to 19.0 in consideration of the balance between dielectric properties, glass transition temperature, moisture and heat resistance, and adhesiveness. Is preferable, and 1.0 to 6.0 is more preferable. In addition, the monomer ratio [m / (n + r)] in the case of containing the monomer unit (c-3) is 0.1 to 0.1 considering the balance between dielectric properties, glass transition temperature, moisture and heat resistance, and adhesiveness. 9.0 is preferable, and 1.0 to 6.0 is more preferable.
The weight average molecular weight of the (C) component copolymer resin is preferably 1,000 to 200,000 in consideration of the balance between heat resistance and mechanical strength and moldability. The weight average molecular weight is a value measured by GPC using tetrahydrofuran as an eluent and converted by a standard polystyrene calibration curve.
本発明の熱硬化性樹脂組成物の（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) of the thermosetting resin composition of the present invention 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-based, bisphenol F-based, biphenyl-based And glycidyl ethers such as novolacs, polyfunctional phenols, naphthalenes, alicyclics, and alcohols, glycidylamines, glycidyl esters, and the like. One type or a mixture of two or more types may be used. it can.
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.
本発明の熱硬化性樹脂組成物には、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、ジシアノジアミド等のアミン化合物、フェノールノボラック、クレゾールノボラック等のフェノール化合物等が挙げられる。これらの中で、耐熱性が良好となる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が好ましく、難燃性や接着性が向上することからクレゾールノボラック型フェノール樹脂が特に好ましい。
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。
The thermosetting resin composition of the present invention may be used in combination with an epoxy resin curing agent or curing accelerator. Examples of epoxy resin curing agents include acid anhydrides such as maleic anhydride and maleic anhydride copolymers, amine compounds such as dicyanodiamide, and phenolic compounds such as phenol novolac and cresol novolac. Of these, phenol compounds such as phenol novolak and cresol novolak that have good heat resistance are preferred, and cresol novolak type phenol resins are particularly preferred because of their improved flame retardancy and adhesion.
Examples of epoxy resin curing accelerators include imidazoles and derivatives thereof, tertiary amines, and quaternary ammonium salts.
本発明の熱硬化性樹脂組成物中の各成分の含有量は、（Ａ）成分の酸性置換基と不飽和マレイミド基を有する硬化剤の固形分換算の質量と(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１〜９５質量部とすることが好ましく、２０〜９５質量部とすることがより好ましく、２０〜９０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、難燃性や接着性、可とう性が向上し、また９５質量部以下とすることにより耐熱性が低下することがない。
（Ｂ）成分は１〜９５質量部とすることが好ましく、２０〜９５質量部とすることがより好ましく、２０〜９０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９５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１〜５０質量部とすることが好ましく、１〜３０質量部とすることがより好ましく、１〜２０質量部とすることが特に好ましい。（Ｃ）成分の含有量を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ない。
（Ｄ）成分は１〜９５質量部とすることが好ましく、２０〜９５質量部とすることがより好ましく、２０〜９０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、難燃性や接着性、耐熱性が向上し、また９５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 each component in the thermosetting resin composition of the present invention is the mass in terms of solid content of the curing agent having an acidic substituent and an unsaturated maleimide group of component (A) and components (B) to (D). As a mass in a total of 100 parts by mass, the following is preferable.
The component (A) is preferably 1 to 95 parts by mass, more preferably 20 to 95 parts by mass, and particularly preferably 20 to 90 parts by mass. When the content of the component (A) is 1 part by mass or more, flame retardancy, adhesiveness, and flexibility are improved, and when the content is 95 parts by mass or less, the heat resistance is not lowered.
(B) It is preferable to set it as 1-95 mass parts, It is more preferable to set it as 20-95 mass parts, It is especially preferable to set it as 20-90 mass parts. By setting the content of the component (B) to 1 part by mass or more, flame retardancy, adhesiveness, and dielectric characteristics are improved, and by setting the content to 95 parts by mass or less, heat resistance does not decrease.
The component (C) is preferably 1 to 50 parts by mass, more preferably 1 to 30 parts by mass, and particularly preferably 1 to 20 parts by mass. By setting the content of component (C) to 1 part 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.
(D) It is preferable to set it as 1-95 mass parts, It is more preferable to set it as 20-95 mass parts, It is especially preferable to set it as 20-90 mass parts. By setting the content of the component (D) to 1 part by mass or more, flame retardancy, adhesiveness, and heat resistance are improved, and by setting the content to 95 parts by mass or less, the dielectric characteristics are not deteriorated.
