CN113490715A - Resin composition, prepreg, metal foil-clad laminate, resin composite sheet, and printed wiring board - Google Patents
Resin composition, prepreg, metal foil-clad laminate, resin composite sheet, and printed wiring board Download PDFInfo
- Publication number
- CN113490715A CN113490715A CN202080016923.XA CN202080016923A CN113490715A CN 113490715 A CN113490715 A CN 113490715A CN 202080016923 A CN202080016923 A CN 202080016923A CN 113490715 A CN113490715 A CN 113490715A
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- Prior art keywords
- resin composition
- group
- mass
- compound
- resin
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 117
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 29
- 239000002184 metal Substances 0.000 title claims abstract description 29
- 239000000805 composite resin Substances 0.000 title claims abstract description 18
- -1 prepreg Substances 0.000 title description 83
- 150000001875 compounds Chemical class 0.000 claims abstract description 117
- 229920000642 polymer Polymers 0.000 claims abstract description 61
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 52
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 30
- 239000007870 radical polymerization initiator Substances 0.000 claims abstract description 20
- 229920005989 resin Polymers 0.000 claims description 41
- 239000011347 resin Substances 0.000 claims description 41
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 26
- 239000000758 substrate Substances 0.000 claims description 15
- 239000000945 filler Substances 0.000 claims description 14
- 239000011888 foil Substances 0.000 claims description 14
- 125000001651 cyanato group Chemical group [*]OC#N 0.000 claims description 10
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 claims description 10
- 239000004020 conductor Substances 0.000 claims description 5
- 125000000524 functional group Chemical group 0.000 claims description 5
- 239000010410 layer Substances 0.000 description 46
- 239000011521 glass Substances 0.000 description 37
- 239000004643 cyanate ester Substances 0.000 description 36
- 229920001955 polyphenylene ether Polymers 0.000 description 36
- 238000000034 method Methods 0.000 description 31
- 125000004432 carbon atom Chemical group C* 0.000 description 27
- 125000000217 alkyl group Chemical group 0.000 description 25
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 20
- 239000000047 product Substances 0.000 description 19
- 239000002904 solvent Substances 0.000 description 18
- 239000002966 varnish Substances 0.000 description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 17
- 239000000463 material Substances 0.000 description 17
- 125000001424 substituent group Chemical group 0.000 description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 150000001491 aromatic compounds Chemical class 0.000 description 14
- 239000011889 copper foil Substances 0.000 description 14
- 239000010408 film Substances 0.000 description 14
- 230000009477 glass transition Effects 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 13
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 12
- 125000003118 aryl group Chemical group 0.000 description 11
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Substances C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 10
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 9
- 238000000465 moulding Methods 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 238000001723 curing Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 238000010030 laminating Methods 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- OMIHGPLIXGGMJB-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]hepta-1,3,5-triene Chemical compound C1=CC=C2OC2=C1 OMIHGPLIXGGMJB-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 4
- 150000002460 imidazoles Chemical class 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 4
- 241000894007 species Species 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 125000001033 ether group Chemical group 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 125000005647 linker group Chemical group 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000002759 woven fabric Substances 0.000 description 3
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical group C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 2
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 239000011363 dried mixture Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000006266 etherification reaction Methods 0.000 description 2
- 229940116333 ethyl lactate Drugs 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 125000005462 imide group Chemical group 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000011968 lewis acid catalyst Substances 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 238000005691 oxidative coupling reaction Methods 0.000 description 2
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000003495 polar organic solvent Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
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- 230000000379 polymerizing effect Effects 0.000 description 2
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- 238000012545 processing Methods 0.000 description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
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- 239000000454 talc Substances 0.000 description 2
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- 230000000930 thermomechanical effect Effects 0.000 description 2
- HGTUJZTUQFXBIH-UHFFFAOYSA-N (2,3-dimethyl-3-phenylbutan-2-yl)benzene Chemical compound C=1C=CC=CC=1C(C)(C)C(C)(C)C1=CC=CC=C1 HGTUJZTUQFXBIH-UHFFFAOYSA-N 0.000 description 1
- OXYKVVLTXXXVRT-UHFFFAOYSA-N (4-chlorobenzoyl) 4-chlorobenzenecarboperoxoate Chemical compound C1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1 OXYKVVLTXXXVRT-UHFFFAOYSA-N 0.000 description 1
- RUEBPOOTFCZRBC-UHFFFAOYSA-N (5-methyl-2-phenyl-1h-imidazol-4-yl)methanol Chemical compound OCC1=C(C)NC(C=2C=CC=CC=2)=N1 RUEBPOOTFCZRBC-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- KTRQRAQRHBLCSQ-UHFFFAOYSA-N 1,2,4-tris(ethenyl)cyclohexane Chemical compound C=CC1CCC(C=C)C(C=C)C1 KTRQRAQRHBLCSQ-UHFFFAOYSA-N 0.000 description 1
- RXSCVLLHYAVKIP-UHFFFAOYSA-N 1,2-bis(ethenoxy)benzene Chemical compound C=COC1=CC=CC=C1OC=C RXSCVLLHYAVKIP-UHFFFAOYSA-N 0.000 description 1
- SKXCTCCZTWNYMD-UHFFFAOYSA-N 1,2-bis(ethenyl)anthracene Chemical compound C1=CC=CC2=CC3=C(C=C)C(C=C)=CC=C3C=C21 SKXCTCCZTWNYMD-UHFFFAOYSA-N 0.000 description 1
- QLLUAUADIMPKIH-UHFFFAOYSA-N 1,2-bis(ethenyl)naphthalene Chemical compound C1=CC=CC2=C(C=C)C(C=C)=CC=C21 QLLUAUADIMPKIH-UHFFFAOYSA-N 0.000 description 1
- OMUZAMZCKXKTBQ-UHFFFAOYSA-N 1,2-bis(ethenyl)phenanthrene Chemical compound C1=CC=C2C3=CC=C(C=C)C(C=C)=C3C=CC2=C1 OMUZAMZCKXKTBQ-UHFFFAOYSA-N 0.000 description 1
- HIACAHMKXQESOV-UHFFFAOYSA-N 1,2-bis(prop-1-en-2-yl)benzene Chemical compound CC(=C)C1=CC=CC=C1C(C)=C HIACAHMKXQESOV-UHFFFAOYSA-N 0.000 description 1
- SYENRPHLJLKTED-UHFFFAOYSA-N 1,3,5-tris(ethenyl)benzene Chemical compound C=CC1=CC(C=C)=CC(C=C)=C1 SYENRPHLJLKTED-UHFFFAOYSA-N 0.000 description 1
- FWFAJEYKHANIJP-UHFFFAOYSA-N 1,3,5-tris(ethenyl)naphthalene Chemical compound C1=CC=C(C=C)C2=CC(C=C)=CC(C=C)=C21 FWFAJEYKHANIJP-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
- HPUCAWBFVXHLDN-UHFFFAOYSA-N 1-but-1-enyl-2-phenylbenzene Chemical group CCC=CC1=CC=CC=C1C1=CC=CC=C1 HPUCAWBFVXHLDN-UHFFFAOYSA-N 0.000 description 1
- SLBOQBILGNEPEB-UHFFFAOYSA-N 1-chloroprop-2-enylbenzene Chemical compound C=CC(Cl)C1=CC=CC=C1 SLBOQBILGNEPEB-UHFFFAOYSA-N 0.000 description 1
- VTPNYMSKBPZSTF-UHFFFAOYSA-N 1-ethenyl-2-ethylbenzene Chemical compound CCC1=CC=CC=C1C=C VTPNYMSKBPZSTF-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- XIRPMPKSZHNMST-UHFFFAOYSA-N 1-ethenyl-2-phenylbenzene Chemical group C=CC1=CC=CC=C1C1=CC=CC=C1 XIRPMPKSZHNMST-UHFFFAOYSA-N 0.000 description 1
- XHUZSRRCICJJCN-UHFFFAOYSA-N 1-ethenyl-3-ethylbenzene Chemical compound CCC1=CC=CC(C=C)=C1 XHUZSRRCICJJCN-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- IYSVFZBXZVPIFA-UHFFFAOYSA-N 1-ethenyl-4-(4-ethenylphenyl)benzene Chemical group C1=CC(C=C)=CC=C1C1=CC=C(C=C)C=C1 IYSVFZBXZVPIFA-UHFFFAOYSA-N 0.000 description 1
- WHFHDVDXYKOSKI-UHFFFAOYSA-N 1-ethenyl-4-ethylbenzene Chemical compound CCC1=CC=C(C=C)C=C1 WHFHDVDXYKOSKI-UHFFFAOYSA-N 0.000 description 1
- WCBXINYQNFNCSF-UHFFFAOYSA-N 1-phenyl-2-prop-1-enylbenzene Chemical group CC=CC1=CC=CC=C1C1=CC=CC=C1 WCBXINYQNFNCSF-UHFFFAOYSA-N 0.000 description 1
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- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 1
- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/082—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
- C08F212/36—Divinylbenzene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2305/00—Condition, form or state of the layers or laminate
- B32B2305/07—Parts immersed or impregnated in a matrix
- B32B2305/076—Prepregs
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
Abstract
Providing: a resin composition having a low dielectric constant and a low dielectric loss tangent and high heat resistance, and a prepreg, a metal foil-clad laminate, a resin composite sheet, and a printed wiring board using the same. The resin composition contains a polyfunctional vinyl aromatic polymer (A) and a thermosetting compound (B), and does not contain a radical polymerization initiator.
Description
Technical Field
The present invention relates to a resin composition, and a prepreg, a metal foil-clad laminate, a resin composite sheet, and a printed wiring board using the same.
Background
In recent years, high integration and miniaturization of semiconductor elements used in electronic devices such as mobile terminals and communication devices have been accelerated. Along with this, a technique capable of realizing high-density mounting of semiconductor elements is required, and among these, improvement of printed wiring boards, which occupy an important position, is also required.
On the other hand, applications of electronic devices and the like are diversified and continue to expand. Under such influence, various characteristics required for printed wiring boards, metal foil-clad laminates used for the printed wiring boards, prepregs, and the like have been diversified and have become severe. In view of such required characteristics, various materials and processing methods have been proposed for obtaining an improved printed wiring board. One of them is improvement and development of a resin material constituting a prepreg.
