CN117836370A - Curable composition, prepreg, resin sheet, metal foil-clad laminate, and printed wiring board - Google Patents
Curable composition, prepreg, resin sheet, metal foil-clad laminate, and printed wiring board Download PDFInfo
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- CN117836370A CN117836370A CN202280054529.4A CN202280054529A CN117836370A CN 117836370 A CN117836370 A CN 117836370A CN 202280054529 A CN202280054529 A CN 202280054529A CN 117836370 A CN117836370 A CN 117836370A
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- Prior art keywords
- epoxy
- curable composition
- compound
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- 239000000203 mixture Substances 0.000 title claims abstract description 179
- -1 prepreg Substances 0.000 title claims description 115
- 229920005989 resin Polymers 0.000 title claims description 76
- 239000011347 resin Substances 0.000 title claims description 76
- 229910052751 metal Inorganic materials 0.000 title claims description 41
- 239000002184 metal Substances 0.000 title claims description 41
- 239000004593 Epoxy Substances 0.000 claims abstract description 142
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 137
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims abstract description 74
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 40
- 150000001875 compounds Chemical class 0.000 claims description 181
- 229920000642 polymer Polymers 0.000 claims description 100
- 125000004432 carbon atom Chemical group C* 0.000 claims description 92
- 125000000217 alkyl group Chemical group 0.000 claims description 55
- 229920000647 polyepoxide Polymers 0.000 claims description 54
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 47
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 44
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 34
- 229930185605 Bisphenol Natural products 0.000 claims description 31
- 125000003342 alkenyl group Chemical group 0.000 claims description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 28
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 26
- 239000007787 solid Substances 0.000 claims description 25
- 239000000758 substrate Substances 0.000 claims description 24
- 125000003118 aryl group Chemical group 0.000 claims description 23
- 239000004643 cyanate ester Substances 0.000 claims description 23
- 125000003700 epoxy group Chemical group 0.000 claims description 20
- 125000002947 alkylene group Chemical group 0.000 claims description 19
- 239000011888 foil Substances 0.000 claims description 17
- 125000000732 arylene group Chemical group 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 239000004020 conductor Substances 0.000 claims description 13
- 239000011256 inorganic filler Substances 0.000 claims description 13
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 8
- 229940014800 succinic anhydride Drugs 0.000 claims description 8
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 7
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 7
- 150000002989 phenols Chemical class 0.000 claims description 7
- 230000000379 polymerizing effect Effects 0.000 claims description 6
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 claims description 5
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- IKFPAKYBSYICFK-UHFFFAOYSA-N 1-[4-(4-propylphenoxy)phenyl]pyrrole-2,5-dione Chemical compound C1=CC(CCC)=CC=C1OC1=CC=C(N2C(C=CC2=O)=O)C=C1 IKFPAKYBSYICFK-UHFFFAOYSA-N 0.000 claims description 4
- YNSSPVZNXLACMW-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)-3-ethyl-5-methylphenyl]methyl]-2-ethyl-6-methylphenyl]pyrrole-2,5-dione Chemical compound C=1C(C)=C(N2C(C=CC2=O)=O)C(CC)=CC=1CC(C=C1CC)=CC(C)=C1N1C(=O)C=CC1=O YNSSPVZNXLACMW-UHFFFAOYSA-N 0.000 claims 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 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 150000008064 anhydrides Chemical class 0.000 claims description 4
- 229910001593 boehmite Inorganic materials 0.000 claims description 4
- LJJQENSFXLXPIV-UHFFFAOYSA-N fluorenylidene Chemical group C1=CC=C2[C]C3=CC=CC=C3C2=C1 LJJQENSFXLXPIV-UHFFFAOYSA-N 0.000 claims description 4
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 4
- 125000004434 sulfur atom Chemical group 0.000 claims description 4
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 3
- 125000006592 (C2-C3) alkenyl group Chemical group 0.000 claims description 3
- 229940126062 Compound A Drugs 0.000 claims description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 66
- 239000011889 copper foil Substances 0.000 description 64
- 239000003822 epoxy resin Substances 0.000 description 50
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 44
- 239000011521 glass Substances 0.000 description 42
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical group C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 36
- 239000000047 product Substances 0.000 description 30
- 239000000126 substance Substances 0.000 description 28
- 229920003986 novolac Polymers 0.000 description 27
- 238000000034 method Methods 0.000 description 26
- 239000004305 biphenyl Chemical group 0.000 description 25
- 235000010290 biphenyl Nutrition 0.000 description 25
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical group C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- 125000001424 substituent group Chemical group 0.000 description 19
- 125000001624 naphthyl group Chemical group 0.000 description 17
- 229920001187 thermosetting polymer Polymers 0.000 description 16
- 238000009413 insulation Methods 0.000 description 15
- 239000002904 solvent Substances 0.000 description 15
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 14
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 12
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 12
- 239000005011 phenolic resin Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 230000001747 exhibiting effect Effects 0.000 description 10
- 239000000945 filler Substances 0.000 description 10
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 9
- 239000006087 Silane Coupling Agent Substances 0.000 description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 9
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 8
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 229930003836 cresol Natural products 0.000 description 8
- 239000011342 resin composition Substances 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical group C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 7
- 125000003545 alkoxy group Chemical group 0.000 description 7
- 125000003710 aryl alkyl group Chemical group 0.000 description 7
- 239000002270 dispersing agent Substances 0.000 description 7
- 239000000835 fiber Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- WOCGGVRGNIEDSZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical compound C=1C=C(O)C(CC=C)=CC=1C(C)(C)C1=CC=C(O)C(CC=C)=C1 WOCGGVRGNIEDSZ-UHFFFAOYSA-N 0.000 description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N Bisphenol F Natural products C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 125000004122 cyclic group Chemical group 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 6
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 6
- 239000002966 varnish Substances 0.000 description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 6
- 238000009736 wetting Methods 0.000 description 6
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 5
- 230000009471 action Effects 0.000 description 5
- 150000002576 ketones Chemical class 0.000 description 5
- 239000002685 polymerization catalyst Substances 0.000 description 5
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- 229920002554 vinyl polymer Polymers 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 4
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 4
- 238000007259 addition reaction Methods 0.000 description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 4
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 4
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 4
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
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- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 4
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- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
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- NUDSREQIJYWLRA-UHFFFAOYSA-N 4-[9-(4-hydroxy-3-methylphenyl)fluoren-9-yl]-2-methylphenol Chemical compound C1=C(O)C(C)=CC(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(C)C(O)=CC=2)=C1 NUDSREQIJYWLRA-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
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- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
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- 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
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- 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
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- B32B15/00—Layered products comprising a layer of metal
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- B32B15/092—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 epoxy resins
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- B32B27/00—Layered products comprising a layer of synthetic resin
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
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- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
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- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
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- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
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- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
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- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08L61/14—Modified phenol-aldehyde condensates
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- 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
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- 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
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
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Abstract
A curable composition comprising an alkenylphenol A, an epoxy-modified silicone B, an epoxy compound C other than the epoxy-modified silicone B, and an acid anhydride D.
Description
Technical Field
The present invention relates to a curable composition, a prepreg, a resin sheet, a metal foil-clad laminate, and a printed wiring board.
Background
In recent years, along with the progress of high functionality and miniaturization of semiconductor packages widely used in electronic devices, communication equipment, personal computers, and the like, the high integration and high density mounting of components for semiconductor packages has been accelerated in recent years. Along with this, various characteristics required for a printed circuit board for a semiconductor package are becoming more and more stringent. The characteristics required for such a printed wiring board include, for example, low thermal expansion, chemical resistance, and peel strength.
Patent document 1 discloses that a thermosetting resin composition containing a specific maleimide compound, a silicone compound having an epoxy group in the molecular structure, and a compound having a phenolic hydroxyl group is excellent in heat resistance and low thermal expansion and is suitable for use in metal foil-clad laminates and multilayer printed wiring boards.
Patent document 2 discloses a method for producing a resin for sealing a semiconductor by reacting polymaleimide, an addition polymer of diglycidyl polysiloxane represented by the following formula (I) and diallyl bisphenol represented by the following formula (II), and an allylated phenol resin represented by the following formula (III) in a predetermined ratio and under a predetermined condition. According to this document, it is disclosed that the polymaleimide has good compatibility with the addition polymer, and that the cured product of the composition using the resin for sealing a semiconductor has excellent characteristics (for example, high glass transition temperature, moisture resistance, and strength at the time of heat) and is highly reliable as a resin composition for sealing a semiconductor, among the resins for sealing a semiconductor obtained by the above-mentioned production method. In this document, it is disclosed that the component b in the following formula (III) reacts with maleimide groups in the resin-forming reaction with polymaleimide, and is an important component for improving compatibility of polymaleimide with polysiloxane.
(wherein R is 1 Represents alkylene or phenylene, R 2 Each independently represents an alkyl group or a phenyl group, and n represents an integer of 1 to 100. )
(wherein R is 4 Represents an ether linkage, methylene, propylidene, or a direct bond (single bond). )
(in the above formulae, a, b, and c each represent a percentage of each composition, satisfying 0 < a, b, c < 100, and a+b+c=100.)
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2012-149554
Patent document 2: japanese patent laid-open No. 4-4213
Disclosure of Invention
Problems to be solved by the invention
As in patent document 1, a resin composition containing a silicone compound having an epoxy group in a molecular structure and a thermosetting resin such as a maleimide compound is excellent in low thermal expansion property. However, the present inventors have found that the above-mentioned resin composition has a problem of moldability because the compatibility of the above-mentioned silicone compound with the thermosetting resin is insufficient. Further, the present inventors have found that the metal foil peel strength (for example, copper foil peel strength) is insufficient when the resin composition is used to prepare a metal foil-clad laminate.
On the other hand, the resin composition described in patent document 2 is used for sealing a semiconductor, and low thermal expansion and copper foil peel strength, which are required as characteristics of a printed wiring board, have not been studied.
The present invention has been made in view of the above-described problems, and an object thereof is to provide a curable composition, a prepreg, a resin sheet, a metal foil-clad laminate, and a printed wiring board, which have excellent low thermal expansibility and copper foil peel strength.
Solution for solving the problem
The present inventors have made intensive studies to solve the above problems. As a result, it has been found that the above problems can be solved by a curable composition containing an alkenylphenol, an epoxy-modified silicone, an epoxy compound other than the epoxy-modified silicone, and an acid anhydride, or by a curable composition containing a polymer having these as a structural unit, and the present invention has been completed.
Namely, the present invention is as follows.
[1]
A curable composition comprising an alkenylphenol A, an epoxy-modified silicone B, an epoxy compound C other than the epoxy-modified silicone B, and an acid anhydride D.
[2]
The curable composition according to the above [1], wherein the average number of phenols of the alkenyl phenol A per 1 molecule is 1 or more and less than 3, the average number of epoxies of the epoxy-modified silicone B per 1 molecule is 1 or more and less than 3, and the average number of epoxies of the epoxy compound C per 1 molecule is 1 or more and less than 3.
[3]
The curable composition according to the above [1] or [2], wherein the alkenylphenol A contains diallyl bisphenol and/or dipropenylbisphenol.
[4]
The curable composition according to any one of [1] to [3], wherein the epoxy-modified silicone B comprises an epoxy-modified silicone having an epoxy equivalent of 140 to 250 g/mol.
[5]
The curable composition according to any one of the above [1] to [4], wherein the epoxy-modified silicone B contains an epoxy-modified silicone represented by the following formula (1).
(wherein R is 1 Each independently represents a single bond, alkylene, arylene or aralkylene, R 2 Each independently represents an alkyl group having 1 to 10 carbon atoms or a phenyl group, and n represents an integer of 0 to 100. )
[6]
The curable composition according to any one of the above [1] to [5], wherein the epoxy compound C contains a compound represented by the following formula (b 2).
(wherein R is a Each independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom. )
[7]
The curable composition according to any one of the above [1] to [6], wherein the content of the epoxy compound C is 20 to 50% by mass relative to 100% by mass of the total amount of the epoxy-modified silicone B and the epoxy compound C.
[8]
The curable composition according to any one of [1] to [7], wherein the acid anhydride D is 1 or more selected from the group consisting of phthalic anhydride, succinic anhydride, maleic anhydride, nadic anhydride and cis-4-cyclohexene-1, 2-dicarboxylic anhydride.
[9]
A curable composition comprising a polymer E containing structural units derived from an alkenylphenol a, structural units derived from an epoxy-modified silicone B, structural units derived from an epoxy compound C, and structural units derived from an anhydride D.
[10]
According to [9] above]The curable composition, wherein the polymer E has a weight average molecular weight of 3.0X10 3 ～5.0×10 4 。
[11]
The curable composition according to the above [9] or [10], wherein the content of the structural unit derived from the epoxy-modified silicone B in the polymer E is 20 to 60% by mass based on the total mass of the polymer E.
[12]
The curable composition according to any one of the above [9] to [11], wherein the alkenyl equivalent of the polymer E is 300 to 1500g/mol.
[13]
The curable composition according to any one of the above [9] to [12], wherein the content of the structural unit derived from the acid anhydride D in the polymer E is 3 to 20% by mass based on the total mass of the polymer E.
