JP7274114B2 - Thermosetting resin compositions, prepregs, laminates, printed wiring boards, and high-speed communication modules - Google Patents
Thermosetting resin compositions, prepregs, laminates, printed wiring boards, and high-speed communication modules Download PDFInfo
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- JP7274114B2 JP7274114B2 JP2022031039A JP2022031039A JP7274114B2 JP 7274114 B2 JP7274114 B2 JP 7274114B2 JP 2022031039 A JP2022031039 A JP 2022031039A JP 2022031039 A JP2022031039 A JP 2022031039A JP 7274114 B2 JP7274114 B2 JP 7274114B2
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- thermosetting resin
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- 239000011342 resin composition Substances 0.000 title claims description 65
- 229920001187 thermosetting polymer Polymers 0.000 title claims description 62
- 238000004891 communication Methods 0.000 title claims description 15
- 229920005989 resin Polymers 0.000 claims description 93
- 239000011347 resin Substances 0.000 claims description 93
- -1 maleimide compound Chemical class 0.000 claims description 88
- 125000004432 carbon atom Chemical group C* 0.000 claims description 52
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 38
- 229920006026 co-polymeric resin Polymers 0.000 claims description 28
- 125000001931 aliphatic group Chemical group 0.000 claims description 27
- 239000003063 flame retardant Substances 0.000 claims description 25
- 229910052698 phosphorus Inorganic materials 0.000 claims description 23
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 21
- 239000011574 phosphorus Substances 0.000 claims description 21
- 239000011256 inorganic filler Substances 0.000 claims description 19
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 19
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 18
- 125000003277 amino group Chemical group 0.000 claims description 16
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 15
- 229920002554 vinyl polymer Polymers 0.000 claims description 14
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 11
- 239000000835 fiber Substances 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 9
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 9
- 238000007259 addition reaction Methods 0.000 claims description 8
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 8
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 48
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 36
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 20
- 229910052751 metal Inorganic materials 0.000 description 18
- 239000002184 metal Substances 0.000 description 18
- 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
- 238000004519 manufacturing process Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- 150000003839 salts Chemical class 0.000 description 14
- 125000002947 alkylene group Chemical group 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 13
- 239000011521 glass Substances 0.000 description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 12
- 239000000758 substrate Substances 0.000 description 12
- 125000001118 alkylidene group Chemical group 0.000 description 11
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 10
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 10
- 229920001971 elastomer Polymers 0.000 description 10
- 239000000806 elastomer Substances 0.000 description 10
- 239000003822 epoxy resin Substances 0.000 description 10
- 229920000647 polyepoxide Polymers 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 229910000679 solder Inorganic materials 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 8
- 239000011889 copper foil Substances 0.000 description 8
- 125000000524 functional group Chemical group 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 229910019142 PO4 Inorganic materials 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 7
- 235000021317 phosphate Nutrition 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 239000007822 coupling agent Substances 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 239000004065 semiconductor Substances 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
- 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 5
- 150000007513 acids Chemical class 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
- 230000000694 effects Effects 0.000 description 5
- 238000005530 etching Methods 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
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 5
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 239000001294 propane Substances 0.000 description 5
- 150000003440 styrenes Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000008961 swelling Effects 0.000 description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- 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 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
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000003963 antioxidant agent 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
- 238000010438 heat treatment Methods 0.000 description 4
- 239000012796 inorganic flame retardant Substances 0.000 description 4
- 125000000468 ketone group Chemical group 0.000 description 4
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 125000004437 phosphorous atom Chemical group 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 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
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- 125000000732 arylene group Chemical group 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000011810 insulating material Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- 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 3
- 239000010452 phosphate Substances 0.000 description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 3
- 229920003192 poly(bis maleimide) Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 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
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 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
- 229920000388 Polyphosphate Polymers 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 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
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 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 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005282 brightening Methods 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- 239000003795 chemical substances by application 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
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 2
- 230000002542 deteriorative effect Effects 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
- 239000004744 fabric Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000009413 insulation Methods 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
- 150000002576 ketones Chemical class 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical class CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 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
- 125000001477 organic nitrogen group Chemical group 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 150000003018 phosphorus compounds Chemical class 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000001205 polyphosphate Substances 0.000 description 2
- 235000011176 polyphosphates Nutrition 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
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 150000003608 titanium Chemical class 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
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- OWICEWMBIBPFAH-UHFFFAOYSA-N (3-diphenoxyphosphoryloxyphenyl) diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1)(=O)OC1=CC=CC=C1 OWICEWMBIBPFAH-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
- LTGTVRSJQNJRCS-UHFFFAOYSA-N 1-[3-[1-[3-(2,5-dioxopyrrol-1-yl)phenoxy]-4-phenylcyclohexa-2,4-dien-1-yl]oxyphenyl]pyrrole-2,5-dione Chemical group O=C1C=CC(=O)N1C1=CC=CC(OC2(C=CC(=CC2)C=2C=CC=CC=2)OC=2C=C(C=CC=2)N2C(C=CC2=O)=O)=C1 LTGTVRSJQNJRCS-UHFFFAOYSA-N 0.000 description 1
- MBNMVPPPCZKPIJ-UHFFFAOYSA-N 1-[3-[3-[3-(2,5-dioxopyrrol-1-yl)phenoxy]phenoxy]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(OC=2C=C(OC=3C=C(C=CC=3)N3C(C=CC3=O)=O)C=CC=2)=C1 MBNMVPPPCZKPIJ-UHFFFAOYSA-N 0.000 description 1
- XUYYHEMUYJTNNL-UHFFFAOYSA-N 1-[3-[4-[1-[4-[3-(2,5-dioxopyrrol-1-yl)phenoxy]phenyl]ethyl]phenoxy]phenyl]pyrrole-2,5-dione Chemical compound C=1C=C(OC=2C=C(C=CC=2)N2C(C=CC2=O)=O)C=CC=1C(C)C(C=C1)=CC=C1OC(C=1)=CC=CC=1N1C(=O)C=CC1=O XUYYHEMUYJTNNL-UHFFFAOYSA-N 0.000 description 1
- TZMMMLIFBVCSKD-UHFFFAOYSA-N 1-[3-[4-[2-[4-[3-(2,5-dioxopyrrol-1-yl)phenoxy]phenyl]butan-2-yl]phenoxy]phenyl]pyrrole-2,5-dione Chemical compound C=1C=C(OC=2C=C(C=CC=2)N2C(C=CC2=O)=O)C=CC=1C(C)(CC)C(C=C1)=CC=C1OC(C=1)=CC=CC=1N1C(=O)C=CC1=O TZMMMLIFBVCSKD-UHFFFAOYSA-N 0.000 description 1
- OYQKHVOHNOPHCU-UHFFFAOYSA-N 1-[3-[4-[2-[4-[3-(2,5-dioxopyrrol-1-yl)phenoxy]phenyl]ethyl]phenoxy]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(OC=2C=CC(CCC=3C=CC(OC=4C=C(C=CC=4)N4C(C=CC4=O)=O)=CC=3)=CC=2)=C1 OYQKHVOHNOPHCU-UHFFFAOYSA-N 0.000 description 1
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- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 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
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000002250 progressing effect Effects 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
- 230000035484 reaction time Effects 0.000 description 1
- 239000013557 residual solvent Substances 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
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 125000004436 sodium atom Chemical group 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
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 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
- 230000001629 suppression Effects 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 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
- 238000010998 test method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 230000000930 thermomechanical effect Effects 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
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- KOWVWXQNQNCRRS-UHFFFAOYSA-N tris(2,4-dimethylphenyl) phosphate Chemical compound CC1=CC(C)=CC=C1OP(=O)(OC=1C(=CC(C)=CC=1)C)OC1=CC=C(C)C=C1C KOWVWXQNQNCRRS-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
- 229910052725 zinc Inorganic materials 0.000 description 1
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。 TECHNICAL FIELD The present invention relates to a thermosetting resin composition, a prepreg, a laminate, a printed wiring board, and a high-speed communication module.
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。 Along with the trend toward smaller size and higher performance of electronic devices in recent years, printed wiring boards are progressing toward higher wiring density and higher integration. There is a growing demand for improved reliability due to improved heat resistance and the like. For such applications, particularly semiconductor package substrate applications, it is required to have both excellent heat resistance and low thermal expansion. In addition, as the amount and speed of information communication in network infrastructure equipment, large-scale computers, etc. has increased significantly, the semiconductor packages mounted in these electronic equipment must be compatible with higher frequencies. There is a need for substrate materials with low dielectric constant and low dissipation factor.