For example, patent document 1 discloses a resin composition comprising: a terminal vinyl compound (a) of a 2-functional phenylene ether oligomer having a polyphenylene ether skeleton, a specific maleimide compound (b), a naphthol aralkyl type cyanate ester resin (c), and a naphthalene skeleton-modified novolak type epoxy resin (d).
Patent document 2 discloses a flame-retardant resin composition comprising a resin having at least one terminal maleimide group (aminobismaleimide resin obtained from N, N '-4, 4' -diphenylmethane bismaleimide and a diamine as raw materials), and a copolymer of brominated styrene represented by formula (c1) and divinylbenzene represented by formula (c 2).
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent application No. 2010-138364
Patent document 2: japanese laid-open patent publication No. H03-006293
Disclosure of Invention
Problems to be solved by the invention
In addition to the above examples, various characteristics of printed wiring boards have been improved by development of materials therefor, but further improvement in performance has been demanded in view of development of technology and expansion of applications. In particular, in recent years, a material having high heat resistance and a low dielectric constant/low dielectric loss tangent has been demanded.
The present invention has been made to solve the above problems, and an object of the present invention is to provide a resin composition having a low dielectric constant and a low dielectric loss tangent and high heat resistance, and a prepreg, a metal foil-clad laminate, a resin composite sheet, and a printed wiring board using the same.
Means for solving the problems
Based on the above-described problems, the present inventors have studied the component composition of a resin composition particularly suitable for use in printed wiring boards such as prepregs, and as a result, have found that a resin composition comprising a combination of a polyfunctional vinyl aromatic polymer and a thermosetting compound exhibits a low dielectric constant/low dielectric loss tangent and high heat resistance. However, it was found that these properties were poor when a radical polymerization initiator was added. The present invention has been completed based on this finding, and specifically, the above-mentioned problems are preferably solved by the following means <1> and <2> to <11 >.
<1> a resin composition comprising a polyfunctional vinyl aromatic polymer (A) and a thermosetting compound (B) and not comprising a radical polymerization initiator.
<2> the resin composition according to <1>, wherein the polyfunctional vinyl aromatic polymer (A) is a polymer having a structural unit represented by the formula (V).
(wherein Ar represents an aromatic hydrocarbon-linking group, which represents a bonding position.)
<3> the resin composition according to <1> or <2>, wherein the thermosetting compound (B) has 1 or more functional groups selected from the group consisting of a cyanato group, a vinyl group, a maleimido group, and a nadimido group.
<4> the resin composition according to any one of <1> to <3>, wherein the content of the thermosetting compound (B) is 5 to 95 parts by mass based on 100 parts by mass of the total amount of the resin components in the resin composition.
<5> the resin composition according to any one of <1> to <4>, wherein the content of the polyfunctional vinyl aromatic polymer (A) is 5 to 95 parts by mass with respect to 100 parts by mass of the total amount of the resin components in the resin composition.
<6> the resin composition according to any one of <1> to <5>, which further comprises a filler (C).
<7> the resin composition according to <6>, wherein the filler (C) is contained in an amount of 10 to 500 parts by mass based on 100 parts by mass of the total amount of the resin components in the resin composition.
<8> a prepreg comprising a substrate and the resin composition according to any one of <1> to <7 >.
<9> a metal-foil-clad laminate comprising: at least 1 layer comprising the prepreg according to <8> and a metal foil disposed on one or both surfaces of the layer comprising the prepreg.
<10> a resin composite sheet comprising: a support, and a layer comprising the resin composition according to any one of <1> to <7> disposed on a surface of the support.
<11> a printed wiring board comprising an insulating layer and a conductor layer disposed on a surface of the insulating layer, wherein the insulating layer comprises: at least one of a layer formed from the resin composition according to any one of <1> to <7> and a layer formed from the prepreg according to <8 >.
ADVANTAGEOUS EFFECTS OF INVENTION
The present invention can provide a resin composition having a low dielectric constant and a low dielectric loss tangent and high heat resistance, and a prepreg, a metal foil-clad laminate, a resin composite sheet, and a printed wiring board using the same.
Detailed Description
Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof. In the present specification, "to" are used in the meaning that the numerical values described before and after the "to" are the lower limit value and the upper limit value.
The resin composition of the present embodiment is characterized by containing a polyfunctional vinyl aromatic polymer (a) and a thermosetting compound (B) and not containing a radical polymerization initiator.
With such a configuration, a resin composition having a low dielectric constant and dielectric loss tangent and high heat resistance can be provided. Further, the peel strength can be improved. In addition, other various performances can be improved. In particular, in recent years, communication and operation signals tend to have higher frequencies, but the resin composition of the present embodiment can realize a low dielectric constant/low dielectric loss tangent and improve heat resistance even in a high frequency region.
The reason is not limited to the following, but can be considered as follows. That is, the resin composition of the present embodiment is a thermosetting resin composition in which the thermosetting groups of the polyfunctional vinyl aromatic polymer (a) and the thermosetting compound (B) are cured by heat. When such a resin composition does not contain a thermal radical polymerization initiator, the polymerization initiation temperature of the polyfunctional vinyl aromatic polymer (a) is close to the polymerization initiation temperature of the thermosetting compound (B), and the polyfunctional vinyl aromatic polymer (a) and the thermosetting compound (B) can be sufficiently cured together, and as a result, a low dielectric constant/low dielectric loss tangent and high heat resistance can be achieved. Further, by not including a photo radical polymerization initiator, it is possible to effectively suppress photocuring of the polyfunctional vinyl aromatic polymer (a) and the thermosetting compound (B) even when light shielding is not performed during storage.
The resin composition of the present embodiment is preferably a non-photosensitive thermosetting resin composition which is not cured by light but is cured mainly by heat.
< polyfunctional vinyl aromatic Polymer (A) >
The resin composition of the present embodiment contains a polyfunctional vinyl aromatic polymer (a).
The polyfunctional vinyl aromatic polymer (a) is preferably a polymer obtained by polymerizing an aromatic compound having 2 or more vinyl groups in the molecule. In the aromatic compound having 2 or more vinyl groups in the molecule, for example, the vinyl group may be a stereoisomer, or a mixture of stereoisomers thereof. More specifically, when the polyfunctional vinyl aromatic polymer (A) is an aromatic compound having 2 vinyl groups in the molecule, it may be m-isomer, p-isomer, o-isomer or a mixture of these stereoisomers, and preferably m-isomer, p-isomer or a mixture of these stereoisomers.
Examples of the monomer constituting the polyfunctional vinyl aromatic polymer (a) include aromatic compounds having 1 or 2 or more vinyl groups (hereinafter, aromatic compounds having 2 or more vinyl groups are also referred to as polyfunctional vinyl aromatic compounds), and aromatic compounds having 1 or 2 vinyl groups are preferable. For example, as the polyfunctional vinyl aromatic polymer (a), a polymer containing a structural unit (a) derived from an aromatic compound having 2 vinyl groups (also referred to as a divinyl aromatic compound) and a structural unit (b) derived from an aromatic compound having 1 vinyl group is exemplified.
The divinylaromatic compound forming the structural unit (a) is preferably a compound having a hydrocarbon aromatic ring, and examples thereof include divinylbenzene, diallylbenzene, bis (vinyloxy) benzene, bis (1-methylvinyl) benzene, divinylnaphthalene, divinylanthracene, divinylbiphenyl, divinylphenanthrene, bis (4-allyloxyphenyl) fluorene, and the like. Among them, divinylbenzene is particularly preferable. The structural units derived from the divinylaromatic compound may be in the polymer in the following manner: (a-1) a mode in which only 1 vinyl group is polymerized and the other 1 vinyl group remains unreacted; and (a-2)2 ways of carrying out the polymerization reaction. In the present embodiment, the preferable mode (a-1) includes a mode in which one vinyl group does not react and remains. The polyfunctional vinyl aromatic compound (preferably a divinyl aromatic compound) may have an arbitrary substituent Z (for example, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, an amino group, a carboxyl group, a halogen atom, or the like) within a range in which the effects of the present invention are exhibited.
The structural unit (a) derived from the above-mentioned polyfunctional vinyl aromatic compound (preferably, a divinyl aromatic compound) preferably contains a structural unit represented by the following formula (V).
In the formula (V), Ar represents an aromatic hydrocarbon linking group. Specific examples thereof include the following L1Examples of (3). Wherein represents a bonding site.
The aromatic hydrocarbon-linking group may be a group formed only of an aromatic hydrocarbon optionally having a substituent, or may be a group formed of a combination of an aromatic hydrocarbon optionally having a substituent and another linking group, and is preferably a group formed only of an aromatic hydrocarbon optionally having a substituent. Among the substituents which the aromatic hydrocarbon optionally has, the substituent Z described above can be mentioned. In addition, the aromatic hydrocarbon preferably has no substituent.
Aromatic hydrocarbon linkages are typically 2-valent linkages.
Specifically, among the aromatic hydrocarbon linking groups, there may be mentioned optionally substituted phenylene, naphthalenediyl, anthracenediyl, phenanthrenediyl, biphenyldiyl and fluorenediyl groups, and among them, an optionally substituted phenylene group is preferred. Among the substituents, the substituent Z described above can be exemplified, but the above-mentioned group such as phenylene preferably has no substituent.
The structural unit (a) derived from a polyfunctional vinyl aromatic compound (preferably a divinyl aromatic compound) more preferably contains at least 1 of a structural unit represented by the following formula (V1), a structural unit represented by the following formula (V2) and a structural unit represented by the following formula (V3). Incidentally, in the following formula, the symbol denotes a bonding position.
In the formulae (V1) to (V3), L1Is an aromatic hydrocarbon linking group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 10 carbon atoms). Specifically, there may be mentioned phenylene, naphthalenediyl, anthracenediyl, phenanthrenediyl, biphenyldiyl and fluorenediyl groups which may be substituted, and among them, phenylene groups which may be substituted are preferred. Among the substituents, the substituent Z described above can be exemplified, but the above-mentioned group such as phenylene preferably has no substituent.
As described above, the polyfunctional vinyl aromatic polymer (A) may be a homopolymer of the structural unit (a) or a copolymer with the structural unit (b) or the like. When the polyfunctional vinyl aromatic polymer (a) is a copolymer, the copolymerization ratio of the structural unit (a) is preferably 5 mol% or more, more preferably 10 mol% or more, and still more preferably 15 mol% or more. The upper limit is actually 90 mol% or less.