[14]
The curable composition according to any one of the above [9] to [13], wherein the content of the polymer E is 5 to 50% by mass relative to 100% by mass of the resin solid content.
[15]
The curable composition according to any one of the above [9] to [14], wherein the alkenylphenol A contains diallyl bisphenol and/or dipropenylbisphenol.
[16]
The curable composition according to any one of [9] to [15], wherein the epoxy-modified silicone B comprises an epoxy-modified silicone having an epoxy equivalent of 140 to 250 g/mol.
[17]
The curable composition according to any one of the above [9] to [16], wherein the epoxy-modified silicone B contains an epoxy-modified silicone represented by the following formula (1).
(wherein R is 1 Each independently represents a single bond, alkylene, arylene or aralkylene, R 2 Each independently represents an alkyl group having 1 to 10 carbon atoms or a phenyl group, and n represents an integer of 0 to 100. )
[18]
The curable composition according to any one of the above [9] to [17], wherein the epoxy compound C contains a compound represented by the following formula (b 2).
(wherein R is a Each independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom. )
[19]
The curable composition according to any one of [9] to [18], wherein the acid anhydride D is 1 or more selected from the group consisting of phthalic anhydride, succinic anhydride, maleic anhydride, nadic anhydride and cis-4-cyclohexene-1, 2-dicarboxylic anhydride.
[20]
The curable composition according to any one of the above [9] to [19], further comprising an epoxy compound C, wherein the epoxy compound C comprises a compound represented by the following formula (3-3) or a compound represented by the following formula (3-4).
(wherein R is 13 Each independently represents a hydrogen atom, a C1-3 alkyl group or a C2-3 alkenyl group. )
(wherein R is 14 Each of which is a single pieceIndependently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or an alkenyl group having 2 to 3 carbon atoms. )
[21]
The curable composition according to any one of [1] to [20] above, further comprising at least 1 compound F selected from the group consisting of maleimide compounds, cyanate ester compounds, phenol compounds A' other than alkenylphenol A, and alkenyl-substituted nadic imide compounds.
[22]
The curable composition according to [21] above, wherein the maleimide compound comprises at least 1 selected from the group consisting of bis (4-maleimidophenyl) methane, 2-bis {4- (4-maleimidophenoxy) -phenyl } propane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, a maleimide compound represented by the following formula (3), and a maleimide compound represented by the following formula (3').
(wherein R is 5 Each independently represents a hydrogen atom or a methyl group, n 1 And represents an integer of 1 or more. )
(in the formula (3'), R 13 Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a phenyl group, n 4 And represents an integer of 1 to 10 inclusive. )
[23]
The curable composition according to the above [21] or [22], wherein the cyanate ester compound comprises a compound represented by the following formula (4) and/or a compound represented by the following formula (5) other than the compound represented by the following formula (4).
(wherein R is 6 Each independently represents a hydrogen atom or a methyl group, n 2 And represents an integer of 1 or more. )
(wherein R is ya Each independently represents an alkenyl group having 2 to 8 carbon atoms or a hydrogen atom, R yb Each independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom, R yc Each independently represents an aromatic ring having 4 to 12 carbon atoms, R yc Optionally forming a condensed structure with the benzene ring, R yc Optionally present or absent, A 1a Each independently represents an alkylene group having 1 to 6 carbon atoms, an aralkylene group having 7 to 16 carbon atoms, an arylene group having 6 to 10 carbon atoms, a fluorenylidene group, a sulfonyl group, an oxygen atom, a sulfur atom or a single bond, R yc In the absence, 1 benzene ring may have more than 2R ya And/or R yb N represents an integer of 1 to 20. )
[24]
The curable composition according to any one of [21] to [23], wherein the phenol compound A' comprises a compound represented by the following formula (8).
(wherein R is 7 Each independently represents a hydrogen atom or a methyl group, n 3 And represents an integer of 1 or more. )
[25]
The curable composition according to any one of [1] to [24], further comprising an inorganic filler, wherein the content of the inorganic filler is 50 to 1000 parts by mass per 100 parts by mass of the resin solid content.
[26]
The curable composition according to [25], wherein the inorganic filler comprises 1 or more selected from the group consisting of silica, boehmite, and alumina.
[27]
The curable composition according to any one of [1] to [26], which is a curable composition for a printed wiring board.
[28]
A prepreg comprising a substrate and the curable composition of any one of [1] to [27] impregnated or coated on the substrate.
[29]
A resin sheet comprising a support and the curable composition according to any one of [1] to [27] disposed on the surface of the support.
[30]
A metal foil-clad laminate comprising:
a laminate formed by using 1 or more selected from the group consisting of the prepreg according to [28] and the resin sheet according to [29], and
and a metal foil disposed on one or both sides of the laminate.
[31]
A printed circuit board, having:
an insulating layer formed using 1 or more selected from the group consisting of the prepreg of [28] and the resin sheet of [29], and
and a conductor layer formed on the surface of the insulating layer.
[32]
A method for producing the curable composition according to any one of [1] to [27], comprising:
a step of polymerizing an alkenylphenol A, an epoxy-modified silicone B, and an epoxy compound C to obtain a prepolymer; and
and reacting the acid anhydride D with the prepolymer.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a curable composition, a prepreg, a resin sheet, a metal foil-clad laminate, and a printed circuit board having excellent low thermal expansion and copper foil peel strength can be provided.
Detailed Description
Hereinafter, embodiments for carrying out the present invention (hereinafter, referred to as "the present embodiment") will be described in detail, but the present invention is not limited to these, and various modifications may be made without departing from the spirit thereof.
The term "resin solid component" in the present specification means a component excluding the solvent and the filler in the curable composition of the present embodiment unless otherwise specified, and 100 parts by mass of the resin solid component means a total of 100 parts by mass of the components excluding the solvent and the filler in the curable composition. The term "100 mass% of the resin solid content" means that the total of the components excluding the solvent and the filler in the curable composition is 100 mass%.
In the curable composition of embodiment 1 described below, "excellent compatibility" means that liquid phase separation does not occur in a state of containing a mixture (for example, varnish) of the alkenylphenol a, the epoxy-modified silicone B, the epoxy compound C, and the acid anhydride D.
In the curable composition of embodiment 2 described below, "excellent compatibility" means that liquid phase separation does not occur in a state of a mixture (for example, varnish) containing the polymer E and other components.
The curable composition of the present embodiment has excellent compatibility, suppresses liquid phase separation during molding, and can give a molded article having excellent appearance, and the obtained molded article tends to have excellent isotropy of physical properties. In the present specification, when the term "curable composition of the present embodiment" is used, both the term "curable composition of embodiment 1" and the term "curable composition of embodiment 2" are included unless otherwise specified.
[ embodiment 1: curable composition ]
The curable composition of embodiment 1 contains an alkenylphenol a, an epoxy-modified silicone B, an epoxy compound C (hereinafter also simply referred to as "epoxy compound C") other than the epoxy-modified silicone B, and an acid anhydride D. Curable compositions containing these components tend to have more excellent compatibility with thermosetting resins (hereinafter also referred to simply as "thermosetting resins") having insufficient compatibility with the epoxy-modified silicone B. Therefore, the curable composition of embodiment 1 can exhibit more excellent compatibility, and is excellent in low thermal expansion and copper foil peel strength. Further, when each of these components is partially reacted (polymerized) in the curable composition, the composition can exhibit more excellent compatibility, and can exhibit more excellent low thermal expansion and copper foil peel strength (the curable composition of embodiment 2).
[ alkenylphenol A ]
The alkenylphenol a is not particularly limited as long as it has a structure in which 1 or more alkenyl groups are directly bonded to the phenolic aromatic ring. The curable composition of the present embodiment can exhibit excellent compatibility by containing the alkenylphenol a.
The alkenyl group is not particularly limited, and examples thereof include alkenyl groups having 2 to 30 carbon atoms such as vinyl, allyl, propenyl, butenyl, hexenyl and the like. Among them, from the viewpoint of more effectively and reliably exerting the action and effect of the present invention, the alkenyl group is preferably an allyl group and/or a propenyl group, and more preferably an allyl group. The number of alkenyl groups directly bonded to 1 phenolic aromatic ring is not particularly limited, and is, for example, 1 to 4. From the viewpoint of more effectively and reliably exerting the operational effects of the present invention, the number of alkenyl groups directly bonded to 1 phenolic aromatic ring is preferably 1 to 2, more preferably 1. The bonding position of the alkenyl group to the phenolic aromatic ring is not particularly limited, and is preferably ortho (2, 6 positions).
The phenolic aromatic ring means one in which 1 or more hydroxyl groups are directly bonded to the aromatic ring, and examples thereof include phenol rings and naphthol rings. The number of hydroxyl groups directly bonded to 1 phenolic aromatic ring is not particularly limited, and is, for example, 1 to 2, preferably 1.
The phenolic aromatic ring may have a substituent other than an alkenyl group. Examples of such a substituent include a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, a linear alkoxy group having 1 to 10 carbon atoms, a branched alkoxy group having 3 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, and a halogen atom. When the phenolic aromatic ring has a substituent other than an alkenyl group, the number of the substituent directly bonded to 1 phenolic aromatic ring is not particularly limited, and is, for example, 1 to 2. The bonding position of the substituent to the phenolic aromatic ring is not particularly limited.
Alkenyl phenol a may have a structure in which 1 or more alkenyl groups are directly bonded to a phenolic aromatic ring. From the viewpoint of more effectively and reliably exerting the action and effect of the present invention, the alkenylphenol a preferably has a structure in which 1 or 2 alkenyl groups are directly bonded to the phenolic aromatic ring, and preferably has 2 alkenyl groups.
The alkenylphenol a may be, for example, a compound represented by the following formula (1A) or the following formula (1B).
(wherein Rxa each independently represents an alkenyl group having 2 to 8 carbon atoms, rxb each independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom, rxc each independently represents an aromatic ring having 4 to 12 carbon atoms, rxc may or may not form a condensed structure with a benzene ring, A represents an alkylene group having 1 to 6 carbon atoms, an aralkylene group having 7 to 16 carbon atoms, an arylene group having 6 to 10 carbon atoms, fluorenylidene, sulfonyl, an oxygen atom, a sulfur atom or a direct bond (single bond), and when Rxc is not present, 1 benzene ring may have 2 or more Rxa and/or Rxb groups.)
(wherein Rxd each independently represents an alkenyl group having 2 to 8 carbon atoms, rxe each independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom, rxf represents an aromatic ring having 4 to 12 carbon atoms, rxf may form a condensed structure with a benzene ring, rxf may be present or absent, and when Rxf is absent, 1 benzene ring may have 2 or more groups of Rxd and/or Rxe.)
In the formulas (1A) and (1B), the alkenyl group having 2 to 8 carbon atoms represented by Rxa and Rxd is not particularly limited, and examples thereof include vinyl, allyl, propenyl, butenyl, hexenyl, and the like.
Examples of the case where the groups represented by Rxc and Rxf in the formulas (1A) and (1B) form a condensed structure with a benzene ring include compounds containing a naphthol ring as a phenolic aromatic ring. Examples of the case where the groups represented by Rxc and Rxf are not present in the formulae (1A) and (1B) include compounds containing a phenol ring as a phenolic aromatic ring.
The alkyl group having 1 to 10 carbon atoms represented by Rxb and Rxe in the formula (1A) and the formula (1B) is not particularly limited, and examples thereof include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl and the like, and branched alkyl groups such as isopropyl, isobutyl, tert-butyl and the like.
In the formula (1A), the alkylene group having 1 to 6 carbon atoms represented by A is not particularly limited, and examples thereof include methylene, ethylene, trimethylene and propylene. The aralkylene group having 7 to 16 carbon atoms represented by a is not particularly limited, and examples thereof include the formula: -CH 2 -Ar-CH 2 -、-CH 2 -CH 2 -Ar-CH 2 -CH 2 -, or-CH 2 -Ar-CH 2 -CH 2 In the formula, ar represents a group represented by phenylene, naphthylene, or biphenylene, and examples of the arylene group having 6 to 10 carbon atoms represented by A include, but are not particularly limited to, phenylene rings.
From the viewpoint of more effectively and reliably exerting the action and effect of the present invention, the compound represented by formula (1B) is preferably one in which Rxf is a benzene ring (a compound containing a dihydroxynaphthalene skeleton).
From the viewpoint of further improving the compatibility, the alkenylphenol a is preferably an alkenylbisphenol in which 1 alkenyl group is bonded to each of 2 phenolic aromatic rings of the bisphenol. From the same viewpoint, the alkenyl bisphenol is preferably diallyl bisphenol in which 1 allyl group is bonded to each of 2 phenolic aromatic rings of the bisphenol, and/or dipropenyl bisphenol in which 1 propenyl group is bonded to each of 2 phenolic aromatic rings of the bisphenol.
Examples of the diallyl bisphenol include, but are not limited to, o '-diallyl bisphenol a (Daiwa Kasei Industry co., ltd. DABPA of product), o' -diallyl bisphenol F, o, o '-diallyl bisphenol S, o, o' -diallyl bisphenol fluorene. The dipropenyl bisphenol is not particularly limited, and examples thereof include o, o '-dipropenyl bisphenol a (Gunei Chemical Industry co., ltd. PBA01 "), o' -dipropenyl bisphenol F, o, o '-dipropenyl bisphenol S, o, o' -dipropenyl bisphenol fluorene.