プリント配線板用の積層板としては、エポキシ樹脂を主剤とした樹脂組成物とガラスクロスとを含むプリプレグを硬化及び一体成形化したものが一般的である。
エポキシ樹脂は、絶縁性、耐熱性、コスト等のバランスに優れるが、近年の半導体パッケージ基板用途において求められる、優れた耐熱性及び低熱膨張性に対応するには、さらなる改良が必要となる。エポキシ樹脂は熱膨張率が大きいため、芳香環を有するエポキシ樹脂の選択及びシリカ等の無機充填材の高充填化によって低熱膨張性化を図っている（例えば、特許文献１参照）。しかし、無機充填材の充填量を増やすことは、吸湿による絶縁信頼性の低下、樹脂と配線層との密着不足、プレス成形不良等を起こすことが知られており、無機充填材の高充填化のみによる低熱膨張性化には限界があった。さらに、エポキシ樹脂を用いた場合、良好な比誘電率及び誘電正接を有する樹脂硬化物は得ることが困難であり、高速通信用材料としては、誘電特性の改善が求められていた。
Laminates for printed wiring boards are generally produced by curing and integrally molding a prepreg containing a resin composition containing an epoxy resin as a main component and glass cloth.
Epoxy resins have an excellent balance of insulating properties, heat resistance, cost, etc., but further improvements are required in order to meet the excellent heat resistance and low thermal expansion properties required for semiconductor package substrate applications in recent years. Since epoxy resins have a large coefficient of thermal expansion, attempts are made to reduce thermal expansion by selecting epoxy resins having aromatic rings and by increasing the filling of inorganic fillers such as silica (see, for example, Patent Document 1). However, increasing the amount of inorganic fillers is known to cause deterioration in insulation reliability due to moisture absorption, insufficient adhesion between the resin and wiring layers, and poor press molding. There was a limit to low thermal expansion by chisel. Furthermore, when an epoxy resin is used, it is difficult to obtain a resin cured product having a good relative permittivity and 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２参照）。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 obtained by introducing a siloxane skeleton into a bismaleimide resin has excellent heat resistance and low thermal expansion without excessively increasing the content of the inorganic filler (see, for example, Patent Document 2). ). In addition, the modified maleimide resin has a low dielectric constant and a low dielectric loss tangent compared to epoxy resins, but has not yet achieved the dielectric constant and 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３参照）、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。
Laminates to which a polybutadiene resin is added as a thermoplastic elastomer have been studied for the purpose of improving dielectric properties. The laminate has excellent dielectric properties, but the prepreg is sticky, has low compatibility with other thermosetting resins, has a large shrinkage rate when cured, and has copper foil and the like. However, there are 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 3). It is necessary to increase the copolymerization ratio of the aromatic compound, and in that case, the problem of deterioration in heat resistance arises.
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４参照）。特許文献４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。 Moreover, in recent years, warping due to the difference in coefficient of thermal expansion between the chip and the substrate and curing shrinkage of the substrate has become a problem in semiconductor package substrates. Methods of reducing the coefficient of thermal expansion of the substrate and reducing the curing shrinkage of the resin have been investigated as methods for improving the warpage. As an approach example, a method of using a modified maleimide resin and a thermoplastic elastomer together has been proposed (see, for example, Patent Document 4). In Patent Document 4, the thermoplastic elastomer is used for the purpose of reducing the cure shrinkage of the resin. Here, when a hydrogenated styrene-based elastomer is used as the thermoplastic elastomer, it exhibits a low dielectric constant and a low dielectric loss tangent because the polarity of the skeleton is very small. Therefore, by using a modified maleimide resin and a hydrogenated styrene-based elastomer together, it is possible to achieve both low thermal expansion and excellent dielectric properties (low dielectric constant and low dielectric loss tangent).
さらに、プリント配線板用の積層板において、環境に配慮したハロゲンフリーで難燃性を有することが求められる。しかしながら、難燃剤としてリン系や無機系難燃剤を添加することで難燃性は確保することが出来るが、難燃剤の種類や量を適正に配合しない場合、耐熱性の低下、誘電特性の悪化が生じてしまう。例えば、リン系難燃剤は、硬化に寄与せず可塑剤として働くため、硬化不足による耐熱性の悪化を起こす。また、無機系難燃剤は、樹脂組成物の吸水率を高くし誘電特性の悪化を起こす。 Furthermore, laminates for printed wiring boards are required to be environment-friendly, halogen-free, and flame-retardant. However, although flame retardancy can be ensured by adding a phosphorus-based or inorganic flame retardant as a flame retardant, if the type and amount of flame retardant are not properly blended, heat resistance will decrease and dielectric properties will deteriorate. occurs. For example, a phosphorus-based flame retardant does not contribute to curing and acts as a plasticizer, and thus causes deterioration in heat resistance due to insufficient curing. In addition, the inorganic flame retardant increases the water absorption rate of the resin composition and deteriorates the dielectric properties.
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。 Although the resin composition using the modified maleimide resin and the thermoplastic elastomer together has no problem in general heat resistance, it is resistant to heat under severe conditions accompanying recent high-density mounting and multi-layered construction of printed wiring boards. That is, there is a problem that the heat resistance after absorbing water is inferior. According to the studies of the present inventors, this is considered to be due to insufficient compatibility between the modified maleimide resin and the thermoplastic elastomer.
本発明の課題は、こうした現状に鑑み、ハロゲンフリーで耐熱性の低下や誘電特性の悪化を抑制しつつ難燃性を備え、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 the current situation, the problem of the present invention is to provide a halogen-free, flame retardant, excellent heat resistance, low thermal expansion, low dielectric constant and low dielectric loss tangent while suppressing deterioration of heat resistance and dielectric properties. and a prepreg, laminate, printed wiring board, and high-speed communication module using the same.
本発明者らは、前記目的を達成するために鋭意研究を重ねた結果、特定の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、難燃剤としてリン系難燃剤を選択することで、特性を悪化させることなく充分な難燃性を付与することができた。
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、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）難燃剤としてリン系難燃剤と、を含有し、
上記（Ｃ）成分の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、上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って、
上記（Ｃ）成分として、上記一般式（Ｃ－１）中のＲＣ１が水素原子、ｘが０であり、かつ上記一般式（Ｃ－１）で表される構造単位と上記一般式（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、熱硬化性樹脂組成物。
As a result of intensive studies to achieve the above object, the present inventors have found that a modified maleimide resin having a specific structure, a thermoplastic elastomer, a copolymer resin containing an aromatic vinyl compound and a carboxylic acid anhydride as raw material monomers. The inventors have found that the above object can be achieved by using the above, and have completed the present invention. Furthermore, by selecting a phosphorus-based flame retardant as the flame retardant, sufficient flame retardancy could be imparted without deteriorating the properties.
That is, the present invention provides the following thermosetting resin composition, prepreg, laminate, printed wiring board, and high-speed communication module.
[1] (A) Addition of maleimide compound (a1) having at least two N-substituted maleimide groups in one molecule with amine compound (a2) having at least two primary amino groups in one molecule (B) a thermoplastic elastomer; (C) a copolymer resin containing a structural unit derived from an aromatic vinyl compound and a structural unit derived from a carboxylic acid anhydride; and (D) a phosphorus-based flame retardant as a flame retardant. containing a fuel and
The structural unit derived from the aromatic vinyl compound of component (C) is represented by the following general formula (C-1), and the structural unit derived from the carboxylic anhydride is represented by the following general formula (C-2). A structural unit derived from maleic anhydride,
As the component (C), R 1 in the general formula (C-1) is a hydrogen atom, x is 0, and the structural unit represented by the general formula (C-1) and the general formula (C A thermosetting resin composition containing a copolymer resin having a content ratio [(C-1)/(C-2)] (molar ratio) of 5 to 10 with respect to the structural unit represented by -2).