本発明の熱硬化性樹脂には、（Ｅ）成分として、任意に無機充填剤を含有させることができる。無機充填剤の例としては、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。
（Ｅ）成分の含有量は、（Ａ）成分の硬化剤の固形分換算の質量と(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。（Ｅ）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 (E). 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 (E) may be 0 to 300 parts by mass with respect to 100 parts by mass of the total mass of the components (A) and the mass of the components (B) to (D). It is preferably 20 to 200 parts by mass, more preferably 20 to 150 parts by mass. (E) 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樹脂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、有機充填剤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、シリコーン樹脂等が挙げられる。
Furthermore, the thermosetting resin composition of the present invention may contain a known thermoplastic resin, elastomer, flame retardant, organic filler, etc. as long as the resin composition does not impair the properties of the thermosetting resin. Can do.
Examples of the thermoplastic resin include polytetrafluoroethylene, polyethylene, polypropylene, polystyrene, polyphenylene ether resin, phenoxy resin, polycarbonate resin, polyester resin, polyamide resin, polyimide resin, xylene resin, petroleum resin, silicone 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、非ハロゲン系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特に好ましい。 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 viewpoint of the environment. In addition, it is particularly 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.
有機充填剤の例としては、シリコーンパウダー、ポリテトラフルオロエチレン、ポリエチレン、ポリプロピレン、ポリスチレン、ポリフェニレンエーテル等の有機物粉末などが挙げられる。 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.
更にまた、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、尿素シランなどの尿素化合物、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。 Furthermore, 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, and is not particularly limited. For example, UV absorbers such as benzotriazoles, antioxidants such as hindered phenols and styrenated phenols, photopolymerization initiators such as benzophenones, benzyl ketals, and thioxanthones, and fluorescent whitening such as stilbene derivatives Agents, 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、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、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 base material and then forming a B-stage. That is, after impregnating or coating the thermosetting resin composition of the present invention on a substrate, 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。
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 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 substrate is not particularly limited. For example, a substrate having a thickness of about 0.03 to 0.5 mm can be used, and the substrate is surface-treated with a silane coupling agent or the like, or mechanically opened. Is suitable from the viewpoints of heat resistance, moisture resistance and processability. After impregnating or coating the base material so that the amount of the resin composition attached to the base material is 20 to 90% by mass in terms of the resin content of the prepreg after drying, the temperature is usually 100 to 200 ° C. Can be heated and dried for 1 to 30 minutes and semi-cured (B-stage) to obtain the prepreg of the present invention.
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。すなわち、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したものである。成形条件は、例えば、電気絶縁材料用積層板及び多層板の手法が適用でき、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、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. That is, for example, the prepreg of the present invention is laminated and molded in a configuration in which, for example, 1 to 20 sheets are stacked and a metal foil such as copper and aluminum is disposed on one side or both sides thereof. As the molding conditions, for example, a method of a laminated plate for an electrical insulating material and a multilayer plate can be applied. For example, a multistage press, a multistage vacuum press, a continuous molding, an autoclave molding machine or the like is used, a temperature of 100 to 250 ° C., a pressure of 0.2 It can shape | mold in the range of 10-10 MPa and heating time 0.1-5 hours. Further, the prepreg of the present invention and the inner layer wiring board can be combined and laminated to produce a multilayer board.
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）銅箔接着性（銅箔ピール強度）の評価
銅張積層板を銅エッチング液に浸漬することにより、１ｃｍ幅の帯部分を残して銅箔を取り除いた評価基板を作製し、オートグラフ〔島津製作所（株）製ＡＧ−１００Ｃ〕を用いて帯部分のピール強度を測定した。
（２）ガラス転移温度（Ｔｇ）の測定
銅張積層板を銅エッチング液に浸漬することにより銅箔を取り除いた５ｍｍ角の評価基板を作製し、ＴＭＡ試験装置〔デュポン（株）製ＴＭＡ２９４０〕を用い、評価基板の熱膨張特性を観察することにより評価した。
(1) Evaluation of copper foil adhesiveness (copper foil peel strength) By immersing a copper-clad laminate in a copper etching solution, an evaluation board was prepared by removing the copper foil while leaving a 1 cm wide band portion. The peel strength of the belt portion was measured using [AG-100C manufactured by Shimadzu Corporation].
(2) Measurement of glass transition temperature (Tg) A 5 mm square evaluation substrate from which copper foil was removed by immersing a copper clad laminate in a copper etching solution was prepared, and a TMA test apparatus [TMA2940 manufactured by DuPont Co., Ltd.] was used. Used and evaluated by observing the thermal expansion characteristics of the evaluation substrate.
