JP5540494B2 - Thermosetting resin composition, and prepreg, laminate and printed wiring board using the same - Google Patents
Thermosetting resin composition, and prepreg, laminate and printed wiring board using the same Download PDFInfo
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- JP5540494B2 JP5540494B2 JP2008279840A JP2008279840A JP5540494B2 JP 5540494 B2 JP5540494 B2 JP 5540494B2 JP 2008279840 A JP2008279840 A JP 2008279840A JP 2008279840 A JP2008279840 A JP 2008279840A JP 5540494 B2 JP5540494 B2 JP 5540494B2
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- acidic substituent
- formula
- sulfonic acid
- resin composition
- Prior art date
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- 229920001187 thermosetting polymer Polymers 0.000 title claims description 33
- 239000011342 resin composition Substances 0.000 title claims description 26
- 230000002378 acidificating effect Effects 0.000 claims description 41
- 229920000647 polyepoxide Polymers 0.000 claims description 41
- 125000001424 substituent group Chemical group 0.000 claims description 41
- 239000003822 epoxy resin Substances 0.000 claims description 40
- -1 maleimide compound Chemical class 0.000 claims description 33
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 19
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 18
- 125000001931 aliphatic group Chemical group 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 16
- 125000005843 halogen group Chemical group 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 12
- 125000001624 naphthyl group Chemical group 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 7
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 125000001118 alkylidene group Chemical group 0.000 claims description 4
- 125000001033 ether group Chemical group 0.000 claims description 4
- 150000002460 imidazoles Chemical class 0.000 claims description 4
- 238000010030 laminating Methods 0.000 claims description 4
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 36
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 32
- 229920005989 resin Polymers 0.000 description 24
- 239000011347 resin Substances 0.000 description 24
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 22
- 238000011156 evaluation Methods 0.000 description 21
- 238000004519 manufacturing process Methods 0.000 description 21
- 229910052802 copper Inorganic materials 0.000 description 18
- 239000010949 copper Substances 0.000 description 18
- 239000011889 copper foil Substances 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 16
- 238000010992 reflux Methods 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 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 11
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 10
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 238000005530 etching Methods 0.000 description 8
- 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 8
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 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
- 239000003063 flame retardant Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 125000000962 organic group Chemical group 0.000 description 6
- 229910000679 solder Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229940018563 3-aminophenol Drugs 0.000 description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000011256 inorganic filler Substances 0.000 description 5
- 229910003475 inorganic filler Inorganic materials 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000005062 Polybutadiene Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 229960004050 aminobenzoic acid Drugs 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
- 229910001593 boehmite Inorganic materials 0.000 description 4
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 230000009257 reactivity Effects 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
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 229910002706 AlOOH Inorganic materials 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000011810 insulating material Substances 0.000 description 3
- 239000012774 insulation 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 229920003192 poly(bis maleimide) Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 description 2
- IKFPAKYBSYICFK-UHFFFAOYSA-N 1-[4-(4-propylphenoxy)phenyl]pyrrole-2,5-dione Chemical compound C1=CC(CCC)=CC=C1OC1=CC=C(N2C(C=CC2=O)=O)C=C1 IKFPAKYBSYICFK-UHFFFAOYSA-N 0.000 description 2
- 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
- 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 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical group C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 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
- 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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene 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
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229910001679 gibbsite Inorganic materials 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- 150000002989 phenols Chemical class 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
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 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
- 239000008096 xylene Substances 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical group C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-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
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical group C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- CQOZJDNCADWEKH-UHFFFAOYSA-N 2-[3,3-bis(2-hydroxyphenyl)propyl]phenol Chemical class OC1=CC=CC=C1CCC(C=1C(=CC=CC=1)O)C1=CC=CC=C1O CQOZJDNCADWEKH-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
- 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 1
- ZAJAQTYSTDTMCU-UHFFFAOYSA-N 3-aminobenzenesulfonic acid Chemical compound NC1=CC=CC(S(O)(=O)=O)=C1 ZAJAQTYSTDTMCU-UHFFFAOYSA-N 0.000 description 1
- XFDUHJPVQKIXHO-UHFFFAOYSA-N 3-aminobenzoic acid Chemical compound NC1=CC=CC(C(O)=O)=C1 XFDUHJPVQKIXHO-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 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
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 0 C*(C*CC*(C)C([n]1c(*)nc(*)c1)=O)CC([n]1c(*)nc(*)c1)=O Chemical compound C*(C*CC*(C)C([n]1c(*)nc(*)c1)=O)CC([n]1c(*)nc(*)c1)=O 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N CN(C(C=C1)=O)C1=O Chemical compound CN(C(C=C1)=O)C1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
- CTTQNYAEEIIAQZ-UHFFFAOYSA-N CNC1=CC#CCC=C1 Chemical compound CNC1=CC#CCC=C1 CTTQNYAEEIIAQZ-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- IQCZLAGMIPVBKE-UHFFFAOYSA-N Oc(cc1)ccc1NC(CC(N1c2ccc(Cc(cc3)ccc3N(C(C=C3)=O)C3=O)cc2)=O)C1=O Chemical compound Oc(cc1)ccc1NC(CC(N1c2ccc(Cc(cc3)ccc3N(C(C=C3)=O)C3=O)cc2)=O)C1=O IQCZLAGMIPVBKE-UHFFFAOYSA-N 0.000 description 1
- MLSXAHSPQFERHS-UHFFFAOYSA-N Oc(cc1)ccc1NC(CC(N1c2ccc(Cc(cc3)ccc3N(C(CC3Nc(cc4)ccc4O)=O)C3=O)cc2)=O)C1=O Chemical compound Oc(cc1)ccc1NC(CC(N1c2ccc(Cc(cc3)ccc3N(C(CC3Nc(cc4)ccc4O)=O)C3=O)cc2)=O)C1=O MLSXAHSPQFERHS-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
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- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
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- 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
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- 238000001879 gelation Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
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- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 1
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- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical group C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
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- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
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- 229920000728 polyester Polymers 0.000 description 1
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- 229920001296 polysiloxane Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
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- 239000010453 quartz Substances 0.000 description 1
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- 235000021286 stilbenes Nutrition 0.000 description 1
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- 125000004434 sulfur atom Chemical group 0.000 description 1
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- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
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- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 1
Images
Description
本発明は、熱硬化性絶縁樹脂組成物、並びにこれを用いたプリプレグ、積層板、及びプリント配線板に関する。 The present invention relates to a thermosetting insulating resin composition, and a prepreg, laminate, and printed wiring board using the same.
熱硬化性樹脂は、熱硬化性樹脂に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、電子部品等の分野において広く使われ、特に銅張積層板や層間絶縁材料においては、近年の高密度化や高信頼性への要求から、高い銅箔接着性や耐熱性が必要とされる。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た熱硬化性樹脂組成物が望まれている。 Thermosetting resins are widely used in the field of electronic components, etc., because the cross-linked structure unique to thermosetting resins expresses high heat resistance and dimensional stability, especially in copper-clad laminates and interlayer insulation materials, Due to the recent demand for higher density and higher reliability, high copper foil adhesion and heat resistance are 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, a thermosetting resin composition composed only of components having low toxicity is desired.
熱硬化性樹脂であるビスマレイミド化合物は、誘電特性、難燃性、耐熱性に優れる樹脂であるが、エポキシ樹脂との硬化反応性を有さない公知のビスマレイミド化合物は、エポキシ硬化系の熱硬化性樹脂にそのまま使用した場合、耐熱性や強靭性が不足する問題があった。特許文献１、特許文献２等に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が開示されているが、これらを銅張積層板や層間絶縁材料として使用した場合も、依然として硬化反応性や強靭性が不足であり、耐熱性や信頼性、加工性等が不足である。 The bismaleimide compound, which is a thermosetting resin, is a resin that is excellent in dielectric properties, flame retardancy, and heat resistance. However, a known bismaleimide compound that does not have curing reactivity with an epoxy resin is an epoxy-curing heat. When used as it is for a curable resin, there is a problem that heat resistance and toughness are insufficient. Examples relating to thermosetting resins that produce and use adducts of bismaleimide compounds and aminophenols are disclosed in Patent Document 1, Patent Document 2, etc., but when these are used as copper-clad laminates or interlayer insulation materials However, curing reactivity and toughness are still insufficient, and heat resistance, reliability, workability, etc. are insufficient.