From the viewpoint of more effectively and reliably exerting the action and effect of the present invention, the average number of phenol groups of the alkenylphenol a per 1 molecule is preferably 1 or more and less than 3, more preferably 1.5 or more and 2.5 or less. The average phenol number is calculated by the following formula.
Wherein Ai represents the number of phenol groups of the alkenylphenol having i phenol groups in the molecule, xi represents the ratio of alkenylphenol having i phenol groups in the molecule to alkenylphenol as a whole, and X 1 +X 2 +…X n ＝1。
[ epoxy-modified Silicone B ]
The epoxy-modified silicone B is not particularly limited as long as it is a silicone compound or resin modified with an epoxy group-containing group. The curable composition of the present embodiment can exhibit excellent low thermal expansion and copper foil peel strength by containing the epoxy-modified silicone (B).
The silicone compound or resin is not particularly limited as long as it is a compound having a polysiloxane skeleton formed by repeating siloxane bonds. The polysiloxane skeleton may be a linear skeleton, a cyclic skeleton, or a network skeleton. Among them, a linear skeleton is preferable from the viewpoint of more effectively and reliably exerting the operational effects of the present invention.
The epoxy group-containing group is not particularly limited, and examples thereof include a group represented by the following formula (a 1).
-R 0 -X (a1)
(wherein R is 0 An alkylene group (e.g., an alkylene group having 1 to 5 carbon atoms such as a methylene group, an ethylene group, and a propylene group), and X represents a 1-valent group represented by the following formula (a 2)Or a 1-valent group represented by the following formula (a 3). )
The epoxy-modified silicone B preferably contains an epoxy-modified silicone having an epoxy equivalent weight of 140 to 250 g/mol. The epoxy-modified silicone B contains an epoxy-modified silicone having an epoxy equivalent in the above range, and thus has excellent compatibility with a thermosetting resin, and thus tends to be more improved in a well-balanced manner in terms of low thermal expansion and copper foil peel strength. From the same viewpoint, the epoxy equivalent is more preferably 145 to 245g/mol, still more preferably 150 to 240g/mol.
The epoxy-modified silicone B preferably contains 2 or more epoxy-modified silicones from the viewpoint of more excellent compatibility with thermosetting resins, and more excellent balance, and further improvement in low thermal expansion and copper foil peel strength. In this case, 2 or more epoxy-modified silicones are preferably different in epoxy equivalent weight, more preferably epoxy-modified silicone having an epoxy equivalent weight of 50 to 350g/mol (hereinafter also referred to as "low-equivalent-weight epoxy-modified silicone B1") and epoxy-modified silicone having an epoxy equivalent weight of 400 to 4000g/mol (hereinafter also referred to as "high-equivalent-weight epoxy-modified silicone B2"), further preferably epoxy-modified silicone having an epoxy equivalent weight of 140 to 250g/mol (low-equivalent-weight epoxy-modified silicone B1 '), and epoxy-modified silicone having an epoxy equivalent weight of 450 to 3000g/mol (high-equivalent-weight epoxy-modified silicone B2').
When the epoxy-modified silicone B contains 2 or more epoxy-modified silicones, the average epoxy equivalent of the epoxy-modified silicone B is preferably 140 to 3000g/mol, more preferably 250 to 2000g/mol, and even more preferably 300 to 1000g/mol. The average epoxy equivalent weight is calculated by the following formula.
(wherein Ei represents the epoxy of 1 epoxy-modified silicone out of 2 or more epoxy-modified siliconesEquivalent weight, wi represents the ratio of the epoxy-modified silicone in the epoxy-modified silicone (B), and is W 1 +W 2 +…W n ＝1。)
From the viewpoint of excellent compatibility with thermosetting resins and a well-balanced improvement in low thermal expansion and copper foil peel strength, the epoxy-modified silicone B preferably contains an epoxy-modified silicone represented by the following formula (1).
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In the formula (1), R 1 Each independently represents a single bond, alkylene, arylene or aralkylene, R 2 Each independently represents an alkyl group having 1 to 10 carbon atoms or a phenyl group, and n represents an integer of 0 to 100.
In the formula (1), R 1 The alkylene group may be linear, branched or cyclic. The carbon number of the alkylene group is preferably 1 to 12, more preferably 1 to 4. Examples of the alkylene group include a methylene group, an ethylene group, and a propylene group. Among these, R 1 Propylene is preferred.
In the formula (1), R 1 The arylene group shown may also have a substituent. The carbon number of the arylene group is preferably 6 to 40, more preferably 6 to 20. Examples of the arylene group include phenylene, cyclohexylphenylene, hydroxyphenyl, cyanophenylene, nitrophenylene, naphthylene, biphenylene, anthrylene, pyrenylene, fluorenylene and the like. These groups may also contain ether linkages, ketone linkages, or ester linkages.
In the formula (1), R 1 The carbon number of the aralkylene group is preferably 7 to 30, more preferably 7 to 13. Examples of the aralkylene group include a group represented by the following formula (X-I).
(in formula (X-I): represents a bond.)
In the formula (1), R 1 Shown in the figureThe group may further have a substituent, and examples of the substituent include a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, a linear alkoxy group having 1 to 10 carbon atoms, a branched alkoxy group having 3 to 10 carbon atoms, and a cyclic alkoxy group having 3 to 10 carbon atoms. Among these, R 1 Propylene is particularly preferred.
In the formula (1), R 2 Each independently represents an alkyl group having 1 to 10 carbon atoms or a phenyl group. The alkyl group and the phenyl group may have a substituent. The alkyl group having 1 to 10 carbon atoms may be any of linear, branched or cyclic. The alkyl group is not particularly limited, and examples thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, and cyclohexyl. Among these, R 2 Preferably methyl or phenyl.
In the formula (1), n represents an integer of 0 or more, for example, 0 to 100. From the viewpoint of more excellent compatibility with thermosetting resins and more improved low thermal expansion and copper foil peel strength in a well-balanced manner, n is preferably 50 or less, more preferably 30 or less, and even more preferably 20 or less.
From the viewpoint of more excellent compatibility with thermosetting resins and a well-balanced further improvement in low thermal expansion and copper foil peel strength, the epoxy-modified silicone B preferably contains 2 or more epoxy-modified silicones represented by formula (1). In this case, it is preferable that at least 2 kinds of epoxy-modified silicones contained have different n, and it is more preferable that the epoxy-modified silicone having n of 1 to 2 in formula (1) and the epoxy-modified silicone having n of 5 to 20 in formula (1) be contained.
From the viewpoint of more effectively and reliably exerting the action and effect of the present invention, the average number of epoxy groups per 1 molecule of the epoxy-modified silicone B is preferably 1 or more and less than 3, more preferably 1.5 or more and 2.5 or less. The average epoxy number is calculated by the following formula.
(wherein Bi represents a molecule having i ringsThe epoxy number of the epoxy-modified silicone having an oxy group, yi represents the ratio of the epoxy-modified silicone having i epoxy groups in the molecule to the entire epoxy-modified silicone, Y 1 +Y 2 +…Y n ＝1。)
From the viewpoint of exhibiting more excellent low thermal expansion and chemical resistance, the content of the epoxy-modified silicone B is preferably 5 to 95 mass%, more preferably 10 to 90 mass%, even more preferably 40 to 85 mass%, and even more preferably 50 to 80 mass%, relative to 100 mass% of the total of the epoxy-modified silicone B and the epoxy compound C.
The epoxy-modified silicone B may be commercially available or manufactured by a known method. Examples of the commercial products include "X-22-163" and "KF-105" of Shin-Etsu Chemical Co., ltd.
[ epoxy Compound C ]
The epoxy compound C is an epoxy compound other than the epoxy-modified silicone B, more specifically, an epoxy compound having no polysiloxane skeleton. The curable composition of the present embodiment contains the epoxy compound C, and thus exhibits excellent compatibility, heat resistance, chemical resistance, copper foil peel strength, and insulation reliability.
The epoxy compound C is not particularly limited as long as it is an epoxy compound other than the epoxy-modified silicone B. As the epoxy compound C in the curable composition of the present embodiment, typically, a 2-functional epoxy compound having 2 epoxy groups in 1 molecule and a multi-functional epoxy compound having 3 or more epoxy groups in 1 molecule can be used. The epoxy compound C preferably contains a 2-functional epoxy compound and/or a multifunctional epoxy compound from the viewpoint of exhibiting more excellent compatibility, heat resistance, chemical resistance, copper foil peel strength, and insulation reliability.
The epoxy compound C in the curable composition of the present embodiment is not particularly limited, and a compound represented by the following formula (3 a) can be used.
(in the formula (3 a), ar 3 Each independently represents a benzene ring or a naphthalene ring, ar 4 Represents a benzene ring, naphthalene ring or biphenyl ring, R 3a Each independently represents a hydrogen atom or a methyl group, k represents an integer of 1 to 50,
here, ar is 3 The benzene ring or naphthalene ring of (a) may further have one or more substituents which may be glycidylether oxy group not shown in the figure or other substituents such as alkyl group having 1 to 5 carbon atoms, phenyl group and the like,
Ar 4 the benzene ring, naphthalene ring or biphenyl ring of (a) may further have one or more substituents which may be glycidoxy or other substituents such as alkyl groups having 1 to 5 carbon atoms, phenyl groups and the like. )
Among the compounds represented by the above formula (3 a), examples of the 2-functional epoxy compound include compounds represented by the following formula (b 1).
(in the formula (b 1), ar 3 Each independently represents a benzene ring or a naphthalene ring, ar 4 Represents a benzene ring, naphthalene ring or biphenyl ring, R 3a Each independently represents a hydrogen atom or a methyl group,
here, ar is 3 The benzene ring or naphthalene ring of (C1-5) may further have one or more substituents other than glycidylether oxy group such as alkyl group or phenyl group,
Ar 4 The benzene ring, naphthalene ring or biphenyl ring may have one or more substituents, and the substituents may be, for example, substituents other than glycidylether oxy group such as alkyl group having 1 to 5 carbon atoms and phenyl group. )
The compound represented by the formula (3 a) is preferably Ar in the formula (3 a) 4 Phenolic novolak type epoxy resins substituted at least with glycidoxy groups. The phenolic novolac type epoxy resin is not particularly limited, and examples thereof includeFor example, a compound having a structure represented by the following formula (3-1) (a naphthalene skeleton-containing polyfunctional epoxy resin having a naphthalene skeleton), and a naphthalene cresol novolak type epoxy resin are obtained.
(wherein Ar is 31 Each independently represents a benzene ring or a naphthalene ring, ar 41 Each independently represents a benzene ring, naphthalene ring or biphenyl ring, R 31a Each independently represents a hydrogen atom or a methyl group, p represents 1, kz represents an integer of 1 to 50, each ring may have a substituent other than glycidyletheroxy group (for example, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a phenyl group), ar 31 And Ar is a group 41 At least one of which represents a naphthalene ring. )
The compound having the structure represented by the formula (3-1) may be a compound having the structure represented by the formula (3-2).
(wherein R represents a methyl group and kz has the same meaning as kz in the above formula (3-1))
The naphthol novolac type epoxy resin is not particularly limited, and is preferably, for example, a cresol/naphthol novolac type epoxy resin represented by the following formula (NE). The compound represented by the following formula (NE) is a random copolymer of a structural unit of cresol novolac epoxy and a structural unit of naphthol novolac epoxy, and both the cresol epoxy and the naphthol epoxy may be terminal.
M and n in the above formula (NE) each represent an integer of 1 or more. The upper limits of m and n and the ratio thereof are not particularly limited, and from the viewpoint of low thermal expansion, m: n (here, m+n=100), preferably 30 to 50:70 to 50, more preferably 45 to 55:55 to 45.
As the naphthalene cresol novolac type epoxy resin, commercially available ones may be used, and products produced by a known method may be used. Examples of the commercial products include "NC-7000", "NC-7300L" manufactured by Kagaku Co., ltd., and "HP-9540", "HP-9500" manufactured by DIC Co., ltd., particularly preferably "HP-9540".
The compound represented by the formula (3 a) may be a compound not belonging to the phenol novolac type epoxy resin (hereinafter also referred to as "aralkyl type epoxy resin").
As the aralkyl type epoxy resin, ar in the formula (3 a) is preferable 3 Is naphthalene ring and Ar 4 A compound which is a benzene ring (also referred to as "naphthol aralkyl type epoxy resin"), and Ar in formula (3 a) 3 Is a benzene ring and Ar 4 Compounds that are biphenyl rings (also known as "biphenyl aralkyl-type epoxy resins"), more preferably biphenyl aralkyl-type epoxy resins.
As the naphthol aralkyl type epoxy resin, a commercially available product may be used, or a product produced by a known method may be used. Examples of the commercial products include "HP-5000", "HP-9900", NIPPON STEEL Chemical Co., ltd., and "ESN-375", "ESN-475" of DIC.
The biphenyl aralkyl type epoxy resin is preferably a compound represented by the following formula (3 b).