（３）はんだ耐熱性の評価
銅張積層板を銅エッチング液に浸漬することにより銅箔を取り除いた５ｃｍ角の評価基板を作製し、プレッシャー・クッカー試験装置〔平山製作所（株）製〕を用いて、１２１℃、０．２ＭＰａの条件に４時間放置し、次いで温度２８８℃のはんだ浴に２０秒間浸漬した後、評価基板の外観を観察することによりはんだ耐熱性を評価した。
（４）銅付き耐熱性（Ｔ−２８８）の評価
銅張積層板から５ｍｍ角の評価基板を作製し、ＴＭＡ試験装置〔デュポン（株）製ＴＭＡ２９４０〕を用い、２８８℃で評価基板の膨れが発生するまでの時間を測定することにより評価した。
(3) Evaluation of solder heat resistance A 5 cm square evaluation board from which the copper foil has been removed is prepared by immersing a copper clad laminate in a copper etching solution, and a pressure cooker test apparatus (manufactured by Hirayama Manufacturing Co., Ltd.) is used. Then, it was left for 4 hours under conditions of 121 ° C. and 0.2 MPa, and then immersed in a solder bath at a temperature of 288 ° C. for 20 seconds, and then the solder heat resistance was evaluated by observing the appearance of the evaluation substrate.
(4) Evaluation of heat resistance with copper (T-288) An evaluation board of 5 mm square was prepared from a copper clad laminate, and the evaluation board was swollen at 288 ° C. using a TMA test apparatus (TMA2940 manufactured by DuPont). It was evaluated by measuring the time until it occurred.
（５）吸湿性（吸水率）の評価
銅張積層板を銅エッチング液に浸漬することにより銅箔を取り除いた評価基板を作製し、プレッシャー・クッカー試験装置〔平山製作所（株）製〕を用いて、１２１℃、０．２ＭＰａの条件に４時間放置した後、評価基板の吸水率を測定した。
（６）難燃性の評価
銅張積層板を銅エッチング液に浸漬することにより銅箔を取り除いた評価基板から、長さ１２７ｍｍ、幅１２．７ｍｍに切り出した評価基板を作製し、ＵＬ９４の試験法（Ｖ法）に準じて評価した。
（７）比誘電率及び誘電正接の測定
得られ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評価基板を作製し、比誘電率測定装置（Ｈｅｗｌｌｅｔ・Ｐａｃｋｅｒｄ社製、ＨＰ４２９１Ｂ）を用いて、周波数１ＧＨｚでの比誘電率及び誘電正接を測定した。
(5) Evaluation of hygroscopicity (water absorption rate) A copper-clad laminate was immersed in a copper etching solution to prepare an evaluation board from which the copper foil was removed, and a pressure cooker test apparatus (manufactured by Hirayama Seisakusho Co., Ltd.) was used. Then, after leaving for 4 hours under the conditions of 121 ° C. and 0.2 MPa, the water absorption rate of the evaluation substrate was measured.
(6) Flame Retardancy Evaluation An evaluation board cut out to a length of 127 mm and a width of 12.7 mm was prepared from an evaluation board obtained by removing a copper foil by immersing a copper-clad laminate in a copper etching solution, and tested for UL94. Evaluation was made according to the method (Method V).
(7) Measurement of relative dielectric constant and dielectric loss tangent An evaluation substrate from which the copper foil was removed by immersing the obtained copper-clad laminate in a copper etching solution was prepared, and a relative dielectric constant measuring device (manufactured by Hewlett-Packard Company, The relative dielectric constant and dielectric loss tangent at a frequency of 1 GHz were measured using HP4291B).
製造例１：硬化剤（Ａ−１）の製造
温度計、攪拌装置、還流冷却管付き水分定量器の付いた加熱及び冷却可能な容積２リットルの反応容器に、ビス（４−マレイミドフェニル）メタン：３５８．０ｇとｍ−アミノフェノール：５４．５ｇ、及びプロピレングリコールモノメチルエーテル：４１２．５gを入れ、還流させながら５時間反応させて硬化剤（Ａ−１）の溶液を得た。
Production Example 1: Production of Curing Agent (A-1) Bis (4-maleimidophenyl) methane was added to a reaction vessel having a volume of 2 liters that can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. : 358.0 g, m-aminophenol: 54.5 g, and propylene glycol monomethyl ether: 412.5 g were added and reacted for 5 hours while refluxing to obtain a solution of the curing agent (A-1).
