JP7081127B2 - Thermosetting resin composition, prepreg, laminated board, printed wiring board and high-speed communication compatible module - Google Patents
Thermosetting resin composition, prepreg, laminated board, printed wiring board and high-speed communication compatible module Download PDFInfo
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- JP7081127B2 JP7081127B2 JP2017233363A JP2017233363A JP7081127B2 JP 7081127 B2 JP7081127 B2 JP 7081127B2 JP 2017233363 A JP2017233363 A JP 2017233363A JP 2017233363 A JP2017233363 A JP 2017233363A JP 7081127 B2 JP7081127 B2 JP 7081127B2
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- resin composition
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- thermosetting resin
- mass
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- 239000011342 resin composition Substances 0.000 title claims description 69
- 229920001187 thermosetting polymer Polymers 0.000 title claims description 69
- 238000004891 communication Methods 0.000 title claims description 15
- 229920005989 resin Polymers 0.000 claims description 97
- 239000011347 resin Substances 0.000 claims description 97
- -1 maleimide compound Chemical class 0.000 claims description 75
- 125000004432 carbon atom Chemical group C* 0.000 claims description 49
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 42
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 40
- 239000000945 filler Substances 0.000 claims description 28
- 229920006026 co-polymeric resin Polymers 0.000 claims description 25
- 125000001931 aliphatic group Chemical group 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 20
- 239000011256 inorganic filler Substances 0.000 claims description 17
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 17
- 229920002554 vinyl polymer Polymers 0.000 claims description 17
- 125000003277 amino group Chemical group 0.000 claims description 15
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 15
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 11
- 239000000835 fiber Substances 0.000 claims description 11
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 9
- 150000003440 styrenes Chemical class 0.000 claims description 9
- 238000007259 addition reaction Methods 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 238000010030 laminating Methods 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 claims description 3
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 claims description 3
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 claims description 3
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 47
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 17
- 238000004519 manufacturing process Methods 0.000 description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 229910052802 copper Inorganic materials 0.000 description 15
- 239000010949 copper Substances 0.000 description 15
- 125000002947 alkylene group Chemical group 0.000 description 13
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 12
- 239000011521 glass Substances 0.000 description 12
- 239000000758 substrate Substances 0.000 description 12
- 125000001118 alkylidene group Chemical group 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 125000000217 alkyl group Chemical group 0.000 description 10
- 229920001971 elastomer Polymers 0.000 description 10
- 239000000806 elastomer Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 125000000524 functional group Chemical group 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- 229910000679 solder Inorganic materials 0.000 description 8
- 239000011889 copper foil Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000007822 coupling agent Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 229920003048 styrene butadiene rubber Polymers 0.000 description 6
- 239000002966 varnish Substances 0.000 description 6
- KHYXYOGWAIYVBD-UHFFFAOYSA-N 4-(4-propylphenoxy)aniline Chemical compound C1=CC(CCC)=CC=C1OC1=CC=C(N)C=C1 KHYXYOGWAIYVBD-UHFFFAOYSA-N 0.000 description 5
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- WOLATMHLPFJRGC-UHFFFAOYSA-N furan-2,5-dione;styrene Chemical compound O=C1OC(=O)C=C1.C=CC1=CC=CC=C1 WOLATMHLPFJRGC-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 125000001033 ether group Chemical group 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 125000000468 ketone group Chemical group 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 230000000930 thermomechanical effect Effects 0.000 description 4
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 3
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 3
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical class CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 3
- 125000000732 arylene group Chemical group 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000006081 fluorescent whitening agent Substances 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000011810 insulating material Substances 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 229920003192 poly(bis maleimide) Polymers 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- XAZPKEBWNIUCKF-UHFFFAOYSA-N 1-[4-[4-[2-[4-[4-(2,5-dioxopyrrol-1-yl)phenoxy]phenyl]propan-2-yl]phenoxy]phenyl]pyrrole-2,5-dione Chemical compound C=1C=C(OC=2C=CC(=CC=2)N2C(C=CC2=O)=O)C=CC=1C(C)(C)C(C=C1)=CC=C1OC(C=C1)=CC=C1N1C(=O)C=CC1=O XAZPKEBWNIUCKF-UHFFFAOYSA-N 0.000 description 2
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 2
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000005456 alcohol based solvent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000011362 coarse particle Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 2
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003759 ester based solvent Substances 0.000 description 2
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 2
- 239000005453 ketone based solvent Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-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
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- HGTUJZTUQFXBIH-UHFFFAOYSA-N (2,3-dimethyl-3-phenylbutan-2-yl)benzene Chemical group C=1C=CC=CC=1C(C)(C)C(C)(C)C1=CC=CC=C1 HGTUJZTUQFXBIH-UHFFFAOYSA-N 0.000 description 1
- PEVRKKOYEFPFMN-UHFFFAOYSA-N 1,1,2,3,3,3-hexafluoroprop-1-ene;1,1,2,2-tetrafluoroethene Chemical group FC(F)=C(F)F.FC(F)=C(F)C(F)(F)F PEVRKKOYEFPFMN-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- FPAZNLSVMWRGQB-UHFFFAOYSA-N 1,2-bis(tert-butylperoxy)-3,4-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=C(OOC(C)(C)C)C(OOC(C)(C)C)=C1C(C)C FPAZNLSVMWRGQB-UHFFFAOYSA-N 0.000 description 1
- PUKLCKVOVCZYKF-UHFFFAOYSA-N 1-[2-(2,5-dioxopyrrol-1-yl)ethyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1CCN1C(=O)C=CC1=O PUKLCKVOVCZYKF-UHFFFAOYSA-N 0.000 description 1
- 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 1
- AQGZJQNZNONGKY-UHFFFAOYSA-N 1-[4-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=C(N2C(C=CC2=O)=O)C=C1 AQGZJQNZNONGKY-UHFFFAOYSA-N 0.000 description 1
- PYVHLZLQVWXBDZ-UHFFFAOYSA-N 1-[6-(2,5-dioxopyrrol-1-yl)hexyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1CCCCCCN1C(=O)C=CC1=O PYVHLZLQVWXBDZ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- ZGDMDBHLKNQPSD-UHFFFAOYSA-N 2-amino-5-(4-amino-3-hydroxyphenyl)phenol Chemical compound C1=C(O)C(N)=CC=C1C1=CC=C(N)C(O)=C1 ZGDMDBHLKNQPSD-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical group C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 1
- QYIMZXITLDTULQ-UHFFFAOYSA-N 4-(4-amino-2-methylphenyl)-3-methylaniline Chemical group CC1=CC(N)=CC=C1C1=CC=C(N)C=C1C QYIMZXITLDTULQ-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- HYDATEKARGDBKU-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]phenoxy]aniline Chemical group C1=CC(N)=CC=C1OC1=CC=C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 HYDATEKARGDBKU-UHFFFAOYSA-N 0.000 description 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
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- SWHUMWPTJNVCBA-UHFFFAOYSA-H C([O-])([O-])=O.[Ca+2].[Si+4].C([O-])([O-])=O.C([O-])([O-])=O Chemical compound C([O-])([O-])=O.[Ca+2].[Si+4].C([O-])([O-])=O.C([O-])([O-])=O SWHUMWPTJNVCBA-UHFFFAOYSA-H 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- SXEHKFHPFVVDIR-UHFFFAOYSA-N [4-(4-hydrazinylphenyl)phenyl]hydrazine Chemical compound C1=CC(NN)=CC=C1C1=CC=C(NN)C=C1 SXEHKFHPFVVDIR-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000004450 alkenylene group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 125000004419 alkynylene group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229940118662 aluminum carbonate Drugs 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 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
- 230000005540 biological transmission Effects 0.000 description 1
- IEJKFDMRQARVHW-UHFFFAOYSA-N butan-2-one;1-methoxypropan-2-ol Chemical compound CCC(C)=O.COCC(C)O IEJKFDMRQARVHW-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004957 naphthylene group Chemical group 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
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920006124 polyolefin elastomer Polymers 0.000 description 1
- 229920001155 polypropylene 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
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 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
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
- Moulding By Coating Moulds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Description
本発明は、熱硬化性樹脂組成物、プリプレグ、積層板、プリント配線板及び高速通信対応モジュールに関する。 The present invention relates to a thermosetting resin composition, a prepreg, a laminated board, a printed wiring board, and a module compatible with high-speed communication.
近年の電子機器の小型化及び高性能化の流れに伴い、プリント配線板では配線密度の高度化及び高集積化が進展しており、これに伴って、プリント配線板用の積層板には、耐熱性の向上等による信頼性向上の要求が強まっている。このような用途、特に半導体パッケージ基板用途においては、優れた耐熱性及び低熱膨張性を兼備することが要求される。また、ネットワークインフラ機器、大型コンピュータ等における情報通信量、速度の著しい向上に伴い、これらの電子機器に搭載される半導体パッケージには高周波化対応が必要となり、伝送損失の低減を可能とする低誘電率及び低誘電正接を有する基板材料が求められている。 With the recent trend toward miniaturization and higher performance of electronic devices, the wiring density of printed wiring boards has become more sophisticated and highly integrated, and along with this, laminated boards for printed wiring boards have become more popular. There is an increasing demand for improved reliability by improving heat resistance and the like. In such applications, particularly semiconductor package substrate applications, it is required to have both excellent heat resistance and low thermal expansion. In addition, with the remarkable improvement in the amount of information communication and speed in network infrastructure equipment, large computers, etc., the semiconductor packages mounted on these electronic equipment need to support higher frequencies, and low dielectric constants that enable reduction of transmission loss. There is a demand for a substrate material having a rate and a low dielectric loss tangent.
ビスマレイミド樹脂にシロキサン骨格を導入した変性マレイミド樹脂が、無機充填材の含有量を過剰に増やすことなく、優れた耐熱性と低熱膨張性を有することが知られている（例えば、特許文献１参照）。また、該変性マレイミド樹脂は、エポキシ樹脂と比較すると低比誘電率及び低誘電正接を有するが、近年求められる比誘電率及び誘電正接を達成するには至っていない。 It is known that a modified maleimide resin in which a siloxane skeleton is introduced into a bismaleimide resin has excellent heat resistance and low thermal expansion without excessively increasing the content of an inorganic filler (see, for example, Patent Document 1). ). Further, the modified maleimide resin has a low relative permittivity and a low dielectric loss tangent as compared with the epoxy resin, but has not yet achieved the relative permittivity and the dielectric loss tangent required in recent years.
誘電特性を向上させることを目的として、熱可塑性エラストマーとしてポリブタジエン樹脂を添加した積層板が検討されている。該積層板は、優れた誘電特性を有するが、プリプレグが粘着性を有してしまうこと、他の熱硬化性樹脂との相溶性が低いこと、硬化時の収縮率が大きいこと、銅箔等の金属箔への接着性が悪いこと等の欠点がある。
これらを改良する方法として、ブタジエン－ビニル芳香族化合物コポリマーを用いる方法が提案されているが（例えば、特許文献２参照）、他の熱硬化性樹脂との十分な相溶性を得るためにはビニル芳香族化合物の共重合比率を高める必要があり、その場合、耐熱性が低下するという問題が生じる。
For the purpose of improving the dielectric property, a laminated board to which a polybutadiene resin is added as a thermoplastic elastomer has been studied. The laminated board has excellent dielectric properties, but the prepreg has adhesiveness, the compatibility with other thermosetting resins is low, the shrinkage rate during curing is large, copper foil, etc. Has drawbacks such as poor adhesion to metal foil.
As a method for improving these, a method using a butadiene-vinyl aromatic compound copolymer has been proposed (see, for example, Patent Document 2), but vinyl is used in order to obtain sufficient compatibility with other thermosetting resins. It is necessary to increase the copolymerization ratio of the aromatic compound, which causes a problem that the heat resistance is lowered.
また、近年、半導体用パッケージ基板でチップと基板との熱膨張率の差、及び基板の硬化収縮に起因する反りが課題とされている。反りを改善する手法として、基材の熱膨張率の低減、樹脂の硬化収縮率を低減する方法が検討されている。アプローチ例として、変性マレイミド樹脂と熱可塑性エラストマーとを併用する方法が提案されている（例えば、特許文献３参照）。特許文献３では、熱可塑性エラストマーは樹脂の硬化収縮率低減を目的として適用している。ここで、熱可塑性エラストマーとして水添スチレン系エラストマーを使用した際に、骨格の極性が非常に小さいことから低比誘電率及び低誘電正接を示す。そのため、変性マレイミド樹脂と水添スチレン系エラストマーを併用することで、低熱膨張性と優れた誘電特性（低比誘電率及び低誘電正接）とを両立させることができる。 Further, in recent years, there have been problems in the package substrate for semiconductors, such as the difference in the coefficient of thermal expansion between the chip and the substrate and the warp caused by the curing shrinkage of the substrate. As a method for improving the warp, a method of reducing the coefficient of thermal expansion of the base material and the rate of curing shrinkage of the resin have been studied. As an example of the approach, a method of using a modified maleimide resin and a thermoplastic elastomer in combination has been proposed (see, for example, Patent Document 3). In Patent Document 3, the thermoplastic elastomer is applied for the purpose of reducing the curing shrinkage rate of the resin. Here, when a hydrogenated styrene-based elastomer is used as the thermoplastic elastomer, the polarity of the skeleton is very small, so that it exhibits a low relative permittivity and a low dielectric loss tangent. Therefore, by using the modified maleimide resin and the hydrogenated styrene-based elastomer in combination, it is possible to achieve both low thermal expansion and excellent dielectric properties (low relative permittivity and low dielectric loss tangent).
上記の変性マレイミド樹脂と熱可塑性エラストマーとを併用した樹脂組成物は、一般的な耐熱性は問題ないものの、近年のプリント配線板の高密度実装及び高多層化構成に伴う厳しい条件下における耐熱性、すなわち、吸水後の耐熱性に劣るという問題があった。これは、本発明者等の検討によると、変性マレイミド樹脂と熱可塑性エラストマーの相溶性が不十分であったためと考えられる。 The resin composition in which the above-mentioned modified maleimide resin and the thermoplastic elastomer are used in combination has no problem in general heat resistance, but has heat resistance under severe conditions due to the recent high-density mounting of printed wiring boards and the high-multilayer configuration. That is, there is a problem that the heat resistance after water absorption is inferior. It is considered that this is because the compatibility between the modified maleimide resin and the thermoplastic elastomer was insufficient according to the study by the present inventors.