また、特許文献３、特許文献４等にシアネート樹脂とアラルキル変性エポキシ樹脂を必須成分として含有する熱硬化性樹脂に関する事例が開示されているが、必須成分であるシアネート樹脂が靭性や硬化反応性に劣る樹脂であるため、この熱硬化性樹脂の硬化反応性や強靭性の改良が依然不足であり、これらを銅張積層板や層間絶縁材料として使用した場合も、耐熱性や信頼性、加工性等が不足である。 Moreover, although the example regarding the thermosetting resin which contains cyanate resin and an aralkyl modified epoxy resin as an essential component is indicated by patent document 3, patent document 4, etc., cyanate resin which is an essential component is toughness and hardening reactivity. Because it is an inferior resin, the improvement in curing reactivity and toughness of this thermosetting resin is still insufficient, and even when these are used as copper-clad laminates or interlayer insulation materials, heat resistance, reliability, workability Etc. are insufficient.
また、特許文献５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。 Further, Patent Document 5 discloses 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, and the like. The temperature is low and the heat resistance to lead-free solder and the heat resistance with copper are insufficient in recent years.
本発明は、低熱膨張性であって、かつ耐熱性、誘電特性に優れる熱硬化性絶縁樹脂組成物、並びにこれを用いたプリプレグ、積層板、及びプリント配線板を提供することを目的とする。 An object of the present invention is to provide a thermosetting insulating resin composition that has low thermal expansion and is excellent in heat resistance and dielectric properties, and a prepreg, a laminate, and a printed wiring board using the same.
本発明は、以下に関する。
１． （１）（ａ）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、（ｂ）一般式（Ｉ）に示す酸性置換基を有するアミン化合物とを反応させて製造される、分子構造中に酸性置換基とＮ−置換マレイミド基を有する化合物、（２）ナフタレン骨格含有エポキシ樹脂、（３）熱分解温度が３００℃以上である金属水和物を成分として含有することを特徴とする熱硬化性樹脂組成物。
The present invention relates to the following.
1. (1) (a) produced by reacting a maleimide compound having at least two N-substituted maleimide groups in one molecule with an amine compound having an acidic substituent represented by (b) general formula (I) A compound having an acidic substituent and an N-substituted maleimide group in the molecular structure, (2) a naphthalene skeleton-containing epoxy resin, and (3) a metal hydrate having a thermal decomposition temperature of 300 ° C. or higher as a component. A thermosetting resin composition.
２． （１）化合物が、一般式（ＩＩ）又は一般式（ＩＩＩ）に示す硬化剤である前記の熱硬化性樹脂組成物。 2. (1) The said thermosetting resin composition whose compound is a hardening | curing agent shown to general formula (II) or general formula (III).
３． 前記の熱硬化性樹脂組成物を基材に含浸又は塗工してなるプリプレグ。
４． 前記のプリプレグを積層成形してなる積層板。
５． 前記の積層板を用いて製造されてなる、プリント配線板。
3. A prepreg obtained by impregnating or coating a base material with the thermosetting resin composition.
4). A laminate obtained by laminating the prepreg.
5. A printed wiring board produced by using the laminated board.
本発明により、低熱膨張性であって、かつ耐熱性、誘電特性に優れる熱硬化性絶縁樹脂組成物、並びにこれを用いたプリプレグ、積層板、及びプリント配線板を提供することが可能となった。 According to the present invention, it is possible to provide a thermosetting insulating resin composition having low thermal expansion and excellent heat resistance and dielectric properties, and a prepreg, a laminate, and a printed wiring board using the same. .
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、下記化合物（１）〜（３）を成分として含有する熱硬化性樹脂組成物である。
（１）（ａ）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、（ｂ）下記一般式（Ｉ）に示す酸性置換基を有するアミン化合物とを反応させて製造される、分子構造中に酸性置換基とＮ−置換マレイミド基を有する化合物。
（２）ナフタレン骨格含有エポキシ樹脂。
（３）熱分解温度が３００℃以上である金属水和物。
Hereinafter, the present invention will be described in detail.
The thermosetting resin composition of the present invention is a thermosetting resin composition containing the following compounds (1) to (3) as components.
(1) (a) produced by reacting a maleimide compound having at least two N-substituted maleimide groups in one molecule with (b) an amine compound having an acidic substituent represented by the following general formula (I) A compound having an acidic substituent and an N-substituted maleimide group in the molecular structure.
(2) Naphthalene skeleton-containing epoxy resin.
(3) Metal hydrate having a thermal decomposition temperature of 300 ° C. or higher.
本発明の成分（１）の分子構造中に酸性置換基とＮ−置換マレイミド基を有する化合物は、（ａ）の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、（ｂ）の一般式（Ｉ）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、必要により加熱・保温しながら０．１時間から１０時間攪拌し反応させて製造される。（ａ）の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は、例えば、ビス（４−マレイミドフェニル）メタン、ポリフェニルメタンマレイミド、ビス（４−マレイミドフェニル）エーテル、ビス（４−マレイミドフェニル）スルホン、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、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、２，２−ビス（４−（４−マレイミドフェノキシ）フェニル）プロパンが好ましく、溶剤への溶解性の点から、３，３−ジメチル−５，５−ジエチル−４，４−ジフェニルメタンビスマレイミド、ビス（４−マレイミドフェニル）メタンがより好ましく、安価である点からビス（４−マレイミドフェニル）メタンが特に好ましい。 The compound having an acidic substituent and an N-substituted maleimide group in the molecular structure of the component (1) of the present invention includes a maleimide compound having at least two N-substituted maleimide groups in one molecule of (a), ( The amine compound having an acidic substituent represented by the general formula (I) of b) is produced by stirring and reacting in an organic solvent for 0.1 to 10 hours, if necessary, while heating and keeping warm. The maleimide compound having at least two N-substituted maleimide groups in one molecule of (a) is, for example, bis (4-maleimidophenyl) methane, polyphenylmethanemaleimide, 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 and the like. Among these, bis (4-maleimidophenyl) methane and bis (4-maleimidophenyl) sulfone which have a high reaction rate and can have higher heat resistance. 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimi 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane is preferred, and 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide from the viewpoint of solubility in a solvent, Bis (4-maleimidophenyl) methane is more preferred, and bis (4-maleimidophenyl) methane is particularly preferred because it is inexpensive.
（ｂ）の一般式（Ｉ）に示す酸性置換基を有するアミン化合物は、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、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、ｐ−アミノフェノールがより好ましく、誘電特性や低熱膨張性、安価である点からｐ−アミノフェノールが特に好ましい。 The amine compound having an acidic substituent represented by the general formula (I) in (b) is, for example, m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, o -Aminobenzoic acid, o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, 3,5-dicarboxyaniline, etc., among these, M-aminophenol, p-aminophenol, p-aminobenzoic acid, and 3,5-dihydroxyaniline are preferable from the viewpoint of solubility and synthesis yield, and o-aminophenol, m-aminophenol, p-Aminophenol is more preferable, and p-aminophenol is particularly preferable in terms of dielectric properties, low thermal expansion, and low cost.