製造例２：硬化剤（Ａ−２）の製造
温度計、攪拌装置、還流冷却管付き水分定量器の付いた加熱及び冷却可能な容積２リットルの反応容器に、ビス（４−マレイミドフェニル）メタン：３５８．０ｇとｐ−アミノフェノール：５４．５ｇ、及びプロピレングリコールモノメチルエーテル：４１２．５ｇを入れ、還流させながら５時間反応させて硬化剤（Ａ−２）の溶液を得た。
Production Example 2: Production of curing agent (A-2) Bis (4-maleimidophenyl) methane 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. : 358.0 g, p-aminophenol: 54.5 g, and propylene glycol monomethyl ether: 412.5 g were added and reacted for 5 hours while refluxing to obtain a solution of the curing agent (A-2).
製造例３：硬化剤（Ａ−３）の製造
温度計、攪拌装置、還流冷却管付き水分定量器の付いた加熱及び冷却可能な容積２リットルの反応容器に、ビス（４−マレイミドフェニル）メタン：３５８．０ｇとｐ−アミノ安息香酸：６８．５ｇ、及びＮ，Ｎ−ジメチルアセトアミド：４２６．５ｇを入れ、１４０℃で５時間反応させて硬化剤（Ａ−３）の溶液を得た。
Production Example 3: Production of Curing Agent (A-3) Bis (4-maleimidophenyl) methane was placed in a reaction vessel with a volume of 2 liters that can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. : 358.0 g, p-aminobenzoic acid: 68.5 g, and N, N-dimethylacetamide: 426.5 g were added and reacted at 140 ° C. for 5 hours to obtain a solution of the curing agent (A-3).
製造例４：硬化剤（Ａ−４）の製造
温度計、攪拌装置、還流冷却管付き水分定量器の付いた加熱及び冷却可能な容積１リットルの反応容器に、ｍ−フェニレンビスマレイミド：２６８．０ｇとｍ−アミノフェノール：５４．５ｇ、及びＮ，Ｎ−ジメチルアセトアミド：３２２．５ｇを入れ、１４０℃で５時間反応させて硬化剤（Ａ−４）の溶液を得た。
Production Example 4: Production of Curing Agent (A-4) m-phenylene bismaleimide: 268. in a reaction vessel with a volume of 1 liter that can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. 0 g, m-aminophenol: 54.5 g, and N, N-dimethylacetamide: 322.5 g were added and reacted at 140 ° C. for 5 hours to obtain a solution of a curing agent (A-4).
製造例５：硬化剤（Ａ−５）の製造
温度計、攪拌装置、還流冷却管付き水分定量器の付いた加熱及び冷却可能な容積２リットルの反応容器に、ビス（４−マレイミドフェニル）スルフォン：４０８．０gとｐ−アミノフェノール：５４．５ｇ、及びN,N−ジメチルアセトアミド：４６２．５gを入れ、１００℃で２時間反応させて硬化剤（Ａ−５）の溶液を得た。
Production Example 5: Production of curing agent (A-5) Bis (4-maleimidophenyl) sulfone 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. : 408.0 g, p-aminophenol: 54.5 g, and N, N-dimethylacetamide: 462.5 g were allowed to react at 100 ° C. for 2 hours to obtain a solution of the curing agent (A-5).
製造例６：硬化剤（Ａ−６）の製造
温度計、攪拌装置、還流冷却管付き水分定量器の付いた加熱及び冷却可能な容積２リットルの反応容器に、ビス（４−マレイミドフェニル）エーテル：３６０．０gとｐ−アミノフェノール：５４．５ｇ及びN,N−ジメチルアセトアミド：４１４．５gを入れ、１００℃で２時間反応させて硬化剤（Ａ−６）の溶液を得た。
Production Example 6: Production of curing agent (A-6) Bis (4-maleimidophenyl) ether was added to a 2 liter reaction vessel with a thermometer, a stirrer, and a moisture meter with a reflux condenser and capable of heating and cooling. : 360.0 g, p-aminophenol: 54.5 g and N, N-dimethylacetamide: 414.5 g were added and reacted at 100 ° C. for 2 hours to obtain a solution of the curing agent (A-6).
製造例７：硬化剤（Ａ−７）の製造
温度計、攪拌装置、還流冷却管付き水分定量器の付いた加熱及び冷却可能な容積２リットルの反応容器に、２，２'−ビス［４−（４−マレイミドフェノキシ）フェニル］プロパン：５７０．０gとｐ−アミノフェノール：５４．５ｇ、及びプロピレングリコールモノメチルエーテル：６２４．５gを入れ、１２０℃で２時間反応させて硬化剤（Ａ−７）の溶液を得た。
Production Example 7: Production of curing agent (A-7) 2,2′-bis [4] was placed in a reaction vessel having a thermometer, a stirrer, and a water quantifier with a reflux condenser and a capacity of 2 liters capable of being heated and cooled. -(4-Maleimidophenoxy) phenyl] propane: 570.0 g, p-aminophenol: 54.5 g, and propylene glycol monomethyl ether: 624.5 g were added and reacted at 120 ° C. for 2 hours to cure the curing agent (A-7 ) Was obtained.