本発明の課題は、こうした現状に鑑み、優れた耐熱性、低熱膨張性、低比誘電率及び低誘電正接を有する熱硬化性樹脂組成物、これを用いたプリプレグ、積層板、プリント配線板及び高速通信対応モジュールを提供することにある。 In view of these circumstances, the subject of the present invention is a thermosetting resin composition having excellent heat resistance, low thermal expansion, low relative permittivity and low dielectric loss tangent, a prepreg, a laminated board, a printed wiring board and a printed wiring board using the same. The purpose is to provide a high-speed communication compatible module.
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、特定の構造を有する変性マレイミド樹脂、熱可塑性エラストマー、芳香族ビニル化合物とカルボン酸無水物を原料モノマーとする共重合樹脂を用いることで、上記の目的を達成し得ることを見出し、本発明を完成するに至った。さらに、誘電特性に優れるフッ素樹脂フィラーを配合することで、より優れた誘電特性を発現することができる。
すなわち、本発明は、以下の熱硬化性樹脂組成物、プリプレグ、積層板及びプリント配線板を提供するものである。
［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（ａ１）と、１分子中に少なくとも２個の１級アミノ基を有するアミン化合物（ａ２）との付加反応物と、
（Ｂ）熱可塑性エラストマーと、
（Ｃ）芳香族ビニル化合物由来の構造単位とカルボン酸無水物由来の構造単位とを含有する共重合樹脂と、
（Ｄ）フッ素樹脂フィラーと、
を含有する熱硬化性樹脂組成物。
［２］前記芳香族ビニル化合物由来の構造単位が、下記一般式（Ｃ－１）で表され、前記カルボン酸無水物由来の構造単位が、下記一般式（Ｃ－２）で表される無水マレイン酸由来の構造単位である、上記［１］に記載の熱硬化性樹脂組成物。
As a result of diligent research to achieve the above object, the present inventors have made a modified maleimide resin having a specific structure, a thermoplastic elastomer, an aromatic vinyl compound and a copolymer resin using a carboxylic acid anhydride as a raw material monomer. We have found that the above object can be achieved by using the above, and have completed the present invention. Further, by blending a fluororesin filler having excellent dielectric properties, more excellent dielectric properties can be exhibited.
That is, the present invention provides the following thermosetting resin compositions, prepregs, laminated boards and printed wiring boards.
[1] (A) Addition of a maleimide compound (a1) having at least two N-substituted maleimide groups in one molecule and an amine compound (a2) having at least two primary amino groups in one molecule. Reactants and
(B) Thermoplastic elastomer and
(C) A copolymer resin containing a structural unit derived from an aromatic vinyl compound and a structural unit derived from a carboxylic acid anhydride,
(D) Fluororesin filler and
Thermosetting resin composition containing.
[2] The structural unit derived from the aromatic vinyl compound is represented by the following general formula (C-1), and the structural unit derived from the carboxylic acid anhydride is represented by the following general formula (C-2). The thermosetting resin composition according to the above [1], which is a structural unit derived from maleic anhydride.
［３］前記（Ｃ）成分として、前記一般式（Ｃ－１）中のＲＣ１が水素原子、ｘが０であり、かつ前記一般式（Ｃ－１）で表される構造単位と前記一般式（Ｃ－２）で表される構造単位との含有比率［（Ｃ－１）／（Ｃ－２）］（モル比）が５～１０である共重合樹脂を含有する、上記［１］又は［２］に記載の熱硬化性樹脂組成物。
［４］前記（Ｂ）成分の含有量が、熱硬化性樹脂組成物中の樹脂成分の固形分１００質量部に対して、４～２０質量部であり、前記（Ｃ）成分の含有量が、熱硬化性樹脂組成物中の樹脂成分の固形分１００質量部に対して、２～２０質量部である、上記［１］～［３］のいずれかに記載の熱硬化性樹脂組成物。
［５］前記（ａ２）成分が、末端にアミノ基を有する変性シロキサンを含有する、上記［１］～［４］のいずれかに記載の熱硬化性樹脂組成物。
［６］（Ｂ）熱可塑性エラストマーが、水添スチレン系熱可塑性エラストマーであり、該水添スチレン系熱可塑性エラストマー中のスチレン由来の構造単位の含有量が、２０～６０質量％である上記［１］～［５］のいずれかに記載の熱硬化性樹脂組成物。
［７］さらに、（Ｄ）フッ素樹脂フィラーが、ポリテトラフルオロエチレンであり、その配合量が（Ａ）成分、（Ｂ）成分、（Ｃ）成分の合計質量を１００としたときに、４０部から１００部である、上記［１］～［６］のいずれかに記載の熱硬化性樹脂組成物。
［８］さらに、（Ｅ）硬化促進剤を含有する、上記［１］～［７］のいずれかに記載の熱硬化性樹脂組成物。
［９］さらに、（Ｆ）無機充填材を含有する、上記［１］～［８］のいずれかに記載の熱硬化性樹脂組成物。
［１０］上記［１］～［９］のいずれかに記載の熱硬化性樹脂組成物を繊維基材に含浸させてなるプリプレグ。
［１１］上記［１０］に記載のプリプレグを積層成形して得られる積層板。
［１２］上記［１０］に記載のプリプレグ又は上記［１１］に記載の積層板を用いて製造されるプリント配線板。
［１３］上記［１２］に記載のプリント配線板を用いて製造される高速通信対応モジュール。
[3] As the component (C), the structural unit represented by the general formula (C-1) in which RC1 in the general formula ( C -1) is a hydrogen atom and x is 0, and the general formula (C-1) are used. [1] above, which contains a copolymer resin having a content ratio [(C-1) / (C-2)] (molar ratio) of 5 to 10 with a structural unit represented by the formula (C-2). Alternatively, the thermosetting resin composition according to [2].
[4] The content of the component (B) is 4 to 20 parts by mass with respect to 100 parts by mass of the solid content of the resin component in the thermosetting resin composition, and the content of the component (C) is The thermosetting resin composition according to any one of the above [1] to [3], which is 2 to 20 parts by mass with respect to 100 parts by mass of the solid content of the resin component in the thermosetting resin composition.
[5] The thermosetting resin composition according to any one of [1] to [4] above, wherein the component (a2) contains a modified siloxane having an amino group at the terminal.
[6] (B) The thermoplastic elastomer is a hydrogenated styrene-based thermoplastic elastomer, and the content of styrene-derived structural units in the hydrogenated styrene-based thermoplastic elastomer is 20 to 60% by mass. 1] The thermosetting resin composition according to any one of [5].
[7] Further, when the (D) fluororesin filler is polytetrafluoroethylene and the blending amount thereof is 100, the total mass of the (A) component, the (B) component, and the (C) component is 40 parts. The thermosetting resin composition according to any one of the above [1] to [6], which is 100 parts to the above.
[8] The thermosetting resin composition according to any one of the above [1] to [7], which further contains (E) a curing accelerator.
[9] The thermosetting resin composition according to any one of the above [1] to [8], which further contains (F) an inorganic filler.
[10] A prepreg obtained by impregnating a fiber base material with the thermosetting resin composition according to any one of the above [1] to [9].
[11] A laminated board obtained by laminating and molding the prepreg according to the above [10].
[12] A printed wiring board manufactured by using the prepreg according to the above [10] or the laminated board according to the above [11].
[13] A high-speed communication compatible module manufactured by using the printed wiring board according to the above [12].
本発明によれば、優れた耐熱性、低熱膨張性、低比誘電率及び低誘電正接を有する熱硬化性樹脂組成物、これを用いたプリプレグ、積層板、プリント配線板及び高速通信対応モジュールを提供することができる。 According to the present invention, a thermosetting resin composition having excellent heat resistance, low thermal expansion, low relative permittivity and low dielectric loss tangent, a prepreg, a laminated board, a printed wiring board and a high-speed communication compatible module using the same are provided. Can be provided.
［熱硬化性樹脂組成物］
本発明の熱硬化性樹脂組成物は、（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（ａ１）と、１分子中に少なくとも２個の１級アミノ基を有するアミン化合物（ａ２）との付加反応物（以下、「（Ａ）変性マレイミド樹脂」ともいう）と、（Ｂ）熱可塑性エラストマーと、（Ｃ）芳香族ビニル化合物由来の構造単位とカルボン酸無水物由来の構造単位とを含有する共重合樹脂（以下、「（Ｃ）共重合樹脂」ともいう）と、（Ｄ）フッ素樹脂フィラーと、を含有する熱硬化性樹脂組成物である。
[Thermosetting resin composition]
The thermosetting resin composition of the present invention (A) has a maleimide compound (a1) having at least two N-substituted maleimide groups in one molecule and at least two primary amino groups in one molecule. Additive reaction product with amine compound (a2) (hereinafter, also referred to as "(A) modified maleimide resin"), (B) thermoplastic elastomer, (C) structural unit derived from aromatic vinyl compound, and carboxylic acid anhydride. It is a thermosetting resin composition containing a copolymer resin containing the derived structural unit (hereinafter, also referred to as “(C) copolymer resin”) and (D) a fluororesin filler.
＜（Ａ）変性マレイミド樹脂＞
（Ａ）変性マレイミド樹脂は、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（ａ１）と、１分子中に少なくとも２個の１級アミノ基を有するアミン化合物（ａ２）との付加反応物である。
<(A) Modified maleimide resin>
(A) The modified maleimide resin includes a maleimide compound (a1) having at least two N-substituted maleimide groups in one molecule and an amine compound (a2) having at least two primary amino groups in one molecule. It is an addition reaction product of.
（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（ａ１））
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（ａ１）（以下、「（ａ１）成分」ともいう）は、１分子中に少なくとも２個のＮ－置換マレイミド基を有している構造であれば、特に限定はされないが、１分子中に２個のＮ－置換マレイミド基を有するマレイミド化合物が好ましく、下記一般式（ａ１－１）で表される化合物がより好ましい。
(Maleimide compound (a1) having at least two N-substituted maleimide groups in one molecule)
The maleimide compound (a1) having at least two N-substituted maleimide groups in one molecule (hereinafter, also referred to as “component (a1)”) has at least two N-substituted maleimide groups in one molecule. The structure is not particularly limited, but a maleimide compound having two N-substituted maleimide groups in one molecule is preferable, and a compound represented by the following general formula (a1-1) is more preferable.
前記一般式（ａ１－２）中、ＲＡ１が表す脂肪族炭化水素基としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔ－ブチル基、ｎ－ペンチル基等の炭素数１～５のアルキル基などが挙げられる。 In the general formula ( a1-2 ), the aliphatic hydrocarbon group represented by RA1 includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group and n. -Examples include an alkyl group having 1 to 5 carbon atoms such as a pentyl group.
前記一般式（ａ１－３）中、ＲＡ２が表す炭素数１～５の脂肪族炭化水素基としては、ＲＡ１の場合と同じものが挙げられる。
ＸＡ２が表す炭素数１～５のアルキレン基としては、メチレン基、１，２－ジメチレン基、１，３－トリメチレン基、１，４－テトラメチレン基、１，５－ペンタメチレン基等が挙げられる。
ＸＡ２が表す炭素数２～５のアルキリデン基としては、エチリデン基、プロピリデン基、イソプロピリデン基、ブチリデン基、イソブチリデン基、ペンチリデン基、イソペンチリデン基等が挙げられる。
In the general formula (a1-3), examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by RA2 are the same as in the case of RA1 .
Examples of the alkylene group having 1 to 5 carbon atoms represented by XA2 include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylethylene group, a 1,4-tetramethylene group, a 1,5-pentamethylene group and the like. Be done.
Examples of the alkylidene group having 2 to 5 carbon atoms represented by XA2 include an ethylidene group, a propyridene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group and an isopentylidene group.
前記一般式（ａ１－３’）中、ＲＡ３が表す炭素数１～５の脂肪族炭化水素基としては、ＲＡ２の場合と同じものが挙げられる。
ＸＡ３が表す炭素数１～５のアルキレン基、炭素数２～５のアルキリデン基としては、ＸＡ２が表す炭素数１～５のアルキレン基、炭素数２～５のアルキリデン基と同じものが挙げられる。
In the general formula (a1-3'), examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by RA3 are the same as those in the case of RA2 .
Examples of the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X A3 include the same alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X A2 . Be done.
前記一般式（ａ１－５）中、ＲＡ４が表す炭素数１～５の脂肪族炭化水素基としては、前記一般式（ａ１－２）中のＲＡ１の場合と同じものが挙げられる。 In the general formula ( a1-5 ), examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by RA4 are the same as those in the case of RA1 in the general formula (a1-2).