ここで、（ａ）のマレイミド化合物と（ｂ）の酸性置換基を有するアミン化合物の使用量は、その当量比が、（ａ）のマレイミド化合物のマレイミド基当量に対し、−ＮＨ２基換算の酸性置換基を有するアミン化合物の当量が次式：２．０≦（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望ましい。１０．０を超えると溶剤への溶解性が不足したり熱硬化性樹脂の耐熱性が低下する場合があり、２．０未満であるとゲル化を起こしたり、熱硬化性樹脂の耐熱性が低下する場合がある。また、有機溶媒の使用量は、（ａ）成分と（ｂ）成分の総和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。有機溶剤の配合量が少ないと溶解性が不足し、また１０００質量部を超えると合成に長時間を要する。 Here, the use amount of the maleimide compound (a) and the amine compound (b) having an acidic substituent is such that the equivalent ratio is in terms of —NH 2 group with respect to the maleimide group equivalent of the maleimide compound (a). The equivalent of the amine compound having an acidic substituent is preferably in the range represented by the following formula: 2.0 ≦ (maleimide group equivalent) / (equivalent in terms of —NH 2 group) ≦ 10.0. If it exceeds 10.0, the solubility in the solvent may be insufficient or the heat resistance of the thermosetting resin may decrease, and if it is less than 2.0, gelation may occur, or the heat resistance of the thermosetting resin may decrease. May decrease. Moreover, it is preferable to set it as 10-1000 mass parts per 100 mass parts of total of (a) component and (b) component, and, as for the usage-amount of an organic solvent, it is more preferable to set it as 100-500 mass parts, 200- It is especially preferable to set it as 500 mass parts. If the amount of the organic solvent is small, the solubility is insufficient, and if it exceeds 1000 parts by mass, a long time is required for synthesis.
この反応で使用される有機溶媒は特に制限されないが、例えばエタノール、プロパノール、ブタノール、メチルセロソルブ、ブチルセロソルブ、プロピレングリコールモノメチルエーテル等のアルコール系溶剤、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶剤、テトラヒドロフラン等のエーテル系溶剤、トルエン、キシレン、メシチレン等の芳香族系溶剤、ジメチルホルムアミド、ジメチルアセトアミド、Ｎ−メチルピロリドン等のＮ原子含有溶剤、ジメチルスルホキシド等のＳ原子含有溶剤等が挙げられ、１種又は２種以上を混合して使用できる。これらの中で、溶解性の点からシクロヘキサノン、プロピレングリコールモノメチルエーテル、メチルセロソルブが好ましく、低毒性である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剤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。 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. , Ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene, mesitylene, N atom containing solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, S atom containing solvents such as dimethyl sulfoxide, and the like. One kind or a mixture of two or more kinds can be used. Among these, 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. The difficult propylene glycol monomethyl ether is particularly preferred.
また、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、特に限定されない。反応触媒の例としては、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。 In this reaction, a reaction catalyst can be optionally used as necessary, and is not particularly limited. Examples of the reaction catalyst include amines such as triethylamine, pyridine, and tributylamine, imidazoles such as methylimidazole and phenylimidazole, and phosphorus-based catalysts such as triphenylphosphine. Can be used.
この反応により、例えば、一般式（ＩＩ）又は式（ＩＩＩ）に示す分子構造中に酸性置換基とＮ−置換マレイミド基を有する化合物が合成され、銅箔接着性、耐熱性、耐湿性、難燃性、誘電特性に優れる熱硬化性樹脂組成物が得られる。 By this reaction, for example, a compound having an acidic substituent and an N-substituted maleimide group in the molecular structure represented by general formula (II) or formula (III) is synthesized, and copper foil adhesion, heat resistance, moisture resistance, difficulty A thermosetting resin composition having excellent flammability and dielectric properties can be obtained.
（２）成分であるナフタレン骨格含有エポキシ樹脂は、下記一般式（Ｖ）〜（ＸＩ）で表されるものである。 The (2) component naphthalene skeleton-containing epoxy resin is represented by the following general formulas (V) to (XI).
一般式（Ｖ）および（ＸＩ）中のＲ６、Ｒ７、Ｒ１０の１価のハロゲン非含有有機基としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基などのアルキル基、フェニル基、ベンジル基、ナフチル基などのアリール基、ピリジル基などが挙げられる。また、一般式（Ｘ）および（ＸＩ）中のＲ８、Ｒ９の２価のハロゲン非含有有機基としては、メチレン基、エチレン基、プロピレン基、ブチレン基、ペンチレン基などのアルキレン基、フェニレン基、ナフチレン基などのアリーレン基、ピリジレン基などが挙げられる。これらの中で作業性、流動性の点から一般式（ＩＸ）、（Ｘ）のようなモノマー型多官能エポキシ樹脂が好ましく、低熱膨張性、耐熱性の点から式（Ｘ）のような４官能型エポキシ樹脂が特に好ましい。 Examples of the monovalent halogen-free organic group represented by R 6 , R 7 and R 10 in the general formulas (V) and (XI) include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group, An aryl group such as a phenyl group, a benzyl group and a naphthyl group, a pyridyl group and the like can be mentioned. The divalent halogen-free organic groups represented by R 8 and R 9 in the general formulas (X) and (XI) include alkylene groups such as methylene group, ethylene group, propylene group, butylene group and pentylene group, phenylene Group, an arylene group such as a naphthylene group, and a pyridylene group. Among these, monomer type polyfunctional epoxy resins such as general formulas (IX) and (X) are preferred from the viewpoint of workability and fluidity, and 4 as represented by formula (X) from the viewpoint of low thermal expansion and heat resistance. Functional epoxy resins are particularly preferred.
また、これらのナフタレン骨格含有エポキシ樹脂は、本発明の効果を阻害しない範囲で、１種類または２種類以上の他のエポキシ樹脂と組み合わせて用いることができる。他のエポキシ樹脂としては、前記一般式（Ｖ）〜（ＸＩ）で示されるエポキシ樹脂以外の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、例えば、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、スチルベン型エポキシ樹脂、トリアジン骨格含有エポキシ樹脂、フルオレン骨格含有エポキシ樹脂、脂環式エポキシ樹脂、グリシジルアミン型エポキシ樹脂、トリフェノールフェノールメタン型エポキシ樹脂、アルキル変性トリフェノールメタン型エポキシ樹脂、ビフェニル型エポキシ樹脂、ジシクロペンタジエン骨格含有エポキシ樹脂、アリールアルキレン型エポキシ樹脂等が挙げられる。 In addition, these naphthalene skeleton-containing epoxy resins can be used in combination with one or more other epoxy resins as long as the effects of the present invention are not impaired. Other epoxy resins include epoxy resins having two or more epoxy groups in one molecule other than the epoxy resins represented by the general formulas (V) to (XI), such as phenol novolac type epoxy resins and cresol novolac types. Epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, stilbene type epoxy resin, triazine skeleton containing epoxy resin, fluorene skeleton containing epoxy resin, alicyclic epoxy resin, glycidylamine type epoxy resin, Examples include triphenolphenol methane type epoxy resin, alkyl-modified triphenol methane type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene skeleton-containing epoxy resin, aryl alkylene type epoxy resin and the like.
（３）成分である熱分解温度が３００℃以上である金属水和物は、ベーマイト型水酸化アルミニウム（ＡｌＯＯＨ）、あるいはギブサイト型水酸化アルミニウム（Ａｌ（ＯＨ）３）を熱処理によりその熱分解温度を３００℃以上に調整した化合物、水酸化マグネシウム等が挙げられる。これらの中で、優れた耐熱性を有するベーマイト型水酸化アルミニウム（ＡｌＯＯＨ）や水酸化マグネシウムがより好ましく、さらに、難燃性に優れる本研究の熱硬化性樹脂と併用する場合、難燃効果はやや劣るが、安価であり、３５０℃以上の特に高い熱分解温度を有するベーマイト型水酸化アルミニウム（ＡｌＯＯＨ）であれば、特に高い耐熱性と難燃性が両立し、特に好ましい。 (3) The metal hydrate having a thermal decomposition temperature of 300 ° C. or higher as the component is obtained by heat treating the boehmite type aluminum hydroxide (AlOOH) or gibbsite type aluminum hydroxide (Al (OH) 3 ) by heat treatment. And a compound prepared by adjusting the temperature to 300 ° C. or higher, magnesium hydroxide, and the like. Among these, boehmite type aluminum hydroxide (AlOOH) and magnesium hydroxide having excellent heat resistance are more preferable, and when used in combination with the thermosetting resin of this research which is excellent in flame retardancy, the flame retardant effect is Boehmite type aluminum hydroxide (AlOOH), which is a little inferior but inexpensive and has a particularly high thermal decomposition temperature of 350 ° C. or higher, is particularly preferable because it has both particularly high heat resistance and flame retardancy.