炭化水素基を示し、ｘは、０～３の整数を示す。）
［２］上記（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、上記（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］項に記載の熱硬化性樹脂組成物。
［３］上記（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］又は［２］項に記載の熱硬化性樹脂組成物。
［４］上記（Ｂ）成分の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る上記［１］～［３］のいずれか一項に記載の熱硬化性樹脂組成物。
［５］上記（Ｄ）成分のリン系難燃剤の配合量が、上記（Ａ）成分、（Ｂ）成分、（Ｃ）成分の合計質量を１００質量部としたときに、リン原子の含有量が１．０～４．０質量部である、上記［１］～［４］のいずれか一項に記載の熱硬化性樹脂組成物。
［６］さらに、（Ｅ）硬化促進剤を含有する、上記［１］～［５］のいずれか一項に記載の熱硬化性樹脂組成物。
［７］さらに、（Ｆ）無機充填材を含有する、上記［１］～［６］のいずれか一項に記載の熱硬化性樹脂組成物。
［８］上記［１］～［７］のいずれか一項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。
［９］上記［８］項に記載のプリプレグを積層成形して得られる積層板。
［１０］上記［８］項に記載のプリプレグ又は上記［９］項に記載の積層板を用いて製造されるプリント配線板。
［１１］上記［１０］項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。
[2] 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 the above [1] item, 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.
[3] The thermosetting resin composition according to [1] or [2] above, wherein the component (a2) contains a modified siloxane having an amino group at its terminal.
[4] The thermosetting resin composition according to any one of [1] to [3] above, wherein the thermoplastic elastomer of component (B) is a hydrogenated styrene thermoplastic elastomer.
[5] The amount of the phosphorus-based flame retardant of component (D) is the content of phosphorus atoms when the total mass of components (A), (B), and (C) is 100 parts by mass. is 1.0 to 4.0 parts by mass, the thermosetting resin composition according to any one of the above [1] to [4].
[6] The thermosetting resin composition according to any one of [1] to [5] above, further comprising (E) a curing accelerator.
[7] The thermosetting resin composition according to any one of [1] to [6] above, further comprising (F) an inorganic filler.
[8] A prepreg obtained by impregnating a fiber base material with the thermosetting resin composition according to any one of [1] to [7] above.
[9] A laminate obtained by laminate-molding the prepreg described in [8] above.
[10] A printed wiring board manufactured using the prepreg described in [8] above or the laminate described in [9] above.
[11] A high-speed communication module manufactured using the printed wiring board according to [10] above.
本発明によれば、ハロゲンフリーで耐熱性の低下や誘電特性の悪化を抑制しつつ難燃性を備え、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, it is halogen-free, has flame retardancy while suppressing deterioration of heat resistance and dielectric properties, and has excellent heat resistance, low thermal expansion, low dielectric constant and low dielectric loss tangent. It is possible to provide a resin composition, a prepreg, a laminate, a printed wiring board, and a module for high-speed communication using the same.
［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）難燃剤としてリン系難燃剤と、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 comprises (A) a maleimide compound (a1) having at least two N-substituted maleimide groups per molecule and at least two primary amino groups per molecule. An addition reaction product with an amine compound (a2) (hereinafter also referred to as “(A) modified maleimide resin”), (B) a thermoplastic elastomer, and (C) a structural unit derived from an aromatic vinyl compound and a carboxylic acid anhydride A thermosetting resin composition containing a copolymer resin (hereinafter also referred to as "(C) copolymer resin") containing structural units derived from .
＜（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 comprises a maleimide compound (a1) having at least two N-substituted maleimide groups per molecule and an amine compound (a2) having at least two primary amino groups per molecule. 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)
A 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. However, maleimide compounds having two N-substituted maleimide groups in one molecule are preferred, and compounds represented by the following general formula (a1-1) are more preferred.
ｑ１は、各々独立に、０～４の整数である。）
Each q1 is independently an integer of 0-4. )
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 R A1 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, n -Alkyl groups having 1 to 5 carbon atoms such as 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 general formula (a1-3), examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R 1 A2 include the same groups as those for R 1 A1 .
Examples of the alkylene group having 1 to 5 carbon atoms represented by X A2 include methylene group, 1,2-dimethylene group, 1,3-trimethylene group, 1,4-tetramethylene group, 1,5-pentamethylene group and the like. be done.
Examples of the alkylidene group having 2 to 5 carbon atoms represented by X A2 include an ethylidene group, a propylidene 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 R 3 A3 are the same as those for R 3 A2 .
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 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 general formula (a1-5), examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R 1 A4 include the same groups as those for R 1 A1 in 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。
Component (a1) includes N,N'-ethylenebismaleimide, N,N'-hexamethylenebismaleimide, N,N'-(1,3-phenylene)bismaleimide, N,N'-[1,3 -(2-methylphenylene)]bismaleimide, N,N'-[1,3-(4-methylphenylene)]bismaleimide, N,N'-(1,4-phenylene)bismaleimide, bis(4- maleimidophenyl)methane, bis(3-methyl-4-maleimidophenyl)methane, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethanebismaleimide, bis(4-maleimidophenyl)ether, Bis(4-maleimidophenyl)ketone, bis(4-maleimidocyclohexyl)methane, 1,4-bis(4-maleimidophenyl)cyclohexane, 1,4-bis(maleimidomethyl)cyclohexane, 1,4-bis(maleimidomethyl) ) benzene, 1,3-bis(4-maleimidophenoxy)benzene, 1,3-bis(3-maleimidophenoxy)benzene, bis[4-(3-maleimidophenoxy)phenyl]methane, bis[4-(4- Maleimidophenoxy)phenyl]methane, 1,1-bis[4-(3-maleimidophenoxy)phenyl]ethane, 1,1-bis[4-(4-maleimidophenoxy)phenyl]ethane, 1,2-bis[4 -(3-maleimidophenoxy)phenyl]ethane, 1,2-bis[4-(4-maleimidophenoxy)phenyl]ethane, 2,2-bis[4-(3-maleimidophenoxy)phenyl]propane, 2,2 -bis[4-(4-maleimidophenoxy)phenyl]propane, 2,2-bis[4-(3-maleimidophenoxy)phenyl]butane, 2,2-bis[4-(4-maleimidophenoxy)phenyl]butane , 4,4-bis(3-maleimidophenoxy)biphenyl, 4,4-bis(4-maleimidophenoxy)biphenyl, bis[4-(3-maleimidophenoxy)phenyl]ketone, bis[4-(4-maleimidophenoxy) ) phenyl]ketone, bis[4-(3-maleimidophenoxy)phenyl]ether, bis[4-(4-maleimidophenoxy)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 solvents, and bis(4-maleimidophenyl)methane, 2,2- Bis[4-(4-maleimidophenoxy)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. and compounds represented by the following general formula (a2-1) are more preferable.
（一般式（ａ２－３）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 general formula (a2-3), R A6 is each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms; Y A2 is an alkylene group having 1 to 5 carbon atoms; is an alkylidene group, an ether group, a carboxyl group, a keto group, a single bond, or a group represented by the following general formula (a2-3′).q2 is each independently an 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 R A5 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, n -Alkyl groups having 1 to 5 carbon atoms such as 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 general formula (a2-3), examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R 1 A6 include the same groups as those for R 1 A5 .
Examples of the alkylene group having 1 to 5 carbon atoms represented by Y A2 include methylene group, 1,2-dimethylene group, 1,3-trimethylene group, 1,4-tetramethylene group and 1,5-pentamethylene group. be done.
Examples of the alkylidene group having 2 to 5 carbon atoms represented by Y A2 include an ethylidene group, a propylidene 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 general formula (a2-3′), examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R 1 A7 include the same groups as those for R 1 A6 .
Examples of the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by Y A3 include the same alkylene group having 1 to 5 carbon atoms and alkylidene group having 2 to 5 carbon atoms represented by Y A2 . 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 general formula (a2-4), the alkyl group having 1 to 5 carbon atoms represented by R A8 is more preferably an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group represented by R A8 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group and the like. groups are preferred.
Examples of substituents in the substituted phenyl group represented by R A8 include alkyl groups, alkenyl groups, alkynyl groups, etc. Among these, alkyl groups are preferred. Examples of the alkyl group include those similar to the alkyl group represented by RA8 .
The divalent organic group represented by R A9 includes an alkylene group, an alkylidene group, an alkenylene group, an alkynylene group, an arylene group, —O—, and a divalent linking group in which these are combined. Among these, an alkylene group and an arylene group are preferred. The alkylene group includes a methylene group, an ethylene group, a propylene group and the like. A phenylene group, a naphthylene group, etc. are mentioned as an arylene 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。
Component (a2) includes modified siloxanes having terminal amino groups, diaminobenzidine, diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, diaminodiphenyl ether, and 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 and the like.