（ａ１）成分としては、Ｎ，Ｎ´－エチレンビスマレイミド、Ｎ，Ｎ´－ヘキサメチレンビスマレイミド、Ｎ，Ｎ´－（１，３－フェニレン）ビスマレイミド、Ｎ，Ｎ´－［１，３－（２－メチルフェニレン）］ビスマレイミド、Ｎ，Ｎ´－［１，３－（４－メチルフェニレン）］ビスマレイミド、Ｎ，Ｎ´－（１，４－フェニレン）ビスマレイミド、ビス（４－マレイミドフェニル）メタン、ビス（３－メチル－４－マレイミドフェニル）メタン、３，３´－ジメチル－５，５´－ジエチル－４，４´－ジフェニルメタンビスマレイミド、ビス（４－マレイミドフェニル）エーテル、ビス（４－マレイミドフェニル）ケトン、ビス（４－マレイミドシクロヘキシル）メタン、１，４－ビス（４－マレイミドフェニル）シクロヘキサン、１，４－ビス（マレイミドメチル）シクロヘキサン、１，４－ビス（マレイミドメチル）ベンゼン、１，３－ビス（４－マレイミドフェノキシ）ベンゼン、１，３－ビス（３－マレイミドフェノキシ）ベンゼン、ビス［４－（３－マレイミドフェノキシ）フェニル］メタン、ビス［４－（４－マレイミドフェノキシ）フェニル］メタン、１，１－ビス［４－（３－マレイミドフェノキシ）フェニル］エタン、１，１－ビス［４－（４－マレイミドフェノキシ）フェニル］エタン、１，２－ビス［４－（３－マレイミドフェノキシ）フェニル］エタン、１，２－ビス［４－（４－マレイミドフェノキシ）フェニル］エタン、２，２－ビス［４－（３－マレイミドフェノキシ）フェニル］プロパン、２，２－ビス［４－（４－マレイミドフェノキシ）フェニル］プロパン、２，２－ビス［４－（３－マレイミドフェノキシ）フェニル］ブタン、２，２－ビス［４－（４－マレイミドフェノキシ）フェニル］ブタン、４，４－ビス（３－マレイミドフェノキシ）ビフェニル、４，４－ビス（４－マレイミドフェノキシ）ビフェニル、ビス［４－（３－マレイミドフェノキシ）フェニル］ケトン、ビス［４－（４－マレイミドフェノキシ）フェニル］ケトン、ビス［４－（３－マレイミドフェノキシ）フェニル］エーテル、ビス［４－（４－マレイミドフェノキシ）フェニル］エーテル等が挙げられる。（ａ１）成分は、単独で用いても２種類以上を混合して用いてもよい。
これらの中でも、溶媒への溶解性が優れる観点から、フェノキシ基を有するマレイミド化合物が好ましく、反応率が高く、より高耐熱性化できる観点から、ビス（４－マレイミドフェニル）メタン、２，２－ビス［４－（４－マレイミドフェノキシ）フェニル］プロパンが好ましい。
As the component (a1), N, N'-ethylene bismaleimide, N, N'-hexamethylene bismaleimide, N, N'-(1,3-phenylene) bismaleimide, N, N'-[1,3 -(2-Methylphenylene)] bismaleimide, N, N'-[1,3- (4-methylphenylene)] bismaleimide, N, N'-(1,4-phenylene) bismaleimide, bis (4-) Maleimidephenyl) methane, bis (3-methyl-4-maleimidephenyl) methane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, bis (4-maleimidephenyl) ether, Bis (4-maleimidephenyl) ketone, bis (4-maleimidecyclohexyl) methane, 1,4-bis (4-maleimidephenyl) cyclohexane, 1,4-bis (maleimidemethyl) cyclohexane, 1,4-bis (maleimidemethyl) ) Benzene, 1,3-bis (4-maleimidephenoxy) benzene, 1,3-bis (3-maleimidephenoxy) benzene, bis [4- (3-maleimidephenoxy) phenyl] methane, bis [4- (4- (4- (4-) Maleimide phenoxy) phenyl] methane, 1,1-bis [4- (3-maleimide phenoxy) phenyl] ethane, 1,1-bis [4- (4-maleimide phenoxy) phenyl] ethane, 1,2-bis [4 -(3-Maleimidephenoxy) phenyl] ethane, 1,2-bis [4- (4-maleimidephenoxy) phenyl] ethane, 2,2-bis [4- (3-maleimidephenoxy) phenyl] propane, 2,2 -Bis [4- (4-maleimide phenoxy) phenyl] propane, 2,2-bis [4- (3-maleimide phenoxy) phenyl] butane, 2,2-bis [4- (4-maleimide phenoxy) phenyl] butane , 4,4-bis (3-maleimide phenoxy) biphenyl, 4,4-bis (4-maleimide phenoxy) biphenyl, bis [4- (3-maleimide phenoxy) phenyl] ketone, bis [4- (4-maleimide phenoxy) ) Phenyl] ketone, bis [4- (3-maleimidephenoxy) phenyl] ether, bis [4- (4-maleimidephenoxy) phenyl] ether and the like. The component (a1) may be used alone or in combination of two or more.
Among these, maleimide compounds having a phenoxy group are preferable from the viewpoint of excellent solubility in a solvent, and bis (4-maleimidephenyl) methane, 2,2- from the viewpoint of high reaction rate and higher heat resistance. Bis [4- (4-maleimidephenoxy) phenyl] propane is preferred.
（１分子中に少なくとも２個の１級アミノ基を有するアミン化合物（ａ２））
１分子中に少なくとも２個の１級アミノ基を有するアミン化合物（ａ２）（以下、「（ａ２）成分」ともいう）は、１分子中に２個の１級アミノ基を有するアミン化合物が好ましく、下記一般式（ａ２－１）で表される化合物がより好ましい。
(Amine compound (a2) having at least two primary amino groups in one molecule)
The amine compound (a2) having at least two primary amino groups in one molecule (hereinafter, also referred to as “component (a2)”) is preferably an amine compound having two primary amino groups in one molecule. , The compound represented by the following general formula (a2-1) is more preferable.
（式中、ＲＡ６は、各々独立に、炭素数１～５の脂肪族炭化水素基である。ＹＡ２は、炭素数１～５のアルキレン基、炭素数２～５のアルキリデン基、エーテル基、カルボオキシ基、ケト基、単結合又は下記一般式（ａ２－３’）で表される基である。ｑ２は、各々独立に、０～４の整数である。）
(In the formula, RA6 is an aliphatic hydrocarbon group having 1 to 5 carbon atoms independently, and YA2 is an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, and an ether group. , Carbooxy group, keto group, single bond or group represented by the following general formula (a2-3'). Q2 is an independently integer of 0 to 4).
前記一般式（ａ２－２）中、ＲＡ５が表す脂肪族炭化水素基としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔ－ブチル基、ｎ－ペンチル基等の炭素数１～５のアルキル基などが挙げられる。 In the general formula (a2-2), the aliphatic hydrocarbon group represented by RA5 includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group and n. -Examples include an alkyl group having 1 to 5 carbon atoms such as a pentyl group.
前記一般式（ａ２－３）中、ＲＡ６が表す炭素数１～５の脂肪族炭化水素基としては、ＲＡ５の場合と同じものが挙げられる。
ＹＡ２が表す炭素数１～５のアルキレン基としては、メチレン基、１，２－ジメチレン基、１，３－トリメチレン基、１，４－テトラメチレン基、１，５－ペンタメチレン基等が挙げられる。
ＹＡ２が表す炭素数２～５のアルキリデン基としては、エチリデン基、プロピリデン基、イソプロピリデン基、ブチリデン基、イソブチリデン基、ペンチリデン基、イソペンチリデン基等が挙げられる。
In the general formula ( a2-3 ), examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by RA6 are the same as those in the case of RA5 .
Examples of the alkylene group having 1 to 5 carbon atoms represented by YA2 include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylethylene group, a 1,4-tetramethylene group, a 1,5-pentamethylene group and the like. Be done.
Examples of the alkylidene group having 2 to 5 carbon atoms represented by YA2 include an ethylidene group, a propyridene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group and an isopentylidene group.
前記一般式（ａ２－３’）中、ＲＡ７が表す炭素数１～５の脂肪族炭化水素基としては、ＲＡ６の場合と同じものが挙げられる。
ＹＡ３が表す炭素数１～５のアルキレン基、炭素数２～５のアルキリデン基としては、ＹＡ２が表す炭素数１～５のアルキレン基、炭素数２～５のアルキリデン基と同じものが挙げられる。
In the general formula (a2-3'), examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by RA7 are the same as those in the case of RA6 .
Examples of the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by YA3 include the same alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by YA2 . Be done.
前記一般式（ａ２－４）中、ＲＡ８が表す炭素数１～５のアルキル基としては、炭素数１～３のアルキル基がより好ましい。ＲＡ８が表すアルキル基としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔ－ブチル基、ｎ－ペンチル基等が挙げられ、これらの中でも、メチル基が好ましい。
ＲＡ８が表す置換フェニル基における置換基としては、アルキル基、アルケニル基、アルキニル基等が挙げられ、これらの中でも、アルキル基が好ましい。アルキル基としては、ＲＡ８が表すアルキル基と同様のものが挙げられる。
ＲＡ９が表す２価の有機基としては、アルキレン基、アルキリデン基、アルケニレン基、アルキニレン基、アリーレン基、－Ｏ－又はこれらが組み合わされた２価の連結基等が挙げられる。これらの中でも、アルキレン基、アリーレン基が好ましい。アルキレン基としては、メチレン基、エチレン基、プロピレン基等が挙げられる。アリーレン基としては、フェニレン基、ナフチレン基等が挙げられる。
In the general formula (a2-4), the alkyl group having 1 to 5 carbon atoms represented by RA8 is more preferably an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group represented by RA8 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group and the like, and among these, methyl. Groups are preferred.
Examples of the substituent in the substituted phenyl group represented by RA8 include an alkyl group, an alkenyl group, an alkynyl group and the like, and among these, an alkyl group is preferable. Examples of the alkyl group include the same as the alkyl group represented by RA8 .
Examples of the divalent organic group represented by RA9 include an alkylene group, an alkylidene group, an alkenylene group, an alkynylene group, an arylene group, —O— or a divalent linking group in which these are combined. Among these, an alkylene group and an arylene group are preferable. Examples of the alkylene group include a methylene group, an ethylene group and a propylene group. Examples of the arylene group include a phenylene group and a naphthylene group.
（ａ２）成分としては、末端にアミノ基を有する変性シロキサン、ジアミノベンジジン、ジアミノジフェニルメタン、３，３´－ジエチル－４，４´－ジアミノジフェニルメタン、ジアミノジフェニルエーテル、３，３´－ジメトキシ－４，４´－ジアミノビフェニル、３，３´－ジメチル－４，４´－ジアミノビフェニル、１，３´－ビス（４－アミノフェノキシ）ベンゼン、２，２´－ビス［４－（４－アミノフェノキシ）フェニル］プロパン、４，４´－ビス（４－アミノフェノキシ）ビフェニル、１，４´－ビス（４－アミノフェノキシ）ベンゼン、２，２´－ジメチル－４，４´－ジアミノビフェニル、４，４´－ジアミノ－３，３´－ビフェニルジオール、等が挙げられる。（ａ２）成分は、単独で用いても２種類以上を混合して用いてもよい。 The components (a2) include modified siloxane having an amino group at the terminal, diaminobenzidine, diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, diaminodiphenyl ether, 3,3'-dimethoxy-4,4. ´-Diaminobiphenyl, 3,3 ′-dimethyl-4,4 ′-diaminobiphenyl, 1,3 ′-bis (4-aminophenoxy) benzene, 2,2 ′-bis [4- (4-aminophenoxy) phenyl ] Propane, 4,4'-bis (4-aminophenoxy) biphenyl, 1,4'-bis (4-aminophenoxy) benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4' -Diamino-3,3'-biphenyldiol, etc. may be mentioned. The component (a2) may be used alone or in combination of two or more.
これらの中でも、高弾性及び高耐熱性が得られる観点からは、３，３´－ジエチル－４，４´－ジアミノジフェニルメタン、２，２´－ビス［４－（４－アミノフェノキシ）フェニル］プロパンが好ましい。
また、低熱膨張性の観点からは、末端にアミノ基を有する変性シロキサンが好ましい。末端にアミノ基を有する変性シロキサンは、市販品を用いてもよく、市販品としては、両末端にアミノ基を有する、「Ｘ－２２－１６１Ａ」（官能基当量８００ｇ／ｍｏｌ）、「Ｘ－２２－１６１Ｂ」（官能基当量１，５００ｇ／ｍｏｌ）（以上、信越化学工業株式会社製）、「ＢＹ１６－８５３Ｕ」（官能基当量４６０ｇ／ｍｏｌ）（以上、東レ・ダウコーニング株式会社製）、「ＸＦ４２－Ｃ５３７９」（官能基当量７５０ｇ／ｍｏｌ）（以上、モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製）等が挙げられる。
Among these, from the viewpoint of obtaining high elasticity and high heat resistance, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 2,2'-bis [4- (4-aminophenoxy) phenyl] propane Is preferable.
Further, from the viewpoint of low thermal expansion, a modified siloxane having an amino group at the terminal is preferable. As the modified siloxane having an amino group at the terminal, a commercially available product may be used, and the commercially available product includes "X-22-161A" (functional group equivalent 800 g / mol) and "X-" having amino groups at both ends. 22-161B ”(functional group equivalent 1,500 g / mol) (above, manufactured by Shin-Etsu Chemical Industry Co., Ltd.),“ BY16-853U ”(functional group equivalent 460 g / mol) (above, manufactured by Toray Dow Corning Co., Ltd.), Examples thereof include "XF42-C5379" (functional group equivalent 750 g / mol) (all manufactured by Momentive Performance Materials Japan GK).
また、（ａ２）成分は、低熱膨張性、高弾性及び高耐熱性を両立させる観点から、末端にアミノ基を有する変性シロキサンと、末端にアミノ基を有する変性シロキサン以外のアミン化合物と、を含有することが好ましく、末端にアミノ基を有する変性シロキサンと、３，３´－ジエチル－４，４´－ジアミノジフェニルメタン及び２，２´－ビス［４－（４－アミノフェノキシ）フェニル］プロパンからなる群から選ばれる１種類以上と、を併用することがより好ましい。
（ａ２）成分として、末端にアミノ基を有する変性シロキサンと、末端にアミノ基を有する変性シロキサン以外のアミン化合物と、を併用する場合、その質量比〔末端にアミノ基を有する変性シロキサン／末端にアミノ基を有する変性シロキサン以外のアミン化合物〕は、３／９７～９０／１０が好ましく、１０／９０～８０／２０がより好ましく、２０／８０～７０／３０がさらに好ましい。
Further, the component (a2) contains a modified siloxane having an amino group at the terminal and an amine compound other than the modified siloxane having an amino group at the terminal from the viewpoint of achieving both low thermal expansion, high elasticity and high heat resistance. It is preferably composed of a modified siloxane having an amino group at the terminal, 3,3'-diethyl-4,4'-diaminodiphenylmethane and 2,2'-bis [4- (4-aminophenoxy) phenyl] propane. It is more preferable to use one or more kinds selected from the group in combination.