本発明の熱硬化性樹脂組成物には、耐熱性や難燃性、銅箔接着性等の向上化のため硬化促進剤を用いることが望ましく、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。その中でもイミダゾール類及びその誘導体が耐熱性や難燃性、銅箔接着性等の点から好ましく、更に下記一般式（ＸＩＩ）で表されるイミダゾール基がエポキシ樹脂によって置換された化合物や、下記一般式（ＸＩＩＩ）で表されるイソシアネート樹脂によって置換された化合物が２００℃以下での比較的低温での硬化成形性とワニスやプリプレグの経日安定性に優れるためより好ましく、下記一般式（ＸＩＶ）又は（ＸＶ）で表される化合物が少量の配合使用でよく、また商業的にも安価であることから特に好ましい。 In the thermosetting resin composition of the present invention, it is desirable to use a curing accelerator for improving heat resistance, flame retardancy, copper foil adhesiveness, etc. Examples of the curing accelerator include imidazoles and their Derivatives, tertiary amines, quaternary ammonium salts and the like. Among them, imidazoles and derivatives thereof are preferable from the viewpoints of heat resistance, flame retardancy, copper foil adhesiveness, and the like, and compounds in which the imidazole group represented by the following general formula (XII) is substituted with an epoxy resin, and the following general A compound substituted by an isocyanate resin represented by the formula (XIII) is more preferable because it is excellent in curing moldability at a relatively low temperature at 200 ° C. or lower and the aging stability of a varnish or a prepreg. Alternatively, the compound represented by (XV) may be used in a small amount, and is particularly preferable because it is commercially inexpensive.
本発明の熱硬化性樹脂組成物は、該成分（１）の使用量が、固形分換算の該成分（２）との総和１００質量部当たり、１〜９９質量部とすることが好ましく、２０〜９０質量部とすることがより好ましく、５０〜８０質量部とすることが特に好ましい。成分（１）の配合量が少ないと難燃性が不足し、また９９質量部を超えると耐熱性、接着性が低下する。該成分（３）の使用量は、固形分換算の該成分（１）と（２）の総和１００質量部当たり、１０〜２００質量部とすることが好ましく、１０〜１５０質量部とすることがより好ましく、５０〜１５０質量部とすることが特に好ましい。１０質量部未満であると難燃性が不足したり、２００質量部を超えると耐めっき液性等の耐薬品性が低下する場合がある。硬化促進剤の使用量は、固形分換算の該成分（１）と（２）の総和１００質量部当たり、０．１〜２０質量部とすることが好ましく、０．１〜１０質量部とすることがより好ましい。硬化促進剤の使用量が少ないと耐熱性や難燃性、銅箔接着性等が不足し、また２０質量部を超える場合も耐熱性や経日安定性が低下する。 In the thermosetting resin composition of the present invention, the amount of the component (1) used is preferably 1 to 99 parts by mass per 100 parts by mass in total with the component (2) in terms of solid content. It is more preferable to set it as -90 mass parts, and it is especially preferable to set it as 50-80 mass parts. If the amount of component (1) is small, the flame retardancy is insufficient, and if it exceeds 99 parts by mass, the heat resistance and adhesiveness are lowered. The amount of component (3) used is preferably 10 to 200 parts by mass, and preferably 10 to 150 parts by mass, per 100 parts by mass of the sum of components (1) and (2) in terms of solid content. More preferred is 50 to 150 parts by mass. If it is less than 10 parts by mass, the flame retardancy may be insufficient, and if it exceeds 200 parts by mass, chemical resistance such as plating solution resistance may be deteriorated. It is preferable that the usage-amount of a hardening accelerator shall be 0.1-20 mass parts per 100 mass parts of sum total of this component (1) and (2) of solid content conversion, and shall be 0.1-10 mass parts. It is more preferable. If the amount of the curing accelerator used is small, the heat resistance, flame retardancy, copper foil adhesiveness, etc. are insufficient, and if it exceeds 20 parts by mass, the heat resistance and aging stability will be reduced.
本発明の熱硬化性樹脂組成物には、任意に他の難燃剤の併用ができるが、臭素や塩素を含有する含ハロゲン系難燃剤や熱分解温度が３００℃未満である金属水酸化物等は本発明の目的にそぐわない。他の難燃剤の併用の例としては、トリフェニルホスフェート、トリクレジルホスフェート、トリスジクロロプロピルホスフェート、リン酸エステル系化合物、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、モリブデン酸亜鉛等の無機難燃助剤等が挙げられる。 The thermosetting resin composition of the present invention can optionally be used in combination with other flame retardants, such as halogen-containing flame retardants containing bromine or chlorine, metal hydroxides having a thermal decomposition temperature of less than 300 ° C., etc. Does not meet the purpose of the present invention. Examples of other flame retardant combinations include triphenyl phosphate, tricresyl phosphate, trisdichloropropyl phosphate, phosphoric ester compounds, phosphazenes, phosphorous flame retardants such as red phosphorus, antimony trioxide, zinc molybdate, etc. Inorganic flame retardant aids and the like.
本発明の熱硬化性樹脂組成物には、任意に無機充填剤の併用ができる。無機充填剤の例としては、シリカ、マイカ、タルク、ガラス短繊維又は微粉末及び中空ガラス、硫酸バリウム、炭酸カルシウム、石英粉末等が挙げられ、これらの中で誘電特性、耐熱性、難燃性の点からシリカが特に好ましい。これら無機充填剤の使用量は、固形分換算の該成分（１）と（２）の総和１００質量部に対し、０〜２００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。無機充填剤の配合量が３００質量部を超えると耐めっき液性等の耐薬品性や成形性が低下する。 In the thermosetting resin composition of the present invention, an inorganic filler can be optionally used in combination. Examples of inorganic fillers include silica, mica, talc, short glass fiber or fine powder and hollow glass, barium sulfate, calcium carbonate, quartz powder, etc. Among them, dielectric properties, heat resistance, flame resistance From this point, silica is particularly preferable. The amount of these inorganic fillers used is preferably 0 to 200 parts by mass, and preferably 20 to 200 parts by mass, with respect to 100 parts by mass of the sum of the components (1) and (2) in terms of solid content. More preferred is 20 to 150 parts by mass. When the compounding amount of the inorganic filler exceeds 300 parts by mass, chemical resistance such as plating solution resistance and moldability are deteriorated.
本発明によれば、任意に公知の熱可塑性樹脂、エラストマー、難燃剤、有機充填剤等の併用ができる。熱可塑性樹脂の例としては、テトラフルオロエチレン、ポリエチレン、ポリプロピレン、ポリスチレン、ポリフェニレンエーテル樹脂、フェノキシ樹脂、ポリカーボネート樹脂、ポリエステル樹脂、ポリアミド樹脂、ポリイミド樹脂、キシレン樹脂、石油樹脂及びシリコーン樹脂等が挙げられる。エラストマーの例としては、ポリブタジエン、アクリロニトリル、エポキシ変性ポリブタジエン、無水マレイン酸変性ポリブタジエン、フェノール変性ポリブタジエン及びカルボキシ変性アクリロニトリル等が挙げられる。 According to the present invention, known thermoplastic resins, elastomers, flame retardants, organic fillers and the like can be used in combination. Examples of the thermoplastic resin include tetrafluoroethylene, polyethylene, polypropylene, polystyrene, polyphenylene ether resin, phenoxy resin, polycarbonate resin, polyester resin, polyamide resin, polyimide resin, xylene resin, petroleum resin, and silicone resin. Examples of the elastomer include polybutadiene, acrylonitrile, epoxy-modified polybutadiene, maleic anhydride-modified polybutadiene, phenol-modified polybutadiene, and carboxy-modified acrylonitrile.
