JP2019099711A - Thermosetting resin composition, prepreg, laminate, printed wiring board and high-speed communication compatible module - Google Patents
Thermosetting resin composition, prepreg, laminate, printed wiring board and high-speed communication compatible module Download PDFInfo
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- JP2019099711A JP2019099711A JP2017233362A JP2017233362A JP2019099711A JP 2019099711 A JP2019099711 A JP 2019099711A JP 2017233362 A JP2017233362 A JP 2017233362A JP 2017233362 A JP2017233362 A JP 2017233362A JP 2019099711 A JP2019099711 A JP 2019099711A
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- Prior art keywords
- resin composition
- group
- thermosetting resin
- structural unit
- component
- Prior art date
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- Granted
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- 239000011342 resin composition Substances 0.000 title claims abstract description 68
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 68
- 238000004891 communication Methods 0.000 title claims abstract description 17
- -1 maleimide compound Chemical class 0.000 claims abstract description 90
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 29
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 29
- 229920006026 co-polymeric resin Polymers 0.000 claims abstract description 26
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 18
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims abstract description 12
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 10
- 229920005989 resin Polymers 0.000 claims description 85
- 239000011347 resin Substances 0.000 claims description 85
- 125000004432 carbon atom Chemical group C* 0.000 claims description 40
- 125000001931 aliphatic group Chemical group 0.000 claims description 22
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 19
- 239000011256 inorganic filler Substances 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 18
- 125000003277 amino group Chemical group 0.000 claims description 14
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 14
- 239000000835 fiber Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
- 238000010030 laminating Methods 0.000 claims description 4
- 206010037660 Pyrexia Diseases 0.000 claims 1
- 238000007259 addition reaction Methods 0.000 abstract description 8
- 239000007795 chemical reaction product Substances 0.000 abstract description 4
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 44
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 21
- 229910052802 copper Inorganic materials 0.000 description 19
- 239000010949 copper Substances 0.000 description 19
- 239000000758 substrate Substances 0.000 description 19
- 238000004519 manufacturing process Methods 0.000 description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 229920002725 thermoplastic elastomer Polymers 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 13
- 239000011521 glass Substances 0.000 description 13
- 125000002947 alkylene group Chemical group 0.000 description 12
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 125000001118 alkylidene group Chemical group 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 239000003822 epoxy resin Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 229920000647 polyepoxide Polymers 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- 239000011889 copper foil Substances 0.000 description 7
- 125000000524 functional group Chemical group 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 6
- 239000000806 elastomer Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 229910000679 solder Inorganic materials 0.000 description 6
- 239000002904 solvent Substances 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
- 239000007822 coupling agent Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- WOLATMHLPFJRGC-UHFFFAOYSA-N furan-2,5-dione;styrene Chemical compound O=C1OC(=O)C=C1.C=CC1=CC=CC=C1 WOLATMHLPFJRGC-UHFFFAOYSA-N 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- KHYXYOGWAIYVBD-UHFFFAOYSA-N 4-(4-propylphenoxy)aniline Chemical compound C1=CC(CCC)=CC=C1OC1=CC=C(N)C=C1 KHYXYOGWAIYVBD-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-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
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- 125000001033 ether group Chemical group 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 125000000468 ketone group Chemical group 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 229920003192 poly(bis maleimide) Polymers 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 125000000732 arylene group Chemical group 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- XAZPKEBWNIUCKF-UHFFFAOYSA-N 1-[4-[4-[2-[4-[4-(2,5-dioxopyrrol-1-yl)phenoxy]phenyl]propan-2-yl]phenoxy]phenyl]pyrrole-2,5-dione Chemical compound C=1C=C(OC=2C=CC(=CC=2)N2C(C=CC2=O)=O)C=CC=1C(C)(C)C(C=C1)=CC=C1OC(C=C1)=CC=C1N1C(=O)C=CC1=O XAZPKEBWNIUCKF-UHFFFAOYSA-N 0.000 description 2
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 2
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical class [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000005456 alcohol based solvent Substances 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
- 239000011362 coarse particle Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 2
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003759 ester based solvent Substances 0.000 description 2
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000006081 fluorescent whitening agent Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000011810 insulating material Substances 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
- 231100000053 low toxicity Toxicity 0.000 description 2
- 238000002156 mixing Methods 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
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 1
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 description 1
- 125000006833 (C1-C5) alkylene group Chemical group 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
- BLTRCTCTKKJRIC-UHFFFAOYSA-N 1-(cyclohexylmethyl)pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1CC1CCCCC1 BLTRCTCTKKJRIC-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
- 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
- AUFOREFOYBAIJZ-UHFFFAOYSA-N 1-[3-[4-[2-[4-[3-(2,5-dioxopyrrol-1-yl)phenoxy]phenyl]propan-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)(C)C(C=C1)=CC=C1OC(C=1)=CC=CC=1N1C(=O)C=CC1=O AUFOREFOYBAIJZ-UHFFFAOYSA-N 0.000 description 1
- JAZKPFCQIJDBSX-UHFFFAOYSA-N 1-[3-[4-[4-[3-(2,5-dioxopyrrol-1-yl)phenoxy]benzoyl]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(=O)C(C=C1)=CC=C1OC(C=1)=CC=CC=1N1C(=O)C=CC1=O JAZKPFCQIJDBSX-UHFFFAOYSA-N 0.000 description 1
- AQGZJQNZNONGKY-UHFFFAOYSA-N 1-[4-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=C(N2C(C=CC2=O)=O)C=C1 AQGZJQNZNONGKY-UHFFFAOYSA-N 0.000 description 1
- KGARIUYNSFEPKD-UHFFFAOYSA-N 1-[4-[1-[4-(2,5-dioxopyrrol-1-yl)phenoxy]-4-phenylcyclohexa-2,4-dien-1-yl]oxyphenyl]pyrrole-2,5-dione Chemical group O=C1C=CC(=O)N1C(C=C1)=CC=C1OC1(OC=2C=CC(=CC=2)N2C(C=CC2=O)=O)C=CC(C=2C=CC=CC=2)=CC1 KGARIUYNSFEPKD-UHFFFAOYSA-N 0.000 description 1
- UGJHILWNNSROJV-UHFFFAOYSA-N 1-[4-[3-[4-(2,5-dioxopyrrol-1-yl)phenoxy]phenoxy]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1OC1=CC=CC(OC=2C=CC(=CC=2)N2C(C=CC2=O)=O)=C1 UGJHILWNNSROJV-UHFFFAOYSA-N 0.000 description 1
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- FUIYMUCYALFQRH-UHFFFAOYSA-N 1-[4-[4-[2-[4-[4-(2,5-dioxopyrrol-1-yl)phenoxy]phenyl]butan-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)(CC)C(C=C1)=CC=C1OC(C=C1)=CC=C1N1C(=O)C=CC1=O FUIYMUCYALFQRH-UHFFFAOYSA-N 0.000 description 1
- IRNWWNHGNUNGKL-UHFFFAOYSA-N 1-[4-[4-[2-[4-[4-(2,5-dioxopyrrol-1-yl)phenoxy]phenyl]ethyl]phenoxy]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1OC(C=C1)=CC=C1CCC(C=C1)=CC=C1OC1=CC=C(N2C(C=CC2=O)=O)C=C1 IRNWWNHGNUNGKL-UHFFFAOYSA-N 0.000 description 1
- MWVPSAKHPCVPHF-UHFFFAOYSA-N 1-[4-[4-[4-[4-(2,5-dioxopyrrol-1-yl)phenoxy]benzoyl]phenoxy]phenyl]pyrrole-2,5-dione Chemical compound C=1C=C(OC=2C=CC(=CC=2)N2C(C=CC2=O)=O)C=CC=1C(=O)C(C=C1)=CC=C1OC(C=C1)=CC=C1N1C(=O)C=CC1=O MWVPSAKHPCVPHF-UHFFFAOYSA-N 0.000 description 1
- LZNGBBXVZZYWMT-UHFFFAOYSA-N 1-[4-[4-[4-[4-(2,5-dioxopyrrol-1-yl)phenoxy]phenoxy]phenoxy]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1OC(C=C1)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N2C(C=CC2=O)=O)C=C1 LZNGBBXVZZYWMT-UHFFFAOYSA-N 0.000 description 1
- PYVHLZLQVWXBDZ-UHFFFAOYSA-N 1-[6-(2,5-dioxopyrrol-1-yl)hexyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1CCCCCCN1C(=O)C=CC1=O PYVHLZLQVWXBDZ-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、熱硬化性樹脂組成物、プリプレグ、積層板、プリント配線板及び高速通信対応モジュールに関する。 The present invention relates to a thermosetting resin composition, a prepreg, a laminate, a printed wiring board, and a module for high-speed communication.
近年の電子機器の小型化及び高性能化の流れに伴い、プリント配線板では配線密度の高度化及び高集積化が進展しており、これに伴って、プリント配線板用の積層板には、耐熱性の向上等による信頼性向上の要求が強まっている。このような用途、特に半導体パッケージ基板用途においては、優れた耐熱性及び低熱膨張性を兼備することが要求される。また、ネットワークインフラ機器、大型コンピュータ等における情報通信量、速度の著しい向上に伴い、これらの電子機器に搭載される半導体パッケージには高周波化対応が必要となり、伝送損失の低減を可能とする低誘電率及び低誘電正接を有する基板材料が求められている。 With the trend of miniaturization and high performance of electronic devices in recent years, in the printed wiring board, advancement of wiring density and high integration progress, and along with this, in laminated boards for printed wiring boards, The demand for reliability improvement by heat resistance improvement etc. is intensifying. In such applications, particularly in semiconductor package substrate applications, it is required to combine excellent heat resistance and low thermal expansion. In addition, with the remarkable improvement in the amount of information communication and speed in network infrastructure equipment, large-sized computers, etc., semiconductor packages mounted on these electronic equipments need to be compatible with high frequency, and the low dielectric constant enables reduction of transmission loss. There is a need for a substrate material having a modulus and a low dielectric loss tangent.