When a modified siloxane having an amino group at the terminal and an amine compound other than the modified siloxane having an amino group at the terminal are used in combination as the component (a2), the mass ratio thereof [modified siloxane having an amino group at the terminal / terminal Amine compounds other than modified siloxanes having an amino group] are preferably 3/97 to 90/10, more preferably 10/90 to 80/20, and even more preferably 20/80 to 70/30.
前記（ａ１）成分と前記（ａ２）成分との付加反応物である（Ａ）変性マレイミド樹脂は、例えば、下記一般式（Ａ－１）で表される構造単位を有するものである。 The (A) modified maleimide resin, which is an addition reaction product of the component (a1) and the component (a2), has, for example, a structural unit represented by the following general formula (A-1).
（（Ａ）変性マレイミド樹脂の製造方法）
（Ａ）変性マレイミド樹脂は、（ａ１）成分と（ａ２）成分とを付加反応させることにより製造することができる。
前記付加反応における（ａ１）成分と（ａ２）成分の配合量としては、ゲル化防止及び耐熱性の観点から、（ａ１）成分のマレイミド基の当量が、（ａ２）成分の１級アミノ基の当量を超える範囲であることが好ましく、（ａ１）成分のマレイミド基の当量と、（ａ２）成分の１級アミノ基の当量との比［（ａ１）成分／（ａ２）成分］が、２～１５であることが好ましく、３～１０であることがより好ましい。
((A) Method for producing modified maleimide resin)
The (A) modified maleimide resin can be produced by subjecting the component (a1) and the component (a2) to an addition reaction.
As for the blending amount of the component (a1) and the component (a2) in the addition reaction, the equivalent of the maleimide group of the component (a1) is the primary amino group of the component (a2) from the viewpoint of preventing gelation and heat resistance. The range is preferably in the range exceeding the equivalent, and the ratio of the equivalent of the maleimide group of the component (a1) to the equivalent of the primary amino group of the component (a2) [(a1) component / (a2) component] is 2 to 2. It is preferably 15, and more preferably 3 to 10.
前記付加反応における反応温度は、生産性及び均一に反応を進行させる観点から、７０～１５０℃が好ましく、１００～１３０℃がより好ましい。また、反応時間は、０．１～１０時間が好ましく、１～６時間がより好ましい。 The reaction temperature in the addition reaction is preferably 70 to 150 ° C., more preferably 100 to 130 ° C. from the viewpoint of productivity and uniform reaction progress. The reaction time is preferably 0.1 to 10 hours, more preferably 1 to 6 hours.
前記付加反応は、有機溶媒中で行うことが好ましい。有機溶媒としては、エタノール、プロパノール、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；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；酢酸エチルエステル等のエステル系溶媒；トルエン等の芳香族系溶媒；ジメチルアセトアミド、Ｎ－メチルピロリドン等の窒素原子含有溶媒などが挙げられる。有機溶媒は、単独で用いても２種類以上を混合して用いてもよい。
これらの中でも、溶解性の観点から、シクロヘキサノン、プロピレングリコールモノメチルエーテル、メチルセロソルブ、γ－ブチロラクトンが好ましく、低毒性であること及び揮発性が高く残溶媒として残りにくい観点から、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好ましい。
有機溶媒の使用量は、溶解性及び反応速度の観点から、（ａ１）成分と（ａ２）成分との合計１００質量部に対し、２５～１，０００質量部が好ましく、５０～５００質量部がより好ましい。
The addition reaction is preferably carried out in an organic solvent. Examples of the organic solvent include alcohol solvents such as ethanol, propanol and propylene glycol monomethyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ester solvents such as acetate ethyl ester; aromatic solvents such as toluene; dimethyl. Examples thereof include nitrogen atom-containing solvents such as acetamide and N-methylpyrrolidone. The organic solvent may be used alone or in combination of two or more.
Among these, cyclohexanone, propylene glycol monomethyl ether, methyl cellosolve, and γ-butyrolactone are preferable from the viewpoint of solubility, and cyclohexanone and propylene glycol monomethyl ether are preferable from the viewpoint of low toxicity and high volatility and less likely to remain as a residual solvent. Is preferable.
From the viewpoint of solubility and reaction rate, the amount of the organic solvent used is preferably 25 to 1,000 parts by mass, preferably 50 to 500 parts by mass, based on 100 parts by mass of the total of the components (a1) and (a2). More preferred.
本発明の熱硬化性樹脂組成物中における（Ａ）変性マレイミド樹脂の含有量は、熱硬化性樹脂組成物中の樹脂成分の固形分１００質量部に対して、５０～９５質量部が好ましく、６０～９０質量部がより好ましく、７０～８７質量部がさらに好ましい。
本明細書において、「固形分」とは、溶媒等の揮発する物質を除いた不揮発分のことであり、該樹脂組成物を乾燥させた際に、揮発せずに残る成分を示し、室温で液状、水飴状及びワックス状のものも含む。ここで、本明細書において室温とは２５℃を示す。
また、「樹脂成分」とは、後述する無機充填材を除く、樹脂又は樹脂の製造に使用される成分であり、具体的には、（Ａ）変性マレイミド樹脂、（Ｂ）熱可塑性エラストマー、（Ｃ）共重合樹脂等が樹脂成分に該当する。
The content of the (A) modified maleimide resin in the thermosetting resin composition of the present invention is preferably 50 to 95 parts by mass with respect to 100 parts by mass of the solid content of the resin component in the thermosetting resin composition. 60 to 90 parts by mass is more preferable, and 70 to 87 parts by mass is further preferable.
In the present specification, the "solid content" is a non-volatile content excluding volatile substances such as a solvent, and indicates a component that remains unvolatile when the resin composition is dried, and at room temperature. Includes liquid, candy-like and wax-like substances. Here, the room temperature is 25 ° C. in the present specification.
The "resin component" is a component used in the production of a resin or a resin, excluding the inorganic filler described later, and specifically, (A) a modified maleimide resin, (B) a thermoplastic elastomer, ( C) Copolymerized resin or the like corresponds to the resin component.
また、本発明の熱硬化性樹脂組成物中における（Ａ）変性マレイミド樹脂の含有量は、弾性率及び低熱膨張性の観点から、熱硬化性樹脂組成物中の（Ａ）変性マレイミド樹脂の量から換算される原料の（ａ１）成分の量が、熱硬化性樹脂組成物中の樹脂成分の固形分１００質量部に対して、３０～９０質量部となる量が好ましく、５０～８５質量部となる量がより好ましい。
また、本発明の熱硬化性樹脂組成物中における（Ａ）変性マレイミド樹脂の含有量は、良好な低熱膨張性及び銅箔接着性の観点から、熱硬化性樹脂組成物中の（Ａ）変性マレイミド樹脂の量から換算される原料の（ａ２）成分の量が、熱硬化性樹脂組成物中の樹脂成分の固形分１００質量部に対して、３～５０質量部となる量が好ましく、５～４０質量部となる量がより好ましい。
The content of the (A) modified maleimide resin in the thermosetting resin composition of the present invention is the amount of the (A) modified maleimide resin in the thermosetting resin composition from the viewpoint of elasticity and low thermal expansion. The amount of the component (a1) of the raw material converted from is preferably 30 to 90 parts by mass with respect to 100 parts by mass of the solid content of the resin component in the thermosetting resin composition, preferably 50 to 85 parts by mass. Is more preferable.
Further, the content of the (A) modified maleimide resin in the thermosetting resin composition of the present invention is (A) modified in the thermosetting resin composition from the viewpoint of good low thermal expansion and copper foil adhesiveness. The amount of the component (a2) of the raw material converted from the amount of the maleimide resin is preferably 3 to 50 parts by mass with respect to 100 parts by mass of the solid content of the resin component in the thermosetting resin composition. An amount of up to 40 parts by mass is more preferable.
＜（Ｂ）熱可塑性エラストマー＞
（Ｂ）熱可塑性エラストマー（以下、「（Ｂ）成分」ともいう）としては、特に制限はなく、従来公知の熱可塑性エラストマーの中から、適宜選択することができる。但し、本発明において、（Ｂ）熱可塑性エラストマーは、後述する（Ｃ）芳香族ビニル化合物由来の構造単位とカルボン酸無水物由来の構造単位とを含有する共重合樹脂を含まないものと定義される。
（Ｂ）熱可塑性エラストマーとしては、スチレン系エラストマー、オレフィン系エラストマー、ウレタン系エラストマー、ポリエステル系エラストマー、ポリアミド系エラストマー、アクリル系エラストマー、シリコーン系エラストマー、これらの誘導体等が挙げられる。（Ｂ）成分は、単独で用いても２種類以上を混合して用いてもよい。
<(B) Thermoplastic Elastomer>
The (B) thermoplastic elastomer (hereinafter, also referred to as “component (B)”) is not particularly limited, and can be appropriately selected from conventionally known thermoplastic elastomers. However, in the present invention, the (B) thermoplastic elastomer is defined as not containing a copolymer resin containing (C) a structural unit derived from an aromatic vinyl compound and a structural unit derived from a carboxylic acid anhydride, which will be described later. Ru.
Examples of the thermoplastic elastomer (B) include styrene-based elastomers, olefin-based elastomers, urethane-based elastomers, polyester-based elastomers, polyamide-based elastomers, acrylic-based elastomers, silicone-based elastomers, and derivatives thereof. The component (B) may be used alone or in combination of two or more.
また、（Ｂ）熱可塑性エラストマーとしては、分子末端又は分子鎖中に反応性官能基を有するものを用いることができる。反応性官能基としては、エポキシ基、水酸基、カルボキシ基、アミノ基、アミド基、イソシアナート基、アクリル基、メタクリル基、ビニル基等が挙げられる。これらの反応性官能基を分子末端又は分子鎖中に有することにより、相溶性が向上し、基板の耐熱性を向上させることが可能となる。
これらの反応性官能基の中でも、金属箔との密着性の観点から、耐熱性及び絶縁信頼性の観点から、カルボキシ基、アミノ基、水酸基を有することがより好ましい。
Further, as the (B) thermoplastic elastomer, one having a reactive functional group at the molecular end or in the molecular chain can be used. Examples of the reactive functional group include an epoxy group, a hydroxyl group, a carboxy group, an amino group, an amide group, an isocyanato group, an acrylic group, a methacryl group, a vinyl group and the like. By having these reactive functional groups at the molecular end or in the molecular chain, the compatibility is improved and the heat resistance of the substrate can be improved.
Among these reactive functional groups, it is more preferable to have a carboxy group, an amino group and a hydroxyl group from the viewpoint of adhesion to the metal foil and from the viewpoint of heat resistance and insulation reliability.
また、変性ポリイミド樹脂との相溶性の観点から、（Ｂ）熱可塑性エラストマーは、スチレン－ブタジエン共重合体、スチレン－イソプレン共重合体が好ましく、誘電特性の観点から、これらの共重合体の二重結合部分を水素添加した、水添スチレン－ブタジエン共重合樹脂、水添スチレン－イソプレン共重合樹脂等の水添スチレン系熱可塑性エラストマーがより好ましい。
さらに、該水添スチレン系熱可塑性エラストマー中のスチレン由来の構造単位の含有量（以下、「スチレン量」ともいう）は、２０～６０％質量であることが好ましく、２５～５５質量％であることがより好ましい。（Ｂ）熱可塑性エラストマーとして、スチレン量が２０～６０質量％である水添スチレン－ブタジエン共重合樹脂、水添スチレン－イソプレン共重合樹脂等の水添スチレン系熱可塑性エラストマーを用いることで、吸湿耐熱性に優れることに加え、塗工後のプリプレグの外観が優れ、プリプレグの粉落ち量が少ない樹脂を達成できる。スチレン量が６０質量％以下であると、基材特性（熱膨張率、誘電特性、耐熱性）が良好であることに加え、塗工後のプリプレグ外観でひび割れが生じ難い傾向にある。これは、スチレンのスタッキング凝集を抑制し、樹脂の柔軟性に優れるために由来すると考えられる。スチレン量が２０質量％以上であると、基材特性（熱膨張率、誘電特性、耐熱性）が良好であることに加え、（Ａ）変性マレイミド樹脂と（Ｂ）熱可塑性エラストマーの相溶性に優れ、樹脂の粉落ち量が少なく、取り扱い性に優れる傾向にある。これは、（Ａ）変性マレイミド樹脂が有するマレイミド基は、ブタジエン、イソプレン等と比較してスチレンと構造が近いことから、（Ｂ）熱可塑性エラストマーのスチレン量が２０質量％以上である場合に、（Ａ）変性マレイミド樹脂とスチレン系の骨格との相溶性が優れるために由来すると考えられる。
スチレン系エラストマーとしては、市販品を用いてもよく、市販品としては、「タフテック（登録商標）Ｈ１０５１」、「タフテックＨ１０５３」、「タフテックＭ１９１１」、「タフテックＭ１９１３」（以上、旭化成ケミカルズ株式会社製）、「セプトン２００２」、「セプトン（登録商標）ＨＧ２５２」（株式会社クラレ製）等が挙げられる。
Further, from the viewpoint of compatibility with the modified polyimide resin, the (B) thermoplastic elastomer is preferably a styrene-butadiene copolymer or a styrene-isoprene copolymer, and from the viewpoint of dielectric properties, these copolymers are two. A hydrogenated styrene-based thermoplastic elastomer such as a hydrogenated styrene-butadiene copolymer resin and a hydrogenated styrene-isoprene copolymer resin to which a double-bonded portion is hydrogenated is more preferable.