(wherein ka represents an integer of 1 or more, preferably 1 to 20, more preferably 1 to 6.)
Among the compounds represented by the above formula (3 b), examples of the 2-functional epoxy compound include compounds having ka of 1 in the formula (3 b).
As the biphenyl aralkyl type epoxy resin, a commercially available product may be used, or a product produced by a known method may be used. Examples of the commercial products include "NC-3000", "NC-3000L", "NC-3000FH" manufactured by Kagaku Co., ltd.
Further, as the epoxy compound C in the curable composition of the present embodiment, a naphthalene type epoxy resin (excluding compounds represented by formula (3 a)) is preferably used. The naphthalene type epoxy resin is preferably a naphthalene ether type epoxy resin from the viewpoint of further improving heat resistance, chemical resistance, copper foil peel strength and insulation reliability.
From the viewpoint of further improving heat resistance, chemical resistance, copper foil peel strength and insulation reliability, the naphthalene ether type epoxy resin is preferably a 2-functional epoxy compound represented by the following formula (3-3), a polyfunctional epoxy compound represented by the following formula (3-4), or a mixture thereof.
(wherein R is 13 Each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (e.g., methyl or ethyl), or an alkenyl group having 2 to 3 carbon atoms (e.g., vinyl, allyl, or propenyl). )
(wherein R is 14 Each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (e.g., methyl or ethyl), or an alkenyl group having 2 to 3 carbon atoms (e.g., vinyl, allyl, or propenyl). )
The naphthalene ether type epoxy resin may be commercially available ones or ones produced by a known method. Examples of the commercial products of the naphthalene ether type epoxy resins include "HP-6000", "EXA-7300", "EXA-7310", "EXA-7311L", "EXA7311-G3", "EXA7311-G4", "EXA-7311G4S", "EXA-7311G5" manufactured by DIC Co., ltd., and the like, and HP-6000 is particularly preferred.
Examples of the naphthalene type epoxy resin other than those described above include, but are not limited to, the following compounds represented by the following formula (b 3).
(in the formula (b 3), R 3b Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms (e.g., methyl or ethyl), an aralkyl group, benzyl group, naphthyl group having at least 1 glycidoxy group, or naphthylmethyl group having at least 1 glycidoxy group, and n represents an integer of 0 or more (e.g., 0 to 2). )
Examples of the commercially available compounds represented by the above formula (b 3) include "HP-4032" (n=0 in the above formula (b 3)) and "HP-4710" (n=0, R in the above formula (b 3)) manufactured by DIC Co., ltd 3b Naphthylmethyl group containing at least 1 glycidoxy group, and the like.
Further, as the epoxy compound C in the curable composition of the present embodiment, a biphenyl type epoxy compound is preferably used (excluding those belonging to the epoxy compound C described above).
The biphenyl type epoxy compound is not particularly limited, and examples thereof include a compound (compound b 2) represented by the following formula (b 2).
(in the formula (b 2), ra independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom.)
In the formula (b 2), the alkyl group having 1 to 10 carbon atoms may be any of linear, branched or cyclic. The alkyl group is not particularly limited, and examples thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, and cyclohexyl.
When the biphenyl type epoxy compound is the compound b2, the biphenyl type epoxy compound may be a mixture of compounds b2 having different numbers of alkyl groups Ra. Specifically, a mixture of biphenyl type epoxy resins having different numbers of alkyl groups, that is, ra is preferable, and a mixture of a compound b2 having 0 number of alkyl groups, that is, ra and a compound b2 having 4 number of alkyl groups, that is, ra is more preferable.
Furthermore, as the epoxy compound C in the curable composition of the present embodiment, dicyclopentadiene type epoxy resin (excluding those belonging to the epoxy compound C described above) can be used.
The dicyclopentadiene type epoxy resin is not particularly limited, and examples thereof include compounds represented by the following formulas (3 to 5).
(wherein R is 3c Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and k2 represents an integer of 0 to 10. )
The compound represented by the above formula (3-5) is not particularly limited, and may be, for example, a compound represented by the following formula (b 4).
(in the formula (b 4), R 3c Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms (e.g., methyl or ethyl). )
The dicyclopentadiene type epoxy resin may be commercially available, or may be produced by a known method. As commercial products of dicyclopentadiene type epoxy resins, "EPICRON HP-7200L", "EPICRON HP-7200H", "EPICRON HP-7000HH" of Dainippon Ink and Chemicals, incorporated products, etc. are mentioned.
Among these, from the viewpoint of more excellent heat resistance, chemical resistance, copper foil peel strength, and insulation reliability, it is preferable that the epoxy compound C is 1 or more selected from the group consisting of an epoxy compound represented by formula (3 a), a naphthalene type epoxy resin, and a biphenyl type epoxy compound, and in this case, it is preferable that the epoxy compound represented by formula (3 a) contains a naphthalene cresol novolac type epoxy resin, and the naphthalene type epoxy resin contains a naphthalene ether type epoxy resin.
The epoxy compound C may contain other epoxy compounds than the above epoxy compounds.
The other epoxy compound is not particularly limited, and examples thereof include bisphenol epoxy resins, triphenol methane epoxy resins, anthracene epoxy resins, glycidyl ester epoxy resins, polyol epoxy resins, isocyanurate ring-containing epoxy resins, fluorene epoxy resins, and epoxy resins composed of bisphenol a type structural units and hydrocarbon type structural units.
Among the above, bisphenol-type epoxy resins may be contained from the viewpoint of further improving heat resistance, chemical resistance, copper foil peel strength and insulation reliability, and as bisphenol-type epoxy resins, for example, diallyl bisphenol-type epoxy resins (for example, diallyl bisphenol a-type epoxy resins, diallyl bisphenol E-type epoxy resins, diallyl bisphenol F-type epoxy resins, diallyl bisphenol S-type epoxy resins, and the like) and the like may be used.
As the epoxy compound C, 1 kind of the epoxy compound and 2 or more kinds of the epoxy resin may be used singly or in combination.
From the viewpoint of more effectively and reliably exhibiting the operational effects of the present embodiment, the average number of epoxy groups of the epoxy compound C per 1 molecule is preferably 1 or more and less than 3, more preferably 1.5 or more and 2.5 or less.
The average epoxy number is calculated by the following formula.
(in the above formula, ci represents the number of epoxy groups of an epoxy compound having i epoxy groups in the molecule, zi represents the ratio of the epoxy compound having i epoxy groups in the molecule to the entire epoxy compound, Z 1 +Z 2 +…Z n ＝1。)
From the viewpoint of exhibiting more excellent heat resistance, chemical resistance, copper foil peel strength and insulation reliability, the content of the epoxy compound C is preferably 5 to 95 mass%, more preferably 10 to 90 mass%, even more preferably 15 to 60 mass%, and particularly preferably 20 to 50 mass%, relative to 100 mass% of the total amount of the epoxy-modified silicone B and the epoxy compound C.
[ anhydride D ]
The curable composition of the present embodiment contains an acid anhydride D. The acid anhydride D reacts with a terminal hydroxyl group or an epoxy group formed by reacting the alkenylphenol a, the epoxy-modified silicone B, and the epoxy compound C other than the epoxy-modified silicone B to form a terminal carboxyl group. Thus, there are a large number of carboxyl groups having high reactivity with the thermosetting resin, and thus compatibility and crosslink density are improved, and low thermal expansion is improved.
The acid anhydride D is not particularly limited, or is not particularly limited if it has a cyclic structure, and is preferably an acid anhydride having 4 to 20 carbon atoms, more preferably an acid anhydride having 4 to 16 carbon atoms, and even more preferably an acid anhydride having 4 to 10 carbon atoms, from the viewpoint of further excellent compatibility with the thermosetting resin.
The acid anhydride D may be, for example, 1 or more selected from the group consisting of phthalic anhydride, succinic anhydride, maleic anhydride, nadic anhydride and cis 4-cyclohexene-1, 2-dicarboxylic anhydride, and among these, phthalic anhydride and succinic anhydride are more preferable from the viewpoint of further excellent compatibility with a thermosetting resin and further improvement of the balance between low thermal expansion and copper foil peel strength.
The content of the acid anhydride D is preferably 0.8 to 15 mass%, more preferably 0.9 to 10 mass%, and even more preferably 1 to 5 mass% with respect to 100 mass% of the solid content of the resin, from the viewpoint that the compatibility with the thermosetting resin is further excellent and the low thermal expansion property and the copper foil peel strength can be improved in a balanced manner.
[ Compound F ]
From the viewpoint of further improving heat resistance, chemical resistance, low thermal expansibility, and copper foil peel strength, the curable composition of the present embodiment preferably further contains at least 1 compound F selected from the group consisting of maleimide compounds, cyanate ester compounds, phenol compounds a' other than the aforementioned alkenyl phenol a, and alkenyl-substituted nadic imide compounds. The compound F is not particularly limited, and is preferably a polyfunctional group having 2 or more functional groups, or may be a polyfunctional group having 3 or more functional groups.
The content of the compound F in the curable composition of the present embodiment is preferably 10 to 80% by mass, more preferably 20 to 60% by mass, and even more preferably 30 to 50% by mass, relative to 100% by mass of the solid resin component.
(Maleimide Compound)
From the viewpoint of further improving low thermal expansibility and copper foil peel strength, a maleimide compound is preferably contained as the compound F. The maleimide compound is not particularly limited as long as it is a compound having 1 or more maleimide groups in 1 molecule, and examples thereof include a mono-maleimide compound having 1 or more maleimide groups in 1 molecule (for example, N-phenylmaleimide, N-hydroxyphenyl maleimide and the like), a polymaleimide compound having 2 or more maleimide groups in 1 molecule (for example, bis (4-maleimidophenyl) methane, 2-bis {4- (4-maleimidophenoxy) -phenyl } propane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, bis (3, 5-dimethyl-4-maleimidophenyl) methane, bis (3, 5-diethyl-4-maleimidophenyl) methane), m-phenylene bismaleimide, 4-methyl-1, 3-phenylene bismaleimide, 1,6' -bismaleimide- (2, 4-trimethyl) hexane, a maleimide compound represented by the following formula (3), a prepolymer of the maleimide compound represented by the following formula (3), and the like.
(in the formula (3), R 5 Each independently represents a hydrogen atom or a methyl group, n 1 And represents an integer of 1 or more. )
n 1 It is 1 or more, preferably 1 to 100, more preferably 1 to 10.
(in the formula (3'), R 13 Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a phenyl group, n 4 And represents an integer of 1 to 10 inclusive. )
These maleimide compounds may be used alone or in combination of 1 or more than 2. Among them, the maleimide compound preferably contains at least 1 selected from the group consisting of bis (4-maleimidophenyl) methane, 2-bis {4- (4-maleimidophenoxy) -phenyl } propane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, a maleimide compound represented by formula (3), and a maleimide compound represented by formula (3') from the viewpoint of further improving low thermal expansibility and copper foil peel strength.
The maleimide compound may be commercially available, or may be produced by a known method. Examples of commercial products of maleimide compounds include "BMI-70", "BMI-80", "BMI-1000P", daiwa Kasei Industry Co of LTD. Products, "BMI-3000", "BMI-4000", "BMI-5100", "BMI-7000", "BMI-2300", and "MIR-3000-70MT" of Japanese chemical Co., ltd. (R in formula (3')) 13 All being hydrogen atoms, n 4 1 to 10. ) Etc.
The content of the maleimide compound is preferably 1 to 50 parts by mass, more preferably 5 to 40 parts by mass, and even more preferably 10 to 40 parts by mass, per 100 parts by mass of the resin solid content, from the viewpoint of further improving the low thermal expansibility and the copper foil peel strength.
(cyanate ester compound)
From the viewpoint of further improving low thermal expansibility and copper foil peel strength, a cyanate ester compound is preferably contained as the compound F. The cyanate ester compound is not particularly limited as long as it is a compound having 2 or more cyanates (cyanate ester groups) in 1 molecule, and examples thereof include naphthol aralkyl cyanate ester compounds such as a compound represented by the following formula (4), novolak type cyanate ester compounds such as a compound represented by the following formula (5) other than a compound represented by the following formula (4), biphenyl aralkyl cyanate ester, diallyl bisphenol type cyanate ester compound, bis (3, 3-dimethyl-4-cyanatophenyl) methane, bis (4-cyanatophenyl) methane, 1, 3-dicyanobenzene, 1, 4-dicyanobenzene, 1,3, 5-tricyanophenyl, 1, 3-dicyanonaphthalene, 1, 4-dicyanonaphthalene, 1, 6-dicyanonaphthalene, 1, 8-dicyanonaphthalene, 2, 6-dicyanonaphthalene, 2, 7-dicyanonaphthalene, 1,3, 6-tris (4, 4' -dicyanophenyl) methane, 1, 4-dicyanophenyl) sulfone, and bis (4-dicyanophenyl) sulfone. These cyanate ester compounds may be used singly or in combination of 1 or more than 2. In the present embodiment, the cyanate ester compound preferably contains a naphthol aralkyl type cyanate ester compound and/or a polyfunctional cyanate ester compound such as a novolac type cyanate ester compound from the viewpoints of heat resistance, low thermal expansion, and copper foil peel strength.