When the polyfunctional vinyl aromatic polymer (a) is a copolymer containing a structural unit (b) derived from a monovinyl aromatic compound, examples of the monovinyl aromatic compound include vinyl aromatic compounds such as styrene, vinyl naphthalene, and vinyl biphenyl; nuclear alkyl-substituted vinyl aromatic compounds such as o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylvinylbenzene, m-ethylvinylbenzene, p-ethylvinylbenzene, methylvinylbiphenyl, ethylvinylbiphenyl, and the like. The monovinylaromatic compounds exemplified herein may also suitably have the substituent Z described above. One or two or more of these monovinyl aromatic compounds may be used.
The structural unit (b) derived from a monovinyl aromatic compound is preferably a structural unit represented by the following formula (V4).
In the formula (V4), L2Is an aromatic hydrocarbon-linking group, and preferable examples thereof include the above-mentioned L1Examples of (3).
RV1The alkyl group is a hydrogen atom or a hydrocarbon group (preferably an alkyl group) having 1 to 12 carbon atoms. RV1When the carbon number is a hydrocarbon group, the number of carbon atoms is preferably 1 to 6, more preferably 1 to 3. RV1And L2May have the above-mentioned substituent Z.
When the polyfunctional vinyl aromatic polymer (a) is a copolymer containing the structural unit (b), the copolymerization ratio of the structural unit (b) is preferably 10 mol% or more, and more preferably 15 mol% or more. The upper limit is preferably 98 mol% or less, more preferably 90 mol% or less, and still more preferably 85 mol% or less.
The polyfunctional vinylaromatic polymer (A) can also have other structural units. Examples of the other structural unit include a structural unit (c) derived from a cycloolefin compound. Examples of the cycloolefin compound include hydrocarbons having a double bond in the ring structure. Specifically, in addition to monocyclic cyclic olefins such as cyclobutene, cyclopentene, cyclohexene, and cyclooctene, compounds having a norbornene ring structure such as norbornene and dicyclopentadiene, and cyclic olefin compounds obtained by condensing aromatic rings such as indene and acenaphthylene are exemplified. Examples of the norbornene compound include those described in paragraphs 0037 to 0043 of Japanese patent application laid-open No. 2018-39995, the contents of which are incorporated herein by reference. The cycloolefin compounds exemplified here may further have the substituent Z described above.
When the polyfunctional vinyl aromatic polymer (a) is a copolymer containing the structural unit (c), the copolymerization ratio of the structural unit (c) is preferably 10 mol% or more, more preferably 20 mol% or more, and still more preferably 30 mol% or more. The upper limit is preferably 90 mol% or less, more preferably 80 mol% or less, further preferably 70 mol% or less, and may be 50 mol% or less, or may be 30 mol% or less.
The polyfunctional vinyl aromatic polymer (a) may further contain a structural unit (d) derived from a different polymerizable compound (hereinafter also referred to as another polymerizable compound). Examples of the other polymerizable compound (monomer) include compounds containing 3 vinyl groups. Specific examples thereof include 1,3, 5-trivinylbenzene, 1,3, 5-trivinylnaphthalene, and 1,2, 4-trivinylcyclohexane. Alternatively, ethylene glycol diacrylate, butadiene, and the like can be mentioned. The copolymerization ratio of the structural unit (d) derived from another polymerizable compound is preferably 30 mol% or less, more preferably 20 mol% or less, and still more preferably 10 mol% or less.
One embodiment of the polyfunctional vinyl aromatic polymer (a) is a polymer which contains the structural unit (a) as an essential component and at least 1 of the structural units (b) to (d). Further, the total of the structural units (a) to (d) is 95 mol% or more, and further 98 mol% or more of the total structural units.
In another embodiment of the polyfunctional vinyl aromatic polymer (a), the structural unit (a) is essential, and among all the structural units except the terminal, the structural unit containing an aromatic ring is preferably 90 mol% or more, more preferably 95 mol% or more, and may be 100 mol%.
When the mole% of all the structural units is calculated, 1 structural unit is derived from 1 molecule of the monomer constituting the polyfunctional vinyl aromatic polymer (A).
The method for producing the polyfunctional vinyl aromatic polymer (a) is not particularly limited, and a general method may be employed, and examples thereof include a method of polymerizing a monomer containing a divinyl aromatic compound (if necessary, a monovinyl aromatic compound, a cycloolefin compound, and the like are made to coexist) in the presence of a lewis acid catalyst. As the lewis acid catalyst, a metal fluoride or a complex thereof may be used.
The structure of the chain end of the polyfunctional vinyl aromatic polymer (a) is not particularly limited, and examples of the group derived from the above-mentioned divinyl aromatic compound include a structure represented by the following formula (E1). L in the formula (E1)1The same as defined in the above formula (V1). Denotes the bonding site.
*-CH=CH-L1-CH=CH2 (E1)
When the group derived from the monovinyl aromatic compound is a chain end, a structure represented by the following formula (E2) is used. L in the formula2And RV1Are as defined for the aforementioned formula (V4). Denotes the bonding site.
*-CH=CH-L2-RV1 (E2)
The molecular weight of the polyfunctional vinyl aromatic polymer (a) is preferably 300 or more, more preferably 500 or more, and further preferably 1000 or more in terms of the number average molecular weight Mn. The upper limit is preferably 100000 or less, more preferably 10000 or less, further preferably 5000 or less, and further preferably 4000 or less. The monodispersity (Mw/Mn) represented by the ratio of the weight average molecular weight Mw to the number average molecular weight Mn is preferably 100 or less, more preferably 50 or less, and still more preferably 20 or less. The lower limit value is actually 1.1 or more. The polyfunctional vinyl aromatic polymer (A) is preferably soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform.
The polyfunctional vinyl aromatic polymer (A) in the present specification is incorporated by reference to the compounds and the synthesis reaction conditions thereof described in paragraphs 0029 to 0058 of International publication No. 2017/115813, the compounds and the synthesis reaction conditions thereof described in paragraphs 0013 to 0058 of Japanese patent application laid-open No. 2018-039995, the compounds and the synthesis reaction conditions thereof described in paragraphs 0008 to 0043 of Japanese patent application laid-open No. 2018-070136, the compounds and the synthesis reaction conditions thereof described in paragraphs 0014 to 0042 of Japanese patent application laid-open No. 2006-070136, the compounds and the synthesis reaction conditions thereof described in paragraphs 0014 to 0061 of Japanese patent application laid-open No. 2006-089683, the compounds and the synthesis reaction conditions thereof described in paragraphs 0008 to 0036 of Japanese patent application laid-open No. 2008-248001, and the like.
The content of the polyfunctional vinyl aromatic polymer (a) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, further preferably 15 parts by mass or more, further preferably 20 parts by mass or more, and further may be 30 parts by mass or more, 40 parts by mass or more, 50 parts by mass or more, or 60 parts by mass or more, with the total amount of the resin components in the resin composition being 100 parts by mass. By setting the content of the polyfunctional vinyl aromatic polymer (a) to the above-mentioned lower limit or more, a low dielectric constant can be particularly effectively achieved. On the other hand, the upper limit of the content of the polyfunctional vinyl aromatic polymer (a) is preferably 95 parts by mass or less, more preferably 90 parts by mass or less, further preferably 85 parts by mass or less, and further preferably 80 parts by mass or less, with respect to 100 parts by mass of the total amount of the resin components in the resin composition.
The polyfunctional vinyl aromatic polymer (a) may contain only 1 species or 2 or more species in the resin composition. When 2 or more are contained, the total amount is preferably in the above range.
The resin component includes the polyfunctional vinyl aromatic polymer (a) and the thermosetting compound (B), and also includes other resin components described later.
< thermosetting Compound (B) >
The resin composition of the present embodiment contains a thermosetting compound (B). The term "thermosetting compound (B)" as used herein means a thermosetting compound other than the polyfunctional vinyl aromatic polymer (A). The thermosetting compound (B) is preferably a compound having 1 or more functional groups selected from the group consisting of a cyanato group, a vinyl group (excluding a group which becomes a polyfunctional vinyl aromatic polymer, a maleimide group, a nadimide group, preferably a vinylphenyl group), a maleimide group, and a nadimide group, more preferably a cyanate ester compound (B1) having a cyanato group, a modified polyphenylene ether compound (B2) having a vinyl group (preferably a vinylphenyl group), a maleimide compound (B3) having a maleimide group, a nadimide compound (B4) having a nadimide group, further preferred are a cyanate ester compound having a cyanato group (B1), a modified polyphenylene ether compound having a vinyl group (preferably a vinylphenyl group) (B2), and a maleimide compound having a maleimide group (B3).
< cyanate ester Compound (B1) >
The cyanate ester compound is a generic name of a compound having a cyanato group. The cyanate ester compound (B1) used in the present invention preferably has 1 or more cyanato groups in 1 molecule, and more preferably has 2 or more cyanato groups. The upper limit of the number of cyanates in the 1-molecule cyanate ester compound (B1) is preferably 12 or less, and more preferably 10 or less. The cyanato group of the cyanate ester compound (B1) is preferably a cyanato group directly bonded to an aromatic ring.
Examples of the cyanate ester compound (B1) include at least 1 selected from the group consisting of naphthol aralkyl type cyanate ester compounds (naphthol aralkyl type cyanate esters), naphthylene ether type cyanate ester compounds, phenol novolac type cyanate ester compounds, biphenyl aralkyl type cyanate ester compounds, bisphenol a type cyanate ester compounds, diallyl bisphenol a type cyanate ester compounds, bisphenol M type cyanate ester compounds, xylene resin type cyanate ester compounds, triphenol methane type cyanate ester compounds, and adamantane skeleton type cyanate ester compounds. Among these, at least 1 selected from the group consisting of naphthol aralkyl type cyanate ester compounds, naphthylene ether type cyanate ester compounds, and xylene resin type cyanate ester compounds is preferable, and naphthol aralkyl type cyanate ester compounds are more preferable. These cyanate ester compounds can be prepared by a known method, and commercially available products can be used.