Further, the content of the structural unit derived from styrene in the hydrogenated styrene-based thermoplastic elastomer (hereinafter, also referred to as “styrene amount”) is preferably 20 to 60% by mass, preferably 25 to 55% by mass. Is more preferable. (B) Moisture absorption is achieved by using a hydrogenated styrene-based thermoplastic elastomer such as a hydrogenated styrene-butadiene copolymer resin or a hydrogenated styrene-isoprene copolymer resin having a styrene content of 20 to 60% by mass as the thermoplastic elastomer. In addition to being excellent in heat resistance, the appearance of the prepreg after coating is excellent, and it is possible to achieve a resin in which the amount of prepreg powder falling off is small. When the amount of styrene is 60% by mass or less, the base material properties (thermal expansion rate, dielectric properties, heat resistance) are good, and the appearance of the prepreg after coating tends to be less likely to be cracked. It is considered that this is because the stacking aggregation of styrene is suppressed and the flexibility of the resin is excellent. When the amount of styrene is 20% by mass or more, the substrate properties (coefficient of thermal expansion, dielectric properties, heat resistance) are good, and in addition, the compatibility between (A) modified maleimide resin and (B) thermoplastic elastomer It is excellent, the amount of resin powder falling off is small, and it tends to be easy to handle. This is because (A) the maleimide group contained in the modified maleimide resin has a structure similar to that of styrene as compared with butadiene, isoprene, etc., and therefore (B) when the amount of styrene in the thermoplastic elastomer is 20% by mass or more. (A) It is considered to be derived from the excellent compatibility between the modified maleimide resin and the styrene-based skeleton.
As the styrene-based elastomer, a commercially available product may be used, and the commercially available products include "Tough Tech (registered trademark) H1051", "Tough Tech H1053", "Tough Tech M1911", and "Tough Tech M1913" (all manufactured by Asahi Kasei Chemicals Co., Ltd.). ), "Septon 2002", "Septon (registered trademark) HG252" (manufactured by Kuraray Co., Ltd.) and the like.
熱硬化性樹脂組成物中の（Ｂ）熱可塑性エラストマーの含有量は、熱硬化性樹脂組成物中の樹脂成分の固形分１００質量部に対して、４～２０質量部が好ましく、６～１５質量部がより好ましい。（Ｂ）熱可塑性エラストマーの含有量が、４質量部以上であると低誘電率化の効果が十分得られ、２０質量部以下であると、（Ｂ）熱可塑性エラストマーが相溶化するため樹脂中に十分に分散し、耐熱性及びピール強度に優れる。 The content of the (B) thermoplastic elastomer in the thermosetting resin composition is preferably 4 to 20 parts by mass, preferably 6 to 15 parts by mass with respect to 100 parts by mass of the solid content of the resin component in the thermosetting resin composition. The mass part is more preferable. When the content of (B) the thermoplastic elastomer is 4 parts by mass or more, the effect of lowering the dielectric constant is sufficiently obtained, and when it is 20 parts by mass or less, (B) the thermoplastic elastomer is compatible with each other in the resin. It disperses sufficiently and has excellent heat resistance and peel strength.
＜（Ｃ）共重合樹脂＞
（Ｃ）共重合樹脂は、芳香族ビニル化合物由来の構造単位とカルボン酸無水物由来の構造単位とを含有する共重合樹脂である。
本発明の熱硬化性樹脂組成物は、（Ｃ）共重合樹脂を含有することにより、特に吸水後の耐熱性に優れるという効果が得られる。このような効果を奏する理由は定かではないが、次のように考えられる。
従来、誘電特性を向上させることを目的として、熱可塑性エラストマーを変性マレイミド樹脂に添加する手法が用いられていたが、熱可塑性エラストマーは変性マレイミド樹脂と骨格の構造が大きく異なるため、互いに相溶し難い状態であった。そのため、単に変性マレイミド樹脂と熱可塑性エラストマーとを配合すると、近年要求される厳しい条件下（例えば、プレッシャークッカーによる吸湿処理後）での耐熱性に問題があった。
本発明の熱硬化性樹脂組成物が含有する（Ｃ）共重合樹脂は、芳香族ビニル化合物由来の構造単位とカルボン酸無水物由来の構造単位とを含有しており、芳香族ビニル化合物由来の構造単位が、熱可塑性エラストマー（特にスチレンを含有するエラストマー）との相溶性に優れ、カルボン酸無水物由来の構造単位が変性マレイミド樹脂との相溶性に優れる。したがって、（Ｃ）共重合樹脂は、（Ａ）変性マレイミド樹脂と（Ｂ）熱可塑性エラストマーとの相溶化剤として機能し、これにより、（Ａ）変性マレイミド樹脂と（Ｂ）熱可塑性エラストマーとの相溶性が向上し、耐熱性が向上したと考えられる。さらには、（Ｃ）共重合樹脂自体も、優れた誘電特性を有することから、誘電特性を損なうことなく、優れた耐熱性を付与することができたと考えられる。
<(C) Copolymer resin>
The (C) copolymer resin is a copolymer resin containing a structural unit derived from an aromatic vinyl compound and a structural unit derived from a carboxylic acid anhydride.
By containing (C) the copolymerized resin, the thermosetting resin composition of the present invention has an effect of being particularly excellent in heat resistance after water absorption. The reason for this effect is not clear, but it is thought to be as follows.
Conventionally, a method of adding a thermoplastic elastomer to a modified maleimide resin has been used for the purpose of improving the dielectric property. However, since the thermoplastic elastomer has a significantly different skeleton structure from the modified maleimide resin, they are compatible with each other. It was in a difficult state. Therefore, if the modified maleimide resin and the thermoplastic elastomer are simply blended, there is a problem in heat resistance under severe conditions required in recent years (for example, after moisture absorption treatment with a pressure cooker).
The (C) copolymer resin contained in the thermosetting resin composition of the present invention contains a structural unit derived from an aromatic vinyl compound and a structural unit derived from a carboxylic acid anhydride, and is derived from the aromatic vinyl compound. The structural unit is excellent in compatibility with a thermoplastic elastomer (particularly an elastomer containing styrene), and the structural unit derived from an carboxylic acid anhydride is excellent in compatibility with a modified maleimide resin. Therefore, the (C) copolymer resin functions as a compatibilizer between the (A) modified maleimide resin and the (B) thermoplastic elastomer, whereby the (A) modified maleimide resin and the (B) thermoplastic elastomer can be combined. It is considered that the compatibility was improved and the heat resistance was improved. Furthermore, since the (C) copolymer resin itself also has excellent dielectric properties, it is considered that excellent heat resistance could be imparted without impairing the dielectric properties.
（Ｃ）共重合樹脂の芳香族ビニル化合物由来の構造単位としては、下記一般式（Ｃ－１）で表される構造単位が好ましい。また、前記（Ｃ）成分のカルボン酸無水物由来の構造単位としては、無水マレイン酸由来の構造単位、無水フタル酸由来の構造単位、無水コハク酸由来の構造単位等が挙げられるが、特に（Ａ）変性マレイミド樹脂との相溶性の観点から、マレイミド基に近い構造を有する下記一般式（Ｃ－２）で表される無水マレイン酸由来の構造単位が好ましい。 As the structural unit derived from the aromatic vinyl compound of the (C) copolymer resin, the structural unit represented by the following general formula (C-1) is preferable. Examples of the structural unit derived from the carboxylic acid anhydride of the component (C) include a structural unit derived from maleic anhydride, a structural unit derived from phthalic anhydride, a structural unit derived from succinic anhydride, and the like. A) From the viewpoint of compatibility with the modified maleimide resin, a structural unit derived from maleic anhydride represented by the following general formula (C-2) having a structure close to that of a maleimide group is preferable.
ＲＣ１及びＲＣ２が示す炭素数１～５の脂肪族炭化水素基としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔ－ブチル基、ｎ－ペンチル基等が挙げられる。これらの中でも、銅箔との接着性及び誘電特性の観点から、炭素数１～３の脂肪族炭化水素基が好ましく、メチル基、エチル基がより好ましい。
ＲＣ２が示す炭素数６～２０の芳香族炭化水素基としては、フェニル基、ナフチル基、アントリル基、ビフェニリル基等が挙げられる。
前記一般式（Ｃ－１）で表される構造単位おいては、ＲＣ１が水素原子であり、かつｘが０である下記式（Ｃ－１’）で表される構造単位が好ましい。
The aliphatic hydrocarbon groups having 1 to 5 carbon atoms indicated by RC1 and RC2 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group and n-. Examples include a pentyl group. Among these, an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferable, and a methyl group and an ethyl group are more preferable, from the viewpoint of adhesion to a copper foil and dielectric properties.
Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms indicated by RC2 include a phenyl group, a naphthyl group, an anthryl group, a biphenylyl group and the like.
In the structural unit represented by the general formula (C-1), the structural unit represented by the following formula ( C -1') in which RC1 is a hydrogen atom and x is 0 is preferable.
（Ｃ）共重合樹脂中における、一般式（Ｃ－１）で表される構造単位と、一般式（Ｃ－２）で表される構造単位との含有比率［（Ｃ－１）／（Ｃ－２）］（モル比）は、２～１２が好ましく、５～１０がより好ましい。当該含有比率が２以上であると、誘電特性及び耐熱性の改善効果が十分となる傾向にあり、１２以下であると、相溶性が良好となる傾向にある。さらに、［（Ｃ－１）／（Ｃ－２）］（モル比）が５～１０であると、良好な基材特性を有することに加え、（Ｂ）熱可塑性エラストマーとの相溶性に優れるスチレン由来の構造単位の含有量が好ましい範囲となることから、（Ａ）変性マレイミド樹脂と（Ｂ）熱可塑性エラストマーとの相溶性がより向上し、プリプレグの粉落ち性も良好となる。
（Ｃ）共重合樹脂中における、一般式（Ｃ－１）で表される構造単位と一般式（Ｃ－２）で表される構造単位との合計含有量は、５０質量％以上が好ましく、７０質量％以上がより好ましく、９０質量％以上がさらに好ましく、実質的に１００質量％が特に好ましい。
(C) Content ratio of the structural unit represented by the general formula (C-1) and the structural unit represented by the general formula (C-2) in the copolymer resin [(C-1) / (C). -2)] (molar ratio) is preferably 2 to 12, more preferably 5 to 10. When the content ratio is 2 or more, the effect of improving the dielectric property and the heat resistance tends to be sufficient, and when the content ratio is 12 or less, the compatibility tends to be good. Further, when [(C-1) / (C-2)] (molar ratio) is 5 to 10, in addition to having good substrate characteristics, (B) is excellent in compatibility with the thermoplastic elastomer. Since the content of the structural unit derived from styrene is in a preferable range, the compatibility between (A) the modified maleimide resin and (B) the thermoplastic elastomer is further improved, and the powder removal property of the prepreg is also improved.
The total content of the structural unit represented by the general formula (C-1) and the structural unit represented by the general formula (C-2) in the (C) copolymer resin is preferably 50% by mass or more. 70% by mass or more is more preferable, 90% by mass or more is further preferable, and substantially 100% by mass is particularly preferable.
（Ｃ）共重合樹脂は、芳香族ビニル化合物と無水マレイン酸とを共重合することにより製造することができる。
芳香族ビニル化合物としては、スチレン、１－メチルスチレン、ビニルトルエン等が挙げられる。これらは単独で用いても２種類以上を混合して用いてもよい。
さらに、芳香族ビニル化合物及び無水マレイン酸以外にも、各種の重合可能な成分を共重合させてもよい。各種の重合可能な成分としては、エチレン、プロピレン、ブタジエン等のビニル化合物などが挙げられる。
(C) The copolymerized resin can be produced by copolymerizing an aromatic vinyl compound with maleic anhydride.
Examples of the aromatic vinyl compound include styrene, 1-methylstyrene, vinyltoluene and the like. These may be used alone or in combination of two or more.
Further, in addition to the aromatic vinyl compound and maleic anhydride, various polymerizable components may be copolymerized. Examples of various polymerizable components include vinyl compounds such as ethylene, propylene and butadiene.
（Ｃ）共重合樹脂としては、市販品を用いることもでき、市販品としては、「ＳＭＡ（登録商標）ＥＦ３０」（スチレン／無水マレイン酸＝３、Ｍｗ（重量平均分子量）＝９，５００）、「ＳＭＡＥＦ４０」（スチレン／無水マレイン酸＝４、Ｍｗ＝１１，０００）、「ＳＭＡＥＦ６０」（スチレン／無水マレイン酸＝６、Ｍｗ＝１１，５００）、「ＳＭＡＥＦ８０」（スチレン／無水マレイン酸＝８、Ｍｗ＝１４，４００）（以上、サートマー社製）等が挙げられる。これらの中でも、「ＳＭＡＥＦ６０」、「ＳＭＡ－ＥＦ８０」が好ましい。 (C) A commercially available product can also be used as the copolymer resin, and the commercially available product is "SMA (registered trademark) EF30" (styrene / maleic anhydride = 3, Mw (weight average molecular weight) = 9,500). , "SMAEF40" (styrene / maleic anhydride = 4, Mw = 11,000), "SMAEF60" (styrene / maleic anhydride = 6, Mw = 11,500), "SMAEF80" (styrene / maleic anhydride = 8) , Mw = 14,400) (all manufactured by Styrene) and the like. Among these, "SMAEF60" and "SMA-EF80" are preferable.
熱硬化性樹脂組成物中の（Ｃ）共重合樹脂の含有量は、熱硬化性樹脂組成物中の樹脂成分の固形分１００質量部に対して、２～２０質量部が好ましく、３～１５質量部がより好ましく、４～１３質量部がさらに好ましい。（Ｃ）共重合樹脂の含有量が、２質量部以上であると、低誘電率化の効果が十分得られ、２０質量部以下であると、（Ｃ）共重合樹脂の分散性に優れ、耐熱性及びピール強度が優れる。 The content of the (C) copolymer resin in the thermosetting resin composition is preferably 2 to 20 parts by mass, preferably 3 to 15 parts by mass, based on 100 parts by mass of the solid content of the resin component in the thermosetting resin composition. Parts by mass are more preferable, and parts by mass of 4 to 13 are even more preferable. When the content of the (C) copolymer resin is 2 parts by mass or more, the effect of lowering the dielectric constant is sufficiently obtained, and when it is 20 parts by mass or less, the dispersibility of the (C) copolymer resin is excellent. Excellent heat resistance and peel strength.