有機充填剤の例としては、シリコーンパウダー、テトラフルオロエチレン、ポリエチレン、ポリプロピレン、ポリスチレン、並びにポリフェニレンエーテル等の有機物粉末等が挙げられる。 Examples of organic fillers include organic powders such as silicone powder, tetrafluoroethylene, polyethylene, polypropylene, polystyrene, and polyphenylene ether.
本発明において、任意に該樹脂組成物に対して、紫外線吸収剤、酸化防止剤、光重合開始剤、蛍光増白剤及び密着性向上剤等の添加も可能であり、特に限定されない。これらの例としては、ベンゾトリアゾール系等の紫外線吸収剤、ヒンダードフェノール系やスチレン化フェノール等の酸化防止剤、ベンゾフェノン類、ベンジルケタール類、チオキサントン系等の光重合開始剤、スチルベン誘導体等の蛍光増白剤、尿素シラン等の尿素化合物やシランカップリング剤等の密着性向上剤等が挙げられる。 In the present invention, an ultraviolet absorber, an antioxidant, a photopolymerization initiator, a fluorescent whitening agent, an adhesion improver, and the like can be arbitrarily added to the resin composition, and the resin composition is not particularly limited. Examples of these include UV absorbers such as benzotriazoles, antioxidants such as hindered phenols and styrenated phenols, photopolymerization initiators such as benzophenones, benzyl ketals, and thioxanthones, and fluorescence such as stilbene derivatives. Examples include brighteners, urea compounds such as urea silane, and adhesion improvers such as silane coupling agents.
本発明のプリプレグは、前記した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なるものである。以下、本発明のプリプレグについて詳述する。
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、加熱等により半硬化（Ｂステージ化）して本発明のプリプレグを製造することができる。本発明の基材として、各種の電気絶縁材料用積層板に用いられている周知のものが使用できる。その材質の例としては、Ｅガラス、Ｄガラス、Ｓガラス及びＱガラス等の無機物繊維、ポリイミド、ポリエステル及びテトラフルオロエチレン等の有機繊維、並びにそれらの混合物等が挙げられる。これらの基材は、例えば、織布、不織布、ロービンク、チョップドストランドマット及びサーフェシングマット等の形状を有するが、材質及び形状は、目的とする成形物の用途や性能により選択され、必要により、単独又は２種類以上の材質及び形状を組み合わせることができる。基材の厚さは、特に制限されず、例えば、約０．０３〜０．５ｍｍを使用することができ、シランカップリング剤等で表面処理したもの又は機械的に開繊処理を施したものが、耐熱性や耐湿性、加工性の面から好適である。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。
The prepreg of the present invention is obtained by impregnating or coating the base material with the above-described thermosetting resin composition of the present invention. Hereinafter, the prepreg of the present invention will be described in detail.
The prepreg of the present invention can be produced by impregnating or coating the base material with the thermosetting resin composition of the present invention and semi-curing (B-stage) by heating or the like. As the base material of the present invention, known materials used for various types of laminates for electrical insulating materials can be used. Examples of the material include inorganic fibers such as E glass, D glass, S glass, and Q glass, organic fibers such as polyimide, polyester, and tetrafluoroethylene, and mixtures thereof. These base materials have, for example, shapes such as woven fabric, non-woven fabric, robink, chopped strand mat, and surfacing mat, but the material and shape are selected depending on the intended use and performance of the molded product, and if necessary, A single material or two or more materials and shapes can be combined. The thickness of the base material is not particularly limited, and for example, about 0.03 to 0.5 mm can be used, and the surface is treated with a silane coupling agent or the like or mechanically subjected to a fiber opening treatment. However, it is suitable from the aspects of heat resistance, moisture resistance, and workability. 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、前述の本発明のプリプレグを用いて、積層成形して、形成することができる。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製造することができる。金属箔は、電気絶縁材料用途で用いるものであれば特に制限されない。また、成形条件は、例えば、電気絶縁材料用積層板及び多層板の手法が適用でき、例えば多段プレス、多段真空プレス、連続成形、オートクレーブ成形機等を使用し、温度１００〜２５０℃、圧力２〜１００ｋｇ／ｃｍ２、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 can be formed by laminate molding using the prepreg of the present invention described above. The prepreg of the present invention can be produced, for example, by laminating 1 to 20 sheets and laminating and forming a metal foil such as copper and aluminum on one or both sides thereof. The metal foil is not particularly limited as long as it is used for electrical insulating material applications. In addition, as the molding conditions, for example, a method of a laminated plate for an electrical insulating material and a multilayer plate can be applied. It can be molded in a range of ˜100 kg / cm 2 and a heating time of 0.1 to 5 hours. Further, the prepreg of the present invention and the inner layer wiring board can be combined and laminated to produce a multilayer board.
本発明に係るプリント配線板は、前記積層板の表面に回路を形成して製造される。すなわち、本発明に係る積層板の導体層を通常のエッチング法によって配線加工し、前述のプリプレグを介して配線加工した積層板を複数積層し、加熱プレス加工することによって一括して多層化する。その後、ドリル加工又はレーザー加工によるスルーホール又はブラインドビアホールの形成と、メッキ又は導電性ペーストによる層間配線の形成を経て多層プリント配線板を製造することができる。 The printed wiring board according to the present invention is manufactured by forming a circuit on the surface of the laminated board. That is, the conductor layer of the laminated board according to the present invention is subjected to wiring processing by a normal etching method, and a plurality of laminated boards subjected to wiring processing through the above-described prepreg are laminated and subjected to hot press processing to be multilayered at once. Then, a multilayer printed wiring board can be manufactured through formation of a through hole or blind via hole by drilling or laser processing and formation of an interlayer wiring by plating or conductive paste.
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いかなる意味においても制限するものではない。
製造例１：酸性置換基と不飽和マレイミド基を有する硬化剤（１−１）の製造
温度計、攪拌装置、還流冷却管付き水分定量器の付いた加熱及び冷却可能な容積２リットルの反応容器に、ビス（４−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：４１２．５０ｇを（マレイミド基当量）／（−ＮＨ２基換算の当量）＝４．０となる比率で配合し、還流させながら５時間反応させて酸性置換基と不飽和マレイミド基を有する硬化剤（１−１）の溶液を得た。また、この溶液をＧＰＣ（ポリスチレン換算、溶離液：テトラヒドロフラン）により分析した結果、図１に示すように溶出時間が約１９分付近に出現するｐ−アミノフェノールのピークが消失しており、付加反応物に由来するピーク（Ｂ）及び（Ｃ）が確認された。ここでピーク（Ａ）は合成原料のビス（４−マレイミドフェニル）メタンであり、ピーク（Ｂ）は化学式（１１）に示す反応生成物であり、ピーク（Ｃ）は化学式（１２）に示す副反応生成物である。
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 in any way.
Production Example 1 Production of Curing Agent (1-1) Having Acidic Substituent and Unsaturated Maleimide Group Heating and cooling reaction vessel with a volume of 2 liters equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser Bis (4-maleimidophenyl) methane: 358.0 g, p-aminophenol: 54.5 g, and propylene glycol monomethyl ether: 412.50 g (maleimide group equivalent) / (equivalent in terms of —NH 2 group) = It mix | blended in the ratio used as 4.0, it was made to react for 5 hours, making it reflux, and the solution of the hardening | curing agent (1-1) which has an acidic substituent and unsaturated maleimide group was obtained. Moreover, as a result of analyzing this solution by GPC (polystyrene conversion, eluent: tetrahydrofuran), as shown in FIG. 1, the peak of p-aminophenol that appeared at about 19 minutes disappeared, and the addition reaction Peaks (B) and (C) derived from the product were confirmed. Here, peak (A) is bis (4-maleimidophenyl) methane as a raw material for synthesis, peak (B) is a reaction product represented by chemical formula (11), and peak (C) is a secondary product represented by chemical formula (12). It is a reaction product.