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。
As a laminate for a printed wiring board, one obtained by curing and integrally molding a prepreg containing a resin composition containing an epoxy resin as a main ingredient and a glass cloth is generally used.
The epoxy resin is excellent in the balance of the insulating property, heat resistance, cost and the like, but further improvement is required to cope with the excellent heat resistance and low thermal expansion required for the recent semiconductor package substrate application. Since the epoxy resin has a large coefficient of thermal expansion, low thermal expansion is achieved by selection of the epoxy resin having an aromatic ring and high filling of an inorganic filler such as silica (see, for example, Patent Document 1). However, increasing the filling amount of the inorganic filler is known to cause deterioration in insulation reliability due to moisture absorption, poor adhesion between the resin and the wiring layer, press forming failure, etc. There is a limit to low thermal expansion by only Furthermore, when an epoxy resin is used, it is difficult to obtain a resin cured product having a good dielectric constant and dielectric loss tangent, and improvement of dielectric characteristics has been required as a material for high-speed communication.
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, although the modified maleimide resin has a low relative dielectric constant and a low dielectric loss tangent as compared with the epoxy resin, it has not been able to achieve the relative dielectric constant and the dielectric loss tangent which are 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。
For the purpose of improving dielectric properties, laminates to which a polybutadiene resin is added as a thermoplastic elastomer have been studied. The laminate has excellent dielectric properties, but the prepreg has tackiness, low compatibility with other thermosetting resins, high shrinkage rate during curing, copper foil, etc. There is a drawback such as poor adhesion to metal foils.
As a method of improving them, a method using butadiene-vinyl aromatic copolymer has been proposed (see, for example, Patent Document 3), but in order to obtain sufficient compatibility with other thermosetting resins, vinyl is used. It is necessary to increase the copolymerization ratio of the aromatic compound, and in that case, there arises a problem that the heat resistance is lowered.
また、近年、半導体用パッケージ基板でチップと基板との熱膨張率の差、及び基板の硬化収縮に起因する反りが課題とされている。反りを改善する手法として、基材の熱膨張率の低減、樹脂の硬化収縮率を低減する方法が検討されている。アプローチ例として、変性マレイミド樹脂と熱可塑性エラストマーとを併用する方法が提案されている（例えば、特許文献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は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熱可塑性エラストマーを併用することで、低熱膨張性と優れた誘電特性（低比誘電率及び低誘電正接）とを両立させることができる。 Further, in recent years, in the package substrate for a semiconductor, the difference in the thermal expansion coefficient between the chip and the substrate, and the warpage caused by the cure shrinkage of the substrate are considered as problems. As a method of improving the warpage, a method of reducing the thermal expansion coefficient of the substrate and reducing the cure shrinkage of the resin has been studied. As an approach example, a method of using a modified maleimide resin and a thermoplastic elastomer in combination has been proposed (see, for example, Patent Document 4). In Patent Document 4, the thermoplastic elastomer is applied for the purpose of reducing the cure shrinkage rate of the resin. Here, the thermoplastic elastomer exhibits a low dielectric constant and a low dielectric loss tangent. Therefore, by using the modified maleimide resin and the thermoplastic elastomer in combination, it is possible to achieve both low thermal expansion and excellent dielectric characteristics (low dielectric constant and low dielectric loss tangent).
しかしながら、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。 However, although the resin composition using the above-mentioned modified maleimide resin and the thermoplastic elastomer in combination has no problem with general heat resistance, it is under severe conditions associated with the recent high density mounting and multilayer construction of the printed wiring board. There is a problem that the heat resistance, that is, the heat resistance after water absorption is inferior. It is considered that this is because the compatibility between the modified maleimide resin and the thermoplastic elastomer was insufficient according to the study of the present inventors.
本発明の課題は、こうした現状に鑑み、優れた耐熱性、低熱膨張性、低比誘電率及び低誘電正接を有する熱硬化性樹脂組成物、これを用いたプリプレグ、積層板、プリント配線板及び高速通信対応モジュールを提供することにある。 The object of the present invention is to provide a thermosetting resin composition having excellent heat resistance, low thermal expansion, low relative dielectric constant and low dielectric loss tangent, a prepreg using the same, a laminate, a printed wiring board, and the like. It is to provide a high-speed communication compatible module.
本発明者らは、前記目的を達成するために鋭意研究を重ねた結果、特定の構造を有する変性マレイミド樹脂、熱可塑性エラストマーとして変性ポリブタジエン、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。
すなわち、本発明は、以下の熱硬化性樹脂組成物、プリプレグ、積層板及びプリント配線板を提供するものである。
［１］（Ａ）１分子中に少なくとも２個のＮ−置換マレイミド基を有するマレイミド化合物（ａ１）と、１分子中に少なくとも２個の１級アミノ基を有するアミン化合物（ａ２）との付加反応物と、
（Ｂ）ポリブタジエンと、
（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、
を含有する熱硬化性樹脂組成物。
［２］前記芳香族ビニル化合物由来の構造単位が、下記一般式（Ｃ−１）で表され、前記カルボン酸無水物由来の構造単位が、下記一般式（Ｃ−２）で表される無水マレイン酸由来の構造単位である、上記［１］に記載の熱硬化性樹脂組成物。
As a result of intensive studies to achieve the above object, the present inventors use a modified maleimide resin having a specific structure, a modified polybutadiene as a thermoplastic elastomer, an aromatic vinyl compound and a carboxylic acid anhydride as raw material monomers. By using a copolymer resin, it discovers that said objective can be achieved, and came to complete this invention.
That is, the present invention provides the following thermosetting resin composition, a prepreg, a laminate and a printed wiring board.
[1] (A) Addition of a maleimide compound (a1) having at least two N-substituted maleimide groups in one molecule and an amine compound (a2) having at least two primary amino groups in one molecule Reactant,
(B) polybutadiene,
(C) A copolymer resin containing a structural unit derived from an aromatic vinyl compound and a structural unit derived from a carboxylic acid anhydride,
A thermosetting resin composition containing
[2] Anhydrous wherein the structural unit derived from the aromatic vinyl compound is represented by the following general formula (C-1), and the structural unit derived from the carboxylic anhydride is represented by the following general formula (C-2) The thermosetting resin composition as described in said [1] which is a structural unit derived from a maleic acid.
［３］前記（Ｃ）成分として、前記一般式（Ｃ−１）中のＲＣ１が水素原子、ｘが０であり、かつ前記一般式（Ｃ−１）で表される構造単位と前記一般式（Ｃ−２）で表される構造単位との含有比率［（Ｃ−１）／（Ｃ−２）］（モル比）が５〜１０である共重合樹脂を含有する、上記［１］又は［２］に記載の熱硬化性樹脂組成物。
［４］前記（Ｂ）成分の含有量が、熱硬化性樹脂組成物中の樹脂成分の固形分１００質量部に対して、４〜４０質量部であり、前記（Ｃ）成分の含有量が、熱硬化性樹脂組成物中の樹脂成分の固形分１００質量部に対して、２〜２０質量部である、上記［１］〜［３］のいずれかに記載の熱硬化性樹脂組成物。
［５］前記（ａ２）成分が、末端にアミノ基を有する変性シロキサンを含有する、上記［１］〜［４］のいずれかに記載の熱硬化性樹脂組成物。
［６］（Ｂ）ポリブタジエンが、カルボン酸変性ポリブタジエンである、上記［１］〜［５］のいずれかに記載の熱硬化性樹脂組成物。
［７］さらに、（Ｄ）硬化促進剤を含有する、上記［１］〜［６］のいずれかに記載の熱硬化性樹脂組成物。
［８］さらに、（Ｅ）無機充填材を含有する、上記［１］〜［７］のいずれかに記載の熱硬化性樹脂組成物。
［９］上記［１］〜［８］のいずれか１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。
［１０］上記［９］に記載のプリプレグを積層成形して得られる積層板。
［１１］上記［９］に記載のプリプレグ又は上記［１０］に記載の積層板を用いて製造されるプリント配線板。
［１２］上記［１１］に記載のプリント配線板を用いて製造される高速通信対応モジュール。
[3] As the component (C), R C1 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 compound [1] containing the copolymer resin whose content ratio [(C-1) / (C-2)] (molar ratio) with the structural unit represented by the formula (C-2) is 5 to 10, Or the thermosetting resin composition as described in [2].
[4] The content of the component (B) is 4 to 40 parts by mass with respect to 100 parts by mass of the solid content of the resin component in the thermosetting resin composition, and the content of the component (C) is The thermosetting resin composition according to any one of the above [1] to [3], which is 2 to 20 parts by mass with respect to 100 parts by mass of the solid content of the resin component in the thermosetting resin composition.
[5] The thermosetting resin composition according to any one of the above [1] to [4], wherein the component (a2) contains a modified siloxane having an amino group at an end.
[6] The thermosetting resin composition according to any one of the above [1] to [5], wherein (B) the polybutadiene is a carboxylic acid-modified polybutadiene.
[7] The thermosetting resin composition according to any one of the above [1] to [6], which further contains (D) a curing accelerator.
[8] The thermosetting resin composition according to any one of the above [1] to [7], further comprising (E) an inorganic filler.
[9] A prepreg formed by impregnating a fiber base material with the thermosetting resin composition according to any one of the above [1] to [8].
[10] A laminate obtained by laminating and forming the prepreg according to the above [9].
[11] A printed wiring board manufactured using the prepreg according to the above [9] or the laminated board according to the above [10].