＜（Ｄ）フッ素樹脂フィラー＞
フッ素樹脂フィラーとしては、誘電特性に優れるものであればよく、例えば、ポリテトラフルオロエチレン（ＰＴＦＥ）フィラー、テトラフルオロエチレン－パーフルオロアルキルビニルエーテル共重合体（ＰＦＡ）フィラー、テトラフルオロエチレン－ヘキサフルオロプロピレン共重合体（ＦＥＰ）フィラー、テトラフルオロエチレン－エチレン共重合体（ＥＴＦＥ）フィラー、ポリクロロトリフルオロエチレン（ＰＣＴＦＥ）フィラーなどが挙げられる。これらの中でも、ＰＴＦＥフィラー（例 アドマテックス株式会社製）が好ましい。
<(D) Fluororesin filler>
The fluororesin filler may be any one having excellent dielectric properties, for example, polytetrafluoroethylene (PTFE) filler, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA) filler, tetrafluoroethylene-hexafluoropropylene. Examples thereof include a copolymer (FEP) filler, a tetrafluoroethylene-ethylene copolymer (ETFE) filler, and a polychlorotrifluoroethylene (PCTFE) filler. Among these, PTFE filler (eg, manufactured by Admatex Co., Ltd.) is preferable.
フッ素樹脂フィラーの含有量は、樹脂組成物の固形分に対して、４０～１００質量％であり、好ましくは４５～９０質量％、より好ましくは５０～８０質量％である。フッ素樹脂フィラーの含有量が４０質量％未満であると、充分な低誘電率化に高い効果を発揮しない。一方、フッ素樹脂フィラーの含有量が８０質量％を超えると、熱膨張率が大きくなり、また耐熱性が悪化する。フッ素樹脂フィラーの平均粒径は、好ましくは０．１～５μｍ、より好ましくは０．５～３μｍである。 The content of the fluororesin filler is 40 to 100% by mass, preferably 45 to 90% by mass, and more preferably 50 to 80% by mass with respect to the solid content of the resin composition. If the content of the fluororesin filler is less than 40% by mass, it does not exert a high effect on sufficiently reducing the dielectric constant. On the other hand, when the content of the fluororesin filler exceeds 80% by mass, the coefficient of thermal expansion increases and the heat resistance deteriorates. The average particle size of the fluororesin filler is preferably 0.1 to 5 μm, more preferably 0.5 to 3 μm.
＜（Ｅ）硬化促進剤＞
本発明の熱硬化性樹脂組成物は、硬化反応を促進する観点から、さらに、（Ｅ）硬化促進剤を含有していてもよい。
（Ｅ）硬化促進剤としては、トリフェニルホスフィン等の有機リン系化合物；イミダゾール類及びその誘導体；第二級アミン類、第三級アミン類、第四級アンモニウム塩等の含窒素化合物；ジクミルパーオキサイド、２，５－ジメチル－２，５－ビス（ｔ－ブチルパーオキシ）ヘキシン－３、２，５－ジメチル－２，５－ビス（ｔ－ブチルパーオキシ）ヘキサン、α，α´－ビス（ｔ－ブチルパーオキシ）ジイソプロピルベンゼン等の有機過酸化物；ナフテン酸亜鉛、ナフテン酸コバルト、オクチル酸錫、オクチル酸コバルト等の有機金属塩などが挙げられる。（Ｅ）硬化促進剤は、単独で用いても２種類以上を混合して用いてもよい。
本発明の熱硬化性樹脂組成物が（Ｅ）硬化促進剤を含有する場合、その含有量は、熱硬化性樹脂組成物中の樹脂成分の固形分１００質量部に対して、０．１～５質量部が好ましく、０．３～２質量部がより好ましい。
<(E) Curing accelerator>
The thermosetting resin composition of the present invention may further contain (E) a curing accelerator from the viewpoint of accelerating the curing reaction.
(E) Examples of the curing accelerator include organic phosphorus compounds such as triphenylphosphine; imidazoles and derivatives thereof; nitrogen-containing compounds such as secondary amines, tertiary amines and quaternary ammonium salts; dicumyl. Peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexin-3, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, α, α'- Organic peroxides such as bis (t-butylperoxy) diisopropylbenzene; organic metal salts such as zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate and the like can be mentioned. (E) The curing accelerator may be used alone or in combination of two or more.
When the thermosetting resin composition of the present invention contains (E) a curing accelerator, the content thereof is 0.1 to 100 parts by mass with respect to 100 parts by mass of the solid content of the resin component in the thermosetting resin composition. 5 parts by mass is preferable, and 0.3 to 2 parts by mass is more preferable.
＜（Ｆ）無機充填材＞
本発明の熱硬化性樹脂組成物は、さらに、（Ｆ）無機充填材を含有していてもよい。
（Ｆ）無機充填材としては、シリカ、アルミナ、酸化チタン、マイカ、チタン酸バリウム、チタン酸ストロンチウム、炭酸アルミニウム、水酸化マグネシウム、水酸化アルミニウム、炭酸カルシウム窒化ケイ素、窒化ホウ素、タルク、炭化ケイ素、石英粉末、ガラス短繊維、ガラス微粉末、中空ガラス等が挙げられる。ガラスとしては、Ｅガラス、Ｔガラス、Ｄガラス等が好ましく挙げられる。（Ｆ）無機充填材は、単独で用いても２種類以上を混合して用いてもよい。
これらの中でも、誘電特性、耐熱性及び低熱膨張性の観点から、シリカが好ましい。シリカとしては、例えば、湿式法で製造され含水率の高い沈降シリカと、乾式法で製造され結合水等をほとんど含まない乾式法シリカが挙げられ、乾式法シリカとしてはさらに、製造法の違いにより、破砕シリカ、フュームドシリカ、溶融球状シリカ等に分類される。これらの中でも、低熱膨張性及び樹脂に充填した際の流動性の観点から、溶融球状シリカが好ましい。
<(F) Inorganic filler>
The thermosetting resin composition of the present invention may further contain (F) an inorganic filler.
(F) Examples of the inorganic filler include silica, alumina, titanium oxide, mica, barium titanate, strontium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, calcium carbonate silicon nitride, boron nitride, talc, silicon carbide, and the like. Examples thereof include quartz powder, short glass fiber, fine glass powder, and hollow glass. As the glass, E glass, T glass, D glass and the like are preferably mentioned. (F) The inorganic filler may be used alone or in combination of two or more.
Among these, silica is preferable from the viewpoint of dielectric properties, heat resistance and low thermal expansion. Examples of silica include precipitated silica manufactured by a wet method and having a high water content, and dry silica manufactured by a dry method and containing almost no bound water or the like. , Crushed silica, fumed silica, fused spherical silica and the like. Among these, fused spherical silica is preferable from the viewpoint of low thermal expansion and fluidity when filled in the resin.
（Ｆ）無機充填材の平均粒子径は、０．１～１０μｍが好ましく、０．３～８μｍがより好ましい。平均粒子径が０．１μｍ以上であると、樹脂に高充填した際の流動性を良好に保つことができ、１０μｍ以下であると、粗大粒子の混入確率を低減し、粗大粒子起因の不良の発生を抑えることができる。ここで、平均粒子径とは、粒子の全体積を１００％として粒子径による累積度数分布曲線を求めたとき、体積５０％に相当する点の粒子径のことであり、レーザ回折散乱法を用いた粒度分布測定装置等で測定することができる。
（Ｆ）無機充填材は、カップリング剤で表面処理されたものであってもよい。カップリング剤による表面処理の方式は、配合前の（Ｆ）無機充填材に対して乾式又は湿式で表面処理する方式であってもよく、表面未処理の（Ｆ）無機充填材を、他の成分に配合して組成物とした後、該組成物にシランカップリング剤を添加する、いわゆるインテグラルブレンド処理方式であってもよい。
カップリング剤としては、シラン系カップリング剤、チタネート系カップリング剤、シリコーンオリゴマー等が挙げられる。
(F) The average particle size of the inorganic filler is preferably 0.1 to 10 μm, more preferably 0.3 to 8 μm. When the average particle size is 0.1 μm or more, the fluidity when the resin is highly filled can be kept good, and when the average particle size is 10 μm or less, the mixing probability of coarse particles is reduced, and defects caused by coarse particles are caused. The occurrence can be suppressed. Here, the average particle diameter is the particle diameter at a point corresponding to a volume of 50% when the cumulative frequency distribution curve by the particle diameter is obtained with the total volume of the particles as 100%, and the laser diffraction scattering method is used. It can be measured with a particle size distribution measuring device or the like.
(F) The inorganic filler may be surface-treated with a coupling agent. The method of surface treatment with a coupling agent may be a method of surface-treating the (F) inorganic filler before compounding by a dry method or a wet method, and the surface-untreated (F) inorganic filler may be used by another method. A so-called inorganic blend treatment method may be used in which a silane coupling agent is added to the composition after blending with the components to form a composition.
Examples of the coupling agent include a silane-based coupling agent, a titanate-based coupling agent, a silicone oligomer and the like.
本発明の熱硬化性樹脂組成物が（Ｆ）無機充填材を含有する場合、その含有量は、熱硬化性樹脂組成物中の樹脂成分の固形分１００質量部に対して、１０～３００質量部が好ましく、５０～２５０質量部がより好ましい。（Ｆ）無機充填材の含有量が前記範囲内であると、成形性及び低熱膨張性が良好となる。 When the thermosetting resin composition of the present invention contains (F) an inorganic filler, the content thereof is 10 to 300% by mass with respect to 100 parts by mass of the solid content of the resin component in the thermosetting resin composition. Parts are preferable, and 50 to 250 parts by mass are more preferable. (F) When the content of the inorganic filler is within the above range, the moldability and the low thermal expansion property are good.
本発明の熱硬化性樹脂組成物が（Ｆ）無機充填材を含有する場合、必要に応じて、三本ロール、ビーズミル、ナノマイザー等の分散機で処理を行って、（Ｆ）無機充填材の分散性を改善することが好ましい。 When the thermosetting resin composition of the present invention contains (F) an inorganic filler, it is treated with a disperser such as a three-roll, a bead mill, or a nanomizer, if necessary, to obtain the (F) inorganic filler. It is preferable to improve the dispersibility.
＜その他の成分＞
本発明の（Ａ）変性マレイミド樹脂は、熱硬化性樹脂であり、単独で良好な熱硬化性を有するが、必要により、他の熱硬化性樹脂と併用することで、接着性、機械強度等を向上させることができる。
併用する熱硬化性樹脂は、特に制限されないが、例えば、エポキシ樹脂、フェノール樹脂、シアネート樹脂、イソシアネート樹脂、ベンゾオキサジン樹脂、アリル樹脂、ジシクロペンタジエン樹脂、シリコーン樹脂、トリアジン樹脂等が挙げられ、これらは単独で、あるいは２種類以上混合して使用してもよい。これらの中でも、成形性及び電気絶縁性の観点から、シアネート樹脂、ベンゾオキサジン樹脂が好ましい。
また、エポキシ樹脂を含有することで良好な接着性を有することができるが、その含有量は熱硬化性樹脂組成物の固形分中、２質量％以下であることが好ましい。エポキシ樹脂の含有量を２質量％以下とすることで、誘電特性及び保存安定性を優れたものとすることができる。
<Other ingredients>
The (A) modified maleimide resin of the present invention is a thermosetting resin and has good thermosetting properties by itself. However, if necessary, it can be used in combination with other thermosetting resins to provide adhesiveness, mechanical strength, etc. Can be improved.
The thermosetting resin to be used in combination is not particularly limited, and examples thereof include epoxy resin, phenol resin, cyanate resin, isocyanate resin, benzoxazine resin, allyl resin, dicyclopentadiene resin, silicone resin, and triazine resin. May be used alone or in combination of two or more. Among these, cyanate resin and benzoxazine resin are preferable from the viewpoint of moldability and electrical insulation.
Further, although good adhesiveness can be obtained by containing an epoxy resin, the content thereof is preferably 2% by mass or less in the solid content of the thermosetting resin composition. By setting the content of the epoxy resin to 2% by mass or less, the dielectric properties and storage stability can be improved.
本発明の熱硬化性樹脂組成物は、任意に公知の有機充填材、紫外線吸収剤、酸化防止剤、光重合開始剤、蛍光増白剤、接着性向上剤等を含有していてもよい。
有機充填材としては、ポリエチレン、ポリプロピレン樹脂等からなる樹脂フィラー、コアシェル構造の樹脂フィラーなどが挙げられる。
紫外線吸収剤としては、ベンゾトリアゾール系紫外線吸収剤が挙げられる。
酸化防止剤としては、ヒンダードフェノール系酸化防止剤、ヒンダードアミン系酸化防止剤等が挙げられる。
光重合開始剤としては、ベンゾフェノン類、ベンジルケタール類、チオキサントン系等の光重合開始剤が挙げられる。
蛍光増白剤としては、スチルベン誘導体の蛍光増白剤等が挙げられる。
接着性向上剤としては、尿素シラン等の尿素化合物、前記カップリング剤などが挙げられる。
The thermosetting resin composition of the present invention may optionally contain a known organic filler, ultraviolet absorber, antioxidant, photopolymerization initiator, fluorescent whitening agent, adhesiveness improver and the like.
Examples of the organic filler include a resin filler made of polyethylene, polypropylene resin and the like, a resin filler having a core-shell structure, and the like.
Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers.
Examples of the antioxidant include a hindered phenol-based antioxidant, a hindered amine-based antioxidant, and the like.
Examples of the photopolymerization initiator include benzophenones, benzyl ketals, thioxanthone-based photopolymerization initiators, and the like.
Examples of the fluorescent whitening agent include a fluorescent whitening agent of a stilbene derivative.
Examples of the adhesiveness improving agent include urea compounds such as ureasilane and the coupling agent.
本発明の熱硬化性樹脂組成物は、プリプレグ等の製造に用いるために、各成分が有機溶媒中に溶解又は分散されたワニスの状態としてもよい。 The thermosetting resin composition of the present invention may be in the state of a varnish in which each component is dissolved or dispersed in an organic solvent for use in the production of a prepreg or the like.