製造例２：酸性置換基と不飽和マレイミド基を有する硬化剤（１−２）の製造
温度計、攪拌装置、還流冷却管付き水分定量器の付いた加熱及び冷却可能な容積２リットルの反応容器に、ビス（４−マレイミドフェニル）メタン：３５８．０ｇとｍ−アミノフェノール：５４．５０ｇ、及びプロピレングリコールモノメチルエーテル：４１２．５ｇを（マレイミド基当量）／（−ＮＨ２基換算の当量）＝４．０となる比率で配合し、還流させながら５時間反応させて酸性置換基と不飽和マレイミド基を有する硬化剤（１−２）の溶液を得た。
Production Example 2: Production of Curing Agent (1-2) Having Acidic Substituent and Unsaturated Maleimide Group A reaction vessel with a volume of 2 liters that can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. Bis (4-maleimidophenyl) methane: 358.0 g, m-aminophenol: 54.50 g, and propylene glycol monomethyl ether: 412.5 g (maleimide group equivalent) / (equivalent in terms of —NH 2 group) = It mix | blended in the ratio used as 4.0, it was made to react for 5 hours, making it reflux, and the solution of the hardening | curing agent (1-2) which has an acidic substituent and unsaturated maleimide group was obtained.
製造例３：酸性置換基と不飽和マレイミド基を有する硬化剤（１−３）の製造
温度計、攪拌装置、還流冷却管付き水分定量器の付いた加熱及び冷却可能な容積２リットルの反応容器に、ビス（４−マレイミドフェニル）メタン：３５８．０ｇとｐ−アミノ安息香酸：２７．４０ｇ、及びＮ，Ｎ−ジメチルアセトアミド：３８５．４ｇを（マレイミド基当量）／（−ＮＨ２基換算の当量）＝１０．０となる比率で配合し、１６０℃で５時間反応させて酸性置換基と不飽和マレイミド基を有する硬化剤（１−３）の溶液を得た。
Production Example 3 Production of Curing Agent (1-3) Having Acidic Substituent and Unsaturated Maleimide Group Heating and cooling reaction vessel with a volume of 2 liters equipped with a thermometer, stirrer, and moisture meter with reflux condenser Bis (4-maleimidophenyl) methane: 358.0 g, p-aminobenzoic acid: 27.40 g, and N, N-dimethylacetamide: 385.4 g in terms of (maleimide group equivalent) / (— NH 2 group equivalent) Equivalents) = 10.0 and mixed at 160 ° C. for 5 hours to obtain a solution of a curing agent (1-3) having an acidic substituent and an unsaturated maleimide group.
製造例４：酸性置換基と不飽和マレイミド基を有する硬化剤（１−４）の製造
温度計、攪拌装置、還流冷却管付き水分定量器の付いた加熱及び冷却可能な容積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：１０９．０ｇ、及びＮ，Ｎ−ジメチルアセトアミド：３７７．０ｇを（マレイミド基当量）／（−ＮＨ２基換算の当量）＝２．０となる比率で配合し、１４０℃で５時間反応させて酸性置換基と不飽和マレイミド基を有する硬化剤（１−４）の溶液を得た。
Production Example 4: Production of Curing Agent (1-4) Having Acidic Substituent and Unsaturated Maleimide Group A reaction vessel with a volume of 1 liter that can be heated and cooled with a thermometer, a stirrer, and a moisture meter with a reflux condenser. M-phenylenebismaleimide: 268.0 g, m-aminophenol: 109.0 g, and N, N-dimethylacetamide: 377.0 g (maleimide group equivalent) / (-NH 2 group equivalent) = 2 Was mixed at a ratio of 0.0 and reacted at 140 ° C. for 5 hours to obtain a solution of a curing agent (1-4) having an acidic substituent and an unsaturated maleimide group.
製造例５：酸性置換基と不飽和マレイミド基を有する硬化剤（１−５）の製造
温度計、攪拌装置、還流冷却管付き水分定量器の付いた加熱及び冷却可能な容積２リットルの反応容器に、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：４４２．０ｇ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：４９６．５ｇを（マレイミド基当量）／（−ＮＨ２基換算の当量）＝４．０となる比率で配合し、還流させながら５時間反応させて酸性置換基と不飽和マレイミド基を有する硬化剤（１−５）の溶液を得た。
Production Example 5 Production of Curing Agent (1-5) Having Acidic Substituent and Unsaturated Maleimide Group Heating and cooling reaction vessel with a volume of 2 liters equipped with a thermometer, stirrer, and moisture meter with a reflux condenser 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide: 442.0 g, p-aminophenol: 54.5 g, and propylene glycol monomethyl ether: 496.5 g (maleimide group equivalent) / (- equivalent of NH 2 groups equivalent) = blended with 4.0 and consisting ratio, the solution to obtain a curing agent (1-5) having reacted for 5 hours acidic substituent and an unsaturated maleimide group at reflux It was.
製造例６：酸性置換基と不飽和マレイミド基を有する硬化剤（１−６）の製造
温度計、攪拌装置、還流冷却管付き水分定量器の付いた加熱及び冷却可能な容積２リットルの反応容器に、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：４４２．０ｇとｏ−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：４９６．５ｇを（マレイミド基当量）／（−ＮＨ２基換算の当量）＝４．０となる比率で配合し、還流させながら５時間反応させて酸性置換基と不飽和マレイミド基を有する硬化剤（１−６）の溶液を得た。
Production Example 6 Production of Curing Agent (1-6) Having Acidic Substituent and Unsaturated Maleimide Group Heating and cooling reaction vessel with a volume of 2 liters equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide: 442.0 g, o-aminophenol: 54.5 g, and propylene glycol monomethyl ether: 496.5 g (maleimide group equivalent) / (-NH 2 group equivalent) = 4.0 is mixed and reacted for 5 hours while refluxing to obtain a solution of the curing agent (1-6) having an acidic substituent and an unsaturated maleimide group. It was.
製造例７：酸性置換基と不飽和マレイミド基を有する硬化剤（１−７）の製造
温度計、攪拌装置、還流冷却管付き水分定量器の付いた加熱及び冷却可能な容積２リットルの反応容器に、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（マレイミド基当量）／（−ＮＨ２基換算の当量）＝４．０となる比率で配合し、１００℃で２時間反応させて酸性置換基と不飽和マレイミド基を有する硬化剤（１−７）の溶液を得た。
Production Example 7 Production of Curing Agent (1-7) Having Acidic Substituent and Unsaturated Maleimide Group Heating and cooling reaction vessel with a volume of 2 liters equipped with a thermometer, stirrer, and moisture meter with reflux condenser Bis (4-maleimidophenyl) sulfone: 408.0 g, p-aminophenol: 54.5 g, and N, N-dimethylacetamide: 462.5 g (maleimide group equivalent) / (-NH 2 group equivalent) ) = 4.0 and blended at 100 ° C. for 2 hours to obtain a solution of a curing agent (1-7) having an acidic substituent and an unsaturated maleimide group.