[12] A high-speed communication compatible module manufactured using the printed wiring board according to the above [11].
本発明によれば、優れた耐熱性、低熱膨張性、低比誘電率及び低誘電正接を有する熱硬化性樹脂組成物、これを用いたプリプレグ、積層板、プリント配線板及び高速通信対応モジュールを提供することができる。 According to the present invention, a thermosetting resin composition having excellent heat resistance, low thermal expansion, low relative dielectric constant and low dielectric loss tangent, prepreg using the same, laminate, printed wiring board and module for high-speed communication Can be provided.
［熱硬化性樹脂組成物］
本発明の熱硬化性樹脂組成物は、（Ａ）１分子中に少なくとも２個のＮ−置換マレイミド基を有するマレイミド化合物（ａ１）と、１分子中に少なくとも２個の１級アミノ基を有するアミン化合物（ａ２）との付加反応物（以下、「（Ａ）変性マレイミド樹脂」ともいう）と、（Ｂ）ポリブタジエン、（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、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 has (A) a maleimide compound (a1) having at least two N-substituted maleimide groups in one molecule, and at least two primary amino groups in one molecule. Addition reaction product with amine compound (a2) (hereinafter, also referred to as “(A) modified maleimide resin”), (B) polybutadiene, (C) structural unit derived from aromatic vinyl compound and structure derived from carboxylic acid anhydride It is a thermosetting resin composition containing a copolymer resin containing units (hereinafter, also referred to as “(C) copolymer resin”).
＜（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 in one molecule, and an amine compound (a2) having at least two primary amino groups in one molecule. An addition reaction product of
（１分子中に少なくとも２個のＮ−置換マレイミド基を有するマレイミド化合物（ａ１））
１分子中に少なくとも２個のＮ−置換マレイミド基を有するマレイミド化合物（ａ１）（以下、「（ａ１）成分」ともいう）は、１分子中に少なくとも２個のＮ−置換マレイミド基を有している構造であれば、特に限定はされないが、１分子中に２個のＮ−置換マレイミド基を有するマレイミド化合物が好ましく、下記一般式（ａ１−１）で表される化合物がより好ましい。
(Maleimide compound (a1) having at least two N-substituted maleimide groups in one molecule)
The maleimide compound (a1) having at least two N-substituted maleimide groups in one molecule (hereinafter also referred to as "component (a1)") has at least two N-substituted maleimide groups in one molecule. No particular limitation is imposed on the structure, but a maleimide compound having two N-substituted maleimide groups in one molecule is preferable, and a compound represented by the following general formula (a1-1) is more preferable.
前記一般式（ａ１−２）中、ＲＡ１が表す脂肪族炭化水素基としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔ−ブチル基、ｎ−ペンチル基等の炭素数１〜５のアルキル基などが挙げられる。 As an aliphatic hydrocarbon group which R A1 represents in said general formula (a1-2), a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n -C1-C5 alkyl groups, such as a pentyl group, etc. are mentioned.
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。
As a C1-C5 aliphatic hydrocarbon group which R < A2 > represents in said general formula (a1-3), the same thing as the case of R <A1> is mentioned.
As the alkylene group having 1 to 5 carbon atoms which X A2 represents, methylene group, 1,2-dimethylene group, a 1,3-trimethylene group, 1,4-tetramethylene group, 1,5-pentamethylene group and the like Be
The alkylidene group having 2 to 5 carbon atoms which X A2 represents, ethylidene group, propylidene group, isopropylidene group, butylidene group, isobutylidene group, pentylidene group, isopentylidene group, and the like.
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。
As a C1-C5 aliphatic hydrocarbon group which R < A3 > represents in said general formula (a1-3 '), the same thing as the case of R <A2> is mentioned.
Examples of the alkylene group of 1 to 5 carbon atoms and the alkylidene group of 2 to 5 carbon atoms represented by X A3 include the same as the alkylene group of 1 to 5 carbon atoms and X 2 to 5 carbon alkylidene groups represented by X A2 Be
前記一般式（ａ１−５）中、ＲＡ４が表す炭素数１〜５の脂肪族炭化水素基としては、前記一般式（ａ１−２）中のＲＡ１の場合と同じものが挙げられる。 In the general formula (a1-5), examples of the aliphatic hydrocarbon group of 1 to 5 carbon atoms which R A4 represents may be the same as those in the case of the R 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。
As the component (a1), 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- (4-methylphenylene)) bismaleimide Maleimidophenyl) methane, bis (3-methyl-4-maleimidophenyl) methane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 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) fe 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) And -maleimidophenoxy) phenyl] ether, bis [4- (4-maleimidophenoxy) phenyl] ether and the like. The component (a1) may be used alone or as a mixture of two or more.
Among these, maleimide compounds having a phenoxy group are preferable from the viewpoint of excellent solubility in a solvent, and from the viewpoint of high conversion and higher heat resistance, 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 having at least two primary amino groups in one molecule (a2))
The amine compound (a2) having at least two primary amino groups in one molecule (hereinafter also referred to as “component (a2)”) is preferably an amine compound having two primary amino groups in one molecule. The compound represented by the following general formula (a2-1) is more preferable.
（式中、ＲＡ６は、各々独立に、炭素数１〜５の脂肪族炭化水素基である。ＹＡ２は、炭素数１〜５のアルキレン基、炭素数２〜５のアルキリデン基、エーテル基、カルボオキシ基、ケト基、単結合又は下記一般式（ａ２−３’）で表される基である。ｑ２は、各々独立に、０〜４の整数である。）
(Wherein, each R A6 is independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms. Y A2 is an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group , A carboxy group, a keto group, a single bond, or a group represented by the following general formula (a2-3 ′) q 2 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), as the aliphatic hydrocarbon group represented by R A5 , 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 -C1-C5 alkyl groups, such as a pentyl group, etc. are mentioned.
前記一般式（ａ２−３）中、ＲＡ６が表す炭素数１〜５の脂肪族炭化水素基としては、ＲＡ５の場合と同じものが挙げられる。
ＹＡ２が表す炭素数１〜５のアルキレン基としては、メチレン基、１，２−ジメチレン基、１，３−トリメチレン基、１，４−テトラメチレン基、１，５−ペンタメチレン基等が挙げられる。
ＹＡ２が表す炭素数２〜５のアルキリデン基としては、エチリデン基、プロピリデン基、イソプロピリデン基、ブチリデン基、イソブチリデン基、ペンチリデン基、イソペンチリデン基等が挙げられる。
In the general formula (a2-3), examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms R A6 represents, include the same ones as for R A5.
As a C1-C5 alkylene group which Y A2 represents, a methylene group, 1,2-dimethylene group, a 1, 3- trimethylene group, a 1, 4- tetramethylene group, a 1, 5- penta methylene group etc. are mentioned. Be
The alkylidene group having 2 to 5 carbon atoms which Y A2 represents, ethylidene group, propylidene group, isopropylidene group, butylidene group, isobutylidene group, pentylidene group, isopentylidene group, and the like.
前記一般式（ａ２−３’）中、ＲＡ７が表す炭素数１〜５の脂肪族炭化水素基としては、ＲＡ６の場合と同じものが挙げられる。
ＹＡ３が表す炭素数１〜５のアルキレン基、炭素数２〜５のアルキリデン基としては、ＹＡ２が表す炭素数１〜５のアルキレン基、炭素数２〜５のアルキリデン基と同じものが挙げられる。
In the general formula (a2-3 '), the aliphatic hydrocarbon group of 1 to 5 carbon atoms which R A7 represents, include the same ones as for R A6.
Examples of the alkylene group of 1 to 5 carbon atoms and the alkylidene group of 2 to 5 carbon atoms represented by Y A3 include the same as the alkylene group of 1 to 5 carbon atoms represented by Y A2 and the alkylidene group of 2 to 5 carbon atoms. Be
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。
As a C1-C5 alkyl group which R < A8 > represents in said general formula (a2-4), a C1-C3 alkyl group is more preferable. Examples of the alkyl group represented by R A8 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group and an n-pentyl group. Groups are preferred.
An alkyl group, an alkenyl group, an alkynyl group etc. are mentioned as a substituent in the substituted phenyl group which RA8 represents, Among these, an alkyl group is preferable. Examples of the alkyl group include the same as the alkyl group represented by R A8 .
Examples of the divalent organic group represented by R A9 include 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 preferable. Examples of the alkylene group include a methylene group, an ethylene group and a propylene group. As an arylene group, a phenylene group, a naphthylene group, etc. are mentioned.
（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。 As the component (a2), modified siloxane having an amino group at the end, diaminobenzidine, diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, diaminodiphenyl ether, 3,3'-dimethoxy-4,4 3'-Diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 1,3'-bis (4-aminophenoxy) benzene, 2,2'-bis [4- (4-aminophenoxy) phenyl Propane, 4,4′-bis (4-aminophenoxy) biphenyl, 1,4′-bis (4-aminophenoxy) benzene, 2,2′-dimethyl-4,4′-diaminobiphenyl, 4,4 ′ -Diamino-3,3'-biphenyldiol, etc. may be mentioned. The component (a2) may be used alone or as a mixture of two or more.