ワニスに用いる有機溶媒としては、エタノール、プロパノール、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；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；酢酸エチルエステル等のエステル系溶媒；トルエン、キシレン等の芳香族系溶媒；ジメチルアセトアミド、Ｎ－メチルピロリドン等の窒素原子含有溶媒などが挙げられる。これらの有機溶媒は、単独で用いても２種類以上を混合して用いてもよい。
これらの中でも、溶解性の観点から、プロピレングリコールモノメチルエーテル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、トルエンが好ましく、低毒性である点から、プロピレングリコールモノメチルエーテル、メチルイソブチルケトン、シクロヘキサノン、トルエンがより好ましい。
ワニスの固形分濃度は、４０～９０質量％が好ましく、５０～８０質量％がより好ましい。ワニスの固形分濃度が前記範囲内であると、塗工性を良好に保ち、適切な樹脂組成物付着量のプリプレグを得ることができる。
The organic solvent used for the varnish includes alcohol solvents such as ethanol, propanol and propylene glycol monomethyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ester solvents such as acetate ethyl ester; aromatics such as toluene and xylene. Group solvents: Nitrogen atom-containing solvents such as dimethylacetamide and N-methylpyrrolidone can be mentioned. These organic solvents may be used alone or in combination of two or more.
Among these, propylene glycol monomethyl ether methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and toluene are preferable from the viewpoint of solubility, and propylene glycol monomethyl ether, methyl isobutyl ketone, cyclohexanone, and toluene are more preferable from the viewpoint of low toxicity.
The solid content concentration of the varnish is preferably 40 to 90% by mass, more preferably 50 to 80% by mass. When the solid content concentration of the varnish is within the above range, the coatability can be kept good and a prepreg having an appropriate amount of the resin composition adhered can be obtained.
［プリプレグ］
本発明のプリプレグは、本発明の熱硬化性樹脂組成物を繊維基材に含浸させてなるものである。
本発明のプリプレグは、本発明の熱硬化性樹脂組成物を、繊維基材に含浸し、加熱等により半硬化（Ｂステージ化）して製造することができる。
繊維基材としては、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、Ｓガラス、低誘電ガラス、Ｑガラス等の無機物繊維；低誘電ガラスポリイミド、ポリエステル、ポリテトラフルオロエチレン等の有機繊維；並びにそれらの混合物などが挙げられる。
[Prepreg]
The prepreg of the present invention is obtained by impregnating a fiber base material with the thermosetting resin composition of the present invention.
The prepreg of the present invention can be produced by impregnating a fiber base material with the thermosetting resin composition of the present invention and semi-curing (B-staged) by heating or the like.
As the fiber base material, well-known materials used for various laminated plates for electrical insulating materials can be used. Examples of the material include inorganic fibers such as E glass, S glass, low dielectric glass, and Q glass; organic fibers such as low dielectric glass polyimide, polyester, and polytetrafluoroethylene; and mixtures thereof.
これらの繊維基材は、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、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、性能等により選択され、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。繊維基材の厚さは、例えば、約０．０３～０．５ｍｍのものを使用することができる。これらの繊維基材は、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、耐湿性、加工性等の面から好適である。 These fiber base materials have shapes such as woven fabrics, non-woven fabrics, robinks, chopped strand mats, and surfaced mats, but the materials and shapes are selected and required according to the intended use and performance of the molded product. Can be used alone or in combination of two or more materials and shapes. As the thickness of the fiber base material, for example, one having a thickness of about 0.03 to 0.5 mm can be used. As these fiber base materials, those surface-treated with a silane coupling agent or the like or those subjected to mechanical opening treatment are suitable from the viewpoints of heat resistance, moisture resistance, processability and the like.
本発明のプリプレグは、例えば、繊維基材に対する熱硬化性樹脂組成物の付着量（プリプレグ中の熱硬化性樹脂組成物の含有量）が、２０～９０質量％となるように、繊維基材に含浸した後、通常、１００～２００℃の温度で１～３０分間加熱乾燥し、半硬化（Ｂステージ化）させて得ることができる。 The prepreg of the present invention is, for example, a fiber base material so that the amount of the thermosetting resin composition adhered to the fiber base material (the content of the thermosetting resin composition in the prepreg) is 20 to 90% by mass. After impregnating with, it can be obtained by heating and drying at a temperature of 100 to 200 ° C. for 1 to 30 minutes and semi-curing (B-stage).
［積層板］
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。
本発明の積層板は、本発明のプリプレグを、例えば、１～２０枚重ね、その片面又は両面に、銅、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。
積層板を製造する際の成形条件は、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、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、積層板を製造することもできる。
[Laminate board]
The laminated board of the present invention is obtained by laminating and molding the prepreg of the present invention.
The laminated board of the present invention can be manufactured by laminating and molding, for example, 1 to 20 prepregs of the present invention in a configuration in which metal foils such as copper and aluminum are arranged on one side or both sides thereof. The metal foil is not particularly limited as long as it is used for electrical insulating material.
As the forming conditions when manufacturing the laminated plate, for example, the method of the laminated plate for electric insulating material and the multilayer plate can be applied, and a multi-stage press, a multi-stage vacuum press, continuous forming, an autoclave forming machine, etc. are used, and the temperature is 100 to 250. It can be molded in the range of ° C., pressure 0.2 to 10 MPa, and heating time 0.1 to 5 hours. Further, the prepreg of the present invention and the wiring board for the inner layer can be combined and laminated to produce a laminated board.
［プリント配線板］
本発明のプリント配線板は、本発明のプリプレグ又は積層板を用いて製造されたものである。
本発明のプリント配線板は、例えば、本発明の積層板の表面に回路を形成して製造することができる。また、本発明の積層板の導体層を通常のエッチング法によって配線加工し、本発明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こともできる。その後、ドリル加工又はレーザ加工によるスルーホール又はブラインドビアホールの形成と、メッキ又は導電性ペーストによる層間配線の形成を経て多層プリント配線板を製造することができる。
[Printed wiring board]
The printed wiring board of the present invention is manufactured by using the prepreg or the laminated board of the present invention.
The printed wiring board of the present invention can be manufactured, for example, by forming a circuit on the surface of the laminated board of the present invention. Further, the conductor layer of the laminated board of the present invention is wired by an ordinary etching method, and a plurality of laminated boards wire-processed via the prepreg of the present invention are laminated and heat-pressed to form a plurality of layers at once. You can also. After that, a multi-layer printed wiring board can be manufactured through the formation of through holes or blind via holes by drilling or laser processing and the formation of interlayer wiring by plating or conductive paste.
［高速通信対応モジュール］
本発明の高速通信対応モジュールは、本発明のプリント配線板を用いて製造される高速通信対応モジュールである。
本発明の高速通信対応モジュールは、例えば、本発明のプリント配線板に半導体チップ等を実装してなる通信モジュール等であり、特にワイヤレス通信機器、ネットワークインフラ機器、等の高周波域の信号を利用し、情報通信量及び速度が大きい用途に好適である。
[High-speed communication compatible module]
The high-speed communication compatible module of the present invention is a high-speed communication compatible module manufactured by using the printed wiring board of the present invention.
The high-speed communication compatible module of the present invention is, for example, a communication module or the like in which a semiconductor chip or the like is mounted on the printed wiring board of the present invention, and particularly uses signals in a high frequency range such as wireless communication equipment and network infrastructure equipment. , Suitable for applications with high information communication volume and speed.
次に、下記の実施例により本発明をさらに詳しく説明するが、これらの実施例は本発明を制限するものではない。
なお、各例で得られた熱硬化性樹脂組成物及び銅張積層板について以下の評価を行った
。
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 thermosetting resin composition and the copper-clad laminate obtained in each example were evaluated as follows.
（１）ガラス転移温度（Ｔｇ）
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×５ｍｍの評価基板を作製し、ＴＭＡ（熱機械分析）装置（ＴＡインスツルメント社製、商品名：Ｑ４００）を用いて圧縮法で熱機械分析を行った。評価基板を前記装置にＸ方向に装着後、荷重５ｇ、昇温速度１０℃／分の測定条件にて連続して２回測定した。２回目の測定における熱膨張曲線の異なる接線の交点で示される点を求め、これをガラス転移温度（Ｔｇ）とした。
(1) Glass transition temperature (Tg)
A 5 mm × 5 mm evaluation board from which the copper foil was removed was prepared by immersing the copper-clad laminate in a copper etching solution, and a TMA (thermomechanical analysis) device (manufactured by TA Instruments, trade name: Q400) was used. Thermomechanical analysis was performed by the compression method. After the evaluation substrate was mounted on the apparatus in the X direction, the measurement was carried out twice in succession under the measurement conditions of a load of 5 g and a heating rate of 10 ° C./min. The points indicated by the intersections of the different tangents of the thermal expansion curves in the second measurement were obtained and used as the glass transition temperature (Tg).
（２）熱膨張率
銅張積層板を銅エッチング液に浸漬することにより銅箔を取り除いた５ｍｍ×５ｍｍの評価基板を作製し、ＴＭＡ（熱機械分析）装置（ＴＡインスツルメント社製、商品名：Ｑ４００）を用いて圧縮法で熱機械分析を行った。評価基板を前記装置にＸ方向に装着後、荷重５ｇ、昇温速度１０℃／分の測定条件にて連続して２回測定した。２回目の測定における３０℃から１００℃までの平均熱膨張率を算出し、これを熱膨張率の値とした。
(2) Coefficient of thermal expansion A 5 mm × 5 mm evaluation substrate from which the copper foil was removed was produced by immersing a copper-clad laminate in a copper etching solution, and a TMA (thermomechanical analysis) device (manufactured by TA Instrument) was manufactured. Name: Q400) was used to perform thermomechanical analysis by the compression method. After the evaluation substrate was mounted on the apparatus in the X direction, the measurement was carried out twice in succession under the measurement conditions of a load of 5 g and a heating rate of 10 ° C./min. The average coefficient of thermal expansion from 30 ° C. to 100 ° C. in the second measurement was calculated and used as the value of the coefficient of thermal expansion.
（３）誘電特性（比誘電率及び誘電正接）
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１００ｍｍ×２ｍｍの評価基板を作製し、空洞共振機装置（株式会社関東電子応用開発製）を用いて、周波数１０ＧＨｚでの比誘電率及び誘電正接を測定した。
(3) Dielectric properties (relative permittivity and dielectric loss tangent)
A 100 mm × 2 mm evaluation board from which the copper foil was removed was prepared by immersing the copper-clad laminate in a copper etching solution, and a cavity resonator device (manufactured by Kanto Denshi Applied Development Co., Ltd.) was used to produce a ratio at a frequency of 10 GHz. The permittivity and the dielectric loss tangent were measured.
（４）銅付きはんだ耐熱性
銅張積層板を２５ｍｍ×２５ｍｍの大きさに切り出した評価基板を作製し、該評価基板を温度２８８℃のはんだ浴に、最大で６０分間フロートしながら、外観を観察することにより、膨れが発生するまでの時間を測定した。評価結果は、６０分間フロートした時点で膨れが確認されなかったものを「＞６０」として表１に記載した。
(4) Heat resistance of solder with copper A copper-clad laminate was cut out to a size of 25 mm × 25 mm to prepare an evaluation board, and the evaluation board was floated in a solder bath at a temperature of 288 ° C for up to 60 minutes to give an appearance. By observing, the time until the swelling occurred was measured. The evaluation results are shown in Table 1 as ">60" in which no swelling was confirmed after floating for 60 minutes.
（５）吸水半銅付はんだ耐熱性
銅張積層板を５０ｍｍ×５０ｍｍの大きさに切断し、一方の表面のみ半面銅を残し、他方の表面については銅エッチング液に浸漬して全面銅を除去することにより５０ｍｍ×５０ｍｍの半銅付評価基板を作製した。プレッシャークッカーテスト（ＰＣＴ）用装置（株式会社平山製作所製）（条件：１２１℃、２．２気圧）中で５時間処理した後の半銅付評価基板を、２８８℃のはんだ浴にそれぞれ２０秒間浸漬後、外観を目視で観察することにより吸水半銅付はんだ耐熱性を評価した。評価結果は、膨れが確認されなかったものを「Ａ」、膨れが確認されたものを「Ｂ」として表１に記載した。
(5) Solder with water-absorbing semi-copper Heat resistance Copper-clad laminate is cut to a size of 50 mm x 50 mm, leaving half-sided copper on only one surface, and immersing the other surface in a copper etching solution to remove copper on the entire surface. By doing so, an evaluation substrate with a half copper of 50 mm × 50 mm was produced. The evaluation board with half-copper after being treated in a pressure cooker test (PCT) device (manufactured by Hirayama Seisakusho Co., Ltd.) (condition: 121 ° C, 2.2 atm) for 5 hours is placed in a solder bath at 288 ° C for 20 seconds each. After immersion, the heat resistance of the solder with water-absorbing half-copper was evaluated by visually observing the appearance. The evaluation results are shown in Table 1 as "A" in which no swelling was confirmed and "B" in which swelling was confirmed.
製造例１：〔変性マレイミド樹脂（Ａ－１）の製造〕
温度計、攪拌装置及び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、両末端ジアミン変性シロキサン（信越化学工業株式会社製、商品名：Ｘ－２２－１６１Ａ）１５．９ｇと、３，３´－ジエチル－４，４´－ジアミノジフェニルメタン（日本化薬株式会社製、商品名：ＫＡＹＡＨＡＲＤ（登録商標）Ａ－Ａ）２８．６ｇと、ビス（４－マレイミドフェニル）メタン（ケイ・アイ化成株式会社製、商品名：ＢＭＩ）２８０．５ｇと、プロピレングリコールモノメチルエーテル２００．０ｇと、を入れ、１２６℃で還流させながら５時間反応させて変性マレイミド樹脂（Ａ－１）の溶液を得た。
Production Example 1: [Production of Modified Maleimide Resin (A-1)]
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, and a double-ended diamine-modified siloxane (manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name: X-22-161A) ) 15.9 g, 3,3'-diethyl-4,4'-diaminodiphenylmethane (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYAHARD (registered trademark) AA) 28.6 g, and bis (4-maleimide). Phenyl) Methane (manufactured by Keiai Kasei Co., Ltd., trade name: BMI) 280.5 g and propylene glycol monomethyl ether 200.0 g are added and reacted at 126 ° C. for 5 hours to modify a modified maleimide resin (A). The solution of -1) was obtained.