製造例８：酸性置換基と不飽和マレイミド基を有する硬化剤（１−８）の製造
温度計、攪拌装置、還流冷却管付き水分定量器の付いた加熱及び冷却可能な容積２リットルの反応容器に、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（マレイミド基当量）／（−ＮＨ２基換算の当量）＝４．０となる比率で配合し、１００℃で２時間反応させて酸性置換基と不飽和マレイミド基を有する硬化剤（１−８）の溶液を得た。
Production Example 8 Production of Curing Agent (1-8) Having Acidic Substituent and Unsaturated Maleimide Group Heating and cooling reaction vessel with a volume of 2 liters equipped with a thermometer, stirrer, and moisture meter with reflux condenser Bis (4-maleimidophenyl) ether: 360.0 g, p-aminophenol: 54.5 g, and N, N-dimethylacetamide: 414.5 g (maleimide group equivalent) / (-NH 2 group equivalent) ) = 4.0 and blended at 100 ° C. for 2 hours to obtain a solution of a curing agent (1-8) having an acidic substituent and an unsaturated maleimide group.
製造例９：酸性置換基と不飽和マレイミド基を有する硬化剤（１−９）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（マレイミド基当量）／（−ＮＨ２基換算の当量）＝４．０となる比率で配合し、１２０℃で２時間反応させて酸性置換基と不飽和マレイミド基を有する硬化剤（１−９）の溶液を得た。
Production Example 9 Production of Curing Agent (1-9) Having Acidic Substituent and Unsaturated Maleimide Group Heating and cooling reaction vessel with a volume of 2 liters equipped with a thermometer, stirrer, and moisture meter with a reflux condenser 2,2′-bis [4- (4-maleimidophenoxy) phenyl] propane: 570.0 g, p-aminophenol: 54.5 g, and propylene glycol monomethyl ether: 624.5 g (maleimide group equivalent) / (Equivalent in terms of —NH 2 group) = 4.0 was blended and reacted at 120 ° C. for 2 hours to obtain a solution of a curing agent (1-9) having an acidic substituent and an unsaturated maleimide group. .
製造例１０：酸性置換基と不飽和マレイミド基を有する硬化剤（１−１０）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Ｎ，Ｎ−ジメチルアセトアミド：３３６．５ｇを（マレイミド基当量）／（−ＮＨ２基換算の当量）＝４．０となる比率で配合し、１２０℃で２時間反応させて酸性置換基と不飽和マレイミド基を有する硬化剤（１−１０）の溶液を得た。
Production Example 10 Production of Curing Agent (1-10) Having Acidic Substituent and Unsaturated Maleimide Group Heating and cooling reaction vessel with a volume of 2 liters equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser 4-methyl-1,3-phenylenebismaleimide: 282.0 g, p-aminophenol: 54.5 g, and N, N-dimethylacetamide: 336.5 g (maleimide group equivalent) / (— NH 2 group (Equivalent equivalent) = 4.0 and blended at 120 ° C. for 2 hours to obtain a solution of a curing agent (1-10) having an acidic substituent and an unsaturated maleimide group.
（実施例１〜２４、比較例１〜６）
成分（１）である製造例１〜１０で得られた成分、成分（２）であるナフタレン骨格含有エポキシ樹脂、また、硬化促進剤、難燃剤、無機充填剤、及び希釈溶剤にメチルエチルケトンを使用して表１から表５に示した配合割合（質量部）で混合して樹脂分６５質量％の均一なワニスを得た。次に、上記ワニスを厚さ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。次に、このプリプレグを４枚重ね、１８μｍの電解銅箔を上下に配置し、圧力２５ｋｇ／ｃｍ２、温度１８５℃で９０分間プレスを行って、銅張積層板を得た。このようにして得られた銅張積層板を用いて、ガラス転移温度、熱膨張率、銅箔接着性（銅箔ピール強度）、はんだ耐熱性、吸湿性（吸水率）、難燃性、比誘電率（１ＧＨｚ）、誘電正接（１ＧＨｚ）について以下の方法で測定・評価し、表６から表１０に評価結果を示した。
(Examples 1-24, Comparative Examples 1-6)
Ingredients obtained in Production Examples 1 to 10 as component (1), naphthalene skeleton-containing epoxy resin as component (2), and methyl ethyl ketone as a curing accelerator, flame retardant, inorganic filler, and diluent solvent. The mixture was mixed at the blending ratio (parts by mass) shown in Tables 1 to 5 to obtain a uniform varnish having a resin content of 65% by mass. Next, the 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. Next, four prepregs were stacked, 18 μm electrolytic copper foils were placed one above the other, and pressed at a pressure of 25 kg / cm 2 and a temperature of 185 ° C. for 90 minutes to obtain a copper clad laminate. Using the copper-clad laminate thus obtained, glass transition temperature, thermal expansion coefficient, copper foil adhesion (copper foil peel strength), solder heat resistance, moisture absorption (water absorption), flame retardancy, ratio The dielectric constant (1 GHz) and dielectric loss tangent (1 GHz) were measured and evaluated by the following methods, and the evaluation results are shown in Tables 6 to 10.
（１）ガラス転移温度（Ｔｇ）の測定
銅張積層板を銅エッチング液に浸漬することにより銅箔を取り除いた５ｍｍ角の評価基板を作製し、ＴＭＡ試験装置（デュポン社製、ＴＭＡ２９４０）を用い、評価基板のＺ方向の熱膨張特性を観察することにより評価した。
（２）熱膨張率の測定
銅張積層板を銅エッチング液に浸漬することにより銅箔を取り除いた５ｍｍ角の評価基板を作製し、ＴＭＡ試験装置（デュポン社製、ＴＭＡ２９４０）を用い、評価基板のＺ方向のＴｇ未満の熱膨張特性を観察することにより評価した。
（３）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幅の銅箔を形成して評価基板を作製し、引張り試験機を用いて銅箔の接着性（ピール強度）を測定した。
（４）はんだ耐熱性の評価
銅張積層板を銅エッチング液に浸漬することにより銅箔を取り除いた５ｃｍ角の評価基板を作製し、平山製作所（株）製プレッシャー・クッカー試験装置を用いて、１２１℃、２ａｔｍの条件で４時間までプレッシャー・クッカー処理を行った後、温度２８８℃のはんだ浴に、評価基板を２０秒間浸漬した後、外観を観察することによりはんだ耐熱性を評価した。
（５）銅付き耐熱性（Ｔ−３００）の評価
銅張積層板から５ｍｍ角の評価基板を作製し、ＴＭＡ試験装置（デュポン社製、ＴＭＡ２９４０）を用い、３００℃で評価基板の膨れが発生するまでの時間を測定することにより評価した。
（６）吸湿性（吸水率）の評価
銅張積層板を銅エッチング液に浸漬することにより銅箔を取り除いた評価基板を作製し、平山製作所（株）製プレッシャー・クッカー試験装置を用いて、１２１℃、２ａｔｍの条件で５時間までプレッシャー・クッカー処理を行った後、評価基板の吸水率を測定した。
（７）難燃性の評価
銅張積層板を銅エッチング液に浸漬することにより銅箔を取り除いた評価基板から、長さ１２５ｍｍ、幅１３．０ｍｍに切り出した試験片を作製し、ＵＬ９４の試験法（Ｖ法）に準じて評価した。
（８）比誘電率及び誘電正接の測定
銅張積層板を銅エッチング液に浸漬することにより銅箔を取り除いた評価基板を作製し、Ｈｅｗｌｌｅｔ・Ｐａｃｋｅｒｄ社製比誘電率測定装置（製品名：ＨＰ４２９１Ｂ）を用いて、周波数１ＧＨｚでの比誘電率及び誘電正接を測定した。
(1) Measurement of glass transition temperature (Tg) A 5-mm square evaluation board from which copper foil was removed by immersing a copper clad laminate in a copper etching solution was prepared, and a TMA test apparatus (manufactured by DuPont, TMA2940) was used. Evaluation was made by observing the thermal expansion characteristics in the Z direction of the evaluation substrate.
(2) Measurement of thermal expansion coefficient A 5 mm square evaluation board from which a copper foil was removed by immersing a copper clad laminate in a copper etching solution was prepared, and an evaluation board was used using a TMA test apparatus (manufactured by DuPont, TMA2940). This was evaluated by observing the thermal expansion characteristics of the Z direction less than Tg.