これらの中でも、高弾性及び高耐熱性が得られる観点からは、３，３´−ジエチル−４，４´−ジアミノジフェニルメタン、２，２´−ビス［４−（４−アミノフェノキシ）フェニル］プロパンが好ましい。
また、低熱膨張性の観点からは、末端にアミノ基を有する変性シロキサンが好ましい。末端にアミノ基を有する変性シロキサンは、市販品を用いてもよく、市販品としては、両末端にアミノ基を有する、「Ｘ−２２−１６１Ａ」（官能基当量８００ｇ／ｍｏｌ）、「Ｘ−２２−１６１Ｂ」（官能基当量１，５００ｇ／ｍｏｌ）（以上、信越化学工業株式会社製）、「ＢＹ１６−８５３Ｕ」（官能基当量４６０ｇ／ｍｏｌ）（以上、東レ・ダウコーニング株式会社製）、「ＸＦ４２−Ｃ５３７９」（官能基当量７５０ｇ／ｍｏｌ）（以上、モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製）等が挙げられる。
Among these, from the viewpoint of obtaining high elasticity and high heat resistance, 3,3′-diethyl-4,4′-diaminodiphenylmethane, 2,2′-bis [4- (4-aminophenoxy) phenyl] propane Is preferred.
In addition, from the viewpoint of low thermal expansion, modified siloxanes having an amino group at the end are preferable. A commercial item may be used for the modified siloxane which has an amino group at the terminal, As a commercial item, "X-22-161A" (functional equivalent 800 g / mol) which has an amino group at both ends, "X- 22-161 B "(functional group equivalent 1,500 g / mol) (above, Shin-Etsu Chemical Co., Ltd. made)," BY16-853 U "(functional group equivalent 460 g / mol) (above, Toray Dow Corning Co., Ltd.), Examples thereof include “XF42-C5379” (functional group equivalent weight 750 g / mol) (above, Momentive Performance Materials Japan GK Co., Ltd.) 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。
Further, the component (a2) contains a modified siloxane having an amino group at an end and an amine compound other than a modified siloxane having an amino group at an end, from the viewpoint of achieving both low thermal expansion, high elasticity and high heat resistance. It is preferable to use a modified siloxane having an amino group at the terminal, and 3,3'-diethyl-4,4'-diaminodiphenylmethane and 2,2'-bis [4- (4-aminophenoxy) phenyl] propane. It is more preferable to use one or more kinds selected from the group in combination.
When a modified siloxane having an amino group at the end and an amine compound other than a modified siloxane having an amino group at the end are used in combination as component (a2), the mass ratio [modified siloxane having an amino group at the end / terminal 3/97 to 90/10 is preferable, 10/90 to 80/20 is more preferable, and 20/80 to 70/30 is more preferable.
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 modified maleimide resin (A) which is an addition reaction product of the component (a1) and the component (a2) has, for example, a structural unit represented by the following general formula (A-1).
（（Ａ）変性マレイミド樹脂の製造方法）
（Ａ）変性マレイミド樹脂は、（ａ１）成分と（ａ２）成分とを付加反応させることにより製造することができる。
前記付加反応における（ａ１）成分と（ａ２）成分の配合量としては、ゲル化防止及び耐熱性の観点から、（ａ１）成分のマレイミド基の当量が、（ａ２）成分の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)
The modified maleimide resin (A) can be produced by the addition reaction of the components (a1) and (a2).
The compounding amount of the component (a1) and the component (a2) in the addition reaction is the equivalent of the maleimide group of the component (a1) from the viewpoint of gelation prevention and heat resistance, that of the primary amino group of the component (a2) The ratio of the equivalent of the maleimide group of the component (a1) to the equivalent of the primary amino group of the component (a2) [(a1) component / (a2) component] is preferably 2 to 15 Is preferably, and more preferably 3 to 10.
前記付加反応における反応温度は、生産性及び均一に反応を進行させる観点から、７０〜１５０℃が好ましく、１００〜１３０℃がより好ましい。また、反応時間は、０．１〜１０時間が好ましく、１〜６時間がより好ましい。 The reaction temperature in the addition reaction is preferably 70 to 150 ° C., and more preferably 100 to 130 ° C. from the viewpoint of productivity and uniform reaction progress. The reaction time is preferably 0.1 to 10 hours, more preferably 1 to 6 hours.
前記付加反応は、有機溶媒中で行うことが好ましい。有機溶媒としては、エタノール、プロパノール、プロピレングリコールモノメチルエーテル等のアルコール系溶媒；メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶媒；酢酸エチルエステル等のエステル系溶媒；トルエン等の芳香族系溶媒；ジメチルアセトアミド、Ｎ−メチルピロリドン等の窒素原子含有溶媒などが挙げられる。有機溶媒は、単独で用いても２種類以上を混合して用いてもよい。
これらの中でも、溶解性の観点から、シクロヘキサノン、プロピレングリコールモノメチルエーテル、メチルセロソルブ、γ−ブチロラクトンが好ましく、低毒性であること及び揮発性が高く残溶媒として残りにくい観点から、シクロヘキサノン、プロピレングリコールモノメチルエーテルが好ましい。
有機溶媒の使用量は、溶解性及び反応速度の観点から、（ａ１）成分と（ａ２）成分との合計１００質量部に対し、２５〜１，０００質量部が好ましく、５０〜５００質量部がより好ましい。
The addition reaction is preferably performed in an organic solvent. Examples of the organic solvent include alcohol solvents such as ethanol, propanol and propylene glycol monomethyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ester solvents such as acetic acid ethyl ester; aromatic solvents such as toluene; Nitrogen atom containing solvents, such as acetamide and N-methyl pyrrolidone, etc. are mentioned. The organic solvents may be used alone or in combination of two or more.
Among these, cyclohexanone, propylene glycol monomethyl ether, methyl cellosolve, and γ-butyrolactone are preferable from the viewpoint of solubility, and cyclohexanone and propylene glycol monomethyl ether are preferable from the viewpoint of low toxicity and high volatility and little residual solvent. Is preferred.
The amount of the organic solvent used is preferably 25 to 1,000 parts by mass and 50 to 500 parts by mass with respect to 100 parts by mass in total of the components (a1) and (a2) from the viewpoint of solubility and reaction rate More preferable.
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）ポリブタジエン、（Ｃ）共重合樹脂等が樹脂成分に該当する。
The content of the (A) modified maleimide resin in the thermosetting resin composition of the present invention is preferably 50 to 95 parts by mass with respect to 100 parts by mass of the solid content of the resin component in the thermosetting resin composition, 60-90 mass parts are more preferable, and 70-87 mass parts are further more preferable.
In the present specification, “solid content” refers to non-volatile components excluding volatile substances such as solvents, and refers to components remaining without volatilization when the resin composition is dried, at room temperature. It also includes liquid, starch syrup and wax. Here, room temperature refers to 25 ° C. in this specification.
Moreover, a "resin component" is a component used for manufacture of resin or resin except the inorganic filler mentioned later, and, specifically, (A) modified maleimide resin, (B) polybutadiene, (C) Copolymer resin etc. correspond to a 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。
In addition, the content of the (A) modified maleimide resin in the thermosetting resin composition of the present invention is the amount of the (A) modified maleimide resin in the thermosetting resin composition from the viewpoint of elastic modulus and low thermal expansion. The amount of the component (a1) of the raw material converted from is preferably 30 to 90 parts by mass with respect to 100 parts by mass of the solid content of the resin component in the thermosetting resin composition, and 50 to 85 parts by mass The amount which becomes is more preferable.
In addition, the content of the (A) modified maleimide resin in the thermosetting resin composition of the present invention is (A) modified in the thermosetting resin composition from the viewpoint of good low thermal expansion and copper foil adhesion. The amount of component (a2) of the raw material converted from the amount of 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 40 to 40 parts by mass is more preferable.
＜（Ｂ）ポリブタジエン＞
熱可塑性エラストマーとして使用する（Ｂ）ポリブタジエン（以下、「（Ｂ）成分」ともいう）としては、特に制限はなく、従来公知のポリブタジエン中から、適宜選択することができる。但し、本発明において、（Ｂ）ポリブタジエンは、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。
熱可塑性エラストマーとして（Ｂ）ポリブタジエンを用いることにより、良い誘電特性を有する樹脂組成物を得ることができる。
<(B) Polybutadiene>
There is no restriction | limiting in particular as (B) polybutadiene (Hereafter, it is also mentioned "(B) component") used as a thermoplastic elastomer, It can select suitably from conventionally well-known polybutadiene. However, in the present invention, (B) polybutadiene is defined as one not including a copolymer resin containing a structural unit derived from an aromatic vinyl compound (C) described later and a structural unit derived from a carboxylic acid anhydride.
By using (B) polybutadiene as the thermoplastic elastomer, a resin composition having good dielectric properties can be obtained.
（Ｂ）ポリブタジエンとしては、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。 Examples of the polybutadiene (B) include styrene-based elastomers, olefin-based elastomers, urethane-based elastomers, polyester-based elastomers, polyamide-based elastomers, acrylic elastomers, silicone-based elastomers, and derivatives thereof. The component (B) may be used alone or as a mixture of two or more.
また、（Ｂ）ポリブタジエンとしては、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好ましい。相溶性に優れるカルボシ基がより好ましく、カルボン酸変性ポリブタジエンがさらに好ましい。
Moreover, as (B) polybutadiene, what has a reactive functional group in a molecular terminal or a molecular chain can be used. As a reactive functional group, an epoxy group, a hydroxyl group, a carboxy group, an amino group, an amido group, an isocyanate group, an acryl group, a methacryl group, a vinyl group etc. are mentioned. By having these reactive functional groups in the molecular terminal or in the molecular chain, the compatibility can be improved and the heat resistance of the substrate can be improved.
Among these reactive functional groups, from the viewpoint of adhesion to the metal foil, it is preferable to have a carboxy group, an amino group and a hydroxyl group from the viewpoint of heat resistance and insulation reliability. A carboxyl group having excellent compatibility is more preferable, and a carboxylic acid-modified polybutadiene is more preferable.