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, 3,3′-diethyl-4,4′-diaminodiphenylmethane and 2,2′-bis[4-(4-aminophenoxy)phenyl]propane are preferred from the viewpoint of obtaining high elasticity and high heat resistance. is preferred.
Moreover, from the viewpoint of low thermal expansion, modified siloxane having an amino group at its terminal is preferable.
Commercially available modified siloxanes having amino groups at their ends may be used, and commercially available products having amino groups at both ends, "X-22-161A" (functional group equivalent weight: 800 g/mol), "X- 22-161B" (functional group equivalent 1,500 g / mol) (manufactured by Shin-Etsu Chemical Co., Ltd.), "BY16-853U" (functional group equivalent 460 g / mol) (manufactured by Dow Corning Toray Co., Ltd.), "XF42-C5379" (functional group equivalent: 750 g/mol) (manufactured by Momentive Performance Materials Japan LLC) and the like.
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。
In addition, from the viewpoint of achieving both low thermal expansion, high elasticity and high heat resistance, the component (a2) contains a modified siloxane having an amino group at its terminal and an amine compound other than the modified siloxane having an amino group at its terminal. It is preferably composed of a modified siloxane having an amino group at the end, 3,3'-diethyl-4,4'-diaminodiphenylmethane and 2,2'-bis[4-(4-aminophenoxy)phenyl]propane It is more preferable to use together with one or more selected from the group.
When a modified siloxane having an amino group at its terminal and an amine compound other than a modified siloxane having an amino group at its terminal are used together as component (a2), the mass ratio [modified siloxane having an amino group at its terminal/modified siloxane having an amino group at its terminal/ Amine compound other than modified siloxane having an amino group] is preferably 3/97 to 90/10, more preferably 10/90 to 80/20, 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 the addition reaction product of the (a1) component and the (a2) component, 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）成分の一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）成分の一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)
(A) Modified maleimide resin can be produced by addition reaction of components (a1) and (a2).
From the standpoint of gelation prevention and heat resistance, the amount of component (a1) and component (a2) to be blended in the addition reaction is such that the equivalent of the maleimide group of component (a1) is the equivalent of the primary amino group of component (a2). and the ratio [component (a1)/component (a2)] of the equivalent weight of maleimide groups in component (a1) to the equivalent weight of primary amino groups in component (a2) is 2 to 15. It is preferably 3 to 10, 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 progress of the reaction. 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 organic solvents 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 ethyl acetate; aromatic solvents such as toluene; 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, high volatility, and little residual solvent. is preferred.
From the viewpoint of solubility and reaction rate, the amount of the organic solvent used is preferably 25 to 1,000 parts by mass, more preferably 50 to 500 parts by mass, per 100 parts by mass of components (a1) and (a2) combined. 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 (A) the 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 even more preferable.
As used herein, the term "solid content" refers to non-volatile content excluding volatile substances such as solvents. Also includes liquid, starch syrup and wax. Here, room temperature indicates 25° C. in this specification.
In addition, the "resin component" is a component used in the production of a resin or a resin, excluding an inorganic filler described later, and specifically includes (A) a modified maleimide resin, (B) a thermoplastic elastomer, ( C) A copolymer 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。
Further, the content of (A) modified maleimide resin in the thermosetting resin composition of the present invention is the amount of (A) modified maleimide resin in the thermosetting resin composition from the viewpoint of elastic modulus and low thermal expansion. The amount of the raw material (a1) component 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, and 50 to 85 parts by mass. is more preferable.
In addition, the content of the (A) modified maleimide resin in the thermosetting resin composition of the present invention is, from the viewpoint of good low thermal expansion and copper foil adhesion, the (A) modified maleimide resin in the thermosetting resin composition. The amount of the raw material component (a2) 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 preferred.
＜（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>
(B) The 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, (B) the thermoplastic elastomer is defined as not including (C) a copolymer resin containing a structural unit derived from an aromatic vinyl compound and a structural unit derived from a carboxylic acid anhydride, which will be described later. be.
(B) Thermoplastic elastomers 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。
As the (B) thermoplastic elastomer, those having a reactive functional group at the molecular terminal or in the molecular chain can be used. Examples of reactive functional groups include epoxy group, hydroxyl group, carboxy group, amino group, amide group, isocyanate group, acrylic group, methacrylic group, vinyl group and the like. By having these reactive functional groups in the molecular terminal or 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 metal foil, 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（登録商標）２００２」、「セプトンＨＧ２５２」（株式会社クラレ製）等が挙げられる。
From the viewpoint of compatibility with the modified polyimide resin, the thermoplastic elastomer (B) is preferably a styrene-butadiene copolymer or a styrene-isoprene copolymer. Hydrogenated styrene-based thermoplastic elastomers such as hydrogenated styrene-butadiene copolymer resins and hydrogenated styrene-isoprene copolymer resins in which the heavy bond portion is hydrogenated are more preferred.
Furthermore, the content of structural units derived from styrene in the hydrogenated styrenic thermoplastic elastomer (hereinafter also referred to as "styrene content") is preferably 20 to 60% by mass, more preferably 25 to 55% by mass. is more preferable. (B) 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 the amount of prepreg falling off is small. When the styrene content is 60% by mass or less, the base material properties (thermal expansion coefficient, dielectric properties, heat resistance) are good, and cracks tend to be less likely to occur in the prepreg appearance after coating. It is considered that this is due to suppression of stacking aggregation of styrene and excellent flexibility of the resin. When the styrene content is 20% by mass or more, in addition to good substrate properties (thermal expansion coefficient, dielectric properties, heat resistance), compatibility between (A) the modified maleimide resin and (B) the thermoplastic elastomer is improved. It tends to be excellent in handleability, with less powder falling off of the resin.
This is because the maleimide groups of (A) the modified maleimide resin are closer in structure to styrene than those of butadiene, isoprene, etc., so when the styrene content of (B) the thermoplastic elastomer is 20% by mass or more, (A) It is believed that this is due to the excellent compatibility between the modified maleimide resin and the styrene-based skeleton.
As the styrene-based elastomer, commercially available products may be used, and commercially available products include "Tuftec (registered trademark) H1051", "Tuftec H1053", "Tuftec M1911", and "Tuftec M1913" (manufactured by Asahi Kasei Chemicals Co., Ltd.). ), “Septon (registered trademark) 2002”, “Septon 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 (B) the thermoplastic elastomer in the thermosetting resin composition is preferably 4 to 20 parts by mass, preferably 6 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 preferred. When the content of the thermoplastic elastomer (B) is 4 parts by mass or more, a sufficient effect of lowering the dielectric constant can be obtained, and when the content is 20 parts by mass or less, the thermoplastic elastomer (B) is compatible with the resin. It disperses well 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>
(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 copolymer resin, the thermosetting resin composition of the present invention has the effect of being particularly excellent in heat resistance after absorbing water. Although the reason why such an effect is produced is not clear, it is considered as follows.
Conventionally, a method of adding a thermoplastic elastomer to a modified maleimide resin has been used for the purpose of improving dielectric properties. was in a difficult situation. Therefore, when a modified maleimide resin and a thermoplastic elastomer are simply blended, there is a problem in heat resistance under severe conditions demanded in recent years (for example, after moisture absorption treatment by 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. Structural units have excellent compatibility with thermoplastic elastomers (especially elastomers containing styrene), and structural units derived from carboxylic anhydrides have excellent compatibility with modified maleimide resins. Therefore, the (C) copolymer resin functions as a compatibilizer between the (A) modified maleimide resin and (B) the thermoplastic elastomer, thereby improving the compatibility between the (A) modified maleimide resin and (B) the thermoplastic elastomer. It is considered that the compatibility was improved and the heat resistance was improved. Furthermore, (C) the copolymer resin itself also has excellent dielectric properties, so it is thought 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 copolymer resin (C), a structural unit represented by the following general formula (C-1) is preferable. Further, the structural unit derived from the carboxylic anhydride of the component (C) includes 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 maleic anhydride-derived structural unit represented by the following general formula (C-2) having a structure close to 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、且つ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。
Examples of aliphatic hydrocarbon groups having 1 to 5 carbon atoms represented by R C1 and R C2 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n
-pentyl group and the like. Among these, aliphatic hydrocarbon groups having 1 to 3 carbon atoms are preferred, and methyl and ethyl groups are more preferred, from the viewpoint of adhesion to copper foil and dielectric properties.
Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms represented by R 2 C2 include phenyl group, naphthyl group, anthryl group and biphenylyl group.
Among the structural units represented by the general formula (C-1), preferred is a structural unit represented by the following formula (C-1′) in which R 1 C1 is a hydrogen atom and x is 0.
（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) the content ratio of the structural unit represented by the general formula (C-1) to 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 dielectric properties and heat resistance tends to be sufficient, and when the content ratio is 12 or less, compatibility tends to be good. Furthermore, when the [(C-1)/(C-2)] (molar ratio) is 5 to 10, in addition to having good base material properties, (B) excellent compatibility with the thermoplastic elastomer Since the content of the structural unit derived from styrene is within the preferable range, the compatibility between (A) the modified maleimide resin and (B) the thermoplastic elastomer is further improved, and the prepreg powder removal property is also improved.
(C) 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 copolymer resin is preferably 50% by mass or more, 70% by mass or more is more preferable, 90% by mass or more is even more 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) Copolymer resin can be produced by copolymerizing an aromatic vinyl compound and maleic anhydride.
Examples of aromatic vinyl compounds include styrene, 1-methylstyrene and vinyltoluene. These may be used alone or in combination of two or more.
Furthermore, in addition to the aromatic vinyl compound and maleic anhydride, various polymerizable components may be copolymerized. Various polymerizable components include vinyl compounds such as ethylene, propylene, butadiene, and the like.
（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＝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。 As the (C) copolymer resin, a commercially available product can be used, and commercially available products include "SMA (registered trademark) EF30" (styrene/maleic anhydride = 3, Mw = 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) (manufactured by Sartomer) 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 weight are more preferred, and 4 to 13 parts by weight are even more preferred. When the content of the copolymer resin (C) is 2 parts by mass or more, the effect of lowering the dielectric constant is sufficiently obtained, and when the content is 20 parts by mass or less, the copolymer resin (C) has excellent dispersibility, Excellent heat resistance and peel strength.
＜（Ｄ）リン系難燃剤＞
積層板に用いる樹脂組成物に難燃性を付与する難燃剤としては、ハロゲン系難燃剤、リン系難燃剤、無機系難燃剤などが挙げられる。近年は環境対応への要求から、ハロゲン系難燃剤は使用しないことが求められている。無機系難燃剤としては、三酸化アンチモンや水酸化アルミニウムなどが挙げられるが、これらの材料は樹脂組成物の吸水率を高くしてしまい、誘電特性を悪化させる。そのため、近年要求される優れた誘電特性を有する樹脂組成物への適用は困難である。
リン系難燃剤は、ハロゲンフリーであり、誘電特性を悪化させることなく難燃性を付与することができる。
<(D) Phosphorus flame retardant>
Examples of the flame retardant that imparts flame retardancy to the resin composition used for the laminate include halogen-based flame retardants, phosphorus-based flame retardants, and inorganic flame retardants. In recent years, due to the demand for environmental friendliness, it is required not to use halogen-based flame retardants. Examples of inorganic flame retardants include antimony trioxide and aluminum hydroxide, but these materials increase the water absorption of the resin composition and deteriorate the dielectric properties. Therefore, it is difficult to apply it to a resin composition having excellent dielectric properties, which is demanded in recent years.
Phosphorus-based flame retardants are halogen-free and can impart flame retardancy without deteriorating dielectric properties.
有機系のリン系難燃剤としては、例えば、芳香族リン酸エステル、１置換ホスホン酸ジエステル、２置換ホスフィン酸エステル、２置換ホスフィン酸の金属塩、有機系含窒素リン化合物、環状有機リン化合物、リン含有フェノール樹脂等が挙げられる。これらの中でも、芳香族リン酸エステル化合物、２置換ホスフィン酸の金属塩、環状有機リン化合物が好ましい。ここで、金属塩としては、リチウム塩、ナトリウム塩、カリウム塩、カルシウム塩、マグネシウム塩、アルミニウム塩、チタン塩、亜鉛塩のいずれかであることが好ましく、アルミニウム塩であることが好ましい。また、有機系のリン系難燃剤の中では、芳香族リン酸エステルがより好ましい。 Examples of organic phosphorus-based flame retardants include aromatic phosphates, monosubstituted phosphonic acid diesters, disubstituted phosphinic acid esters, metal salts of disubstituted phosphinic acids, organic nitrogen-containing phosphorus compounds, cyclic organic phosphorus compounds, Phosphorus-containing phenolic resins and the like can be mentioned. Among these, aromatic phosphoric acid ester compounds, metal salts of disubstituted phosphinic acids, and cyclic organic phosphorus compounds are preferred. Here, the metal salt is preferably any one of lithium salt, sodium salt, potassium salt, calcium salt, magnesium salt, aluminum salt, titanium salt and zinc salt, preferably aluminum salt. Among the organic phosphorus-based flame retardants, aromatic phosphate esters are more preferable.
芳香族リン酸エステルとしては、例えば、トリフェニルホスフェート、トリクレジルホスフェート、トリキシレニルホスフェート、クレジルジフェニルホスフェート、クレジルジ－２，６－キシレニルホスフェート、レゾルシノールビス（ジフェニルホスフェート）、１，３－フェニレンビス（ジ－２，６－キシレニルホスフェート）、ビスフェノールＡ－ビス（ジフェニルホスフェート）、１，３－フェニレンビス（ジフェニルホスフェート）等が挙げられる。
１置換ホスホン酸ジエステルとしては、例えば、フェニルホスホン酸ジビニル、フェニルホスホン酸ジアリル、フェニルホスホン酸ビス（１－ブテニル）等が挙げられる。
２置換ホスフィン酸エステルとしては、例えば、ジフェニルホスフィン酸フェニル、ジフェニルホスフィン酸メチル等が挙げられる。
２置換ホスフィン酸の金属塩としては、ジアルキルホスフィン酸の金属塩、ジアリルホスフィン酸の金属塩、ジビニルホスフィン酸の金属塩、ジアリールホスフィン酸の金属塩等が挙げられる。これらの金属塩は、前述と同様、リチウム塩、ナトリウム塩、カリウム塩、カルシウム塩、マグネシウム塩、アルミニウム塩、チタン塩、亜鉛塩のいずれかであることが好ましい。
Examples of aromatic phosphates include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl di-2,6-xylenyl phosphate, resorcinol bis(diphenyl phosphate), 1,3 -phenylene bis(di-2,6-xylenyl phosphate), bisphenol A-bis(diphenyl phosphate), 1,3-phenylene bis(diphenyl phosphate) and the like.
The monosubstituted phosphonic acid diesters include, for example, divinyl phenylphosphonate, diallyl phenylphosphonate, bis(1-butenyl) phenylphosphonate and the like.
Disubstituted phosphinate esters include, for example, phenyl diphenylphosphinate and methyl diphenylphosphinate.
The metal salts of disubstituted phosphinic acids include metal salts of dialkylphosphinic acid, metal salts of diallylphosphinic acid, metal salts of divinylphosphinic acid, and metal salts of diarylphosphinic acid. As mentioned above, these metal salts are preferably lithium salts, sodium salts, potassium salts, calcium salts, magnesium salts, aluminum salts, titanium salts, or zinc salts.
有機系含窒素リン化合物としては、例えば、ビス（２－アリルフェノキシ）ホスファゼン、ジクレジルホスファゼン等のホスファゼン化合物；リン酸メラミン；ピロリン酸メラミン；ポリリン酸メラミン；ポリリン酸メラムなどが挙げられる。
環状有機リン化合物としては、９，１０－ジヒドロ－９－オキサ－１０－ホスファフェナントレン－１０－オキシド、１０－（２，５－ジヒドロキシフェニル）－９，１０－ジヒドロ－９－オキサ－１０－ホスファフェナントレン－１０－オキシド等が挙げられる。
これらの中でも、芳香族リン酸エステル、２置換ホスフィン酸の金属塩及び環状有機リン化合物から選択される少なくとも１種類であることが好ましく、芳香族リン酸エステル、２置換ホスフィン酸の金属塩がより好ましい。
Examples of organic nitrogen-containing phosphorus compounds include phosphazene compounds such as bis(2-allylphenoxy)phosphazene and dicresylphosphazene; melamine phosphate; melamine pyrophosphate; melamine polyphosphate; and melam polyphosphate.