The cyanate ester compound (B1) may be a naphthol aralkyl type cyanate ester compound represented by the following formula (S1). The naphthol aralkyl type cyanate ester compound represented by the formula (S1) is obtained by condensing a naphthol aralkyl resin obtained by reacting a naphthol such as α -naphthol or β -naphthol with p-xylene glycol, α' -dimethoxy-p-xylene, 1, 4-bis (2-hydroxy-2-propyl) benzene, or the like, with a cyanogen halide. The production method is not particularly limited, and the cyanate ester can be produced by any method existing in cyanate ester synthesis.
In the formula (S1), RC1~RC4Each independently represents a hydrogen atom or a methyl group. n isCIs a number of 1 to 10. May also contain more than 2 nCA different compound.
Regarding the cyanate ester compound (B1), the contents thereof can be referred to paragraphs 0024 and 0025 of jp 2010-138364 a, which is incorporated herein.
< modified polyphenylene ether Compound (B2) >
The thermosetting compound (B) is preferably a modified polyphenylene ether compound (B2) which is end-modified with a substituent containing a vinyl group (preferably a vinylphenyl group). The modified polyphenylene ether compound (B2) used in the present invention preferably has 1 or more vinyl groups in 1 molecule, more preferably 2 or more vinyl groups. The upper limit of the number of vinyl groups in the 1-molecule modified polyphenylene ether compound (B2) is preferably 5 or less, and more preferably 3 or less.
The modified polyphenylene ether compound (B2) is, for example, a modified product in which all or a part of the terminal of polyphenylene ether is terminal-modified with a vinyl group or a vinylphenyl group. The term "polyphenylene ether" as used herein means a compound having a polyphenylene ether skeleton represented by the following formula (X1).
In the formula (X1), R24、R25、R26And R27May be the same or different and represents an alkyl group having 6 or less carbon atoms, an aryl group, a halogenAn atom, or a hydrogen atom. Denotes the bonding site.
The modified polyphenylene ether may further comprise a repeating unit represented by the formula (X2) or the formula (X3).
In the formula (X2), R28、R29、R30、R34、R35The alkyl groups may be the same or different and each represents an alkyl group having 6 or less carbon atoms or a phenyl group. R31、R32、R33The alkyl groups may be the same or different and each represents a hydrogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group. Denotes the bonding site.
In the formula (X3), R36、R37、R38、R39、R40、R41、R42、R43The alkyl groups may be the same or different and each represents a hydrogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group. A is a linear, branched or cyclic 2-valent hydrocarbon having 1 to 20 carbon atoms. Denotes the bonding site.
The modified polyphenylene ether compound (B2) may be a modified polyphenylene ether in which a part or all of the compound is functionalized with an ethylenically unsaturated group such as a vinylbenzyl group, an epoxy group, an amino group, a hydroxyl group, a mercapto group, a carboxyl group, a silyl group, or the like. These may also be used in 1 or more than 2. Examples of the polyphenylene ether having a hydroxyl group at the terminal include SABIC INNOVATIVE PLASTICS co, SA90 manufactured by ltd.
The method for producing the modified polyphenylene ether compound (B2) is not particularly limited as long as the effects of the present invention can be obtained. For example, a modified polyphenylene ether compound functionalized with a vinylbenzyl group can be produced by dissolving a 2-functional phenylene ether oligomer and vinylbenzyl chloride in a solvent, reacting the resulting solution with heating and stirring while adding a base, and then solidifying the resin. The modified polyphenylene ether compound functionalized with a carboxyl group can be produced, for example, by melt-kneading an unsaturated carboxylic acid or a derivative functionalized with the unsaturated carboxylic acid into a polyphenylene ether in the presence or absence of a radical initiator and reacting the mixture. Alternatively, the polyphenylene ether can be produced by dissolving the polyphenylene ether and the unsaturated carboxylic acid or functional derivative thereof in an organic solvent in the presence or absence of a radical initiator and reacting the resultant solution.
The modified polyphenylene ether compound (B2) is preferably a modified polyphenylene ether having an ethylenically unsaturated group at least at one end (preferably both ends) (hereinafter sometimes referred to as "modified polyphenylene ether (g)"). Examples of the ethylenically unsaturated group include an alkenyl group such as a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, a propenyl group, a butenyl group, a hexenyl group, and an octenyl group, a cycloalkenyl group such as a cyclopentenyl group and a cyclohexenyl group, and an alkenylaryl group such as a vinylphenyl group, a vinylbenzyl group, and a vinylnaphthyl group. The two terminal 2 ethylenically unsaturated groups may be the same functional group or different functional groups.
The modified polyphenylene ether (g) may have a structure represented by the following formula (1).
In the formula (1), XaRepresents an aromatic group, (Y)a-O) m represents a polyphenylene ether moiety, R1、R2、R3Each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group, m represents a number of 1 to 100, n represents a number of 1 to 6, and q represents a number of 1 to 4. Preferably R1、R2、R3Is a hydrogen atom. Preferably, m is a number of 1 to 50 inclusive, more preferably 1 to 30 inclusive. N is preferably a number of 1 to 4, more preferably n is 1 or 2, and still more preferably n is 1. Further, q is preferably a number of 1 to 3, more preferably q is 1 or 2, and still more preferably q is 2.
It may contain 2 or more compounds different in m, n and q.
The modified polyphenylene ether (g) is preferably represented by the formula (2).
At least one of a and b in the formula (2) is not 0 and represents a number of 0 to 100. a and b are preferably a number of 1 to 50, more preferably a number of 1 to 30.
Here, - (O-X-O) -is preferably represented by the formula (3) or the formula (4). It may also contain more than 2 compounds different in a and b.
In the formula (3), R4、R5、R6、R10、R11The alkyl groups may be the same or different and each represents an alkyl group having 6 or less carbon atoms or a phenyl group. R7、R8、R9The alkyl groups may be the same or different and each represents a hydrogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group. Denotes the bonding site.
In the formula (4), R12、R13、R14、R15、R16、R17、R18、R19The alkyl groups may be the same or different and each represents a hydrogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group. A. the1Is a linear, branched or cyclic 2-valent hydrocarbon group having 20 or less carbon atoms. Denotes the bonding site.
In addition, - (Y-O) -in the formula (2) is preferably represented by the formula (5).
In the formula (5), R22、R23The alkyl groups may be the same or different and each represents a hydrogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group. R20、R21May be the same or differentDifferent from this, it is an alkyl group having 6 or less carbon atoms or a phenyl group.
As A in formula (4)1Examples thereof include, but are not limited to, 2-valent organic groups such as methylene, ethylidene, 1-methylethylidene, 1-propylidene, 2-propylidene, 1, 4-phenylenebis (1-methylethylidene), 1, 3-phenylenebis (1-methylethylidene), cyclohexylidene, phenylmethylene, naphthylmethylene, and 1-phenylethynyl.
Among the above modified polyphenylene ethers, R is preferred4、R5、R6、R10、R11、R20、R21Is an alkyl group having 3 or less carbon atoms, R7、R8、R9、R12、R13、R14、R15、R16、R17、R18、R19、R22、R23The polyphenylene ether is a polyphenylene ether having a hydrogen atom or an alkyl group having 3 or less carbon atoms, and particularly more preferably has a structure in which- (O-X-O) -represented by the formula (3) or the formula (4) is the formula (9), the formula (10) and/or the formula (11), and- (Y-O) -represented by the formula (5) is the formula (12) or the formula (13), or the formula (12) and the formula (13) are randomly arranged.
In the formula (10), R44、R45、R46、R47Which may be the same or different, is a hydrogen atom or a methyl group. A. the2Is a linear, branched or cyclic 2-valent hydrocarbon group having 20 or less carbon atoms. Is a bonding site. A in the formulae (10) and (11)2Examples thereof include those represented by the formula (4) wherein A is1The same as the specific examples in (1) will be given as specific examples.
The number average molecular weight of the modified polyphenylene ether compound (B2) in terms of polystyrene by GPC method is preferably 500 or more and 3000 or less. When the number average molecular weight is not less than the lower limit, the resin composition of the present embodiment tends to be further inhibited from being sticky when formed into a coating film. When the number average molecular weight is not more than the upper limit, the solubility in a solvent tends to be further improved.
The modified polyphenylene ether compound (B2) preferably has a weight average molecular weight in terms of polystyrene by GPC of 800 or more and 10000 or less, more preferably 800 or more and 5000 or less. When the lower limit value is not less than the above-mentioned lower limit value, the dielectric constant and the dielectric loss tangent of the resin composition tend to be further lowered, and when the upper limit value is not more than the above-mentioned upper limit value, the solubility in a solvent, the low viscosity and the moldability tend to be further improved.
Further, the equivalent weight of the carbon-carbon unsaturated double bond at the terminal of the modified polyphenylene ether compound (B2) is preferably 400 to 5000g, more preferably 400 to 2500g, per carbon-carbon unsaturated double bond. When the dielectric constant is not less than the lower limit, the dielectric constant and the dielectric loss tangent tend to be further decreased. When the content is not more than the above upper limit, the solubility in a solvent, the low viscosity and the moldability tend to be further improved.
The method for producing the modified polyphenylene ether compound (B2) is not particularly limited, and for example, a step (oxidative coupling step) of subjecting a 2-functional phenol compound and a 1-functional phenol compound to oxidative coupling to obtain a 2-functional phenylene ether oligomer; and a step (vinylbenzyl etherification step) of vinylbenzyl etherification of the terminal phenolic hydroxyl group of the obtained 2-functional phenylene ether oligomer. As such a modified polyphenylene ether compound (B2), for example, Mitsubishi gas chemical (OPE-2St1200, etc.) can be used.
< Maleimide Compound (B3) >
The maleimide compound (B3) is a compound having 1 or more maleimide groups in the molecule. The maleimide compound (B3) used in the present invention preferably has 1 or more maleimide groups in 1 molecule, more preferably 2 or more. The upper limit of the number of maleimide groups in the 1-molecule maleimide compound (B3) is preferably 15 or less, and more preferably 13 or less. Among them, preferred are bismaleimide compounds and polymaleimide compounds having 2 or more maleimide groups in the molecule, and more preferred are 4,4 '-diphenylmethane maleimide, 4' -diphenylether bismaleimide, m-phenylene bismaleimide, 1, 6-bismaleimide- (2,2, 4-trimethyl) hexane, and compounds containing a structural unit represented by any of the following formulae (31) to (34).