熱硬化性樹脂組成物中の（Ｂ）ポリブタジエンの含有量は、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、４〜４０質量部が好ましく、６〜２５質量部がより好ましい。（Ｂ）ポリブタジエンの含有量が、４質量部以上であると低誘電率化の効果が十分得られ、２５質量部以下であると、（Ｂ）ポリブタジエン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。 4-40 mass parts is preferable with respect to 100 mass parts of solid content of the resin component in a thermosetting resin composition, as for content of (B) polybutadiene in a thermosetting resin composition, 6-25 mass parts Is more preferred. When the content of (B) polybutadiene is 4 parts by mass or more, the effect of lowering the dielectric constant is sufficiently obtained, and when it is 25 parts by mass or less, (B) the polybutadiene is compatibilized and sufficiently dispersed in resin Excellent in 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）ポリブタジエン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）ポリブタジエンとの相溶性が向上し、耐熱性が向上したと考えられる。さらには、（Ｃ）共重合樹脂自体も、優れた誘電特性を有することから、誘電特性を損なうことなく、優れた耐熱性を付与することができたと考えられる。
<(C) copolymer resin>
The copolymer resin (C) is a copolymer resin containing a structural unit derived from an aromatic vinyl compound and a structural unit derived from a carboxylic acid anhydride.
In the thermosetting resin composition of the present invention, the effect of being excellent in heat resistance particularly after water absorption is obtained by containing the (C) copolymer resin. Although the reason which produces such an effect is not certain, 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, but the thermoplastic elastomer is compatible with each other because the structure of the modified maleimide resin and the skeleton are largely different. It was a difficult condition. Therefore, when the modified maleimide resin and the thermoplastic elastomer are simply blended, there is a problem in the heat resistance under severe conditions (for example, after the moisture absorption treatment by a pressure cooker) required in recent years.
The (C) copolymer resin contained in the thermosetting resin composition of the present invention contains a structural unit derived from an aromatic vinyl compound and a structural unit derived from a carboxylic acid anhydride, and is derived from an aromatic vinyl compound The structural unit is excellent in compatibility with a thermoplastic elastomer (in particular, an elastomer containing styrene), and the structural unit derived from carboxylic acid anhydride is excellent in compatibility with a modified maleimide resin. Therefore, the (C) copolymer resin functions as a compatibilizer between the (A) modified maleimide resin and the (B) polybutadiene, thereby improving the compatibility between the (A) modified maleimide resin and the (B) polybutadiene. The heat resistance is considered to be improved. Furthermore, since the (C) copolymer resin itself also has excellent dielectric properties, it is considered that excellent heat resistance could be imparted without impairing the dielectric properties.
（Ｃ）共重合樹脂の芳香族ビニル化合物由来の構造単位としては、下記一般式（Ｃ−１）で表される構造単位が好ましい。また、前記（Ｃ）成分のカルボン酸無水物由来の構造単位としては、無水マレイン酸由来の構造単位、無水フタル酸由来の構造単位、無水コハク酸由来の構造単位等が挙げられるが、特に（Ａ）変性マレイミド樹脂との相溶性の観点から、マレイミド基に近い構造を有する下記一般式（Ｃ−２）で表される無水マレイン酸由来の構造単位が好ましい。 As a structural unit derived from the aromatic vinyl compound of (C) copolymer resin, the structural unit represented by the following general formula (C-1) is preferable. Examples of the structural unit derived from the carboxylic acid anhydride of the component (C) include structural units derived from maleic anhydride, structural units derived from phthalic anhydride, structural units derived from succinic anhydride, etc. A) From the viewpoint of compatibility with the modified maleimide resin, a structural unit derived from maleic anhydride represented by the following general formula (C-2) having a structure close to a maleimide group is preferable.
ＲＣ１及びＲＣ２が示す炭素数１〜５の脂肪族炭化水素基としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔ−ブチル基、ｎ−ペンチル基等が挙げられる。これらの中でも、銅箔との接着性及び誘電特性の観点から、炭素数１〜３の脂肪族炭化水素基が好ましく、メチル基、エチル基がより好ましい。
ＲＣ２が示す炭素数６〜２０の芳香族炭化水素基としては、フェニル基、ナフチル基、アントリル基、ビフェニリル基等が挙げられる。
前記一般式（Ｃ−１）で表される構造単位おいては、ＲＣ１が水素原子であり、かつｘが０である下記式（Ｃ−１’）で表される構造単位が好ましい。
As a C1- C5 aliphatic hydrocarbon group which R < C1> and R <C2> show, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, an isobutyl group, t-butyl group, n- A pentyl group etc. are mentioned. Among these, an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferable, and a methyl group and an ethyl group are more preferable from the viewpoint of adhesion to a copper foil and dielectric properties.
The aromatic hydrocarbon group having 6 to 20 carbon atoms R C2 represents a phenyl group, a naphthyl group, an anthryl group, etc. biphenylyl group.
In the structural unit represented by the general formula (C-1), a structural unit represented by the following formula (C-1 ′) in which R C1 is a hydrogen atom and x is 0 is preferable.
（Ｃ）共重合樹脂中における、一般式（Ｃ−１）で表される構造単位と、一般式（Ｃ−２）で表される構造単位との含有比率［（Ｃ−１）／（Ｃ−２）］（モル比）は、２〜１２が好ましく、５〜１０がより好ましい。当該含有比率が２以上であると、誘電特性及び耐熱性の改善効果が十分となる傾向にあり、１２以下であると、相溶性が良好となる傾向にある。さらに、［（Ｃ−１）／（Ｃ−２）］（モル比）が５〜１０であると、良好な基材特性を有することに加え、（Ｂ）ポリブタジエン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）ポリブタジエン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) In the copolymer resin, the content ratio [(C-1) / (C) of the structural unit represented by the general formula (C-1) and the structural unit represented by the general formula (C-2) 2-12 are preferable and 2-12 are preferable, and 5-10 are more preferable. When the content ratio is 2 or more, the effect of improving the dielectric properties and heat resistance tends to be sufficient, and when it is 12 or less, the compatibility tends to be good. Furthermore, in addition to having a favorable base-material characteristic as [(C-1) / (C-2)] (molar ratio) is 5-10, the styrene origin which is excellent in compatibility with the (B) polybutadiene Since the content of the structural unit of (1) is in the preferable range, the compatibility between the (A) modified maleimide resin and (B) polybutadiene is further improved, and the powder removal properties of the prepreg are also improved.
The total content of the structural unit represented by Formula (C-1) and the structural unit represented by Formula (C-2) in the copolymer resin (C) is preferably 50% by mass or more. 70 mass% or more is more preferable, 90 mass% or more is further preferable, and substantially 100 mass% is especially 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。
The copolymer resin (C) can be produced by copolymerizing an aromatic vinyl compound and maleic anhydride.
Examples of the aromatic vinyl compound include styrene, 1-methylstyrene, vinyl toluene and the like. These may be used alone or as a mixture of two or more.
Furthermore, various polymerizable components may be copolymerized in addition to the aromatic vinyl compound and maleic anhydride. Various polymerizable components include vinyl compounds such as ethylene, propylene and butadiene.
（Ｃ）共重合樹脂としては、市販品を用いることもでき、市販品としては、「ＳＭＡ（登録商標）ＥＦ３０」（スチレン／無水マレイン酸＝３、Ｍｗ＝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。 A commercial item can also be used as (C) copolymer resin, As a commercial item, "SMA (registered trademark) EF30" (styrene / maleic anhydride = 3, Mw = 9,500), "SMAEF 40" ( Styrene / maleic anhydride = 4, Mw = 11,000), “SMAEF 60” (styrene / maleic anhydride = 6, Mw = 11,500), “SMAEF 80” (styrene / maleic anhydride = 8, Mw = 14, 400) (manufactured by Sartmar Inc.) 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 (C) copolymer resin in the thermosetting resin composition is preferably 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, and 3 to 15 A mass part is more preferable, and 4-13 mass parts is further more preferable. 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 it is 20 parts by mass or less, the dispersibility of the copolymer resin (C) is excellent. Excellent heat resistance and peel strength.
＜（Ｄ）硬化促進剤＞
本発明の熱硬化性樹脂組成物は、硬化反応を促進する観点から、さらに、（Ｄ）硬化促進剤を含有していてもよい。
（Ｄ）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。（Ｄ）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（Ｄ）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。
<(D) Hardening accelerator>
The thermosetting resin composition of the present invention may further contain (D) a curing accelerator from the viewpoint of promoting the curing reaction.
(D) As curing accelerators, organophosphorus compounds such as triphenylphosphine; imidazoles and derivatives thereof; nitrogen-containing compounds such as secondary amines, tertiary amines, 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; organic metal salts such as zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate and the like. The curing accelerator (D) may be used alone or in combination of two or more.
When the thermosetting resin composition of the present invention contains (D) a curing accelerator, the content thereof is 0.1 to 0.1 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.
＜（Ｅ）無機充填材＞
本発明の熱硬化性樹脂組成物は、さらに、（Ｅ）無機充填材を含有していてもよい。
（Ｅ）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。（Ｅ）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。
<(E) Inorganic filler>
The thermosetting resin composition of the present invention may further contain (E) an inorganic filler.
(E) As an inorganic filler, silica, alumina, titanium oxide, mica, barium titanate, strontium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, calcium carbonate silicon nitride, boron nitride, talc, silicon carbide, Quartz powder, short glass fiber, fine glass powder, hollow glass and the like can be mentioned. As glass, E glass, T glass, D glass etc. are mentioned preferably. The inorganic filler (E) 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 the silica include precipitated silica manufactured by a wet method and having a high water content, and dry silica manufactured by a dry method and hardly containing bound water and the like. The dry silica further includes a difference in production method. , Crushed silica, fumed silica, fused spherical silica and the like. Among these, fused spherical silica is preferred from the viewpoints of low thermal expansion and fluidity when filled in a resin.