(in the formula (4), R 6 Each independently represents a hydrogen atom or a methyl group, n 2 And represents an integer of 1 or more. )
(in the formula (5), rya each independently represents an alkenyl group having 2 to 8 carbon atoms or a hydrogen atom, ryb each independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom, ryc each independently represents an aromatic ring having 4 to 12 carbon atoms, ryc may form a condensed structure with a benzene ring, ryc may be present or absent, and A) 1a Each independently represents an alkylene group having 1 to 6 carbon atoms, an aralkylene group having 7 to 16 carbon atoms, an arylene group having 6 to 10 carbon atoms, a fluorenylidene group, a sulfonyl group, an oxygen atom, a sulfur atom, or a direct bond (single bond), and when Ryc is not present, it may have 2 or more Rya and/or Ryb groups on 1 benzene ring. n represents an integer of 1 to 20. )
Among them, the cyanate ester compound preferably contains a compound represented by formula (4) and/or formula (5) from the viewpoint of further improving heat resistance, low thermal expansion and copper foil peel strength.
In the formula (4), n 2 An integer of 1 or more is represented, and an integer of 1 to 20 is preferable, and an integer of 1 to 10 is more preferable.
In the formula (5), the alkenyl group having 2 to 8 carbon atoms represented by Rya is not particularly limited, and examples thereof include vinyl, allyl, propenyl, butenyl, hexenyl and the like.
In the formula (5), the alkyl group having 1 to 10 carbon atoms represented by Ryb is not particularly limited, and examples thereof include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and hexyl; branched alkyl groups such as isopropyl, isobutyl, and tert-butyl.
In the formula (5), A is 1a The alkylene group having 1 to 6 carbon atoms is not particularly limited, and examples thereof include methylene, ethylene, trimethylene and propylene. In formula (5), A is 1a The aralkylene group having 7 to 16 carbon atoms is not particularly limited, and examples thereof include-CH 2 -Ar-CH 2 -、-CH 2 -CH 2 -Ar-CH 2 -CH 2 -, or-CH 2 -Ar-CH 2 -CH 2 - (wherein Ar represents a phenylene group, a naphthylene group, or a biphenylene group). Further, as A 1a The arylene group having 6 to 10 carbon atoms is not particularly limited, and examples thereof include phenylene rings.
In the formula (5), n represents an integer of 1 to 20, preferably an integer of 1 to 15, and more preferably an integer of 1 to 10.
The compound represented by the formula (5) is preferably a compound represented by the following formula (c 1).
(in the formula (c 1), rx each independently represents a hydrogen atom or a methyl group, R each independently represents an alkenyl group having 2 to 8 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a hydrogen atom, and n represents an integer of 1 to 10.)
These cyanate ester compounds can also be produced according to a known method. Specific examples of the production method include those described in Japanese patent application laid-open No. 2017-195334 (particularly paragraphs 0052 to 0057).
The content of the cyanate ester compound as the compound F is preferably 10 to 70 parts by mass, more preferably 10 to 60 parts by mass, and even more preferably 10 to 40 parts by mass, per 100 parts by mass of the resin solid content, from the viewpoint of further improving the low thermal expansibility and the copper foil peel strength.
(phenol compounds A' other than alkenylphenol A)
As the compound F, a phenol compound a' other than the alkenyl phenol a may be contained from the viewpoint of being capable of exhibiting more excellent copper foil peel strength. The phenol compound a' is not particularly limited, and examples thereof include bisphenol type phenol resins (e.g., bisphenol a type resin, bisphenol E type resin, bisphenol F type resin, bisphenol S type resin, etc.), phenol type novolac resins (e.g., phenol novolac resin, naphthol novolac resin, cresol novolac resin, etc.), glycidyl ester type novolac resins, naphthalene type novolac resins, anthracene type novolac resins, dicyclopentadiene type novolac resins, biphenyl type novolac resins, alicyclic type novolac resins, polyhydric alcohol type novolac resins, aralkyl type novolac resins, phenol modified aromatic hydrocarbon formaldehyde resins, fluorene type novolac resins, etc. These phenol compounds may be used singly or in combination of 1 or more than 2.
Among them, the phenol compound a' preferably contains a 2-functional phenol compound having 2 phenolic hydroxyl groups in 1 molecule from the viewpoint of exhibiting more excellent compatibility and copper foil peel strength.
The 2-functional phenol compound is not particularly limited, and examples thereof include bisphenols, bisphenols having a fluorene skeleton (for example, bisphenols having a fluorene skeleton, etc.), biphenols (for example, p, p '-biphenol, etc.), dihydroxydiphenyl ethers (e.g., 4' -dihydroxydiphenyl ether, etc.), dihydroxydiphenyl ketones (e.g., 4 '-dihydroxydiphenyl ketone, etc.), dihydroxydiphenyl sulfides (e.g., 4' -dihydroxydiphenyl sulfide, etc.), dihydroxyaromatic hydrocarbons (e.g., hydroquinone, etc.). These 2-functional phenol compounds may be used singly or in combination of 1 or more than 2. Among them, the 2-functional phenol compound preferably contains at least 1 selected from the group consisting of bisphenol, xylenol, and bisphenol having a fluorene skeleton, from the viewpoint of being capable of exhibiting more excellent peel strength of copper foil. From the same viewpoints as described above, bisphenol having a fluorene skeleton is preferably bisphenol fluorene.
Examples of the aralkyl type phenol resin include compounds represented by the following formula (c 2).
(wherein Ar is 1 Each independently represents a benzene ring or a naphthalene ring, ar 2 Represents a benzene ring, naphthalene ring, or biphenyl ring, R 2a Each independently represents a hydrogen atom or a methyl group, m represents an integer of 1 to 50, and each ring may have a substituent other than a hydroxyl group (for example, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or the like). )
From the viewpoint of further improving the peel strength of the copper foil, the compound represented by the formula (c 2) is preferably Ar in the formula (c 2) 1 Is naphthalene ring and Ar 2 A compound which is a benzene ring (hereinafter also referred to as "naphthol aralkyl type phenol resin"), and Ar in the formula (c 2) 1 Is a benzene ring and Ar 2 A compound which is a biphenyl ring (hereinafter also referred to as "biphenyl aralkyl type phenol resin").
The naphthol aralkyl type phenol resin is preferably a compound represented by the following formula (8).
(wherein R is 7 Each independently represents a hydrogen atom or a methyl group, n 3 And represents an integer of 1 or more. )
In the formula (8), n 3 An integer of 1 or more is represented, and an integer of 1 to 10 is preferable, and an integer of 1 to 6 is more preferable.
The biphenyl aralkyl type phenol resin is preferably a compound represented by the following formula (2 c).
(wherein R is 2b Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a phenyl group (preferably a hydrogen atom), and m1 represents an integer of 1 to 20 (preferably an integer of 1 to 6). )
From the viewpoint of further improving low thermal expansibility and copper foil peel strength, the phenol compound a' preferably contains a compound represented by the above formula (8).
The aralkyl type phenol resin may be commercially available ones, or may be produced by a known method. Examples of the commercially available aralkyl type phenol resin include "KAYAHARD GPH-65", "KAYAHARD GPH-78", "KAYAHARD GPH-103" (biphenyl aralkyl type phenol resin) manufactured by japan chemical corporation, and "SN-495" (naphthol aralkyl type phenol resin) manufactured by NIPPON STEEL Chemical & Material co.
From the viewpoint of exhibiting more excellent compatibility, the content of the alkenylphenol a as the compound F is preferably 1 to 50 parts by mass, more preferably 3 to 30 parts by mass, and even more preferably 5 to 20 parts by mass, relative to 100 parts by mass of the total amount of the alkenylphenol a, the epoxy-modified silicone B, the epoxy compound C, and the phenol compound a'.
From the viewpoint of being able to exhibit more excellent low thermal expansibility and copper foil peel strength in a balanced manner, the content of the epoxy-modified silicone B in the curable composition of the present embodiment is preferably 5 to 70 parts by mass, more preferably 10 to 60 parts by mass, and even more preferably 20 to 55 parts by mass, relative to 100 parts by mass of the total amount of the alkenylphenol a, the epoxy-modified silicone B, the epoxy compound C, and the phenol compound a'.
The content of the epoxy compound C in the curable composition of the present embodiment is preferably 5 to 50 parts by mass, more preferably 10 to 30 parts by mass, and even more preferably 15 to 25 parts by mass, relative to 100 parts by mass of the total amount of the alkenylphenol a, the epoxy-modified silicone B, the epoxy compound C, and the phenol compound a', from the viewpoint of exhibiting more excellent compatibility, heat resistance, chemical resistance, copper foil peel strength, and insulation reliability.
The content of the phenol compound a 'in the curable composition of the present embodiment is preferably 5 to 30 parts by mass, more preferably 10 to 25 parts by mass, and even more preferably 15 to 20 parts by mass, relative to 100 parts by mass of the total amount of the alkenylphenol a, the epoxy-modified silicone B, the epoxy compound C, and the phenol compound a', in terms of exhibiting more excellent peel strength of the copper foil.
When the curable composition does not contain the phenol compound a', the respective contents of the alkenylphenol a, the epoxy-modified silicone B, and the epoxy compound C represent the contents of 100 parts by mass relative to the total amount of the alkenylphenol a, the epoxy-modified silicone B, and the epoxy compound C.
(alkenyl substituted nadic imide compound)
As the compound F, an alkenyl-substituted nadic imide compound is preferably contained from the viewpoint of further improving heat resistance. The alkenyl-substituted nadimide compound is not particularly limited as long as it is a compound having 1 or more alkenyl-substituted nadimide groups in 1 molecule, and examples thereof include a compound represented by the following formula (2 d).
(in the formula (2 d), R 1 Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (e.g., methyl or ethyl), R 2 An alkylene group having 1 to 6 carbon atoms, a phenylene group, a biphenylene group, a naphthylene group, or a group represented by the following formula (6) or the following formula (7). )
(in the formula (6), R 3 Represents methylene, isopropylidene, CO, O, S or SO 2 。)
(in the formula (7), R 4 Each independently represents an alkylene group having 1 to 4 carbon atoms or a cycloalkylene group having 5 to 8 carbon atoms. )
The alkenyl-substituted nadic imide compound represented by the formula (2 d) may be commercially available ones or ones produced by a known method. As commercial products, maruzen Petrochemical Co., ltd. Products "BANI-M" and "BANI-X" are mentioned.
The content of the alkenyl-substituted nadimide compound as the compound F is preferably 1 to 40 parts by mass, more preferably 5 to 35 parts by mass, and even more preferably 10 to 30 parts by mass, per 100 parts by mass of the resin solid content, from the viewpoint of improving heat resistance.
[ embodiment 2: curable composition ]
The curable composition according to embodiment 2 includes a polymer E containing a structural unit derived from an alkenylphenol a, a structural unit derived from an epoxy-modified silicone B, a structural unit derived from an epoxy compound C other than the epoxy-modified silicone B, and a structural unit derived from an acid anhydride D. Alkenyl phenol a, epoxy-modified silicone B, epoxy compound C, and acid anhydride D are as described in the above description. Hereinafter, the curable resin composition of embodiment 2 including a polymer E containing a structural unit derived from an alkenylphenol a, a structural unit derived from an epoxy-modified silicone B, a structural unit derived from an epoxy compound C, and a structural unit derived from an acid anhydride D are distinguished from the curable composition of embodiment 1 described above in the manner of not containing the polymer E.
The polymer E can exhibit sufficient compatibility even when mixed with a thermosetting resin lacking compatibility with a silicone-based compound. Thus, the curable composition containing the polymer E and the thermosetting resin can give a uniform varnish or cured product. Cured products such as prepregs obtained by using the curable composition are uniformly compatible with each other, and are inhibited from having non-uniform physical properties due to non-uniform components.
In addition to the polymer E, the curable composition of embodiment 2 may contain 1 or more selected from the group consisting of an alkenylphenol a, an epoxy-modified silicone B, an epoxy compound C, and an acid anhydride D. In this case, the alkenylphenol a, the epoxy-modified silicone B, the epoxy compound C, and the acid anhydride D contained in the curable composition of embodiment 2 may be unreacted components remaining after polymerization of the polymer E, or may be components added again to the synthesized polymer E.
In addition, the curable composition according to embodiment 2 may further contain, in addition to the polymer E, at least 1 compound F selected from the group consisting of the above maleimide compound, cyanate ester compound, phenol compound a' other than the above alkenylphenol a, and alkenyl-substituted nadic imide compound, if necessary. The compound F may be an unreacted component remaining after polymerization of the polymer E or a component added to the synthesized polymer E again.
[ Polymer E ]
The polymer E contains structural units derived from an alkenylphenol a, structural units derived from an epoxy-modified silicone B, structural units derived from an epoxy compound C, and structural units derived from an acid anhydride D, and may further contain structural units derived from at least 1 compound F selected from the group consisting of a maleimide compound, a cyanate ester compound, a phenol compound a' other than the alkenylphenol a, and an alkenyl-substituted nadimide compound, as required. When the polymer E has a structural unit derived from the compound F, the compound F is preferably a compound having a 2-functional group. In the present specification, "structural unit derived from alkenylphenol a", "structural unit derived from epoxy-modified silicone B", "structural unit derived from epoxy compound C", "structural unit derived from acid anhydride D", and "structural unit derived from compound F" are defined as that the polymer E contains structural units obtained by polymerizing each component of alkenylphenol a, epoxy-modified silicone B, epoxy compound C, acid anhydride D, and compound F, and also contains structural units formed by a reaction or the like that can provide the same structural units. Hereinafter, each of the constituent units will also be referred to as constituent unit A, B, C, D, F. By using the polymer E, the curable composition of embodiment 2 has further excellent compatibility, and further excellent heat resistance, chemical resistance, low thermal expansion, copper foil peel strength, and insulation reliability.