In the formula (31), R51、R52、R53And R54Each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a phenyl group.
In the formula (31), R51、R52、R53And R54Preferably each independently a methyl group, an ethyl group, a phenyl group or a hydrogen atom, more preferably a hydrogen atom.
n1 is a number of 1 to 10, more preferably a number of 1 to 4. It may also comprise more than 2 different compounds of n 1.
In the formula (32), R56Each independently represents methyl or ethyl, R57Each independently represents a hydrogen atom or a methyl group.
Preferably 4R56Among them, 1 to 3 are methyl groups, and the remaining 3 to 1 are ethyl groups; more preferably 4R56Of these, 2 are methyl groups and the remaining 2 are ethyl groups. Further, 2 substituted R are more preferable for 2 aromatic rings56Methyl and ethyl respectively.
In the formula (33), R58Each independently represents a hydrogen atom, a methyl group or an ethyl group.
R58Preferably methyl or ethyl, more preferably methyl.
In the formula (34), R59Each independently represents a hydrogen atom, a methyl group or an ethyl group.
R59Preferably methyl or ethyl, more preferably methyl.
The equivalent of the unsaturated imide group in the maleimide compound (B3) is preferably 200g/eq or more, and preferably 400g/eq or less. When 2 or more maleimide compounds are contained, the equivalent weight herein is the equivalent weight of the unsaturated imide group in the weighted average, taking into account the mass of each maleimide compound contained in the resin composition.
< nadimide Compound (B4) >
The nadimide compound (B4) is a compound having a nadimide group in a molecule. The nadimide compound (B4) used in the present invention preferably has 1 or more nadimide groups in 1 molecule, and more preferably 2 or more nadimide groups. The upper limit of the number of nadimide groups in 1-molecule nadimide compound (B4) is preferably 5 or less, and more preferably 3 or less. More specifically, the nadimide compound (B4) preferably has a group represented by the following formula (N1) or (N2). Denotes the bonding site.
In the formulae (N1) and (N2), R1Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Further preferable examples of the nadimide compound include compounds represented by the following formula (N3).
In the formula (N3), R1Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R2Represents an alkylene group having 1 to 6 carbon atoms or a 2-valent linking group containing an aromatic ring. As the 2-valent linking group containing an aromatic ring, phenylene is exemplifiedMesitylene, biphenylene, and naphthylene.
Further, as the nadimide compound (B4), the contents of paragraphs 0026 to 0035 of international publication No. 2015/105109 can be referred to, and these contents are incorporated in the present specification.
The content of the thermosetting compound (B) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, further preferably 15 parts by mass or more, and further preferably 20 parts by mass or more, relative to 100 parts by mass of the total amount of the resin components in the resin composition of the present embodiment. The upper limit is preferably 95 parts by mass or less, more preferably 80 parts by mass or less, and still more preferably 70 parts by mass or less.
Further, it is preferably 1 part by mass or more, more preferably 10 parts by mass or more, and further preferably 20 parts by mass or more, per 100 parts by mass of the polyfunctional vinyl aromatic polymer (a). The upper limit is preferably 1900 parts by mass or less, more preferably 900 parts by mass or less, further preferably 400 parts by mass or less, and may be 120 parts by mass or less, 80 parts by mass or less, or 60 parts by mass or less.
The resin composition may contain only one kind of the thermosetting compound (B) or two or more kinds thereof. When 2 or more are contained, the total amount is preferably in the above range.
When the resin composition of the present embodiment does not contain the filler (C) described later, the resin component is preferably 90% by mass or more, more preferably 95% by mass or more, and still more preferably 98% by mass or more of the resin composition.
When the resin composition of the present embodiment contains the filler (C), the resin component is preferably 15% by mass or more, more preferably 20% by mass or more, and further preferably 30% by mass or more of the resin composition. The upper limit is preferably 90% by mass or less, more preferably 85% by mass or less, and still more preferably 80% by mass or less of the resin component in the resin composition.
< free radical polymerization initiator >
The resin composition of the present embodiment does not contain a radical polymerization initiator. Here, "not to include" means that the compounding is not actively performed, and does not include a case where impurities and the like are unintentionally compounded. The case where impurities or the like are inadvertently added means, for example, 4ppm or less, and further 1ppm or less on a mass basis. In the present invention, 0ppm is preferable.
The type of the radical polymerization initiator is not particularly limited, and examples thereof include a thermal radical polymerization initiator and a photo radical polymerization initiator.
Specific examples of the radical polymerization initiator include peroxides (peroxides), azo compounds, benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, and phosphine oxide compounds.
Examples of the peroxide include compounds having a peroxy group (-O-) in the molecule, and preferably compounds having a t-butylperoxy group, compounds having a cumylperoxy group, and compounds having a benzoyl peroxide. Specific examples thereof include Benzoyl Peroxide (BPO), p-chlorobenzoyl peroxide, dicumyl peroxide (dicup), di-t-butyl peroxide, diisopropyl peroxycarbonate, 2, 5-dimethyl-2, 5-di-t-butyl peroxyhexyne (DYBP), and 2, 5-dimethyl-2, 5-di-t-butyl peroxyhexane. Commercially available products include PERBUTYL H, PERBUTYL P, PERBUTYL PV, PERCUTYL H, PERCUTYL P, PERCUTYL D, PERCUCTA H, and PERHEXA 25B, which are available from Nichigan oil Co., Ltd.
The azo compound is a compound having an azo group (-N ═ N-) in the molecule, and specifically, Azobisisobutyronitrile (AIBN) is exemplified. Examples of commercially available products include Fuji films and AIBN, V-70 and V-65 manufactured by Wako pure chemical industries, Ltd.
Although not a peroxide, 2, 3-dimethyl-2, 3-diphenylbutane is also mentioned as a radical polymerization initiator. Examples of commercially available products include ノフマー BC-90.
Further, a radical polymerization initiator described in paragraph 0042 of international publication No. 2013/047305 is exemplified and incorporated herein.
On the other hand, the resin composition of the present embodiment may be configured not to contain a cationic polymerization initiator. Further, the resin composition of the present embodiment may be configured not to contain a photopolymerization initiator.
< Filler (C) >
The resin composition of the present embodiment preferably contains a filler (C), preferably an inorganic filler, for the purpose of improving low dielectric constant, low dielectric loss tangent, flame resistance and low thermal expansion. As the filler (C) to be used, known ones can be suitably used, and the kind thereof is not particularly limited, and those generally used in the art can be suitably used. Specific examples thereof include silicas such as natural silica, fused silica, synthetic silica, amorphous silica, AEROSIL and hollow silica, white carbon, titanium white, zinc oxide, magnesium oxide, zirconium oxide, boron nitride, agglomerated boron nitride, silicon nitride, aluminum nitride, barium sulfate, aluminum hydroxide and aluminum hydroxide heat-treated products (those obtained by heat-treating aluminum hydroxide to reduce a part of crystal water), metal hydrates such as boehmite and magnesium hydroxide, molybdenum compounds such as molybdenum oxide and zinc molybdate, zinc borate, zinc stannate, aluminum oxide, clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, E-glass, A-glass, NE-glass, C-glass, L-glass, D-glass, S-glass, M-glass G20, Glass short fibers (including glass fine powders such as E glass, T glass, D glass, S glass, and Q glass), inorganic fillers such as hollow glass and spherical glass, and organic fillers such as rubber powders of styrene type, butadiene type, and acrylic type, core-shell type, silicone resin powder, silicone rubber powder, and silicone composite powder.
Of these, 1 or 2 or more selected from the group consisting of silica, aluminum hydroxide, boehmite, magnesium oxide and magnesium hydroxide are preferable, and silica is more preferable. The silica is preferably spherical silica. The spherical silica may be hollow silica.
By using these fillers, the resin composition has improved properties such as thermal expansion properties, dimensional stability, and flame retardancy.
The content of the filler (C) in the resin composition of the present embodiment may be appropriately set according to the desired characteristics, and is not particularly limited, and is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, further preferably 30 parts by mass or more, and may be 50 parts by mass or more, when the total amount of the resin components in the resin composition is 100 parts by mass. The upper limit is preferably 500 parts by mass or less, more preferably 400 parts by mass or less, further preferably 300 parts by mass or less, further preferably 250 parts by mass or less, and may be 200 parts by mass or less.
The filler (C) may be used in 1 kind or 2 or more kinds. When 2 or more species are used, the total amount is preferably in the above range.
< other resin Components >
The resin composition of the present embodiment may contain other resin components than the above-mentioned polyfunctional vinyl aromatic polymer (a) and thermosetting compound (B). Examples of the other resin component include 1 or more selected from the group consisting of an epoxy resin, a phenol resin, an oxetane resin, a benzoxazine compound, a compound having a polymerizable unsaturated group, an elastomer, and an active ester compound.
In the resin composition of the present embodiment, the total content of the polyfunctional vinyl aromatic polymer (a) and the thermosetting compound (B) in the resin component is preferably 50% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, and may be 95% by mass or more, may be 97% by mass or more, and may be 98% by mass or more.
< Cure Accelerator (catalyst) >
The resin composition of the present embodiment may further include a curing accelerator. The curing accelerator is not particularly limited, and examples thereof include organic metal salts (e.g., zinc octoate, zinc naphthenate, cobalt naphthenate, copper naphthenate, iron acetylacetonate, nickel octoate, manganese octoate, etc.), phenol compounds (e.g., phenol, xylenol, cresol, resorcinol, catechol, octylphenol, nonylphenol, etc.), alcohols (e.g., 1-butanol, 2-ethylhexanol, etc.), imidazoles (e.g., 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4, 5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, etc.), and the like, And derivatives of these imidazoles such as carboxylic acids and acid anhydride adducts thereof, amines (for example, dicyandiamide, benzyldimethylamine, 4-methyl-N, N-dimethylbenzylamine, etc.), phosphorus compounds (for example, phosphine compounds, phosphine oxide compounds, phosphonium salt compounds, diphosphine compounds, etc.), and epoxy-imidazole adduct compounds.
Preferred curing accelerators are imidazoles and organometallic salts, more preferably imidazoles.
The lower limit of the content of the curing accelerator is preferably 0.005 parts by mass or more, more preferably 0.01 parts by mass or more, and still more preferably 0.1 parts by mass or more, based on 100 parts by mass of the total amount of the resin components in the resin composition. The upper limit of the content of the curing accelerator is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and still more preferably 2 parts by mass or less, relative to 100 parts by mass of the total amount of the resin components in the resin composition.