（Ｅ）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。
（Ｅ）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（Ｅ）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（Ｅ）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。
0.1-10 micrometers is preferable and, as for the average particle diameter of an inorganic filler, 0.3-8 micrometers is more preferable. When the average particle diameter is 0.1 μm or more, the flowability at the time of high loading into the resin can be kept good, and when it is 10 μm or less, the mixing probability of coarse particles is reduced, and defects due to coarse particles The occurrence can be suppressed. Here, the average particle diameter is the particle diameter of a point corresponding to 50% volume when the cumulative frequency distribution curve by particle diameter is determined with the total volume of particles as 100%, and the laser diffraction scattering method is used. It can measure with the particle size distribution measuring device etc.
(E) The inorganic filler may be surface-treated with a coupling agent. The method of surface treatment with a coupling agent may be a method in which the surface treatment is carried out dry or wet with respect to the (E) inorganic filler before compounding, and the surface untreated (E) inorganic filler is It may be a so-called integral blend processing system in which a silane coupling agent is added to the composition after being formulated into a composition.
As a coupling agent, a silane coupling agent, a titanate coupling agent, a silicone oligomer, etc. are mentioned.
本発明の熱硬化性樹脂組成物が（Ｅ）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。（Ｅ）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 (E) an inorganic filler, the content thereof is 10 to 300 mass relative to 100 parts by mass of the solid content of the resin component in the thermosetting resin composition. A part is preferable and 50-250 mass parts is more preferable. (E) When the content of the inorganic filler is in the above range, the moldability and the low thermal expansion property become good.
本発明の熱硬化性樹脂組成物が（Ｅ）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、（Ｅ）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 (E) an inorganic filler, it is treated with a dispersing machine such as a triple roll, bead mill, nanomizer, etc. as necessary to obtain (E) an inorganic filler. It is preferred to improve the dispersibility.
＜その他の成分＞
本発明の（Ａ）変性マレイミド樹脂は、熱硬化性樹脂であり、単独で良好な熱硬化性を有するが、必要により、他の熱硬化性樹脂と併用することで、接着性、機械強度等を向上させることができる。
併用する熱硬化性樹脂は、特に制限されないが、例えば、エポキシ樹脂、フェノール樹脂、シアネート樹脂、イソシアネート樹脂、ベンゾオキサジン樹脂、アリル樹脂、ジシクロペンタジエン樹脂、シリコーン樹脂、トリアジン樹脂等が挙げられ、これらは単独で、あるいは２種類以上混合して使用してもよい。これらの中でも、成形性及び電気絶縁性の観点から、シアネート樹脂、ベンゾオキサジン樹脂が好ましい。
また、エポキシ樹脂を含有することで良好な接着性を有することができるが、その含有量は熱硬化性樹脂組成物の固形分中、２質量％以下であることが好ましい。エポキシ樹脂の含有量を２質量％以下とすることで、誘電特性及び保存安定性を優れたものとすることができる。
<Other ingredients>
The (A) modified maleimide resin of the present invention is a thermosetting resin and has good thermosetting properties alone, but if necessary, it can be used in combination with other thermosetting resins to improve adhesion, mechanical strength, etc. Can be improved.
The thermosetting resin to be used in combination is not particularly limited, and examples thereof include epoxy resin, phenol resin, cyanate resin, isocyanate resin, benzoxazine resin, allyl resin, dicyclopentadiene resin, silicone resin, triazine resin, etc. These may be used alone or in combination of two or more. Among these, cyanate resins and benzoxazine resins are preferable from the viewpoint of moldability and electrical insulation.
Moreover, although it can have favorable adhesiveness by containing an epoxy resin, it is preferable that the content is 2 mass% or less in solid content of a thermosetting resin composition. By setting the content of the epoxy resin to 2% by mass or less, the dielectric characteristics and storage stability can be made excellent.
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、難燃剤、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。
難燃剤としては、芳香族リン酸エステル化合物、ホスファゼン化合物、ホスフィン酸エステル、ホスフィン酸化合物の金属塩、赤リン、９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキシド及びその誘導体等のリン系難燃剤；硫酸メラミン、ポリリン酸メラミン等の窒素系難燃剤；三酸化アンチモン等の無機系難燃剤などが挙げられる。
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 optionally contains known organic fillers, flame retardants, ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent brighteners, adhesion improvers, etc. It is also good.
Examples of the organic filler include resin fillers made of polyethylene, polypropylene resin and the like, and resin fillers having a core-shell structure.
As a flame retardant, aromatic phosphoric acid ester compounds, phosphazene compounds, phosphinic acid esters, metal salts of phosphinic acid compounds, red phosphorus, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and the like Phosphorus flame retardants such as derivatives; Nitrogen flame retardants such as melamine sulfate and melamine polyphosphate; Inorganic flame retardants such as antimony trioxide and the like.
As an ultraviolet absorber, a benzotriazole type ultraviolet absorber is mentioned.
Examples of the antioxidant include hindered phenol-based antioxidants, hindered amine-based antioxidants, and the like.
As a photoinitiator, photoinitiators, such as benzophenones, benzyl ketals, and thioxanthone type | system | group, are mentioned.
Examples of the fluorescent whitening agent include fluorescent whitening agents of stilbene derivatives.
Examples of the adhesion improver include urea compounds such as ureasilane, the above-mentioned coupling agent and the like.
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 a prepreg or the like.
ワニスに用いる有機溶媒としては、エタノール、プロパノール、プロピレングリコールモノメチルエーテル等のアルコール系溶媒；メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶媒；酢酸エチルエステル等のエステル系溶媒；トルエン、キシレン等の芳香族系溶媒；ジメチルアセトアミド、Ｎ−メチルピロリドン等の窒素原子含有溶媒などが挙げられる。これらの有機溶媒は、単独で用いても２種類以上を混合して用いてもよい。
これらの中でも、溶解性の観点から、プロピレングリコールモノメチルエーテルメチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、トルエンが好ましく、低毒性である点から、プロピレングリコールモノメチルエーテル、メチルイソブチルケトン、シクロヘキサノン、トルエンがより好ましい。
ワニスの固形分濃度は、４０〜９０質量％が好ましく、５０〜８０質量％がより好ましい。ワニスの固形分濃度が前記範囲内であると、塗工性を良好に保ち、適切な樹脂組成物付着量のプリプレグを得ることができる。
Organic solvents used for the varnish 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 acetic acid ethyl ester; and aroma such as toluene and xylene Group solvents; solvents containing nitrogen atom such as dimethyl acetamide, N-methyl pyrrolidone and the like; These organic solvents may be used alone or in combination of two or more.
Among these, propylene glycol monomethyl ether methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and toluene are preferable from the viewpoint of solubility, and propylene glycol mono methyl ether, methyl isobutyl ketone, cyclohexanone and toluene are more preferable from the viewpoint of low toxicity.
40-90 mass% is preferable, and, as for solid content concentration of a varnish, 50-80 mass% is more preferable. When the solid content concentration of the varnish is within the above range, the coatability can be kept good, and a prepreg having an appropriate amount of resin composition attached can be obtained.
［プリプレグ］
本発明のプリプレグは、本発明の熱硬化性樹脂組成物を繊維基材に含浸させてなるものである。
本発明のプリプレグは、本発明の熱硬化性樹脂組成物を、繊維基材に含浸し、加熱等により半硬化（Ｂステージ化）して製造することができる。
繊維基材としては、各種の電気絶縁材料用積層板に用いられている周知のものが使用できる。その材質の例としては、Ｅガラス、Ｓガラス、低誘電ガラス、Ｑガラス等の無機物繊維；低誘電ガラスポリイミド、ポリエステル、ポリテトラフルオロエチレン等の有機繊維；並びにそれらの混合物などが挙げられる。
[Prepreg]
The prepreg of the present invention is obtained by impregnating the thermosetting resin composition of the present invention into a fiber substrate.
The prepreg of the present invention can be manufactured by impregnating a fiber base material with the thermosetting resin composition of the present invention and semi-curing (B-staging) by heating or the like.
As a fiber base material, the well-known thing used for the laminated board for various electric insulation materials can be used. Examples of the material include inorganic fibers such as E glass, S glass, low dielectric glass, Q glass, etc .; organic fibers such as low dielectric glass polyimide, polyester, polytetrafluoroethylene and the like; and mixtures thereof.
これらの繊維基材は、例えば、織布、不織布、ロービンク、チョップドストランドマット、サーフェシングマット等の形状を有するが、材質及び形状は、目的とする成形物の用途、性能等により選択され、必要により、単独又は２種類以上の材質及び形状を組み合わせることができる。繊維基材の厚さは、例えば、約０．０３〜０．５ｍｍのものを使用することができる。これらの繊維基材は、シランカップリング剤等で表面処理したもの又は機械的に開繊処理を施したものが、耐熱性、耐湿性、加工性等の面から好適である。 These fiber substrates have, for example, shapes such as woven fabric, non-woven fabric, robink, chopped strand mat, surfacing mat, etc., and the material and shape are selected according to the intended use of the molded object, performance, etc. Thus, one or more materials and shapes can be combined. The thickness of the fiber substrate can be, for example, about 0.03 to 0.5 mm. As these fiber substrates, those which have been surface-treated with a silane coupling agent or the like, or those which have been subjected to an opening treatment mechanically are preferable in terms of heat resistance, moisture resistance, processability and the like.
本発明のプリプレグは、例えば、繊維基材に対する熱硬化性樹脂組成物の付着量（プリプレグ中の熱硬化性樹脂組成物の含有量）が、２０〜９０質量％となるように、繊維基材に含浸した後、通常、１００〜２００℃の温度で１〜３０分間加熱乾燥し、半硬化（Ｂステージ化）させて得ることができる。 The prepreg of the present invention is, for example, a fiber base such that the adhesion amount of the thermosetting resin composition to the fiber base (content of the thermosetting resin composition in the prepreg) is 20 to 90 mass%. After being impregnated, it is usually dried by heating at a temperature of 100 to 200.degree. C. for 1 to 30 minutes, and can be obtained by semi-curing (B-staging).