For the weight average molecular weight of the polymer E, the polystyrene conversion by gel permeation chromatography is preferably 3.0X10 3 ～5.0×10 4 More preferably 3.0X10 3 ～2.0×10 4 . By making the weight average molecular weight 3.0X10 3 As described above, the curable composition of embodiment 2 tends to exhibit more excellent heat resistance, chemical resistance, low thermal expansion, copper foil peel strength, and insulation reliability. By making the weight average molecular weight 5.0X10 4 Hereinafter, the curable composition of embodiment 2 tends to exhibit more excellent compatibility.
The content of the structural unit a in the polymer E is preferably 5 to 50 mass% relative to the total mass of the polymer E. When the content of the structural unit a is within the above range, the curable composition of embodiment 2 tends to exhibit more excellent compatibility. From the same viewpoint, the content of the structural unit a is preferably 10 to 45 mass%, more preferably 15 to 40 mass%.
The content of the structural unit B in the polymer E is preferably 20 to 60 mass% relative to the total mass of the polymer E. When the content of the structural unit B is within the above range, the curable composition of embodiment 2 tends to exhibit more excellent low thermal expansibility and copper foil peel strength in a balanced manner. From the same viewpoint, the content of the structural unit B is more preferably 25 to 55 mass%, and still more preferably 30 to 50 mass%.
The structural unit B preferably contains structural units derived from an epoxy-modified silicone having an epoxy equivalent weight of 50 to 350g/mol (low-equivalent weight epoxy-modified silicone B1) and an epoxy-modified silicone having an epoxy equivalent weight of 400 to 4000g/mol (high-equivalent weight epoxy-modified silicone B2). The low-equivalent weight epoxy-modified silicone B1 and the high-equivalent weight epoxy-modified silicone B2 are more preferably an epoxy-modified silicone having an epoxy equivalent weight of 140 to 250g/mol (low-equivalent weight epoxy-modified silicone B1 '), and an epoxy-modified silicone having an epoxy equivalent weight of 450 to 3000g/mol (high-equivalent weight epoxy-modified silicone B2'), respectively.
The content of the structural unit B1 derived from the low equivalent weight epoxy-modified silicone B1 in the polymer E is preferably 5 to 25% by mass, more preferably 7.5 to 20% by mass, and still more preferably 10 to 17% by mass, relative to the total mass of the polymer E.
The content of the structural unit B2 derived from the high equivalent weight epoxy-modified silicone B2 in the polymer E is preferably 15 to 55 mass%, more preferably 20 to 52.5 mass%, and even more preferably 25 to 50 mass%, relative to the total mass of the polymer E.
The mass ratio of the content of the structural unit B2 to the content of the structural unit B1 is preferably 1.5 to 4, more preferably 1.7 to 3.5, and still more preferably 1.9 to 3.1. By having the above-described relationship between the content of the structural unit B1 and the content of the structural unit B2, the curable composition of embodiment 2 tends to be more improved in low thermal expansibility and peel strength of the copper foil.
The structural unit C in the polymer E is preferably a unit derived from at least 1 selected from the group consisting of the compound represented by the above formula (b 1), the compound represented by the above formula (b 2), the compound represented by the above formula (b 3), and the compound represented by the above formula (b 4).
The content of the structural unit C in the polymer E is preferably 5 to 40 mass% relative to the total mass of the polymer E. When the content of the structural unit C is within the above range, the curable composition of embodiment 2 tends to have more excellent compatibility, and can exhibit more excellent heat resistance, chemical resistance, copper foil peel strength, and insulation reliability. From the same viewpoint, the content of the structural unit C is preferably 10 to 30 mass%, more preferably 15 to 25 mass%.
The content of the structural unit C is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, still more preferably 15 to 60% by mass, and particularly preferably 20 to 50% by mass, based on the total mass of the structural unit B and the structural unit C. By having the above-described relationship between the content of the structural unit B and the content of the structural unit C, the curable composition of embodiment 2 tends to have more excellent compatibility, more improved heat resistance, chemical resistance, low thermal expansion, copper foil peel strength, and insulation reliability.
The content of the structural unit D in the polymer E is preferably 3 to 20 mass% relative to the total mass of the polymer E. When the content of the structural unit D is within the above range, the curable composition of embodiment 2 tends to exhibit further excellent low thermal expansibility and copper foil peel strength in a well-balanced manner. From the same viewpoint, the content of the structural unit D is more preferably 5 to 15 mass%, and still more preferably 5 to 10 mass%.
When the polymer E has a structural unit derived from the compound F, the content of the structural unit F in the polymer E is preferably 3 to 40% by mass relative to the total mass of the polymer E. When the content of the structural unit F is within the above range, the curable composition of embodiment 2 tends to exhibit more excellent heat resistance, chemical resistance, low thermal expansion, copper foil peel strength, and insulation reliability. From the same viewpoint, the content of the structural unit F is preferably 5 to 35% by mass, more preferably 10 to 30% by mass.
When the polymer E has a structural unit derived from a phenol compound a ' other than the alkenylphenol a (hereinafter also referred to as "structural unit a '"), the content of the structural unit a ' in the polymer E is preferably 5 to 30% by mass relative to the total mass of the polymer E. When the content of the structural unit a' is within the above range, the curable composition of embodiment 2 tends to exhibit more excellent heat resistance, chemical resistance, low thermal expansion, copper foil peel strength, and insulation reliability. From the same viewpoint, the content of the structural unit a' is more preferably 10 to 27.5% by mass, still more preferably 10 to 25% by mass.
The alkenyl equivalent in polymer E is preferably 300 to 1500g/mol. When the alkenyl equivalent is 300g/mol or more, the cured product of the curable composition according to embodiment 2 tends to have a further lower elastic modulus, and as a result, the thermal expansion coefficient of a substrate or the like obtained by using the cured product tends to be further reduced. When the alkenyl equivalent is 1500g/mol or less, the compatibility, heat resistance, chemical resistance, low thermal expansion, copper foil peel strength and insulation reliability of the curable composition of embodiment 2 tend to be further improved. From the same viewpoint, the alkenyl equivalent is preferably 350 to 1200g/mol, more preferably 400 to 1000g/mol.
The content of the polymer E in the curable composition according to embodiment 2 is preferably 5 to 50% by mass, more preferably 10 to 45% by mass, and even more preferably 15 to 40% by mass, based on 100% by mass of the solid resin component. When the content is within the above range, the curable composition tends to have more excellent compatibility and to exhibit low thermal expansion and copper foil peel strength in a balanced manner.
The polymer E can be obtained, for example, by a step of reacting an alkenylphenol a, an epoxy-modified silicone B, an epoxy compound C, an acid anhydride D, and, if necessary, a compound F in the presence of a polymerization catalyst G. The reaction may also be carried out in the presence of an organic solvent.
More specifically, in the above step, after the addition reaction of the hydroxyl group of the epoxy-modified silicone B and the epoxy group of the epoxy compound C with the hydroxyl group of the alkenylphenol a, the addition reaction of the hydroxyl group of the obtained addition reaction product with the epoxy group of the epoxy-modified silicone B and the epoxy compound C, and the like are performed, the addition reaction of the terminal hydroxyl group and the epoxy group with the acid anhydride D is further performed, whereby the polymer E can be obtained.
The method for producing the curable composition of the present embodiment (particularly the curable composition of embodiment 2) preferably includes:
a step of polymerizing an alkenylphenol A, an epoxy-modified silicone B, and an epoxy compound C to obtain a prepolymer; and
and a step of reacting the prepolymer with an acid anhydride D.
After the prepolymer obtained by polymerizing the alkenylphenol a, the epoxy-modified silicone B, and the epoxy compound C is produced, the acid anhydride D is reacted with the prepolymer, and thus a curable composition having a low thermal expansion property and further excellent copper foil peel strength tends to be obtained.
[ polymerization catalyst G ]
The polymerization catalyst G is not particularly limited, and examples thereof include 1 or more of an imidazole compound and an organic phosphorus compound. These catalysts may be used singly or in combination of 1 or more than 2. Among them, imidazole compounds are preferable.
Examples of the imidazole compound include, but are not particularly limited to, imidazoles such as 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, 2, 3-dihydro-1H-pyrrolo [1,2-a ] benzimidazole (TBZ "manufactured by Kabushiki Kaisha, ltd.), and 2,4, 5-triphenylimidazole (Tokyo Chemical Industry Co., ltd., product" TPIZ "). Among these, 2, 3-dihydro-1H-pyrrolo [1,2-a ] benzimidazole and/or 2,4, 5-triphenylimidazole are preferable from the viewpoint of preventing the epoxy component from polymerizing alone.
The amount of the polymerization catalyst G (preferably an imidazole compound) used is not particularly limited, and is, for example, 0.1 to 10 parts by mass based on 100 parts by mass of the total amount of the alkenylphenol a, the epoxy-modified silicone B, the epoxy compound C, the acid anhydride D, and the compound F. The amount of the polymerization catalyst G used is preferably 0.5 parts by mass or more, more preferably 4.0 parts by mass or less, from the viewpoint of increasing the weight average molecular weight of the polymer E.
[ organic solvent ]
The organic solvent is not particularly limited, and for example, a polar solvent or a nonpolar solvent may be used. The polar solvent is not particularly limited, and examples thereof include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and the like; cellosolve (Cellosolve) solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; ester solvents such as ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate, and methyl hydroxyisobutyrate; amides such as dimethylacetamide and dimethylformamide. The nonpolar solvent is not particularly limited, and examples thereof include aromatic hydrocarbons such as toluene and xylene. These solvents may be used singly or in combination of 1 or more than 2.
The amount of the organic solvent used is not particularly limited, and is, for example, 50 to 150 parts by mass based on 100 parts by mass of the total amount of the alkenylphenol a, the epoxy-modified silicone B, the epoxy compound C, the acid anhydride D, and the compound F.
The reaction temperature is not particularly limited, and may be, for example, 100 to 170 ℃. The reaction time is not particularly limited, and may be, for example, 3 to 8 hours.
After the completion of the reaction in this step, the polymer E may be isolated and purified from the reaction mixture by a conventional method.
As described above, the curable composition of embodiment 2 may further contain a compound F, as required, in addition to the polymer E. By further containing the compound F in addition to the polymer E, the curable composition of embodiment 2 tends to be more improved in heat resistance, chemical resistance, low thermal expansion and copper foil peel strength.
When the curable composition of embodiment 2 contains the polymer E and the compound F, the content of the polymer E in the curable composition of embodiment 2 is preferably 5 to 60% by mass, more preferably 10 to 55% by mass, and even more preferably 20 to 50% by mass, relative to 100% by mass of the total of the polymer E and the compound F. When the content is within the above range, the curable composition tends to have more excellent compatibility and to exhibit low thermal expansion and copper foil peel strength in a well-balanced manner.
When the curable composition of embodiment 2 contains the polymer E and the compound F, the content of the compound F in the curable composition of embodiment 2 is preferably 20 to 80% by mass, more preferably 35 to 75% by mass, and even more preferably 45 to 65% by mass, relative to 100% by mass of the total of the polymer E and the compound F.
The curable composition of the present embodiment may further contain other resins, as long as the effects of the present embodiment are not impaired. Examples of the other resin include oxetane resins, benzoxazine compounds, and compounds having polymerizable unsaturated groups. These resins may be used singly or in combination of 1 or more than 2.
Examples of oxetane resins include oxetane, 2-methyl oxetane, 2-dimethyl oxetane, 3-methyl oxetane, 3-dimethyl oxetane and other alkyl oxetanes, 3-methyl-3-methoxymethyl oxetane, 3' -bis (trifluoromethyl) perfluorooxetane, 2-chloromethyloxetane, 3-bis (chloromethyl) oxetane, biphenyl oxetane, TOAGOSEI CO., LTD product "OXT-101", "OXT-121" and the like.
The term "benzoxazine compound" in the present specification means a compound having 2 or more dihydrobenzoxazine rings in 1 molecule. Examples of the benzoxazine compound include "bisphenol F-type benzoxazine BF-BXZ", "bisphenol S-type benzoxazine BS-BXZ" of ltd.
Examples of the compound having a polymerizable unsaturated group include vinyl compounds such as ethylene, propylene, styrene, divinylbenzene, and divinylbenzene; 1-or polyol (meth) acrylates such as methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like; epoxy (meth) acrylates such as bisphenol a type epoxy (meth) acrylate and bisphenol F type epoxy (meth) acrylate; benzocyclobutene resins, and the like.