製造例８：硬化剤（Ａ−８）の製造
温度計、攪拌装置、還流冷却管付き水分定量器の付いた加熱及び冷却可能な容積２リットルの反応容器に、４−メチル−１，３−フェニレンビスマレイミド：２８２．０gとｐ−アミノフェノール：５４．５ｇ、及びプロピレングリコールモノメチルエーテル：３３６．５gを入れ、１２０℃で２時間反応させて硬化剤（Ａ−８）の溶液を得た。
Production Example 8 Production of Curing Agent (A-8) In a reaction vessel having a volume of 2 liters that can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser, 4-methyl-1,3- Phenylene bismaleimide: 282.0 g, p-aminophenol: 54.5 g, and propylene glycol monomethyl ether: 336.5 g were added and reacted at 120 ° C. for 2 hours to obtain a solution of a curing agent (A-8).
製造例９：共重合樹脂（Ｃ−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、スチレン（ｍ）と無水マレイン酸（ｎ）の共重合樹脂（エルフ・アトケム社製、商品名ＥＦ−４０、モノマー比率（ｍ／ｎ）＝４．０、重量平均分子量：１０，０００）：５１４．０ｇ、及びシクロヘキサノン：４６２．６ｇ、トルエン：５１．４ｇを入れ、７０℃に昇温して均一に溶解した後、アニリン：４６．５ｇを少量づつ滴下した。次いで還流温度まで昇温し、発生する縮合水を除去しながら５時間反応させてスチレンと無水マレイン酸とＮ−フェニルマレイミドからなる共重合樹脂の溶液（Ｃ−１）を得た。（Ｃ−１）のスチレン（ｍ）と無水マレイン酸（ｎ）とＮ−フェニルマレイミド（ｒ）のモノマー比率は、ｍ／（ｎ＋ｒ）＝４．０、重量平均分子量は１１，０００であった。
Production Example 9 Production of Copolymer Resin (C-1) Styrene (m) and anhydrous maleate were placed in a reaction vessel with a volume of 2 liters that can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. Copolymer resin of acid (n) (manufactured by Elf Atchem, trade name EF-40, monomer ratio (m / n) = 4.0, weight average molecular weight: 10,000): 514.0 g, and cyclohexanone: 462 .6 g and toluene: 51.4 g were added, and the mixture was heated to 70 ° C. and dissolved uniformly. Then, 46.5 g of aniline was added dropwise little by little. Next, the temperature was raised to the reflux temperature, and the reaction was carried out for 5 hours while removing the generated condensed water to obtain a copolymer resin solution (C-1) comprising styrene, maleic anhydride and N-phenylmaleimide. The monomer ratio of (C-1) styrene (m), maleic anhydride (n) and N-phenylmaleimide (r) was m / (n + r) = 4.0, and the weight average molecular weight was 11,000. .
製造例１０：共重合樹脂（Ｃ−２）の製造
温度計、攪拌装置、還流冷却管付き水分定量器の付いた加熱及び冷却可能な容積１リットルの反応容器に、イソブチレン（ｍ）と無水マレイン酸（ｎ）の共重合樹脂（クラレ社製、商品名イソバン−６００、ｍ／ｎ＝１．０、重量平均分子量：６，０００）：１５４．０ｇ、及びＮ．Ｎ−ジメチルアセトアミド：３０８．０ｇ、トルエン：３０．８ｇを入れ、７０℃に昇温して均一に溶解した後、ｐ−アミノフェノール：５４．５ｇを少量づつ添加した。次いで還流温度まで昇温し、発生する縮合水を除去しながら５時間反応させてイソブチレンと無水マレイン酸とＮ−ヒドロキシフェニルマレイミドからなる共重合樹脂の溶液（Ｃ−２）を得た。（Ｃ−２）のイソブチレン（ｍ）と無水マレイン酸（ｎ）とｐ−ヒドロキシフェニルマレイミド（ｒ）のモノマー比率は、ｍ／（ｎ＋ｒ）＝１．０、重量平均分子量は７，０００であった。
Production Example 10 Production of Copolymer Resin (C-2) Isobutylene (m) and anhydrous maleate were added to a reaction vessel having a volume of 1 liter which can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. A copolymer resin of acid (n) (manufactured by Kuraray Co., Ltd., trade name: Isoban-600, m / n = 1.0, weight average molecular weight: 6,000): 154.0 g; N-dimethylacetamide: 308.0 g and toluene: 30.8 g were added, and the mixture was heated to 70 ° C. and dissolved uniformly. Then, 54.5 g of p-aminophenol was added little by little. Next, the temperature was raised to the reflux temperature, and the reaction was carried out for 5 hours while removing the generated condensed water to obtain a copolymer resin solution (C-2) composed of isobutylene, maleic anhydride and N-hydroxyphenylmaleimide. The monomer ratio of (C-2) isobutylene (m), maleic anhydride (n) and p-hydroxyphenylmaleimide (r) was m / (n + r) = 1.0, and the weight average molecular weight was 7,000. It was.