(3) Evaluation of copper foil adhesion (copper foil peel strength) A copper-clad laminate is immersed in a copper etching solution to form a 1 cm-wide copper foil to produce an evaluation substrate, and copper is tested using a tensile tester. The adhesion (peel strength) of the foil was measured.
(4) Evaluation of solder heat resistance A 5 cm square evaluation board from which a copper foil was removed by immersing a copper clad laminate in a copper etching solution was prepared using a pressure cooker test apparatus manufactured by Hirayama Seisakusho Co., Ltd. After performing the pressure-cooker treatment for 4 hours under the conditions of 121 ° C. and 2 atm, the evaluation substrate was 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.
(5) Evaluation of heat resistance with copper (T-300) A 5 mm square evaluation board was produced from a copper clad laminate, and the evaluation board swelled at 300 ° C. using a TMA test apparatus (manufactured by DuPont, TMA2940). It was evaluated by measuring the time to do.
(6) Evaluation of hygroscopicity (water absorption rate) A copper-clad laminate was immersed in a copper etching solution to prepare an evaluation substrate from which the copper foil was removed, and a pressure cooker test apparatus manufactured by Hirayama Seisakusho was used. After performing the pressure-cooker treatment for 5 hours under the conditions of 121 ° C. and 2 atm, the water absorption rate of the evaluation substrate was measured.
(7) Evaluation of flame retardancy A test piece cut out to a length of 125 mm and a width of 13.0 mm was prepared from an evaluation substrate obtained by removing a copper foil by immersing a copper clad laminate in a copper etching solution, and a UL94 test was performed. Evaluation was made according to the method (Method V).
(8) Measurement of relative dielectric constant and dielectric loss tangent An evaluation board from which copper foil was removed by immersing a copper clad laminate in a copper etching solution was prepared, and a relative dielectric constant measuring apparatus (product name: HP4291B) manufactured by Hewlett-Packard Company. ) Was used to measure the dielectric constant and dielectric loss tangent at a frequency of 1 GHz.
表中の数字は、固形分の質量部により示されている。注書きは、それぞれ
＊１：β−ナフトール骨格含有多官能型エポキシ樹脂（新日鐵化学社製；商品名ＥＳＮ−１７５ＳＶ）
＊２：ナフタレンジオール骨格含有多官能型エポキシ樹脂（新日鐵化学社製；商品名ＥＳＮ−３７５）
＊３：ナフタレン骨格含有４官能エポキシ樹脂（大日本インキ社製；商品名ＥＸＡ−４７００）
＊４：ナフタレン骨格含有２官能エポキシ樹脂（大日本インキ社製；商品名ＥＸＡ−４０３２Ｄ）
＊５：α−ナフトール骨格含有多官能型エポキシ樹脂（日本化薬社製；商品名ＮＣ−７０００Ｌ）
＊６：β−ナフトール骨格含有多官能型エポキシ樹脂（日本化薬社製；商品名ＮＣ−７３００Ｌ）
＊７：下記に示す構造のヘキサメチレンジイソシアネート樹脂と２−エチル−４−メチルイミダゾールの付加反応物
The numbers in the table are indicated by mass parts of solid content. * 1: β-naphthol skeleton-containing polyfunctional epoxy resin (manufactured by Nippon Steel Chemical Co., Ltd .; trade name ESN-175SV)
* 2: Polyfunctional epoxy resin containing naphthalenediol skeleton (manufactured by Nippon Steel Chemical Co., Ltd .; trade name ESN-375)
* 3: Naphthalene skeleton-containing tetrafunctional epoxy resin (Dainippon Ink, trade name EXA-4700)
* 4: Naphthalene skeleton-containing bifunctional epoxy resin (Dainippon Ink Co., Ltd .; trade name EXA-4032D)
* 5: α-naphthol skeleton-containing polyfunctional epoxy resin (Nippon Kayaku Co., Ltd .; trade name NC-7000L)
* 6: Polyfunctional epoxy resin containing β-naphthol skeleton (manufactured by Nippon Kayaku Co., Ltd .; trade name NC-7300L)
* 7: Addition reaction product of hexamethylene diisocyanate resin having the structure shown below and 2-ethyl-4-methylimidazole
＊８：下記に示す構造のビスフェノールＡ型エポキシ樹脂と２−フェニルイミダゾールの付加反応物 * 8: Addition reaction product of bisphenol A type epoxy resin and 2-phenylimidazole having the structure shown below
＊９：溶融シリカ（アドマテック社製；商品名ＳＣ２０５０−ＫＣ）
＊１０：ベーマイト型水酸化アルミニウム
＊１１：水酸化マグネシウム
＊１２ビス（４−マレイミドフェニル）メタン
＊１３：２，２’−ビス［４−（４−マレイミドフェノキシ）フェニル］プロパン
＊１４：ビスフェノールＡ型エポキシ樹脂（ジャパンエポキシレジン社製；商品名エピコート８２８）
＊１５：ビスフェノールＦ型エポキシ樹脂（ジャパンエポキシレジン社製；商品名エピコート８０７）
＊１６：２−フェニルイミダゾール
＊１７：ギブサイト型水酸化アルミニウムを意味する。
* 9: Fused silica (manufactured by Admatech; trade name SC2050-KC)
* 10: Boehmite type aluminum hydroxide * 11: Magnesium hydroxide * 12 Bis (4-maleimidophenyl) methane * 13: 2,2'-bis [4- (4-maleimidophenoxy) phenyl] propane * 14: Bisphenol A Type epoxy resin (made by Japan Epoxy Resin Co., Ltd .; trade name Epicoat 828)
* 15: Bisphenol F type epoxy resin (manufactured by Japan Epoxy Resin; trade name Epicoat 807)
* 16: 2-phenylimidazole * 17: Gibbsite type aluminum hydroxide.
表から明らかなように、本発明に係る実施例の熱硬化性絶縁樹脂組成物は、比較例の熱硬化性絶縁樹脂組成物と比べて、特に低熱膨張性であって、かつ耐熱性、誘電特性に優れていることがわかる。 As is clear from the table, the thermosetting insulating resin compositions of the examples according to the present invention are particularly low in thermal expansion and have heat resistance and dielectric properties as compared with the thermosetting insulating resin compositions of the comparative examples. It can be seen that the characteristics are excellent.
本発明は、低熱膨張性であって、かつ耐熱性、誘電特性に優れる熱硬化性絶縁樹脂組成物、並びにこれを用いたプリプレグ、積層板、及びプリント配線板を提供することができる。 The present invention can provide a thermosetting insulating resin composition having low thermal expansion and excellent heat resistance and dielectric properties, and a prepreg, a laminate and a printed wiring board using the same.
（Ａ）：ビス（４−マレイミドフェニル）メタンに関するピーク
（Ｂ）：化学式（１１）に示す反応生成物に関するピーク
（Ｃ）：化学式（１２）に示す反応生成物に関するピーク
(A): peak related to bis (4-maleimidophenyl) methane (B): peak related to the reaction product shown in chemical formula (11) (C): peak related to the reaction product shown in chemical formula (12)
Claims (5)
前記（１）化合物が、一般式（ＩＩ）又は一般式（ＩＩＩ）に示す硬化剤であることを特徴とする熱硬化性樹脂組成物。
The thermosetting resin composition, wherein the compound (1) is a curing agent represented by the general formula (II) or the general formula (III) .
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| JP5652028B2 (en) * | 2010-07-15 | 2015-01-14 | 日立化成株式会社 | Thermosetting resin composition, prepreg and laminate using the same |
| JP2012111930A (en) * | 2010-11-01 | 2012-06-14 | Hitachi Chemical Co Ltd | Thermocurable resin composition, prepreg using the thermocurable resin composition, laminated plate, and printed wiring board |
| JP6040606B2 (en) * | 2012-07-18 | 2016-12-07 | 日立化成株式会社 | Thermosetting resin composition, prepreg, laminate and printed wiring board using the same |
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