The curing accelerator may be used singly or in combination of two or more. When 2 or more species are used, the total amount is in the above range.
< solvent >
The resin composition of the present embodiment may contain a solvent, and preferably contains an organic solvent. In this case, the resin composition of the present embodiment is a form (solution or varnish) in which at least a part, preferably all, of the various resin components described above are dissolved or compatible in a solvent. The solvent is not particularly limited as long as it is a polar organic solvent or a nonpolar organic solvent capable of dissolving or dissolving at least a part, preferably all, of the various resin components described above, and examples of the polar organic solvent include ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), cellosolves (e.g., propylene glycol monomethyl ether acetate, etc.), esters (e.g., ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate, methyl hydroxyisobutyrate, etc.) amides (e.g., dimethoxyacetamide, dimethylformamides, etc.), and examples of the nonpolar organic solvent include aromatic hydrocarbons (e.g., toluene, xylene, etc.).
One kind of solvent may be used alone, or two or more kinds may be used in combination.
< other ingredients >
The resin composition of the present embodiment may contain, in addition to the above-described components, a flame retardant, an ultraviolet absorber, an antioxidant, a fluorescent brightener, a photosensitizer, a dye, a pigment, a thickener, a flow regulator, a lubricant, an antifoaming agent, a dispersant, a leveling agent, a gloss agent, a polymerization inhibitor, a silane coupling agent, and the like, within a range not to impair the effects of the present invention. These additives may be used singly or in combination of two or more.
< Properties of resin composition >
When the resin composition of the present embodiment is molded into a plate-like cured product having a thickness of 1.6mm, the dielectric constant (Dk) at 10GHz may be 2.6 or less, or 2.5 or less. The lower limit of the dielectric constant is preferably 1.0, but is practically 2.1 or more.
When the resin composition of the present embodiment is molded into a sheet-like cured product having a thickness of 1.6mm, the dielectric loss tangent (Df) at 10GHz may be 0.0030 or less, or 0.0025 or less, or 0.0020 or less, or 0.0015 or less. The lower limit of the dielectric constant is preferably 0, but it is practically 0.0001 or more.
The dielectric constant and the dielectric loss tangent were measured by the methods described in the examples below.
In the resin composition according to the preferred embodiment of the present invention, a low Coefficient of Thermal Expansion (CTE) can be achieved. For example, from the viewpoint of the CTE (ppm/° c) defined by JlSC 64815.19, it is preferably 75 or less, more preferably 72 or less, and still more preferably 70 or less. The lower limit is not particularly limited, and is actually 50 or more.
When the resin composition of the present embodiment is molded into a sheet-like cured product having a thickness of 1.6mm, the glass transition temperature may be 230 ℃ or higher, may be 235 ℃ or higher, and may be 240 ℃ or higher. The upper limit of the glass transition temperature is not particularly limited, and is practically 400 ℃ or lower, and further 350 ℃ or lower.
When the resin composition of the present embodiment is molded into a 1.6mm thick sheet-like cured product, the glass transition temperature is preferably 8 ℃ or higher, more preferably 10 ℃ or higher, than the glass transition temperature of a 1.6mm thick sheet-like cured product formed from a resin composition containing a thermal radical polymerization initiator (for example, PERBUTYL P (trade name)) in an amount corresponding to 1 mass% of the resin components contained in the resin composition. The upper limit is, for example, 25 ℃ or lower.
The glass transition temperature was measured by the method described in the examples below.
< method for producing resin composition >
The resin composition of the present embodiment can be produced by a usual method. For example, a mode of mixing the polyfunctional vinyl aromatic polymer (A) and the thermosetting compound (B) may be mentioned. Preferred contents in this case are as described above. In the resin composition of the present embodiment, the filler (C), other resin components, and other additives may be appropriately mixed and kneaded. Other resin components may be blended to improve the appearance and optimize other properties.
An example of the resin composition of the present embodiment is a varnish containing a solvent. Further, another example of the resin composition of the present embodiment is a plate-like cured product or a film. Further, the resin composition of the present embodiment is preferably used for the following applications.
< use >
The resin composition of the present embodiment can be used as a cured product. Specifically, the resin composition of the present embodiment can be suitably used as a low dielectric constant material and/or a low dielectric loss tangent material for an insulating layer of a printed wiring board or a material for a semiconductor package. The resin composition of the present embodiment can be suitably used as a prepreg, a metal foil-clad laminate formed from the prepreg, a resin composite sheet, and a material constituting a printed wiring board.
When the resin composition of the present embodiment is used to form a layered molded article, the thickness is preferably 5 μm or more, and more preferably 10 μm or more. The upper limit value is preferably 2mm or less, and more preferably 1mm or less. For example, when the resin composition of the present embodiment is impregnated into a glass cloth or the like, the thickness of the layered molded article means the thickness including the glass cloth.
The molded article such as a film formed from the resin composition of the present embodiment can be used for the purpose of forming a pattern by exposure and development, and can also be used for the purpose of not performing exposure and development. It is particularly suitable for the use without exposure development.
< prepreg > <
The prepreg of the preferred embodiment is formed of a substrate (prepreg substrate) and the resin composition of the present embodiment. The prepreg of the present embodiment is obtained, for example, by applying the resin composition of the present embodiment to a substrate (for example, impregnation or coating), and then semi-curing the applied resin composition by heating (for example, a method of drying the resin composition at 120 to 220 ℃ for 2 to 15 minutes). In this case, the amount of the resin composition adhering to the base material, that is, the amount of the resin composition (including the filler) relative to the total amount of the prepreg after semi-curing is preferably in the range of 20 to 99 mass%.
The substrate is not particularly limited as long as it is a substrate used for various printed circuit board materials. Examples of the material of the substrate include glass fibers (e.g., E glass, D glass, L glass, S glass, T glass, Q glass, UN glass, NE glass, spherical glass, etc.), inorganic fibers other than glass (e.g., quartz, etc.), and organic fibers (e.g., polyimide, polyamide, polyester, liquid crystal polyester, etc.). The form of the substrate is not particularly limited, and examples thereof include substrates made of layered fibers such as woven fabric, nonwoven fabric, roving, chopped glass mat, and surfacing mat. In particular, a base material made of long fibers such as glass cloth is preferable. The long fibers herein mean, for example, ones having a number average fiber length of 6mm or more. These base materials may be used singly or in combination of two or more. Among these substrates, woven fabrics subjected to a super-splitting treatment and a plugging treatment are preferable from the viewpoint of dimensional stability, glass woven fabrics subjected to a surface treatment with a silane coupling agent such as an epoxysilane treatment and an aminosilane treatment are preferable from the viewpoint of moisture absorption and heat resistance, and low dielectric glass cloths formed of glass fibers exhibiting low dielectric constant properties and low dielectric loss tangent such as L-glass, NE-glass, and Q-glass are preferable from the viewpoint of electrical characteristics. The thickness of the substrate is not particularly limited, and may be, for example, about 0.01 to 0.19 mm.
< Metal foil clad laminate >)
A preferred embodiment of the metal foil-clad laminate comprises: at least 1 layer formed of the prepreg of the present embodiment, and a metal foil disposed on one or both surfaces of the layer formed of the prepreg. The metal foil-clad laminate of the present embodiment can be produced, for example, by the following method: at least 1 prepreg of the present embodiment is arranged (preferably, 2 or more prepregs are stacked), and a metal foil is arranged on one surface or both surfaces thereof to perform lamination molding. More specifically, the prepreg can be produced by laminating and molding a metal foil made of copper, aluminum, or the like on one surface or both surfaces of the prepreg. The number of the prepreg is preferably 1 to 10, more preferably 2 to 10, and still more preferably 2 to 7. The metal foil is not particularly limited as long as it can be used as a material for a printed wiring board, and examples thereof include a copper foil such as a rolled copper foil and an electrolytic copper foil. The thickness of the copper foil is not particularly limited, and may be about 1.5 to 70 μm. The molding method includes a method generally used for molding a laminate plate or a multilayer plate for a printed wiring board, and more specifically, a method using a multistage press, a multistage vacuum press, a continuous molding machine, an autoclave molding machine, or the like, at a temperature of about 180 to 350 ℃, a heating time of about 100 to 300 minutes, and a surface pressure of 20 to 100kg/cm2And a method of performing lamination molding on the left and right sides. Further, a multilayer board can be produced by combining the prepreg of the present embodiment with a separately produced inner layer circuit board (also referred to as an inner layer circuit board) and then laminating and molding the same. As a plurality ofA method for producing a multilayer board can be carried out by, for example, arranging copper foils of about 35 μm on both surfaces of 1 sheet of the prepreg of the present embodiment, laminating the prepregs by the above-described molding method to form an inner layer circuit, blackening the circuit to form an inner layer circuit board, alternately arranging the inner layer circuit board and 1 sheet of the prepreg of the present embodiment, further arranging copper foils on the outermost layers, and laminating the prepregs under the above-described conditions, preferably in vacuum to form a multilayer board. The metal foil-clad laminate of the present embodiment can be suitably used as a printed wiring board.
< printed Circuit Board >
A printed wiring board according to a preferred embodiment includes an insulating layer and a conductor layer disposed on a surface of the insulating layer, and the insulating layer includes at least one of a layer formed from the resin composition according to the present embodiment and a layer formed from the prepreg according to the above-described embodiment. Such a printed wiring board can be produced by a usual method, and the production method thereof is not particularly limited. An example of a method for manufacturing a printed wiring board is shown below. First, a metal-clad laminate such as the above copper-clad laminate is prepared. Next, the surface of the metal foil-clad laminate is etched to form an inner layer circuit, thereby producing an inner layer substrate. If necessary, the surface of the inner layer circuit of the inner layer substrate is subjected to a surface treatment for improving the adhesive strength, and then a required number of the prepregs are stacked on the surface of the inner layer circuit, and further a metal foil for the outer layer circuit is stacked on the outer side of the prepregs, and then the prepregs are heated and pressed to be integrally molded. In this manner, a multilayer laminated board in which an insulating layer formed of a cured product of a base material and a thermosetting resin composition is formed between metal foils for an inner layer circuit and an outer layer circuit is manufactured. Then, the multilayer laminated board is subjected to drilling for via holes and via holes, and then a plating metal film for conducting the metal foil for the inner layer circuit and the metal foil for the outer layer circuit is formed on the wall surface of the holes, and further the metal foil for the outer layer circuit is subjected to etching treatment to form the outer layer circuit, thereby manufacturing a printed wiring board.