[ inorganic filler ]
The curable composition in the present embodiment preferably further contains an inorganic filler from the viewpoint of further improving low thermal expansion. Examples of the inorganic filler include, but are not limited to, silica, silicon compounds (e.g., white carbon), metal oxides (e.g., alumina, titanium white, zinc oxide, magnesium oxide, and zirconium oxide), metal nitrides (e.g., boron nitride, agglomerated boron nitride, silicon nitride, and aluminum nitride), metal sulfates (e.g., barium sulfate), metal hydroxides (e.g., aluminum hydroxide heat-treated products (e.g., those obtained by heat-treating aluminum hydroxide to remove a part of crystal water), boehmite, magnesium hydroxide, and the like), molybdenum compounds (e.g., molybdenum oxides, zinc molybdate, and the like), zinc compounds (e.g., zinc borate, zinc stannate, and the like), clays, 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 staple fibers (including glass micropowders such as E glass, T glass, D glass, S glass, and Q glass), hollow glass, and spherical glass. These inorganic fillers may be used singly or in combination of 1 or more than 2. Among these, from the viewpoint of further improving low thermal expansion, the inorganic filler is preferably at least 1 selected from the group consisting of silica, metal hydroxide and metal oxide, more preferably contains 1 or more selected from the group consisting of silica, boehmite and alumina, and still more preferably is silica.
Examples of the silica include natural silica, fused silica, synthetic silica, AEROSIL, and hollow silica. These silica types may be used singly or in combination of 1 or more than 2. Among them, from the viewpoint of dispersibility, fused silica is preferable, and from the viewpoints of filling property and flowability, 2 or more kinds of fused silica having different particle sizes are more preferable.
The content of the inorganic filler is preferably 50 to 1000 parts by mass, more preferably 70 to 500 parts by mass, and even more preferably 100 to 300 parts by mass, based on 100 parts by mass of the resin solid content, from the viewpoint of further improving the low thermal expansibility.
[ silane coupling agent ]
The curable composition of the present embodiment may further contain a silane coupling agent. The curable composition of the present embodiment contains a silane coupling agent, so that the dispersibility of the inorganic filler can be further improved, and the adhesive strength between the components of the curable composition of the present embodiment and a substrate to be described later tends to be further improved.
The silane coupling agent is not particularly limited, and examples thereof include an aminosilane compound (for example, γ -aminopropyl triethoxysilane, N- β - (aminoethyl) - γ -aminopropyl trimethoxysilane, etc.), an epoxysilane compound (for example, γ -glycidoxypropyl trimethoxysilane, etc.), an acrylic silane compound (for example, γ -acryloxypropyl trimethoxysilane, etc.), a cationic silane compound (for example, N- β - (N-vinylbenzyl aminoethyl) - γ -aminopropyl trimethoxysilane hydrochloride, etc.), a styrylsilane compound, a phenylsilane compound, etc., which are generally used for the surface treatment of an inorganic substance. The silane coupling agent may be used alone or in combination of 1 or more than 2. Among them, the silane coupling agent is preferably an epoxy silane compound. Examples of the epoxysilane compound include "KBM-403", "KBM-303", "KBM-402" and "KBE-403" of Shin-Etsu Chemical Co., ltd.
The content of the silane coupling agent is not particularly limited, and may be 0.1 to 5.0 parts by mass based on 100 parts by mass of the resin solid component.
[ wetting dispersant ]
The curable composition of the present embodiment may further contain a wetting dispersant. The curable composition tends to further improve the dispersibility of the filler by containing the wetting dispersant.
Examples of the wetting dispersant include known dispersants (dispersion stabilizers) for dispersing the filler, and examples thereof include DISPER BYK-110, 111, 118, 180, 161, BYK-W996, W9010, and W903 manufactured by BYK JAPAN KK..
The content of the wetting dispersant is not particularly limited, but is preferably 0.5 parts by mass or more and 5.0 parts by mass or less relative to 100 parts by mass of the resin solid content.
[ solvent ]
The curable composition of the present embodiment may further contain a solvent. The curable composition of the present embodiment, when containing a solvent, tends to lower the viscosity at the time of preparation of the curable composition, to further improve the handleability (handling property), or to further improve the impregnation property into a substrate.
The solvent is not particularly limited as long as it can dissolve a part or all of the components in the curable composition, and examples thereof include ketones (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbons (toluene, xylene, etc.), amides (dimethyl formaldehyde, etc.), propylene glycol monomethyl ether, and acetate esters thereof. These solvents may be used singly or in combination of 1 or more than 2.
The method for producing the curable composition of the present embodiment is not particularly limited, and examples thereof include a method in which the above-described components are blended into a solvent at once or in divided portions and stirred. In this case, a known process such as stirring, mixing, and kneading may be used to uniformly dissolve or disperse the components.
[ use ]
As described above, the curable composition of the present embodiment has excellent compatibility, and can exhibit more excellent low thermal expansion and copper foil peel strength. Therefore, the curable composition of the present embodiment can be suitably used for metal foil-clad laminates and printed wiring boards. That is, the cured product of the present embodiment can be suitably used as a cured composition for a printed wiring board.
In particular, in the above-mentioned use, the curable composition according to embodiment 2 preferably contains at least an epoxy compound C (an epoxy compound C that is present separately from the structural unit C in the polymer E) in addition to the polymer E.
In this case, the unit of the polymer E as the unit derived from the epoxy compound C preferably has a unit derived from the 2-functional epoxy compound, more preferably has a unit derived from the biphenyl-type epoxy compound, more preferably has a unit derived from the compound (compound b 2) represented by the formula (b 2), and still more preferably has a unit derived from R a R of a number 0 of compounds b2 and alkyl a The number of units of compound b2 (trade name "YL-6121HA", etc. manufactured by Mitsubishi chemical corporation, for example) of 4.
The epoxy compound C which is present separately from the structural unit C in the polymer E preferably contains the naphthalene ether type epoxy resin (commercially available products such as "HP-6000" from DIC Co., ltd.) and/or the naphthalene cresol novolak type epoxy resin (commercially available products such as "HP-9540" from DIC Co., ltd.).
[ prepreg ]
The prepreg of the present embodiment includes a base material and the curable composition of the present embodiment impregnated into or coated on the base material. As described above, the prepreg may be a prepreg obtained by a known method, and specifically, may be obtained by impregnating or coating a substrate with the curable composition of the present embodiment, and then semi-curing (B-stage curing) the composition by heating and drying the composition at 100 to 200 ℃.
The prepreg of the present embodiment also includes a cured product obtained by thermally curing the prepreg in a semi-cured state at a heating temperature of 180 to 230 ℃ and a heating time of 60 to 180 minutes.
The content of the curable composition in the prepreg is preferably 30 to 90% by volume, more preferably 35 to 85% by volume, and even more preferably 40 to 80% by volume in terms of the solid content of the prepreg, relative to the total amount of the prepreg. When the content of the curable composition is within the above range, moldability tends to be more improved. The content calculation of the curable composition described herein also includes the cured product of the curable composition of the present embodiment. The solid component of the prepreg described herein means a component obtained by removing the solvent from the prepreg, and for example, the filler is contained in the solid component of the prepreg.
The substrate is not particularly limited, and examples thereof include known substrates used for various printed wiring board materials. Specific examples of the substrate include a glass substrate, an inorganic substrate other than glass (for example, an inorganic substrate made of inorganic fibers other than glass such as quartz), and an organic substrate (for example, an organic substrate made of organic fibers such as wholly aromatic polyamide, polyester, poly-p-phenylene benzoxazole, polyimide). These substrates may be used singly or in combination of 1 or more than 2. Among them, from the viewpoint of more excellent dimensional stability under heating, glass substrates are preferred.
Examples of the fibers constituting the glass substrate include fibers such as E glass, D glass, S glass, T glass, Q glass, L glass, NE glass, and HME glass. Among them, from the viewpoint of more excellent strength and low water absorption, the fibers constituting the glass substrate are preferably 1 or more fibers selected from the group consisting of E glass, D glass, S glass, T glass, Q glass, L glass, NE glass and HME glass.
The form of the substrate is not particularly limited, and examples thereof include woven fabrics, nonwoven fabrics, rovings, short glass fiber mats, surface mats (surface mats), and the like. The weaving method of the woven fabric is not particularly limited, and for example, a plain weave, a basket weave, a twill weave, or the like is known, and may be appropriately selected from those known in the art according to the intended use and performance. Further, glass woven fabrics obtained by subjecting them to a fiber opening treatment and surface treatment with a silane coupling agent or the like are suitably used. The thickness and mass of the base material are not particularly limited, and generally about 0.01 to 0.1mm is suitably used.
[ resin sheet ]
The resin sheet of the present embodiment includes a support and the curable composition of the present embodiment disposed on the surface of the support. The resin sheet according to the present embodiment may be formed by, for example, applying the curable composition according to the present embodiment to one or both surfaces of a support. The resin sheet of the present embodiment can be produced by directly coating and drying a curable composition used for prepregs or the like on a support such as a metal foil or a film.
The support is not particularly limited, and for example, a known one used for various printed wiring board materials can be used, and a resin sheet or a metal foil is preferable. Examples of the resin sheet and the metal foil include a resin sheet such as a polyimide film, a polyamide film, a polyester film, a polyethylene terephthalate (PET) film, a polybutylene terephthalate (PBT) film, a polypropylene (PP) film, and a Polyethylene (PE) film, and a metal foil such as an aluminum foil, a copper foil, and a gold foil. Among them, the support is preferably an electrolytic copper foil or a PET film.
The resin sheet according to the present embodiment can be obtained by, for example, applying the curable composition according to the present embodiment to a support and then semi-curing (B-stage curing) the same. The method for producing the resin sheet of the present embodiment is preferably a method for producing a composite of a B-stage resin and a support in general. Specifically, for example, a method of applying the curable composition to a support such as a copper foil, and then semi-curing the support by heating the support in a dryer at 100 to 200 ℃ for 1 to 60 minutes, and the like can be used to produce a resin sheet. The amount of the curable composition to be attached to the support is preferably in the range of 1.0 μm to 300 μm based on the resin thickness of the resin sheet. The resin sheet according to the present embodiment can be used as a laminate material for a printed wiring board.
[ Metal foil-clad laminate ]
The metal foil-clad laminate of the present embodiment includes: a laminate formed of 1 or more selected from the group consisting of the prepreg and the resin sheet of the present embodiment, and a metal foil disposed on one or both sides of the laminate are used. The laminate may be formed of 1 prepreg or resin sheet, or may be formed of a plurality of prepregs and/or resin sheets.
The metal foil (conductor layer) may be any metal foil used for various printed wiring board materials, and examples thereof include copper foil such as copper and aluminum, and examples thereof include copper foil such as rolled copper foil and electrolytic copper foil. The thickness of the conductor layer is, for example, 1 to 70. Mu.m, preferably 1.5 to 35. Mu.m.
The method for forming the metal foil-clad laminate and the conditions for forming the same are not particularly limited, and general methods and conditions for laminating a printed circuit board and a multilayer board can be used. For example, a multi-stage press, a multi-stage vacuum press, a continuous molding machine, an autoclave molding machine, or the like can be used for molding a laminate (the laminate) or a metal foil-clad laminate. In the formation (lamination) of a laminate (the laminate) or a metal foil-clad laminate, the temperature is generally 100 to 300℃and the pressure is generally 2 to 100kgf/cm 2 Heating time is in the range of 0.05 to 5 hours. Further, the post-curing may be performed at a temperature of 150 to 300℃as required. In particular using multiple stagesIn the case of the press, the temperature is preferably 200 to 250℃and the pressure is preferably 10 to 40kgf/cm from the viewpoint of sufficiently promoting curing of the prepreg 2 The heating time is 80 to 130 minutes, more preferably at a temperature of 215 to 235℃and a pressure of 25 to 35kgf/cm 2 Heating time is 90-120 minutes. The prepreg and the wiring board for an inner layer which is separately manufactured are combined and laminated to form a multilayer board.
[ printed Circuit Board ]
The printed circuit board of the present embodiment includes: an insulating layer formed of 1 or more selected from the group consisting of the prepreg and the resin sheet of the present embodiment, and a conductor layer formed on the surface of the insulating layer. For example, the printed circuit board of the present embodiment can be formed by etching the metal foil of the metal foil-clad laminate of the present embodiment into a predetermined wiring pattern to form a conductor layer.
Specifically, the printed circuit board of the present embodiment can be manufactured by, for example, the following method. First, a metal foil-clad laminate of the present embodiment is prepared. An inner layer substrate having a conductor layer (inner layer circuit) is produced by etching a metal foil of a metal foil-clad laminate into a predetermined wiring pattern. Then, a predetermined number of insulating layers and metal foils for outer layer circuits are laminated in this order on the surface of the conductor layer (built-in circuit) of the inner layer substrate, and the laminate is obtained by heating and pressing to integrally form (laminate forming). The method of lamination and the molding conditions thereof are the same as those of the laminate and the metal foil-clad laminate. Then, a hole for a through hole (via hole) or a via hole (via hole) is formed in the laminate, and a plated metal film for making a conductor layer (built-in circuit) conductive with a metal foil for an outer layer circuit is formed on a wall surface of the hole formed by the hole. Then, the metal foil for the outer layer circuit is etched into a predetermined wiring pattern to produce an outer layer substrate having a conductor layer (outer layer circuit). The printed circuit board is fabricated in this manner.