Cyclic organic phosphorus compounds include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10- and phosphaphenanthrene-10-oxide.
Among these, at least one selected from aromatic phosphates, metal salts of disubstituted phosphinic acids and cyclic organic phosphorus compounds is preferable, and aromatic phosphates and metal salts of disubstituted phosphinic acids are more preferred. preferable.
また、前記芳香族リン酸エステルは、下記一般式（Ｄ－１）もしくは（Ｄ－２）で表される芳香族リン酸エステルであることが好ましく、前記２置換ホスフィン酸の金属塩は、下記一般式（Ｄ-３）で表される２置換ホスフィン酸の金属塩であることが好ましい。 Further, the aromatic phosphate ester is preferably an aromatic phosphate ester represented by the following general formula (D-1) or (D-2), and the metal salt of the disubstituted phosphinic acid is the following: A metal salt of a disubstituted phosphinic acid represented by general formula (D-3) is preferred.
（一般式（Ｄ-１）～（Ｄ-３）中、ＲＥ１～ＲＥ５は各々独立に、炭素数１～５の脂肪族炭化水素基又は水素原子である。ｅ及びｆは各々独立に０～５の整数であり、ｇ、ｈ及
びｉは各々独立に０～４の整数である。ＲＥ６及びＲＥ７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６～１４の芳香族炭化水素基である。Ｍは、リチウム原子、
ナトリウム原子、カリウム原子、カルシウム原子、マグネシウム原子、アルミニウム原子、チタン原子、亜鉛原子である。）
ＲＥ１～ＲＥ５が表す炭素数１～５の脂肪族炭化水素基及び水素原子としては、前記各一般式と同様、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。 ｅ及びｆは、０～２の整数であることが好ましく、２であることが好ましい。ｇ、ｈ及びｉは、０～２の整数であることが好ましく、０又は１であることが好ましく、０であることが好ましい。
ＲＥ６及びＲＥ７が表す炭素数１～５の脂肪族炭化水素基としては、前記ＲＥ１～ＲＥ５と同じものが挙げられる。該脂肪族炭化水素基としては、炭素数１～３の脂肪族炭化水
素基であることが好ましく、エチル基であることが好ましい。
ＲＥ６及びＲＥ７が表す炭素数６～１４の芳香族炭化水素基としては、例えば、フェニル基、ナフチル基、ビフェニリル基、アントリル基等が挙げられる。該芳香族炭化水素基
としては、炭素数６～１０の芳香族炭化水素基であることが好ましい。
ｊは金属イオンの価数を表しており、つまり、Ｍの種類に対応して１～４の範囲内で変化する。Ｍとしては、アルミニウム原子であることが好ましい。なお、Ｍがアルミニウム原子である場合、ｊは３である。
(In general formulas (D-1) to (D-3), R E1 to R E5 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a hydrogen atom. e and f are each independently is an integer of 0 to 5, g, h and i are each independently an integer of 0 to 4. R E6 and R E7 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or 6 carbon atoms; is an aromatic hydrocarbon group of ~ 14. M is a lithium atom;
A sodium atom, a potassium atom, a calcium atom, a magnesium atom, an aluminum atom, a titanium atom, and a zinc atom. )
The aliphatic hydrocarbon group having 1 to 5 carbon atoms and the hydrogen atom represented by R E1 to R E5 are, as in the above general formulas, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group,
isobutyl group, t-butyl group, n-pentyl group and the like. Preferably, e and f are integers from 0 to 2, preferably 2. g, h and i are preferably integers of 0 to 2, preferably 0 or 1, preferably 0;
Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R E6 and R E7 include the same groups as those described above for R E1 to R E5 . The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, preferably an ethyl group.
Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms represented by R 1 E6 and R 2 E7 include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group and the like. The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms.
j represents the valence of the metal ion, ie, varies from 1 to 4 depending on the type of M. M is preferably an aluminum atom. Note that j is 3 when M is an aluminum atom.
上述のリン系難燃剤は、単独で用いても、複数種類用いても良い。
（Ｄ）成分のリン系難燃剤の配合量については、（Ａ）成分、（Ｂ）成分、（Ｃ）成分の合計質量を１００質量部としたときに、リン原子の含有量が１．０～４．０質量部であることが好ましく、１．２質量部から３．５質量部であることがより好ましい。リン原子の含有量が１．０質量部未満であると、充分な難燃性を付与することができない。リン原子の含有量が４．０質量部を超えると、リン系難燃剤が可塑剤として作用するため耐熱性の悪化が生じる。
The phosphorus-based flame retardants described above may be used singly or in combination.
Regarding the amount of the phosphorus-based flame retardant of component (D), the content of phosphorus atoms is 1.0 when the total mass of components (A), (B), and (C) is 100 parts by mass. It is preferably up to 4.0 parts by mass, more preferably 1.2 to 3.5 parts by mass. If the phosphorus atom content is less than 1.0 parts by mass, sufficient flame retardancy cannot be imparted. If the phosphorus atom content exceeds 4.0 parts by mass, the phosphorus-based flame retardant acts as a plasticizer, resulting in deterioration of heat resistance.
＜（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、更に、（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>
From the viewpoint of accelerating the curing reaction, the thermosetting resin composition of the present invention may further contain (E) a curing accelerator.
(E) Curing accelerators include organophosphorus compounds such as triphenylphosphine; imidazoles and their derivatives; nitrogen-containing compounds such as secondary amines, tertiary amines and quaternary ammonium salts; dicumyl Peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, α,α'- organic peroxides such as bis(t-butylperoxy)diisopropylbenzene; and organic metal salts such as zinc naphthenate, cobalt naphthenate, tin octylate, and cobalt octylate. (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 0.1 parts per 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、更に、（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) Inorganic fillers include silica, alumina, titanium oxide, mica, barium titanate, strontium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, calcium carbonate, silicon nitride, boron nitride, talc, and silicon carbide. , quartz powder, short glass fibers, fine glass powder, hollow glass, and the like. As the glass, E glass, T glass, D glass and the like are preferably used.
(F) Inorganic fillers 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, which is produced by a wet method and has a high water content, and dry-process silica, which is produced by a dry method and contains almost no bound water. , crushed silica, fumed silica, fused spherical silica, etc. Among these, fused spherical silica is preferable from the viewpoint of low thermal expansion and fluidity when filled in a 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 inorganic filler preferably has an average particle size of 0.1 to 10 μm, more preferably 0.3 to 8 μm. When the average particle diameter is 0.1 μm or more, good fluidity can be maintained when the resin is highly filled. occurrence can be suppressed. Here, the average particle size is the particle size at the point corresponding to 50% volume when the cumulative frequency distribution curve by particle size is obtained with the total volume of the particles being 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 dry or wet surface treatment of the (F) inorganic filler before blending, and the surface untreated (F) inorganic filler may be treated with another A so-called integral blend treatment method may be employed in which a silane coupling agent is added to the composition after blending it with the components to form a composition.
Examples of coupling agents include silane-based coupling agents, titanate-based coupling agents, and silicone oligomers.
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, its content is 10 to 300 parts by mass with respect to 100 parts by mass of the solid content of the resin component in the thermosetting resin composition. parts is preferred, and 50 to 250 parts by mass is more preferred. (F) When the content of the inorganic filler is within the above range, good moldability and low thermal expansion properties are obtained.
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, if necessary, it is treated with a dispersing machine such as a triple roll, a bead mill, or a nanomizer to remove (F) the inorganic filler. Improved dispersibility is preferred.
＜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. can be improved.
Thermosetting resins to be used in combination are not particularly limited, and examples thereof include epoxy resins, phenol resins, cyanate resins, isocyanate resins, benzoxazine resins, allyl resins, dicyclopentadiene resins, silicone resins, triazine resins, and the like. may be used alone or in combination of two or more. Among these, cyanate resins and benzoxazine resins are preferred from the viewpoint of moldability and electrical insulation.
In addition, the content of the epoxy resin is preferably 2% by mass or less based on the solid content of the thermosetting resin composition, although good adhesiveness can be obtained by containing the epoxy resin. By setting the content of the epoxy resin to 2% by mass or less, excellent dielectric properties and storage stability can be obtained.
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 known organic fillers, ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent whitening agents, adhesion improvers and the like.
Examples of organic fillers include resin fillers made of polyethylene, polypropylene resin, etc., and resin fillers having a core-shell structure.