製造例２：〔変性マレイミド樹脂（Ａ－２）の製造〕
温度計、攪拌装置及び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、両末端ジアミン変性シロキサン（信越化学工業株式会社製、商品名：Ｘ－２２－１６１Ｂ）１４．４ｇと、２，２´－ビス［４－（４－アミノフェノキシ）フェニル］プロパン（和歌山精化工業株式会社製、商品名：ＢＡＰＰ）５６．９ｇと、ビス（４－マレイミドフェニル）メタン（ケイ・アイ化成株式会社製、商品名：ＢＭＩ）２５３．７ｇと、プロピレングリコールモノメチルエーテル２００．０ｇと、を入れ、１２６℃で還流させながら５時間反応させて変性マレイミド樹脂（Ａ－２）の溶液を得た。
Production Example 2: [Production of Modified Maleimide Resin (A-2)]
In a reaction vessel with a volume of 2 liters that can be heated and cooled with a thermometer, a stirrer and a water meter with a reflux cooling tube, both-ended diamine-modified siloxane (manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name: X-22-161B) ) 14.4 g and 2,2'-bis [4- (4-aminophenoxy) phenyl] propane (manufactured by Wakayama Seika Kogyo Co., Ltd., trade name: BAPP) 56.9 g and bis (4-maleimidephenyl) 253.7 g of methane (manufactured by Keiai Kasei Co., Ltd., trade name: BMI) and 200.0 g of propylene glycol monomethyl ether are added and reacted at 126 ° C. for 5 hours to make a modified maleimide resin (A-2). ) Was obtained.
製造例３：〔変性マレイミド樹脂（Ａ－３）の製造〕
温度計、攪拌装置及び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、両末端ジアミン変性シロキサン（信越化学工業株式会社製、商品名：Ｘ－２２－１６１Ｂ）１５．６ｇと、３，３´－ジエチル－４，４´－ジアミノジフェニルメタン（日本化薬株式会社製、商品名：ＫＡＹＡＨＡＲＤ Ａ－Ａ）２１．８ｇと、２，２－ビス［４－（４－マレイミドフェノキシ）フェニル］プロパン（大和化成工業株式会社製、商品名：ＢＭＩ－４０００）２７４．２ｇと、プロピレングリコールモノメチルエーテル：２００．０ｇと、を入れ、１２０℃で４時間反応させて変性マレイミド樹脂（Ａ－３）の溶液を得た。
Production Example 3: [Production of Modified Maleimide Resin (A-3)]
In a reaction vessel with a volume of 2 liters that can be heated and cooled with a thermometer, a stirrer and a moisture meter with a reflux cooling tube, both-ended diamine-modified siloxane (manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name: X-22-161B) ) 15.6 g, 3,3'-diethyl-4,4'-diaminodiphenylmethane (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYAHARD A-A) 21.8 g, 2,2-bis [4- (4) 4-Maleimide phenoxy) phenyl] propane (manufactured by Daiwa Kasei Kogyo Co., Ltd., trade name: BMI-4000) 274.2 g and propylene glycol monomethyl ether: 200.0 g are added and reacted at 120 ° C. for 4 hours for modification. A solution of maleimide resin (A-3) was obtained.
製造例４：〔変性マレイミド樹脂（Ａ－４）の製造〕
温度計、攪拌装置及び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、両末端ジアミン変性シロキサン（信越化学工業株式会社製、商品名：Ｘ－２２－１６１Ａ）１６．６ｇと、２，２´－ビス［４－（４－アミノフェノキシ）フェニル］プロパン（和歌山精化工業株式会社製、商品名：ＢＡＰＰ）２５．５ｇと、２，２－ビス［４－（４－マレイミドフェノキシ）フェニル］プロパン（大和化成工業株式会社製、商品名：ＢＭＩ－４０００）２９２．６ｇと、プロピレングリコールモノメチルエーテル２００．０ｇと、を入れ、１２６℃で還流させながら６時間反応させて変性マレイミド樹脂（Ａ－４）の溶液を得た。
Production Example 4: [Production of Modified Maleimide Resin (A-4)]
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 cooling tube, and a double-ended diamine-modified siloxane (manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name: X-22-161A) ) 16.6 g and 2,2'-bis [4- (4-aminophenoxy) phenyl] propane (manufactured by Wakayama Seika Kogyo Co., Ltd., trade name: BAPP) 25.5 g and 2,2-bis [4 -(4-Maleimide phenoxy) phenyl] Propane (manufactured by Daiwa Kasei Kogyo Co., Ltd., trade name: BMI-4000) 292.6 g and propylene glycol monomethyl ether 200.0 g are added and refluxed at 126 ° C for 6 hours. The reaction was carried out to obtain a solution of the modified maleimide resin (A-4).
実施例１～８及び比較例１～５
表１に示す配合割合（表中の数値は固形分の質量部であり、溶液（有機溶媒を除く）又は分散液の場合は固形分換算量である。）に従って組成物を配合及び混合し、溶媒にメチルエチルケトン及びトルエンを用いて固形分濃度６５質量％のワニスを作製した。
次に、このワニスを厚さ０．０３ｍｍのＥガラスクロス（日東紡績株式会社製）に含浸塗工し、１６０℃で５分間加熱乾燥し、熱硬化性樹脂組成物の含有量が７１質量％のプリプレグを得た。
このプリプレグを８枚重ね、１２μｍの電解銅箔を上下に配置し、圧力２．５ＭＰａ、温度２００℃で９０分間プレスを行って、銅張積層板を得た。得られた銅張積層板の評価結果を表１に示す。
Examples 1 to 8 and Comparative Examples 1 to 5
The composition was blended and mixed according to the blending ratio shown in Table 1 (the numerical value in the table is the mass part of the solid content, which is the solid content conversion amount in the case of a solution (excluding the organic solvent) or the dispersion liquid). A varnish having a solid content concentration of 65% by mass was prepared by using methyl ethyl ketone and toluene as a solvent.
Next, this varnish was impregnated and coated on an E glass cloth (manufactured by Nitto Boseki Co., Ltd.) having a thickness of 0.03 mm, and dried by heating at 160 ° C. for 5 minutes, and the content of the thermosetting resin composition was 71% by mass. I got the prepreg of.
Eight prepregs were stacked, 12 μm electrolytic copper foils were placed one above the other, and pressed at a pressure of 2.5 MPa and a temperature of 200 ° C. for 90 minutes to obtain a copper-clad laminate. Table 1 shows the evaluation results of the obtained copper-clad laminate.
配合に用いた各成分について以下に示す。 Each component used in the formulation is shown below.
［（Ａ）変性マレイミド樹脂］
変性マレイミド樹脂（Ａ－１）：製造例１で調製した変性マレイミド樹脂（Ａ－１）
変性マレイミド樹脂（Ａ－２）：製造例２で調製した変性マレイミド樹脂（Ａ－２）
変性マレイミド樹脂（Ａ－３）：製造例３で調製した変性マレイミド樹脂（Ａ－３）
変性マレイミド樹脂（Ａ－４）：製造例４で調製した変性マレイミド樹脂（Ａ－４）
[(A) Modified maleimide resin]
Modified maleimide resin (A-1): Modified maleimide resin (A-1) prepared in Production Example 1.
Modified maleimide resin (A-2): Modified maleimide resin (A-2) prepared in Production Example 2.
Modified Maleimide Resin (A-3): Modified Maleimide Resin (A-3) Prepared in Production Example 3
Modified Maleimide Resin (A-4): Modified Maleimide Resin (A-4) Prepared in Production Example 4
［（Ｂ）熱可塑性エラストマー］
・タフテックＨ１０５１：水添スチレン－ブタジエン共重合樹脂（スチレン量：４２質量％）（旭化成ケミカルズ株式会社製）
・タフテックＨ１０５３：水添スチレン－ブタジエン共重合樹脂（スチレン量：２９質量％）（旭化成ケミカルズ株式会社製）
・タフテックＭ１９１３：カルボン酸変性水添スチレン－ブタジエン共重合樹脂（スチレン量：３０質量％）（旭化成ケミカルズ株式会社製）
・セプトン２００２：水添スチレン－イソプレン共重合樹脂（スチレン量：３０質量％）（株式会社クラレ製）
[(B) Thermoplastic Elastomer]
Tough Tech H1051: Hydrogenated Styrene-butadiene copolymer resin (styrene amount: 42% by mass) (manufactured by Asahi Kasei Chemicals Co., Ltd.)
-Tough Tech H1053: Hydrogenated styrene-butadiene copolymer resin (styrene amount: 29% by mass) (manufactured by Asahi Kasei Chemicals Co., Ltd.)
Tough Tech M1913: Carboxylic acid-modified hydrogenated styrene-butadiene copolymer resin (styrene amount: 30% by mass) (manufactured by Asahi Kasei Chemicals Co., Ltd.)
Septon 2002: Hydrogenated styrene-isoprene copolymer resin (styrene amount: 30% by mass) (manufactured by Kuraray Co., Ltd.)
［（Ｃ）芳香族ビニル化合物由来の構造単位と無水マレイン酸由来の構造単位とを含有する共重合樹脂］
・ＳＭＡ－ＥＦ８０（スチレン／無水マレイン酸モル比＝８）（サートマー社製）
[(C) Copolymer resin containing a structural unit derived from an aromatic vinyl compound and a structural unit derived from maleic anhydride]
SMA-EF80 (styrene / maleic anhydride molar ratio = 8) (manufactured by Sartmer)
［（Ｄ）フッ素樹脂フィラー］
・ＰＴＦＥフィラー：（株式会社アドマテックス製）
[(D) Fluororesin filler]
-PTFE filler: (manufactured by Admatex Co., Ltd.)
［（Ｅ）硬化促進剤］
・ＴＰＰ－ＭＫ：テトラフェニルホスホニウムテトラ－ｐ－トリルボレート（北興化学工業株式会社製）
・パーブチル－Ｐ：α，α´－ビス（ｔ－ブチルパーオキシ）ジイソプロピルベンゼン（日油株式会社製）
・２Ｅ４ＭＺ：２－エチル－４－メチルイミダゾール（四国化成工業株式会社製）
・２Ｅ４ＭＺ－Ａ：２，４－ジアミノ－６－［２´－エチル－４´－メチルイミダゾリル－（１´）］－エチル－ｓ－トリアジン（四国化成工業株式会社製）
[(E) Curing accelerator]
-TPP-MK: Tetraphenylphosphonium tetra-p-tolylborate (manufactured by Hokuko Chemical Industry Co., Ltd.)
-Perbutyl-P: α, α'-bis (t-butylperoxy) diisopropylbenzene (manufactured by NOF CORPORATION)
2E4MZ: 2-ethyl-4-methylimidazole (manufactured by Shikoku Chemicals Corporation)
2E4MZ-A: 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')] -ethyl-s-triazine (manufactured by Shikoku Chemicals Corporation)
［（Ｆ）無機充填材］
・球状溶融シリカ（株式会社アドマテックス製、平均粒子径：０．５μｍ）
[(F) Inorganic filler]
・ Spherical fused silica (manufactured by Admatex Co., Ltd., average particle size: 0.5 μm)
表１から明らかなように、実施例１～８で得られた積層板は、ガラス転移温度、熱膨張率、誘電特性、銅付はんだ耐熱性、吸水半銅付はんだ耐熱性の全てに優れている。一方、比較例１～５は、誘電特性、低熱膨張性又は吸水半銅付はんだ耐熱性いずれかの特性に劣っている。 As is clear from Table 1, the laminated plates obtained in Examples 1 to 8 are excellent in all of the glass transition temperature, the coefficient of thermal expansion, the dielectric property, the heat resistance of solder with copper, and the heat resistance of solder with water-absorbing semi-copper. There is. On the other hand, Comparative Examples 1 to 5 are inferior in either the dielectric property, the low thermal expansion property, or the heat resistance of the solder with water-absorbing half-copper.
本発明の熱硬化性樹脂組成物を用いて得られるプリント配線板は、高ガラス転移温度、低熱膨張性、低誘電特性、高耐熱性を有するため、高集積化された半導体パッケージ及び高速通信に対応した電子機器用プリント配線板として有用である。 The printed wiring board obtained by using the thermosetting resin composition of the present invention has high glass transition temperature, low thermal expansion, low dielectric property, and high heat resistance, so that it can be used for highly integrated semiconductor packages and high-speed communication. It is useful as a printed wiring board for compatible electronic devices.
Claims (13)
（Ｂ）水添スチレン系熱可塑性エラストマーと、
（Ｃ）芳香族ビニル化合物由来の構造単位とカルボン酸無水物由来の構造単位とを含有する共重合樹脂と、
（Ｄ）フッ素樹脂フィラーと、
を含有する熱硬化性樹脂組成物であって、
前記（Ｄ）フッ素樹脂フィラーの含有量が、熱硬化性樹脂組成物の固形分に対して４０～８０質量％である、熱硬化性樹脂組成物。 (A) An addition reaction product of a maleimide compound (a1) having at least two N-substituted maleimide groups in one molecule and an amine compound (a2) having at least two primary amino groups in one molecule. ,
(B) Hydrogenated styrene-based thermoplastic elastomer and
(C) A copolymer resin containing a structural unit derived from an aromatic vinyl compound and a structural unit derived from a carboxylic acid anhydride,
(D) Fluororesin filler and
A thermosetting resin composition containing
A thermosetting resin composition in which the content of the fluororesin filler (D) is 40 to 80% by mass with respect to the solid content of the thermosetting resin composition .
（式中、ＲＣ１は、水素原子又は炭素数１～５の脂肪族炭化水素基を示し、ＲＣ２は、各々独立に、炭素数１～５の脂肪族炭化水素基又は炭素数６～２０の芳香族炭化水素基を示し、ｘは、０～３の整数を示す。） The structural unit derived from the aromatic vinyl compound is represented by the following general formula (C-1), and the structural unit derived from the carboxylic acid anhydride is derived from maleic anhydride represented by the following general formula (C-2). The thermosetting resin composition according to claim 1, which is the structural unit of the above.
(In the formula, RC1 represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms, and RC2 independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or 6 to 20 carbon atoms. Indicates an aromatic hydrocarbon group of, and x indicates an integer of 0 to 3.)
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| JPS5823851A (en) * | 1982-07-29 | 1983-02-12 | Mitsubishi Gas Chem Co Inc | Heat-resistant resin composition |
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