［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。
[Laminated board]
The laminate of the present invention is obtained by laminating and molding the prepreg of the present invention.
The laminate of the present invention can be produced, for example, by laminating and forming the prepreg of the present invention in a configuration in which 1 to 20 sheets of the laminate of the present invention are stacked and metal foils such as copper and aluminum are disposed on one side or both sides. The metal foil is not particularly limited as long as it is used for an electrical insulating material application.
As the molding conditions for producing the laminated plate, for example, the method of laminated plate for electric insulating material and multi-layer plate can be applied, using multistage press, multistage vacuum press, continuous molding, autoclave molding machine etc. C., pressure 0.2 to 10 MPa, heating time 0.1 to 5 hours. Moreover, the prepreg of this invention and the wiring board for inner layers can be combined, and it can laminate-mold, and can also manufacture a laminated board.
［プリント配線板］
本発明のプリント配線板は、本発明のプリプレグ又は積層板を用いて製造されたものである。
本発明のプリント配線板は、例えば、本発明の積層板の表面に回路を形成して製造することができる。また、本発明の積層板の導体層を通常のエッチング法によって配線加工し、本発明のプリプレグを介して配線加工した積層板を複数積層し、加熱プレス加工することによって一括して多層化することもできる。その後、ドリル加工又はレーザ加工によるスルーホール又はブラインドビアホールの形成と、メッキ又は導電性ペーストによる層間配線の形成を経て多層プリント配線板を製造することができる。
[Printed wiring board]
The printed wiring board of the present invention is manufactured 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. In addition, the conductor layer of the laminate of the present invention is subjected to wiring processing by a common etching method, and a plurality of laminates subjected to wiring processing via the prepreg of the present invention are laminated in multiple layers and collectively subjected to multilayering by heat pressing. You can also. Thereafter, a multilayer printed wiring board can be manufactured through formation of through holes or blind via holes by drilling or laser processing and 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 support module]
The high-speed communication support module of the present invention is a high-speed communication support module manufactured using the printed wiring board of the present invention.
The high-speed communication support 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 in particular, uses signals in high frequency band such as wireless communication devices and network infrastructure devices. It is suitable for applications where the amount of information communication and the speed are large.
次に、下記の実施例により本発明をさらに詳しく説明するが、これらの実施例は本発明を制限するものではない。
なお、各例で得られた熱硬化性樹脂組成物及び銅張積層板について以下の評価を行った
。
The present invention will now be described in more detail by the following examples, which should not be construed as limiting the invention.
In addition, the following evaluation was performed about the thermosetting resin composition and copper clad laminated board which were obtained in each case.
（１）ガラス転移温度（Ｔｇ）
銅張積層板を銅エッチング液に浸漬することにより銅箔を取り除いた５ｍｍ×５ｍｍの評価基板を作製し、ＴＭＡ（熱機械分析）装置（ＴＡインスツルメント社製、商品名：Ｑ４００）を用いて圧縮法で熱機械分析を行った。評価基板を前記装置にＸ方向に装着後、荷重５ｇ、昇温速度１０℃／分の測定条件にて連続して２回測定した。２回目の測定における熱膨張曲線の異なる接線の交点で示される点を求め、これをガラス転移温度（Ｔｇ）とした。
(1) Glass transition temperature (Tg)
A copper-clad laminate is immersed in a copper etching solution to prepare a 5 mm × 5 mm evaluation substrate from which the copper foil has been removed, and a TMA (Thermal Mechanical Analysis) apparatus (trade name: Q400, manufactured by TA Instruments) is used. The thermomechanical analysis was performed by the compression method. After the evaluation substrate was mounted on the apparatus in the X direction, measurement was performed twice continuously under the measurement conditions of a load of 5 g and a temperature rising rate of 10 ° C./min. The point indicated by the intersection of different tangents of the thermal expansion curve in the second measurement was determined, and this was 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×５ｍｍの評価基板を作製し、ＴＭＡ（熱機械分析）装置（ＴＡインスツルメント社製、商品名：Ｑ４００）を用いて圧縮法で熱機械分析を行った。評価基板を前記装置にＸ方向に装着後、荷重５ｇ、昇温速度１０℃／分の測定条件にて連続して２回測定した。２回目の測定における３０℃から１００℃までの平均熱膨張率を算出し、これを熱膨張率の値とした。
(2) Thermal expansion coefficient A 5 mm × 5 mm evaluation substrate from which a copper foil is removed by immersing a copper-clad laminate in a copper etching solution is manufactured, and a TMA (Thermal Mechanical Analysis) device (manufactured by TA Instruments Co., Ltd.) Name: Q400) was used for thermomechanical analysis by compression method. After the evaluation substrate was mounted on the apparatus in the X direction, measurement was performed twice continuously under the measurement conditions of a load of 5 g and a temperature rising rate of 10 ° C./min. The average coefficient of thermal expansion from 30 ° C. to 100 ° C. in the second measurement was calculated and used as the value of coefficient of thermal expansion.
（３）誘電特性（比誘電率及び誘電正接）
銅張積層板を銅エッチング液に浸漬することにより銅箔を取り除いた１００ｍｍ×２ｍｍの評価基板を作製し、空洞共振機装置（株式会社関東電子応用開発製）を用いて、周波数１０ＧＨｚでの比誘電率及び誘電正接を測定した。
(3) Dielectric characteristics (relative dielectric constant and dielectric loss tangent)
A copper-clad laminate is immersed in a copper etching solution to make a 100 mm × 2 mm evaluation substrate from which the copper foil is removed, and the ratio at a frequency of 10 GHz is obtained using a cavity resonator device (Kanto Electronics Application Development Co., Ltd.) The dielectric constant and the dielectric loss tangent were measured.
（４）銅付きはんだ耐熱性
銅張積層板を２５ｍｍ×２５ｍｍの大きさに切り出した評価基板を作製し、該評価基板を温度２８８℃のはんだ浴に、最大で６０分間フロートしながら、外観を観察することにより、膨れが発生するまでの時間を測定した。評価結果は、６０分間フロートした時点で膨れが確認されなかったものを「＞６０」として表１に記載した。
(4) Solder heat resistance with copper An evaluation substrate is prepared by cutting a copper clad laminate into a size of 25 mm × 25 mm, and the evaluation substrate floats in a solder bath at a temperature of 288 ° C. for up to 60 minutes while the appearance is made By observing, the time until blistering occurred was measured. The evaluation results are shown in Table 1 as ">60" in which swelling was not confirmed when floated for 60 minutes.
（５）吸水半銅付はんだ耐熱性
銅張積層板を５０ｍｍ×５０ｍｍの大きさに切断し、一方の表面のみ半面銅を残し、他方の表面については銅エッチング液に浸漬して全面銅を除去することにより５０ｍｍ×５０ｍｍの半銅付評価基板を作製した。プレッシャークッカーテスト（ＰＣＴ）用装置（株式会社平山製作所製）（条件：１２１℃、２．２気圧）中で５時間処理した後の半銅付評価基板を、２８８℃のはんだ浴にそれぞれ２０秒間浸漬後、外観を目視で観察することにより吸水半銅付はんだ耐熱性を評価した。評価結果は、膨れが確認されなかったものを「Ａ」、膨れが確認されたものを「Ｂ」として表１に記載した。
(5) Soldering heat resistance with copper and water absorption copper The copper clad laminate is cut to a size of 50 mm × 50 mm, leaving half copper on one surface only, and immersing the other surface in a copper etching solution to remove copper on the entire surface As a result, a 50 mm × 50 mm evaluation board with a half copper was prepared. Evaluation board with a half copper after treatment for 5 hours in equipment for pressure cooker test (PCT) (manufactured by Hirayama Seisakusho Co., Ltd. (conditions: 121 ° C, 2.2 atm), each for 20 seconds in a solder bath at 288 ° C After immersion, the heat resistance was evaluated by observing the appearance visually. The evaluation results are shown in Table 1 as "A" for which no blister was confirmed and "B" for those whose blister was confirmed.
製造例１：〔変性マレイミド樹脂（Ａ−１）の製造〕
温度計、攪拌装置及び還流冷却管付き水分定量器の付いた加熱及び冷却可能な容積２リットルの反応容器に、両末端ジアミン変性シロキサン（信越化学工業株式会社製、商品名：Ｘ−２２−１６１Ａ）１５．９ｇと、３，３´−ジエチル−４，４´−ジアミノジフェニルメタン（日本化薬株式会社製、商品名：ＫＡＹＡＨＡＲＤ（登録商標）Ａ−Ａ）２８．６ｇと、ビス（４−マレイミドフェニル）メタン（ケイ・アイ化成株式会社製、商品名：ＢＭＩ）２８０．５ｇと、プロピレングリコールモノメチルエーテル２００．０ｇと、を入れ、１２６℃で還流させながら５時間反応させて変性マレイミド樹脂（Ａ−１）の溶液を得た。
Production Example 1: [Production of modified maleimide resin (A-1)]
A 2-liter reaction vessel capable of heating and cooling, equipped with a thermometer, a stirrer and a water content meter with a reflux condenser, both-end diamine modified siloxane (Shin-Etsu Chemical Co., Ltd., trade name: X-22-161A ) 25.9 g of 15.9 g, 3,3'-diethyl-4,4'-diaminodiphenylmethane (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYAHARD (registered trademark) A-A), and bis (4-maleimide) 280.5 g of phenyl) methane (manufactured by Kei 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 obtain a modified maleimide resin (A A solution of -1) was obtained.