Examples of ultraviolet absorbers include benzotriazole-based ultraviolet absorbers.
Antioxidants include hindered phenol antioxidants, hindered amine antioxidants, and the like.
Photopolymerization initiators include benzophenones, benzyl ketals, thioxanthone-based photopolymerization initiators, and the like.
Examples of fluorescent brightening agents include fluorescent brightening agents of stilbene derivatives.
Examples of the adhesion improver include urea compounds such as urea silane and the above coupling agents.
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 form of a varnish in which each component is dissolved or dispersed in an organic solvent for use in the production of prepregs and 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。
Examples of organic solvents used in varnishes 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 ethyl acetate; fragrances such as toluene and xylene. family solvents; nitrogen atom-containing solvents such as dimethylacetamide and N-methylpyrrolidone. 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 preferred from the viewpoint of solubility, and propylene glycol monomethyl ether, methyl isobutyl ketone, cyclohexanone, and toluene are more preferred from the viewpoint of low toxicity.
The solid content concentration of the varnish is preferably 40-90% by mass, more preferably 50-80% by mass. When the solid content concentration of the varnish is within the above range, good coatability can be maintained, and a prepreg having an appropriate resin composition adhesion amount 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、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 it by heating or the like (to B-stage).
As the fiber base material, well-known ones used for various laminates for electrical insulating materials can be used. Examples of materials thereof 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 tetrafluoroethylene; and mixtures thereof.
これらの繊維基材は、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 fabric, non-woven fabric, roving, chopped strand mat, surfacing mat, etc. The material and shape are selected depending on the intended use, performance, etc. of the molded product, and if necessary, It can be used singly or in combination of two or more types of materials and shapes. The thickness of the fiber base material can be, for example, about 0.03-0.5 mm. These fiber substrates are preferably surface-treated with a silane coupling agent or the like or mechanically fiber-opened from the standpoint 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 prepared, for example, so that the adhesion amount of the thermosetting resin composition to the fiber base material (the content of the thermosetting resin composition in the prepreg) is 20 to 90% by mass. After impregnation, it is usually dried by heating at a temperature of 100 to 200° C. for 1 to 30 minutes, and semi-cured (to 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]
The laminate of the present invention is obtained by laminate-molding the prepreg of the present invention.
The laminate of the present invention can be produced by stacking, for example, 1 to 20 sheets of the prepreg of the present invention, and laminating a metal foil such as copper or aluminum on one or both sides thereof. The metal foil is not particularly limited as long as it is used as an electrical insulating material.
As for the molding conditions for producing the laminate, for example, the technique of laminates for electrical insulating materials and multilayer boards can be applied, using a multistage press, a multistage vacuum press, continuous molding, an autoclave molding machine, etc., at a temperature of 100 to 250. C., pressure 0.2 to 10 MPa, and heating time 0.1 to 5 hours. A laminate can also be produced by combining the prepreg of the present invention and an inner-layer wiring board and performing lamination molding.
［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 using the prepreg or laminate of the present invention.
The printed wiring board of the present invention can be produced, for example, by forming a circuit on the surface of the laminate of the present invention. Alternatively, the conductor layer of the laminate of the present invention may be subjected to wiring processing by an ordinary etching method, a plurality of laminates subjected to wiring processing via the prepreg of the present invention may be laminated, and the laminate may be multi-layered at once by hot pressing. can also Thereafter, a multilayer 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 module]
The high-speed communication module of the present invention is a high-speed communication module manufactured using the printed wiring board of the present invention.
The high-speed communication module of the present invention is, for example, a communication module or the like obtained by mounting a semiconductor chip or the like on the printed wiring board of the present invention. , and is suitable for applications where information communication volume and speed are large.
次に、下記の実施例により本発明を更に詳しく説明するが、これらの実施例は本発明を制限するものではない。
なお、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。
The present invention will now be described in more detail with reference to the following examples, but these examples are not intended to limit the invention.
The thermosetting resin composition and 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角の評価基板を作製し、ＴＭＡ試験装置（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 copper-clad laminate was immersed in a copper etching solution to prepare a 5 mm square evaluation board from which the copper foil was removed, and heat was applied by a compression method using a TMA test device (manufactured by TA Instruments, trade name: Q400). Machine analysis was performed. After the evaluation substrate was mounted on the apparatus in the X direction, the measurement was continuously performed twice under the measurement conditions of a load of 5 g and a temperature increase rate of 10° C./min. A point indicated by the intersection of different tangents of the thermal expansion curve in the second measurement was determined and taken 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角の評価基板を作製し、ＴＭＡ試験装置（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 copper clad laminate was immersed in a copper etchant to remove the copper foil to prepare a 5 mm square evaluation board, and a TMA test device (manufactured by TA Instruments, trade name: Q400) was tested. Thermo-mechanical analysis was performed by compression method. After the evaluation substrate was mounted on the apparatus in the X direction, the measurement was continuously performed twice under the measurement conditions of a load of 5 g and a temperature increase rate of 10° C./min. The average coefficient of thermal expansion from 30° C. to 100° C. in the second measurement was calculated and used as the 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（縦×横）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)
An evaluation board of 100 mm × 2 mm (vertical × horizontal) was prepared by removing the copper foil by immersing the copper-clad laminate in a copper etching solution, and using a cavity resonator device (manufactured by Kanto Denshi Applied Development Co., Ltd.), Relative permittivity and dielectric loss tangent were measured at a frequency of 10 GHz.
（４）銅付きはんだ耐熱性
銅張積層板を２５ｍｍ角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) Solder heat resistance with copper An evaluation board was prepared by cutting a copper-clad laminate into a size of 25 mm square, and the evaluation board was floated in a solder bath at a temperature of 288 ° C. for up to 60 minutes while observing the appearance. By doing so, the time until swelling occurred was measured. The evaluation results are shown in Table 1 as ">60" when swelling was not confirmed after 60 minutes of floating.
（５）吸水半銅付はんだ耐熱性
銅張積層板を５０ｍｍ角の大きさに切断し、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角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「ＯＫ」、膨れが確認されたものを「膨れ」として表１に記載した。
(5) Solder heat resistance with water-absorbing semi-copper A copper-clad laminate is cut into a size of 50 mm square, and only half of one surface is left with copper, and the other surface is immersed in a copper etching solution to remove copper from the entire surface. Thus, a 50 mm square evaluation board with half-copper was produced. After being treated for 5 hours in a pressure cooker test (PCT) device (manufactured by Hirayama Seisakusho Co., Ltd.) (conditions: 121 ° C., 2.2 atm), the evaluation board with half copper was placed in a solder bath at 288 ° C. for 20 seconds. After immersion, the heat resistance of the solder with water-absorbing solder was evaluated by visually observing the appearance. The evaluation results are shown in Table 1 as "OK" when no swelling was observed, and as "swelling" when swelling was observed.
（６）難燃性
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、長さ１２５ｍｍ、幅１２．５ｍｍの評価基板を作製し、ＵＬ－９４垂直試験法に準拠して測定した。
(6) Flame retardancy An evaluation board with a length of 125 mm and a width of 12.5 mm was prepared by removing the copper foil by immersing the copper-clad laminate in a copper etching solution, and conforming to the UL-94 vertical test method. It was measured.