比較製造例１：硬化剤（Ａ−９）の製造
特許文献１の実施例を参考にし、蒸気加熱装置を付けた容積１リットルのニーダーに、ビス（４−マレイミドフェニル）メタン：３５８．０ｇとｍ−アミノフェノール：５４．５ｇを入れ、１３５〜１４０℃で１５分間加熱混練した後冷却し、粉砕して硬化剤（Ａ−９）の粉末を得た。
Comparative Production Example 1: Production of Curing Agent (A-9) With reference to the example of Patent Document 1, a kneader having a volume of 1 liter equipped with a steam heating device and bis (4-maleimidophenyl) methane: 358.0 g m-Aminophenol: 54.5 g was added, heated and kneaded at 135 to 140 ° C. for 15 minutes, cooled, and pulverized to obtain a hardener (A-9) powder.
比較製造例２：硬化剤（Ａ−１０）の製造
特許文献９の実施例を参考にし、蒸気加熱装置を付けた容積１リットルのニーダーに、ビス（４−マレイミドフェニル）メタン：３５８．０ｇとｍ−アミノ安息香酸：６８．５ｇを入れ、１３５〜１４０℃で１５分間加熱混練した後冷却し、粉砕して硬化剤（Ａ−１０）の粉末を得た。
Comparative Production Example 2: Production of Curing Agent (A-10) Referring to the example of Patent Document 9, with a 1 liter kneader equipped with a steam heating device, bis (4-maleimidophenyl) methane: 358.0 g m-Aminobenzoic acid: 68.5 g was added, heated and kneaded at 135 to 140 ° C. for 15 minutes, cooled and pulverized to obtain a hardener (A-10) powder.
実施例１〜１０、比較例１〜６
（Ａ）成分の酸性置換基と不飽和マレイミド基を有する硬化剤として上記の製造例１〜８で得られた硬化剤（Ａ−１〜８）又は比較製造例で得られた硬化剤（Ａ−９、１０）、（Ｂ）成分の６−置換グアナミン化合物としてベンゾグアナミン〔日本触媒（株）製〕 、（Ｃ）成分の共重合樹脂として、上記の製造例９〜１０で得られた共重合樹脂（Ｃ−１、２）、スチレンと無水マレイン酸の共重合樹脂（Ｃ−３：エルフ・アトケム社製、商品名ＥＦ−４０、ｍ／ｎ＝４．０、重量平均分子量：１０，０００）又はイソブチレンと無水マレイン酸の共重合樹脂（Ｃ−４：クラレ社製、商品名イソバン−６００、ｍ／ｎ＝１．０、重量平均分子量：６，０００）、（Ｄ）成分のエポキシ樹脂として、フェノールノボラック型エポキシ樹脂〔Ｄ−１：大日本インキ化学工業（株）製、商品名：エピクロンＮ−７７０〕又はジシクロペンタジエン型エポキシ樹脂〔Ｄ−２：大日本インキ化学工業（株）製、商品名：ＨＰ−７２００Ｈ〕、エポキシ硬化剤としてクレゾールノボラック型フェノール樹脂〔大日本インキ化学工業（株）製、商品名：ＫＡ−１１６５〕、（Ｅ）成分の無機充填剤として破砕シリカ〔Ｅ−１：福島窯業（株）製、商品名：Ｆ０５−３０、平均粒径１０μｍ〕および水酸化アルミニウム〔Ｅ−２：昭和電工（株）製、商品名：ＨＤ−３６０、平均粒径３μｍ〕、また希釈溶剤にメチルエチルケトンを使用して第１表〜第３表に示す配合割合（質量部）で混合して樹脂分７０質量％の均一なワニスを得た。
次に、得られたワニスを厚さ０．２ｍｍのＥガラスクロスに含浸塗工し、１６０℃で１０分加熱乾燥して樹脂含有量５５質量％のプリプレグを得た。このプリプレグを４枚重ね、１８μｍの電解銅箔を上下に配置し、圧力２．４５ＭＰａ、温度１８５℃で９０分間プレスを行って、銅張積層板を得た。
このようにして得られた銅張積層板を用いて、銅箔接着性（銅箔ピール強度）、ガラス転移温度(Ｔｇ)、はんだ耐熱性(Ｔ-２８８)、吸湿性（吸水率）、難燃性、比誘電率（１ＧＨｚ）及び誘電正接（１ＧＨｚ）について前記の方法で測定・評価した。評価結果を第１表〜第３表に示す。
Examples 1-10, Comparative Examples 1-6
(A) Curing agent (A-1 to 8) obtained in Production Examples 1 to 8 above or a curing agent obtained in Comparative Production Example (A) as a curing agent having an acidic substituent and an unsaturated maleimide group of component (A) -9, 10), benzoguanamine [manufactured by Nippon Shokubai Co., Ltd.] as the 6-substituted guanamine compound of component (B), and the copolymer obtained in Production Examples 9-10 as a copolymer resin of component (C) Resin (C-1, 2), copolymer resin of styrene and maleic anhydride (C-3: manufactured by Elf Atchem, trade name: EF-40, m / n = 4.0, weight average molecular weight: 