製造例２：〔変性マレイミド樹脂（Ａ−２）の製造〕
温度計、攪拌装置及び還流冷却管付き水分定量器の付いた加熱及び冷却可能な容積２リットルの反応容器に、両末端ジアミン変性シロキサン（信越化学工業株式会社製、商品名：Ｘ−２２−１６１Ｂ）１４．４ｇと、２，２´−ビス［４−（４−アミノフェノキシ）フェニル］プロパン（和歌山精化工業株式会社製、商品名：ＢＡＰＰ）５６．９ｇと、ビス（４−マレイミドフェニル）メタン（ケイ・アイ化成株式会社製、商品名：ＢＭＩ）２５３．７ｇと、プロピレングリコールモノメチルエーテル２００．０ｇと、を入れ、１２６℃で還流させながら５時間反応させて変性マレイミド樹脂（Ａ−２）の溶液を得た。
Production Example 2: [Production of Modified Maleimide Resin (A-2)]
A 2-liter reaction vessel capable of heating and cooling, equipped with a thermometer, a stirrer and a water content meter with a reflux condenser, both-end diamine modified siloxane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X-22-161B ) 14.4 g, 56.9 g of 2,2'-bis [4- (4-aminophenoxy) phenyl] propane (manufactured by Wakayama Seika Kogyo Co., Ltd., trade name: BAPP), and bis (4-maleimidophenyl) Add 253.7 g of methane (Ki Eye Chemical Co., Ltd., trade name: BMI) and 200.0 g of propylene glycol monomethyl ether, and react for 5 hours while refluxing at 126 ° C. to react with modified maleimide resin (A-2) ) Solution was obtained.
製造例３：〔変性マレイミド樹脂（Ａ−３）の製造〕
温度計、攪拌装置及び還流冷却管付き水分定量器の付いた加熱及び冷却可能な容積２リットルの反応容器に、両末端ジアミン変性シロキサン（信越化学工業株式会社製、商品名：Ｘ−２２−１６１Ｂ）１５．６ｇと、３，３´−ジエチル−４，４´−ジアミノジフェニルメタン（日本化薬株式会社製、商品名：ＫＡＹＡＨＡＲＤ Ａ−Ａ）２１．８ｇと、２，２−ビス［４−（４−マレイミドフェノキシ）フェニル］プロパン（大和化成工業株式会社製、商品名：ＢＭＩ−４０００）２７４．２ｇと、プロピレングリコールモノメチルエーテル：２００．０ｇと、を入れ、１２０℃で４時間反応させて変性マレイミド樹脂（Ａ−３）の溶液を得た。
Production Example 3: [Production of Modified Maleimide Resin (A-3)]
A 2-liter reaction vessel capable of heating and cooling, equipped with a thermometer, a stirrer and a water content meter with a reflux condenser, both-end diamine modified siloxane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X-22-161B 2) 15.6 g, 21.8 g of 3,3′-diethyl-4,4′-diaminodiphenylmethane (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYAHARD A-A), 2,2-bis [4- (4) Add 274.2 g of 4-maleimidophenoxy) phenyl] propane (trade name: BMI-4000, manufactured by Daiwa Kasei Kogyo Co., Ltd.) and 200.0 g of propylene glycol monomethyl ether, and react at 120 ° C. for 4 hours to modify A solution of maleimide resin (A-3) was obtained.
製造例４：〔変性マレイミド樹脂（Ａ−４）の製造〕
温度計、攪拌装置及び還流冷却管付き水分定量器の付いた加熱及び冷却可能な容積２リットルの反応容器に、両末端ジアミン変性シロキサン（信越化学工業株式会社製、商品名：Ｘ−２２−１６１Ａ）１６．６ｇと、２，２´−ビス［４−（４−アミノフェノキシ）フェニル］プロパン（和歌山精化工業株式会社製、商品名：ＢＡＰＰ）２５．５ｇと、２，２−ビス［４−（４−マレイミドフェノキシ）フェニル］プロパン（大和化成工業株式会社製、商品名：ＢＭＩ−４０００）２９２．６ｇと、プロピレングリコールモノメチルエーテル２００．０ｇと、を入れ、１２６℃で還流させながら６時間反応させて変性マレイミド樹脂（Ａ−４）の溶液を得た。
Production Example 4: [Production of modified maleimide resin (A-4)]
A 2-liter reaction vessel capable of heating and cooling, equipped with a thermometer, a stirrer and a water content meter with a reflux condenser, both-end diamine modified siloxane (Shin-Etsu Chemical Co., Ltd., trade name: X-22-161A ) 16.6 g, 25.5 g of 2,2'-bis [4- (4-aminophenoxy) phenyl] propane (Wakayama Seika Kogyo Co., Ltd., trade name: BAPP), 2,2-bis [4 -(4-Maleimido phenoxy) phenyl] propane (Daiwa Kasei Kogyo Co., Ltd., trade name: BMI-4000) 292.6 g and propylene glycol monomethyl ether 200.0 g are added, and refluxing at 126 ° C. for 6 hours The reaction was carried out to obtain a solution of modified maleimide resin (A-4).
実施例１〜８及び比較例１〜５
表１に示す配合割合（表中の数値は固形分の質量部であり、溶液（有機溶媒を除く）又は分散液の場合は固形分換算量である。）に従って組成物を配合及び混合し、溶媒にメチルエチルケトン及びトルエンを用いて固形分濃度６５質量％のワニスを作製した。
次に、このワニスを厚さ０．１ｍｍ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 to 8 and Comparative Examples 1 to 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 a solution (excluding organic solvent) or dispersion, it is solid equivalent). Methyl ethyl ketone and toluene were used as the solvent to prepare a varnish having a solid content concentration of 65% by mass.
Next, this varnish is impregnated and coated on an E glass cloth (manufactured by Nitto Boseki Co., Ltd.) having a thickness of 0.1 mm, and dried by heating at 160 ° C. for 5 minutes. Was obtained.
Four pieces of this prepreg were stacked, 12 μm thick electrodeposited copper foils were vertically disposed, pressed at a pressure of 2.5 MPa and a temperature of 200 ° C. for 90 minutes to obtain a copper-clad laminate. The evaluation results of the obtained copper clad laminate are shown in Table 1.
配合に用いた各成分について以下に示す。 It shows below about each component used for combination.
［（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）ポリブタジエン］
・Ｂ−３０００（未変性ポリブタジエン）（日本曹達株式会社製）
・ＰＯＬＹＶＥＳＴ １１０（カルボン酸変性ポリブタジエン）（エボニック社製）
[(B) polybutadiene]
・ B-3000 (unmodified polybutadiene) (manufactured by Nippon Soda Co., Ltd.)
· POLYVEST 110 (carboxylic acid-modified polybutadiene) (manufactured by Evonik)
［（Ｃ）芳香族ビニル化合物由来の構造単位と無水マレイン酸由来の構造単位とを含有する共重合樹脂］
・ＳＭＡ−ＥＦ８０（スチレン／無水マレイン酸モル比＝８）（サートマー社製）
[(C) Copolymer resin containing a structural unit derived from an aromatic vinyl compound and a structural unit derived from maleic anhydride]
SMA-EF80 (styrene / maleic anhydride molar ratio = 8) (Sartmar company)
［（Ｄ）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）
[(D) curing accelerator]
TPP-MK: tetraphenylphosphonium tetra-p-tolylborate (manufactured by Hokuko Chemical Co., Ltd.)
Perbutyl-P: α, α′-bis (t-butylperoxy) diisopropylbenzene (manufactured by NOF Corporation)
2E4MZ: 2-ethyl-4-methylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd.)
2E4MZ-A: 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ')]-ethyl-s-triazine (manufactured by Shikoku Kasei Kogyo Co., Ltd.)
［（Ｅ）無機充填材］
・ＳＣ２０５０−ＫＣ：（株式会社アドマテックス製）
[(E) Inorganic filler]
・ SC2050-KC: (made by Admatex Co., Ltd.)
表１から明らかなように、実施例１〜８で得られた積層板は、ガラス転移温度、熱膨張率、誘電特性、銅付はんだ耐熱性、吸水半銅付はんだ耐熱性の全てに優れている。一方、比較例１〜５は、誘電特性又は吸水半銅付はんだ耐熱性いずれかの特性に劣っている。 As apparent from Table 1, the laminates obtained in Examples 1 to 8 are excellent in all of glass transition temperature, thermal expansion coefficient, dielectric characteristics, solder heat resistance with copper, and solder heat resistance with water absorption half copper. There is. On the other hand, Comparative Examples 1 to 5 are inferior in either the dielectric characteristics or the heat resistance to water absorption and copper absorption with solder.
本発明の熱硬化性樹脂組成物を用いて得られるプリント配線板は、高ガラス転移温度、低熱膨張性、低誘電特性、高耐熱性を有するため、高集積化された半導体パッケージ及び高速通信に対応した電子機器用プリント配線板として有用である。 The printed wiring board obtained by using the thermosetting resin composition of the present invention has a high glass transition temperature, low thermal expansion, low dielectric characteristics, and high heat resistance, so it can be used for highly integrated semiconductor packages and high speed communication. It is useful as a corresponding printed wiring board for electronic devices.
Claims (12)
（Ｂ）ポリブタジエンと、
（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、
を含有する熱硬化性樹脂組成物。 (A) An addition product of a maleimide compound (a1) having at least two N-substituted maleimide groups in one molecule and an amine compound (a2) having at least two primary amino groups in one molecule ,
(B) polybutadiene,
(C) A copolymer resin containing a structural unit derived from an aromatic vinyl compound and a structural unit derived from a carboxylic acid anhydride,
A thermosetting resin composition containing
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