The printed wiring board obtained in the above-described manufacturing example includes an insulating layer and a conductor layer formed on a surface of the insulating layer, and the insulating layer is configured to include the resin composition of the present embodiment. That is, the prepreg of the present embodiment (for example, a prepreg formed of a base material and the resin composition of the present embodiment impregnated or applied thereto) and the layer formed of the resin composition of the metal foil-clad laminate of the present embodiment are the insulating layer of the present embodiment.
< resin composite sheet >)
The resin composite sheet of the preferred embodiment comprises: a support and a layer made of the resin composition of the present embodiment disposed on the surface of the support. The resin composite sheet can be used as a film for lamination or a dry film solder resist. The method for producing the resin composite sheet is not particularly limited, and for example, a method in which a solution obtained by dissolving the resin composition of the present embodiment in a solvent is applied (coated) to a support and dried to obtain a resin composite sheet is given.
Examples of the support used herein include, but are not particularly limited to, polyethylene films, polypropylene films, polycarbonate films, polyethylene terephthalate films, ethylene tetrafluoroethylene copolymer films, release films in which a release agent is applied to the surfaces of these films, organic film substrates such as polyimide films, conductor foils such as copper foils and aluminum foils, glass plates, SUS plates, and FRPs.
Examples of the coating method (coating method) include a method of coating a solution obtained by dissolving a resin composition in a solvent on a support by using a bar coater, a die coater, a doctor blade, a baker's applicator, or the like. After drying, the support may be peeled from the resin composite sheet obtained by laminating the support and the resin composition or may be etched to form a single-layer sheet. The resin composition of the present embodiment may be formed into a sheet shape by supplying a solution in which the resin composition is dissolved in a solvent into a mold having a sheet-shaped cavity, drying the solution, and the like, and may be obtained as a single-layer sheet without using a support.
In the production of the resin composite sheet of the present embodiment, the drying conditions for removing the solvent are not particularly limited, and the solvent is likely to remain in the resin composition at a low temperature, and the resin composition is cured at a high temperature, and therefore, the temperature is preferably from 20 ℃ to 200 ℃ for 1 to 90 minutes. In the resin composite sheet, the resin composition may be used in an uncured state in which only the solvent is dried, or may be used in a semi-cured (B-stage) state as necessary. The thickness of the resin layer of the resin composite sheet of the present embodiment can be adjusted by the concentration of the solution of the resin composition of the present embodiment and the coating thickness, and is not particularly limited, but is preferably 0.1 to 500 μm in view of the fact that the solvent is likely to remain when drying when the coating thickness is increased.
Examples
The present invention will be described in more detail below with reference to examples. The materials, amounts used, ratios, processing contents, processing steps and the like shown in the following examples may be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples described below.
In the present example, unless otherwise specified, the measurement was carried out at 23 ℃.
< example 1>
75 parts by mass of a polyfunctional vinylbenzene polymer (ap) synthesized as described below, 25 parts by mass of biphenylaralkyl type maleimide (product name of MIR-3000, manufactured by Nippon Kagaku K.K.) and 0.5 part by mass of an imidazole catalyst (product name of 2E4MZ, manufactured by Sikko Kagaku K.K.) were dissolved in methyl ethyl ketone and mixed to obtain a varnish.
(Synthesis of polyfunctional Vinylbenzene Polymer (ap))
2.25 mol (292.9g) of divinylbenzene, 1.32 mol (172.0g) of ethylvinylbenzene, 11.43 mol (1190.3g) of styrene and 15.0 mol (1532.0g) of n-propyl acetate were charged in a reactor, and 600 mmol of a diethyl ether complex of boron trifluoride was added thereto at 70 ℃ to carry out a reaction for 4 hours. After the polymerization solution was stopped by an aqueous sodium bicarbonate solution, the oil layer was washed with pure water 3 times, and devolatilized at 60 ℃ under reduced pressure to recover the polyfunctional vinylbenzene polymer (ap). The obtained polyfunctional vinylbenzene polymer (ap) was weighed, and it was confirmed that 860.8g of the polyfunctional vinylbenzene polymer (ap) was obtained.
The obtained polyfunctional vinyl-benzene polymer (ap) had Mn of 2060, Mw of 30700 and Mw/Mn of 14.9. By carrying out13C-NMR and1H-NMR analysis, resonance lines derived from the respective monomer units were observed in the polyfunctional vinylbenzene polymer (ap). The ratio of the structural unit of the polyfunctional vinylbenzene polymer (ap) calculated based on the results of NMR measurement and GC analysis is as follows.
Structural units derived from divinylbenzene: 20.9 mol% (24.3 mass%)
Structural units derived from ethylvinylbenzene: 9.1 mol% (10.7 mass%)
Structural units derived from styrene: 70.0 mol% (65.0 mass%)
Further, the structural unit having a residual vinyl group derived from divinylbenzene was 16.7 mol% (18.5 mass%).
< production of test piece of cured sheet having thickness of 1.6mm >)
The solvent was distilled off from the resulting varnish by evaporation to obtain a mixed resin powder. The mixed resin powder was filled in a mold with a thickness of 1.6mm and a side of 1mm of 100mm, and a copper foil (3EC-M3-VLP, manufactured by Mitsui Metal mining Co., Ltd.) of 12 μ M was disposed on both sides of the mold at a pressure of 30kg/cm2Vacuum pressing was carried out at 220 ℃ for 120 minutes to obtain a cured sheet having 1 edge of 100mm and a thickness of 1.6 mm.
The physical properties (dielectric properties (Dk, Df), peel strength, glass transition temperature, and Coefficient of Thermal Expansion (CTE)) of the obtained cured sheet having a thickness of 1.6mm were evaluated by the following methods.
< example 2>
A varnish was obtained in the same manner as in example 1 except that 12.5 parts by mass of biphenylaralkyl maleimide and 12.5 parts by mass of phenylene ether maleimide (BMI-80 (trade name), manufactured by KI chemical Co., Ltd.) were added. From the varnish thus obtained, a cured plate having a thickness of 1.6mm was obtained in the same manner as in example 1. The obtained cured sheet having a thickness of 1.6mm was evaluated for physical properties and the like according to the methods described below.
< example 3>
A varnish was obtained in the same manner as in example 1 except that 25 parts by mass of BisM type maleimide (BMI-BisM (trade name), manufactured by KI chemical Co., Ltd.) was used in place of 25 parts by mass of biphenylaralkyl type maleimide. From the varnish thus obtained, a cured plate having a thickness of 1.6mm was obtained in the same manner as in example 1. The obtained cured sheet having a thickness of 1.6mm was evaluated for physical properties and the like according to the methods described below.
< example 4>
A varnish was obtained in the same manner as in example 1 except that 25 parts by mass of an end-modified polyphenylene ether (OPE-2St1200 (trade name) available from Mitsubishi gas chemical Co., Ltd.) was used in place of 25 parts by mass of biphenylaralkylmaleimide and no imidazole catalyst was used. From the varnish thus obtained, a cured plate having a thickness of 1.6mm was obtained in the same manner as in example 1. The obtained cured sheet having a thickness of 1.6mm was evaluated for physical properties and the like according to the methods described below.
< example 5>
A varnish was obtained in the same manner as in example 1 except that 25 parts by mass of the following naphthol aralkyl type cyanate ester resin was used in place of 25 parts by mass of biphenyl aralkyl type maleimide and 0.1 part by mass of an organometallic catalyst (Oct-Mn (trade name) manufactured by japan chemical industries) was used in place of 0.5 part by mass of an imidazole catalyst. From the varnish thus obtained, a cured plate having a thickness of 1.6mm was obtained in the same manner as in example 1. The obtained cured sheet having a thickness of 1.6mm was evaluated for physical properties and the like according to the methods described below.
(Synthesis of alpha-Naphthol aralkyl type cyanate ester resin)
An α -naphthol aralkyl resin (SN495V, OH group equivalent: 236g/eq., manufactured by Nippon iron chemical Co., Ltd.; contains 1 to 5 naphthol aralkyl repeating units) in an amount of 0.47 mol (in terms of OH group) was dissolved in 500mL of chloroform, and 0.7 mol of triethylamine was added to the solution to prepare solution 1. While maintaining the temperature at-10 ℃ and charging a chloroform solution (300 g) of 0.93 mol of cyanogen chloride into the reactor, the solution 1 was dropwise added over 1.5 hours, and after completion of the dropwise addition, the mixture was stirred for 30 minutes. Then, a mixed solution of 0.1 mol of triethylamine and 30g of chloroform was added dropwise to the reaction solutionThe reaction was terminated by stirring in the reactor for 30 minutes. After the by-produced hydrochloride salt of triethylamine was filtered off from the reaction solution, the obtained filtrate was washed with 500mL of 0.1N hydrochloric acid, and then washing with 500mL of water was repeated 4 times. Drying the mixture over sodium sulfate, evaporating the dried mixture at 75 ℃ and then degassing the dried mixture under reduced pressure at 90 ℃ to obtain a brown solid of an α -naphthol aralkyl type cyanate ester compound represented by the formula (S1) (R in the formula)C1~RC4All being hydrogen atoms, ncIs a mixture of 1 to 5. ). The obtained alpha-naphthol aralkyl type cyanate ester compound was analyzed by infrared absorption spectroscopy, and the result was 2264cm-1Absorption of the cyanate ester group was confirmed in the vicinity.
< reference example 1>
A varnish was obtained in the same manner as in example 1 except that 1 part by mass of a thermal radical polymerization initiator (product name of PERBUTYL P, manufactured by Nikkiso K.K.) was added. From the varnish thus obtained, a cured plate having a thickness of 1.6mm was obtained in the same manner as in example 1. The obtained cured sheet having a thickness of 1.6mm was evaluated for physical properties and the like according to the methods described below.