10,000 ) Or a copolymer resin of isobutylene and maleic anhydride (C-4: manufactured by Kuraray Co., Ltd., trade name: Isoban-600, m / n = 1.0, weight average molecular weight: 6,000), (D) component epoxy resin Phenol novolac epoxy resin [D-1 : Dainippon Ink & Chemicals, Inc., trade name: Epicron N-770] or dicyclopentadiene type epoxy resin [D-2: Dainippon Ink & Chemicals, trade name: HP-7200H], epoxy Cresol novolak type phenolic resin (Dainippon Ink Chemical Co., Ltd., trade name: KA-1165) as a curing agent, crushed silica [E-1: Fukushima Ceramics Co., Ltd., Product name: F05-30, average particle size 10 μm] and aluminum hydroxide [E-2: Showa Denko Co., Ltd., product name: HD-360, average particle size 3 μm], and methyl ethyl ketone as a diluent solvent It mixed by the mixture ratio (mass part) shown to Table 1-Table 3, and obtained the uniform varnish with a resin content of 70 mass%.
Next, the obtained varnish was impregnated and applied to an E glass cloth having a thickness of 0.2 mm and dried by heating at 160 ° C. for 10 minutes to obtain a prepreg having a resin content of 55% by mass. Four prepregs were stacked, 18 μm electrolytic copper foils were placed one above the other, and pressed at a pressure of 2.45 MPa and a temperature of 185 ° C. for 90 minutes to obtain a copper clad laminate.
Using the copper-clad laminate thus obtained, copper foil adhesion (copper foil peel strength), glass transition temperature (Tg), solder heat resistance (T-288), hygroscopicity (water absorption), difficulty Flammability, relative dielectric constant (1 GHz) and dielectric loss tangent (1 GHz) were measured and evaluated by the above methods. The evaluation results are shown in Tables 1 to 3.
なお、比較例５及び６は、熱硬化性樹脂が均一に溶解したワニスが得られず、プリプレグを作製できなかった。
第１表及び第２表から明らかなように、本発明の実施例では、銅箔接着性（銅箔ピール強度）、ガラス転移温度(Ｔｇ)、はんだ耐熱性(Ｔ-２８８)、吸湿性（吸水率）、難燃性、比誘電率（１ＧＨｚ）及び誘電正接（１ＧＨｚ）の全てにおいてバランスがとれている。
一方、第３表から明らかなように、比較例では、プリプレグを作製できなかったり、また、銅箔接着性、ガラス転移温度、はんだ耐熱性、吸湿性、難燃性、比誘電率及び誘電正接の全てにバランスがとれたものは無く、いずれかの特性に劣っている。
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は、銅箔接着性、ガラス転移温度、はんだ耐熱性、吸湿性、難燃性、比誘電率及び誘電正接の全てにおいてバランスがとれており、電子機器用プリント配線板として有用である。
In Comparative Examples 5 and 6, a varnish in which the thermosetting resin was uniformly dissolved was not obtained, and a prepreg could not be produced.
As apparent from Tables 1 and 2, in the examples of the present invention, copper foil adhesion (copper foil peel strength), glass transition temperature (Tg), solder heat resistance (T-288), hygroscopicity ( Water absorption), flame retardancy, relative dielectric constant (1 GHz) and dielectric loss tangent (1 GHz) are all balanced.