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)]
In a reaction vessel with a volume of 2 liters that can be heated and cooled, equipped with a thermometer, a stirrer and a water meter with a reflux condenser, diamine-modified siloxane at both ends (manufactured by Shin-Etsu Chemical 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 280.5 g of phenyl)methane (manufactured by K.I. Kasei Co., Ltd., trade name: BMI) and 200.0 g of propylene glycol monomethyl ether are added and reacted under reflux at 126° C. for 5 hours to obtain a modified maleimide resin (A -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, equipped with a thermometer, a stirrer and a water meter with a reflux condenser, diamine-modified siloxane at both ends (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X-22-161B ) 14.4 g, 2,2′-bis[4-(4-aminophenoxy)phenyl]propane (manufactured by Wakayama Seika Kogyo Co., Ltd., trade name: BAPP) 56.9 g, and bis(4-maleimidophenyl) 253.7 g of methane (manufactured by K.I. Kasei Co., Ltd., trade name: BMI) and 200.0 g of propylene glycol monomethyl ether are added and reacted for 5 hours while refluxing at 126° C. to give 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：ＫＡＹＡＨＡＲＤＡ－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, equipped with a thermometer, a stirrer and a water meter with a reflux condenser, diamine-modified siloxane at both ends (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X-22-161B ) 15.6 g, 3,3′-diethyl-4,4′-diaminodiphenylmethane (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYAHARDA-A) 21.8 g, and 2,2-bis[4-(4 -Maleimidophenoxy)phenyl]propane (manufactured by Daiwa Kasei Kogyo Co., Ltd., trade name: BMI-4000) 274.2 g and propylene glycol monomethyl ether: 200.0 g were added and reacted at 120 ° C. for 4 hours to modify maleimide. A solution of 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)]
In a reaction vessel with a volume of 2 liters that can be heated and cooled, equipped with a thermometer, a stirrer and a water meter with a reflux condenser, diamine-modified siloxane at both ends (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X-22-161A ) 16.6 g, 2,2′-bis[4-(4-aminophenoxy)phenyl]propane (manufactured by Wakayama Seika Kogyo Co., Ltd., trade name: BAPP) 25.5 g, 2,2-bis[4 -(4-maleimidophenoxy)phenyl]propane (manufactured by Daiwa Kasei Kogyo Co., Ltd., trade name: BMI-4000) 292.6 g and propylene glycol monomethyl ether 200.0 g were added, and the mixture was refluxed at 126°C for 6 hours. A solution of modified maleimide resin (A-4) was obtained by reaction.
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０．１ｍｍ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４６質量％のプリプレグを得た。
このプリプレグを４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 1-8 and Comparative Examples 1-5
The composition is blended and mixed according to the blending ratio shown in Table 1 (the numerical values in the table are parts by mass of solid content, and in the case of solutions (excluding organic solvents) or dispersions, the amount is converted to solid content), Using methyl ethyl ketone and toluene as solvents, a varnish having a solid concentration of 65% by mass was produced.
Next, this varnish is impregnated and coated on a 0.1 mm thick E glass cloth (manufactured by Nitto Boseki Co., Ltd.), dried by heating at 160 ° C. for 5 minutes, and the content of the thermosetting resin composition is 46% by mass. of prepreg was obtained.
Four sheets of this prepreg were stacked, 12 μm electrolytic copper foils were placed on top and bottom, 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 for blending 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]
・ Tuftec H1051: Hydrogenated styrene-butadiene copolymer resin (styrene content: 42% by mass) (manufactured by Asahi Kasei Chemicals Co., Ltd.)
・ Tuftec H1053: Hydrogenated styrene-butadiene copolymer resin (styrene content: 29% by mass) (manufactured by Asahi Kasei Chemicals Co., Ltd.)
・ Tuftec M1913: Carboxylic acid-modified hydrogenated styrene-butadiene copolymer resin (styrene content: 30% by mass) (manufactured by Asahi Kasei Chemicals Co., Ltd.)
・ Septon 2002: Hydrogenated styrene-isoprene copolymer resin (styrene content: 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 Structural Unit Derived from Aromatic Vinyl Compound and Structural Unit Derived from Maleic Anhydride]
· SMA-EF80 (styrene/maleic anhydride molar ratio = 8) (manufactured by Sartomer)
［（Ｄ）リン系難燃剤］
・ＰＸ－２００：芳香族リン酸エステル（下記構造式参照、１，３－フェニレン－ビス－（ジ－２，６－キシレニルホスフェート））リン含有量９質量％（大八化学工業株式会
社製）
[(D) Phosphorus flame retardant]
・ PX-200: Aromatic phosphate ester (see the structural formula below, 1,3-phenylene-bis-(di-2,6-xylenyl phosphate)) phosphorus content 9% by mass (Daihachi Chemical Industry Co., Ltd. made)
・ＳＰＢ－１００：シクロホスファゼン、リン含有量１３質量％（大塚化学株式会社製）・ＨＣＡ－ＨＱ－ＨＳ：１０－（２，５－ジヒドロキシフェニル）－９,１０－ジヒドロ－９－オキサ－１０－フォスファフェナントレン－１０－オキサイドの微粉砕品、リン含有量９．６質量％（三光株式会社製、平均粒子径１．５μｍ）
・SPB-100: cyclophosphazene, phosphorus content 13% by mass (manufactured by Otsuka Chemical Co., Ltd.) ・HCA-HQ-HS: 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10 - finely ground product of phosphaphenanthrene-10-oxide, phosphorus content 9.6% by mass (manufactured by Sanko Co., Ltd., average particle size 1.5 μm)
［（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 Hokko Chemical Industry Co., Ltd.)
・ Perbutyl-P: α, α'-bis (t-butylperoxy) diisopropylbenzene (manufactured by NOF Corporation)
・ 2E4MZ: 2-ethyl-4-methylimidazole (manufactured by Shikoku Chemical Industry Co., Ltd.)
・ 2E4MZ-A: 2,4-diamino-6-[2′-ethyl-4′-methylimidazolyl-(1′)]-ethyl-s-triazine (manufactured by Shikoku Chemical Industry Co., Ltd.)
［（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 Admatechs 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、難燃性の全てに優れている。
一方、比較例１～５は、誘電特性又は吸水半銅付はんだ耐熱性、難燃性のいずれかの特性に劣っている。
As is clear from Table 1, the laminates obtained in Examples 1 to 8 have glass transition temperature, thermal expansion coefficient, dielectric properties, solder heat resistance with copper, solder heat resistance with water-absorbing semi-copper, and flame retardancy. Excellent in everything.
On the other hand, Comparative Examples 1 to 5 are inferior in dielectric properties, solder heat resistance with water-absorbing semicopper, or flame retardancy.
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 using the thermosetting resin composition of the present invention has a high glass transition temperature, low thermal expansion, low dielectric properties, and high heat resistance, so it is suitable for highly integrated semiconductor packages and high-speed communication. It is useful as a corresponding printed wiring board for electronic equipment.
Claims (11)
（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）難燃剤としてリン系難燃剤と、
を含有し、
前記（Ｃ）成分の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って、
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、熱硬化性樹脂組成物。
(B) a thermoplastic elastomer;
(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) a phosphorus-based flame retardant as a flame retardant;
contains
The structural unit derived from the aromatic vinyl compound of component (C) is represented by the following general formula (C-1), and the structural unit derived from the carboxylic anhydride is represented by the following general formula (C-2). A structural unit derived from maleic anhydride,
As the component (C), R 1 in the general formula (C-1) is a hydrogen atom, x is 0, and a structural unit represented by the general formula (C-1) and the general formula (C A thermosetting resin composition containing a copolymer resin having a content ratio [(C-1)/(C-2)] (molar ratio) of 5 to 10 with respect to the structural unit represented by -2).
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008111096A (en) | 2006-10-03 | 2008-05-15 | Hitachi Chem Co Ltd | Thermosetting resin composition and prepreg and laminate obtained with the same |
| JP2014024926A (en) | 2012-07-25 | 2014-02-06 | Hitachi Chemical Co Ltd | Thermosetting resin composition and prepreg, laminate sheet, and multilayer printed wiring board using the same |
| JP2016529205A (en) | 2013-05-03 | 2016-09-23 | アルベマール・コーポレーシヨン | Butadiene 2,3-diyl bonded DI-DOPO derivatives as flame retardants |
| JP2017210545A (en) | 2016-05-25 | 2017-11-30 | 日立化成株式会社 | Thermosetting resin composition, and prepreg, copper-clad laminate and printed wiring board using the same |
| JP2018520919A (en) | 2015-07-13 | 2018-08-02 | ストラタシス リミテッド | Waste disposal for 3D printing |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008111096A (en) | 2006-10-03 | 2008-05-15 | Hitachi Chem Co Ltd | Thermosetting resin composition and prepreg and laminate obtained with the same |
| JP2014024926A (en) | 2012-07-25 | 2014-02-06 | Hitachi Chemical Co Ltd | Thermosetting resin composition and prepreg, laminate sheet, and multilayer printed wiring board using the same |
| JP2016529205A (en) | 2013-05-03 | 2016-09-23 | アルベマール・コーポレーシヨン | Butadiene 2,3-diyl bonded DI-DOPO derivatives as flame retardants |
| JP2018520919A (en) | 2015-07-13 | 2018-08-02 | ストラタシス リミテッド | Waste disposal for 3D printing |
| JP2017210545A (en) | 2016-05-25 | 2017-11-30 | 日立化成株式会社 | Thermosetting resin composition, and prepreg, copper-clad laminate and printed wiring board using the same |
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