< reference example 2>
A varnish was obtained in the same manner as in example 4, except that 1 part by mass of a thermal radical polymerization initiator (product name of PERBUTYL P, manufactured by Nikkiso K.K.) was added. From the varnish thus obtained, a cured plate having a thickness of 1.6mm was obtained in the same manner as in example 4. The obtained cured sheet having a thickness of 1.6mm was evaluated for physical properties and the like according to the methods described below.
< reference example 3>
A varnish was obtained in the same manner as in example 5, except that 1 part by mass of a thermal radical polymerization initiator (product name of PERBUTYL P, manufactured by Nikkiso K.K.) was added. From the varnish thus obtained, a cured plate having a thickness of 1.6mm was obtained in the same manner as in example 5. The obtained cured sheet having a thickness of 1.6mm was evaluated for physical properties and the like according to the methods described below.
< dielectric characteristics (Dk and Df) >
The relative dielectric constant (Dk) and dielectric loss tangent (Df) at 10GHz were measured using a perturbation cavity resonator on a test piece obtained by removing the copper foil of the cured plate having a thickness of 1.6mm obtained by etching. The measurement temperature was set at 23 ℃.
The perturbation cavity resonator was made using Agilent technologies, inc. article, Agilent8722 ES.
< peeling Strength >
The cured sheet obtained as described above was used to measure the peel strength (adhesive force) of the copper foil 2 times in accordance with the 5.7 "peel strength" of JIS C6481, and the average value was determined. The measurement temperature was set at 23 ℃.
< glass transition temperature >
The glass transition temperature (Tg) was measured in accordance with JIS C64815.17.2 using a Dynamic viscoelasticity analyzer by a DMA (Dynamic Mechanical Analysis) bending method using a test piece obtained by removing the copper foil of the cured plate having a thickness of 1.6mm obtained by etching. The glass transition temperature was evaluated from the obtained tan δ graph.
The dynamic viscoelasticity analyzer used was a TA INSTRUMENTS system.
< Coefficient of Thermal Expansion (CTE) >
(CTE:Coefficient of linear Thermal Expansion)
The thermal expansion coefficient of the cured plate was measured by TMA method (Thermo-Mechanical Analysis) specified by JlS C64815.19 on a test piece obtained by removing the copper foil of the cured plate having a thickness of 1.6mm by etching, and the value was determined. Specifically, after removing the copper foil on both sides of the cured sheet obtained above by etching, the temperature was raised from 40 ℃ to 340 ℃ at 10 ℃ per minute by a thermomechanical analyzer (manufactured by TA INSTRUMENTS), and the linear thermal expansion coefficient (ppm/. degree. C.) was measured. ppm is volume ratio. The other details are in accordance with JIS C64815.19 described above.
[ Table 1]
(in the table note)
Dk: relative dielectric constant at 10GHz
Df: dielectric loss tangent at 10GHz
Peel strength: results of peeling test of copper foil
Glass transition temperature: glass transition temperature estimated from tan delta determined by DMA method
CTE (CTE): coefficient of thermal expansion measured by TMA method
From the results of table 1, it is understood that the resin composition obtained by combining the polyfunctional vinyl aromatic polymer (a) (polyfunctional vinyl benzene polymer (ap)) of the present embodiment and the thermosetting compound (B) is excellent in dielectric characteristics (low dielectric constant, low dielectric loss tangent), and has a high glass transition temperature and a low thermal expansion coefficient. Further, the peel strength is high.
On the other hand, when the radical polymerization initiator is contained, the comparison of reference example 1 with example 1, reference example 2 with example 4, reference example 3 with example 5 shows that the dielectric loss tangent is increased, the glass transition temperature is lowered, and the thermal expansion coefficient is also increased. Further, the peel strength is also low.
Claims (11)
1. A resin composition comprising a polyfunctional vinyl aromatic polymer (A) and a thermosetting compound (B), and not comprising a radical polymerization initiator.
3. The resin composition according to claim 1 or 2, wherein the thermosetting compound (B) has 1 or more functional groups selected from the group consisting of a cyanato group, a vinyl group, a maleimide group and a nadimidyl group.
4. The resin composition according to any one of claims 1 to 3, wherein the content of the thermosetting compound (B) is 5 to 95 parts by mass relative to 100 parts by mass of the total amount of the resin components in the resin composition.
5. The resin composition according to any one of claims 1 to 4, wherein the content of the polyfunctional vinyl aromatic polymer (A) is 5 to 95 parts by mass relative to 100 parts by mass of the total amount of the resin components in the resin composition.
6. The resin composition according to any one of claims 1 to 5, further comprising a filler (C).
7. The resin composition according to claim 6, wherein the content of the filler (C) is 10 to 500 parts by mass with respect to 100 parts by mass of the total amount of the resin components in the resin composition.
8. A prepreg formed from a substrate and the resin composition of any one of claims 1 to 7.
9. A metal-foil-clad laminate comprising: at least one layer formed from the prepreg according to claim 8, and a metal foil disposed on one or both surfaces of the layer formed from the prepreg.
10. A resin composite sheet, comprising: a support, and a layer comprising the resin composition according to any one of claims 1 to 7, disposed on a surface of the support.
11. A printed circuit board comprising an insulating layer and a conductor layer disposed on a surface of the insulating layer, the insulating layer comprising at least one of a layer formed from the resin composition according to any one of claims 1 to 7 and a layer formed from the prepreg according to claim 8.
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JP2019035456 | 2019-02-28 | ||
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PCT/JP2020/007686 WO2020175537A1 (en) | 2019-02-28 | 2020-02-26 | Resin composition, prepreg, metal foil-clad laminate board, resin composite sheet, and, printed circuit board |
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KR (1) | KR20210133230A (en) |
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JP7190649B2 (en) * | 2018-04-27 | 2022-12-16 | パナソニックIpマネジメント株式会社 | Resin composition, prepreg, resin-coated film, resin-coated metal foil, metal-clad laminate, and wiring board |
JP2022150088A (en) | 2021-03-26 | 2022-10-07 | 日鉄ケミカル&マテリアル株式会社 | Polyimide, resin composition, resin film, laminate, coverlay film, copper foil with resin, metal-clad laminate, and circuit board |
CN117836341A (en) | 2021-08-25 | 2024-04-05 | 三菱瓦斯化学株式会社 | Resin composition, cured product, prepreg, metal foil-clad laminate, resin sheet, and printed wiring board |
WO2023047782A1 (en) * | 2021-09-27 | 2023-03-30 | 三菱瓦斯化学株式会社 | Resin composition, prepreg, metal foil-clad laminate, resin composite sheet, printed wiring board, and semiconductor device |
WO2023047783A1 (en) * | 2021-09-27 | 2023-03-30 | 三菱瓦斯化学株式会社 | Resin composition, prepreg, metal foil-clad laminated sheet, composite resin sheet, printed wiring board, and semiconductor device |
TW202348646A (en) * | 2022-03-11 | 2023-12-16 | 日商三菱瓦斯化學股份有限公司 | Resin composition, cured product, prepreg, metal-foil-clad laminate, resin composite sheet, printed circuit board, and semiconductor device |
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JPH0413751A (en) * | 1990-05-08 | 1992-01-17 | Sumitomo Bakelite Co Ltd | Thermosetting resin composition |
CN101570640A (en) * | 2008-04-28 | 2009-11-04 | 日立化成工业株式会社 | Prepreg and printed wiring board using thin quartz glass cloth |
CN103339206A (en) * | 2011-01-31 | 2013-10-02 | 住友电木株式会社 | Resin composition and semiconductor device |
CN105936745A (en) * | 2015-12-09 | 2016-09-14 | 中山台光电子材料有限公司 | Resin composition |
WO2018216647A1 (en) * | 2017-05-26 | 2018-11-29 | 三菱瓦斯化学株式会社 | Resin composition, prepreg, resin sheet, metal foil-clad laminate, printed wiring board, and production method for resin composition |
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JPH0413756A (en) * | 1990-05-08 | 1992-01-17 | Sumitomo Bakelite Co Ltd | Thermosetting resin composition |
JPH0415215A (en) * | 1990-05-08 | 1992-01-20 | Sumitomo Bakelite Co Ltd | Thermosetting resin composition for laminate |
JP2002114823A (en) | 2000-10-10 | 2002-04-16 | Mitsubishi Gas Chem Co Inc | Flame-retardant cyanate resin for high-frequency use |
JP5233710B2 (en) | 2008-02-12 | 2013-07-10 | 三菱瓦斯化学株式会社 | Resin composition, prepreg and metal foil-clad laminate |
WO2017115813A1 (en) | 2015-12-28 | 2017-07-06 | 新日鉄住金化学株式会社 | Soluble polyfunctional vinyl aromatic copolymer, method for producing same and curable composition |
US11130861B2 (en) * | 2017-03-30 | 2021-09-28 | Nippon Steel Chemical & Material Co., Ltd. | Soluble polyfunctional vinyl aromatic copolymer, method for producing same, curable resin composition and cured product thereof |
JP2020029504A (en) | 2018-08-22 | 2020-02-27 | 日立化成株式会社 | Curable composition |
-
2020
- 2020-02-26 CN CN202080016923.XA patent/CN113490715A/en active Pending
- 2020-02-26 JP JP2021502311A patent/JP7409369B2/en active Active
- 2020-02-26 WO PCT/JP2020/007686 patent/WO2020175537A1/en active Application Filing
- 2020-02-26 KR KR1020217028419A patent/KR20210133230A/en active Search and Examination
- 2020-02-26 TW TW109106260A patent/TW202039595A/en unknown
Patent Citations (5)
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JPH0413751A (en) * | 1990-05-08 | 1992-01-17 | Sumitomo Bakelite Co Ltd | Thermosetting resin composition |
CN101570640A (en) * | 2008-04-28 | 2009-11-04 | 日立化成工业株式会社 | Prepreg and printed wiring board using thin quartz glass cloth |
CN103339206A (en) * | 2011-01-31 | 2013-10-02 | 住友电木株式会社 | Resin composition and semiconductor device |
CN105936745A (en) * | 2015-12-09 | 2016-09-14 | 中山台光电子材料有限公司 | Resin composition |
WO2018216647A1 (en) * | 2017-05-26 | 2018-11-29 | 三菱瓦斯化学株式会社 | Resin composition, prepreg, resin sheet, metal foil-clad laminate, printed wiring board, and production method for resin composition |
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WO2020175537A1 (en) | 2020-09-03 |
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