On the other hand, as is apparent from Table 3, in the comparative example, the prepreg could not be produced, and copper foil adhesion, glass transition temperature, solder heat resistance, hygroscopicity, flame retardancy, relative dielectric constant and dielectric loss tangent None of these are balanced and inferior to any of the properties.
A prepreg obtained by impregnating or coating a base material with the thermosetting resin composition of the present invention, and a laminate produced by laminating the prepreg, have copper foil adhesion, glass transition temperature, solder heat resistance. Are balanced in all of properties, hygroscopicity, flame retardancy, relative dielectric constant and dielectric loss tangent, and are useful as printed wiring boards for electronic devices.
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| JP2008163305A (en) * | 2006-12-05 | 2008-07-17 | Hitachi Chem Co Ltd | Flame retardant resin compound, and thermosetting resin composition, prepreg and laminated plate using the same |
| DE102009042390A1 (en) | 2009-02-04 | 2010-08-19 | Mitsubishi Electric Corp. | Power semiconductor module and method for its production |
| JP2010229356A (en) * | 2009-03-27 | 2010-10-14 | Hitachi Chem Co Ltd | Thermosetting insulating resin composition and insulating film with substrate, prepreg, laminated board, and multilayer printed wiring board using the same |
| JP2010248495A (en) * | 2009-03-27 | 2010-11-04 | Hitachi Chem Co Ltd | Thermosetting insulating resin composition, and insulating film with support, prepreg, laminate plate and multilayer printed wiring board using the same |
| JP2011225645A (en) * | 2010-04-15 | 2011-11-10 | Tokyo Univ Of Science | Fine particle for curing epoxy resin, and method for producing the same |
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| JP2002317085A (en) * | 2001-01-30 | 2002-10-31 | Hitachi Chem Co Ltd | Thermosetting resin composition and use thereof |
| JP2003229647A (en) * | 2002-02-05 | 2003-08-15 | Hitachi Chem Co Ltd | Prepreg for nonhalogen based printed wiring board and its use |
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| JPS5251499A (en) * | 1975-10-23 | 1977-04-25 | Toshiba Chem Corp | Theremosetting resin compositions |
| JPS557861A (en) * | 1978-07-03 | 1980-01-21 | Toshiba Chem Corp | Thermosetting resin composition |
| JPS5690589A (en) * | 1979-12-25 | 1981-07-22 | Toshiba Chem Prod | Copperrcoated laminated board |
| JPS644635A (en) * | 1987-06-26 | 1989-01-09 | Toshiba Chem Corp | Thermosetting resin composition |
| JPH01121356A (en) * | 1987-11-04 | 1989-05-15 | Hitachi Ltd | Thermosetting resin composition and prepreg and laminated board produced by using same |
| JPH01221413A (en) * | 1987-11-19 | 1989-09-04 | Dainippon Ink & Chem Inc | Epoxy resin composition and preparation of prepreg and laminated sheet therefrom |
| JP2002317085A (en) * | 2001-01-30 | 2002-10-31 | Hitachi Chem Co Ltd | Thermosetting resin composition and use thereof |
| JP2003229647A (en) * | 2002-02-05 | 2003-08-15 | Hitachi Chem Co Ltd | Prepreg for nonhalogen based printed wiring board and its use |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008163305A (en) * | 2006-12-05 | 2008-07-17 | Hitachi Chem Co Ltd | Flame retardant resin compound, and thermosetting resin composition, prepreg and laminated plate using the same |
| JP2012153896A (en) * | 2006-12-05 | 2012-08-16 | Hitachi Chemical Co Ltd | Flame retardant resin compound, thermosetting resin composition using the same, prepreg, and laminate |
| DE102009042390A1 (en) | 2009-02-04 | 2010-08-19 | Mitsubishi Electric Corp. | Power semiconductor module and method for its production |
| JP2010229356A (en) * | 2009-03-27 | 2010-10-14 | Hitachi Chem Co Ltd | Thermosetting insulating resin composition and insulating film with substrate, prepreg, laminated board, and multilayer printed wiring board using the same |
| JP2010248495A (en) * | 2009-03-27 | 2010-11-04 | Hitachi Chem Co Ltd | Thermosetting insulating resin composition, and insulating film with support, prepreg, laminate plate and multilayer printed wiring board using the same |
| JP2011225645A (en) * | 2010-04-15 | 2011-11-10 | Tokyo Univ Of Science | Fine particle for curing epoxy resin, and method for producing the same |
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| JP5266685B2 (en) | 2013-08-21 |
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