When the metal foil-clad laminate is not used, a printed wiring board may be produced by forming a conductor layer to be a circuit on the insulating layer. In this case, the conductor layer may be formed by electroless plating.
Examples
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
Example 1
5.0 parts by mass of diallyl bisphenol a (DABPA, daiwa Kasei Industry co., ltd.) 5.5 parts by mass of biscresolfluorene (BCF, osaka Gas Chemicals co., ltd.) 5.5 parts by mass of epoxy-modified silicone compound a (X-22-163, shin-Etsu Chemical co., ltd.), 4.1 parts by mass of epoxy-modified silicone compound B (KF-105, shin-Etsu Chemical co., ltd.), 500 g/eq.) 8.4 parts by mass of biphenyl-type epoxy compound a (YL-6121 HA, mitsubishi Chemical co.), 5.5 parts by mass of propylene glycol monomethyl ether acetate (DOWANOL PMA, dow Japan) 30.0 parts by mass as a solvent were added to a three-neck flask equipped with a thermometer, a dimu Luo Lengning device, and stirred under heating in an oil bath to 120 ℃. After confirming that the raw material was dissolved in the solvent, 0.3 part by mass of imidazole catalyst A (TBZ, manufactured by Kagaku Kogyo Co., ltd.) was added and the temperature was raised to 140 ℃, the mixture was stirred for 5 hours, and the mixture was cooled to obtain a phenoxy polymer solution (solid content: 50 mass%) (polymer production step). The diallyl bisphenol a corresponds to "alkenylphenol a", the epoxy-modified silicone compound a and the epoxy-modified silicone compound B correspond to "epoxy-modified silicone B", and the biphenyl-type epoxy compound a corresponds to "epoxy compound C". The phenoxy polymer solution contains a polymer containing a structural unit derived from an alkenylphenol a, a structural unit derived from an epoxy-modified silicone B, and a structural unit derived from an epoxy compound C.
After heating the phenoxy polymer solution to 100℃by an oil bath, 1.5 parts by mass of succinic anhydride as acid anhydride D was added thereto, and the mixture was stirred for 2 hours and cooled to obtain a modified phenoxy polymer solution (solid content: 50% by mass) (polymer modification step). The modified phenoxy polymer solution contains a polymer containing a structural unit derived from an alkenylphenol a, a structural unit derived from an epoxy-modified silicone B, a structural unit derived from an epoxy compound C, and a structural unit derived from an acid anhydride D. The polymer modification step may be performed continuously with the polymer production step.
[ method for measuring weight average molecular weight Mw ]
The weight average molecular weight Mw of the modified phenoxy polymer obtained in the above manner was measured in the following manner. 20. Mu.L of a solution obtained by dissolving 0.5g of the modified phenoxy polymer solution in 2g of THF was poured into a high performance liquid chromatograph (manufactured by Shimadzu corporation, pump: LC-20 AD) and analyzed. The columns used were 4 pieces of Shodex GPC KF-804 (length 30 cm. Times. Inner diameter 8 mm), shodex GPC KF-803 (length 30 cm. Times. Inner diameter 8 mm), shodex GPC KF-802 (length 30 cm. Times. Inner diameter 8 mm), shodex GPC KF-801 (length 30 cm. Times. Inner diameter 8 mm) and THF (solvent) were used as the mobile phase, the flow rate was 1mL/min, and RID-10A was used as the detector. The weight average molecular weight Mw was determined by GPC method using standard polystyrene as a standard substance.
The weight average molecular weight Mw of the modified phenoxy polymer measured as described above was 12,000.
To the modified phenoxy polymer solution, 25 parts by mass of a naphthol aralkyl type phenol compound (SN-495V,NIPPON STEEL Chemical&Material Co, ltd.) 9 parts by mass of a novolak type maleimide compound (BMI-2300,Daiwa Kasei Industry Co, ltd.) 9 parts by mass of a phenylene ether type maleimide compound (BMI-80,Daiwa Kasei Industry Co, ltd.) 9 parts by mass of a naphthalene ether type epoxy compound (HP-6000, dic corporation) 27 parts by mass, 200 parts by mass of spherical silica (SC-2050MB,ADMATECHS COMPANY LIMITED), 1 part by mass of a wetting dispersant (DISPERBYK-161, byk Japan), and 5 parts by mass of a silane coupling agent (KBM-403, shin-Etsu Chemical co., ltd.) were mixed to obtain a varnish (varnish forming step). The varnish was dip-coated on an S-glass fabric (thickness 100 μm) and dried by heating at 150 ℃ for 3 minutes to obtain a prepreg having a solid content (including filler) of 58.2% by volume of the curable composition (prepreg production step).
Example 2
A prepreg having a solid content (including filler) of 58.2% by volume of a curable composition was obtained in the same manner as in example 1, except that the amount of diallyl bisphenol a added was set to 4.7 parts by mass from 5.0 parts by mass, the amount of biscresolfluorene added was set to 5.2 parts by mass from 5.5 parts by mass, the amount of epoxy-modified silicone a added was set to 3.8 parts by mass from 4.1 parts by mass, the amount of epoxy-modified silicone B added was set to 8.1 parts by mass from 8.4 parts by mass, the amount of biphenyl epoxy compound a added was set to 5.2 parts by mass from 5.5 parts by mass, and the amount of anhydride D added was set to 3.0 parts by mass from 1.5 parts by mass in the polymer modification step in the polymer production step.
The modified phenoxy polymer solution contains a polymer containing a structural unit derived from an alkenylphenol a, a structural unit derived from an epoxy-modified silicone B, a structural unit derived from an epoxy compound C, and a structural unit derived from an acid anhydride D.
In addition, the weight average molecular weight Mw of the modified phenoxy polymer in example 2 measured by the aforementioned method was 12,000.
Example 3
In the polymer modification step, a prepreg having a solid content (including a filler) of 58.2 vol% in the curable composition was obtained in the same manner as in example 2, except that 3.0 parts by mass of succinic anhydride was changed to 3.0 parts by mass of phthalic anhydride.
The modified phenoxy polymer solution contains a polymer containing a structural unit derived from an alkenylphenol a, a structural unit derived from an epoxy-modified silicone B, a structural unit derived from an epoxy compound C, and a structural unit derived from an acid anhydride D.
In addition, the weight average molecular weight Mw of the modified phenoxy polymer in example 3, which was measured by the aforementioned method, was 12,000.
Comparative example 1
In the polymer production step, a prepreg having a resin composition solid content (including filler) of 58.2% by volume was obtained in the same manner as in example 1, except that the amount of diallyl bisphenol a added was 5.3 parts by mass, the amount of biscresolfluorene added was 5.5 parts by mass, the amount of epoxy-modified silicone a added was 4.4 parts by mass, the amount of epoxy-modified silicone B added was 8.4 parts by mass, the amount of biphenyl epoxy compound a added was 5.8 parts by mass, the amount of imidazole catalyst a added was 1.2 parts by mass, and the polymer modification step was not performed, respectively, in the range of 5.0 parts by mass, 5.3 parts by mass, 5.5 parts by mass, and 4.4 parts by mass, respectively.
The weight average molecular weight Mw of the phenoxy polymer in comparative example 1 measured by the aforementioned method was 12,000.
The prepregs obtained in each of examples 1 to 3 and comparative example 1 were stacked 2 sheets, and electrolytic copper foil (3 EC-M2S-VLP, manufactured by Mitsui Metal mineral Co., ltd.) having a thickness of 12 μm was further placed on top of each other at a pressure of 30kgf/cm 2 The laminate was subjected to lamination at 220℃for 120 minutes to obtain a copper-clad laminate including an insulating layer having a thickness of 0.2mm as a metal-clad laminate. The properties of the obtained copper-clad laminate were evaluated by the following methods. The evaluation results are shown in table 1.
[ copper foil peel Strength ]
The copper foil-clad laminate (10 mm. Times.150 mm. Times.0.2 mm) obtained by the above method was used to measure the peel strength (unit: kN/m) of copper foil in accordance with JIS C6481.
[ coefficient of Linear thermal expansion (CTE) ]
The insulating layer of the laminate was measured for the linear thermal expansion coefficient in the longitudinal direction of the glass cloth. Specifically, after removing copper foil on both sides of the copper-clad laminate (10 mm. Times.6 mm. Times.0.2 mm) obtained by the above method by etching, the laminate was heated in a constant temperature bath at 220℃for 2 hours to remove stress generated by molding. Thereafter, the temperature was increased from 40℃to 320℃at 10℃per minute by using a thermal expansion coefficient measuring apparatus (horizontal dilatometer manufactured by LINSEIS Co.) to measure the coefficient of linear thermal expansion (CTE) (unit: ppm/. Degree.C.) from 60℃to 260 ℃.
TABLE 1
As shown in table 1 above, the copper-clad laminate (examples 1 to 3) using the curable composition of the present embodiment has excellent low thermal expansion and copper foil peel strength.
The present application is based on Japanese patent application (Japanese patent application No. 2021-128743) filed by App. 2021, 8, 5 to the Japanese patent application, the contents of which are incorporated herein by reference.
Claims (34)
1. A curable composition comprising an alkenylphenol A, an epoxy-modified silicone B, an epoxy compound C other than the epoxy-modified silicone B, and an acid anhydride D.
2. The curable composition according to claim 1, wherein the average number of phenols of the alkenyl phenol a per 1 molecule is 1 or more and less than 3, the average number of epoxies of the epoxy-modified silicone B per 1 molecule is 1 or more and less than 3, and the average number of epoxies of the epoxy compound C per 1 molecule is 1 or more and less than 3.
3. The curable composition according to claim 1 or 2, wherein the alkenylphenol a contains diallyl bisphenol and/or dipropenylbisphenol.
4. The curable composition according to claim 1 or 2, wherein the epoxy-modified silicone B comprises an epoxy-modified silicone having an epoxy equivalent weight of 140 to 250 g/mol.
5. The curable composition according to claim 1 or 2, wherein the epoxy-modified silicone B contains an epoxy-modified silicone represented by the following formula (1),
Wherein R is 1 Each independently represents a single bond, alkylene, arylene or aralkylene, R 2 Each independently represents an alkyl group having 1 to 10 carbon atoms or a phenyl group, and n represents an integer of 0 to 100.
6. The curable composition according to claim 1 or 2, wherein the epoxy compound C contains a compound represented by the following formula (b 2),
wherein R is a Each independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom.
7. The curable composition according to claim 1 or 2, wherein the content of the epoxy compound C is 20 to 50 mass% relative to 100 mass% of the total amount of the epoxy-modified silicone B and the epoxy compound C.
8. The curable composition according to claim 1 or 2, wherein the acid anhydride D is 1 or more selected from the group consisting of phthalic anhydride, succinic anhydride, maleic anhydride, nadic anhydride, and cis-4-cyclohexene-1, 2-dicarboxylic anhydride.
9. A curable composition comprising a polymer E containing structural units derived from an alkenylphenol a, structural units derived from an epoxy-modified silicone B, structural units derived from an epoxy compound C, and structural units derived from an anhydride D.
10. The curable composition according to claim 9, wherein the polymer E has a weight average molecular weight of 3.0X10 3 ～5.0×10 4 。
11. The curable composition according to claim 9 or 10, wherein the content of the structural unit derived from the epoxy-modified silicone B in the polymer E is 20 to 60 mass% relative to the total mass of the polymer E.
12. The curable composition according to claim 9 or 10, wherein the alkenyl equivalent of the polymer E is 300 to 1500g/mol.
13. The curable composition according to claim 9 or 10, wherein the content of the structural unit derived from the acid anhydride D in the polymer E is 3 to 20 mass% relative to the total mass of the polymer E.
14. The curable composition according to claim 9 or 10, wherein the content of the polymer E is 5 to 50% by mass relative to 100% by mass of the resin solid content.
15. The curable composition according to claim 9 or 10, wherein the alkenylphenol a contains diallyl bisphenol and/or dipropenylbisphenol.
16. The curable composition according to claim 9 or 10, wherein the epoxy-modified silicone B comprises an epoxy-modified silicone having an epoxy equivalent weight of 140 to 250 g/mol.
17. The curable composition according to claim 9 or 10, wherein the epoxy-modified silicone B contains an epoxy-modified silicone represented by the following formula (1),
Wherein R is 1 Each independently represents a single bond, alkylene, arylene or aralkylene, R 2 Each independently represents an alkyl group having 1 to 10 carbon atoms or a phenyl group, and n represents an integer of 0 to 100.
18. The curable composition according to claim 9 or 10, wherein the epoxy compound C contains a compound represented by the following formula (b 2),
wherein R is a Each independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom.
19. The curable composition according to claim 9 or 10, wherein the acid anhydride D is 1 or more selected from the group consisting of phthalic anhydride, succinic anhydride, maleic anhydride, nadic anhydride, and cis-4-cyclohexene-1, 2-dicarboxylic anhydride.
20. The curable composition according to claim 9 or 10, further comprising an epoxy compound C comprising a compound represented by the following formula (3-3) or a compound represented by the following formula (3-4),
wherein R is 13 Each independently represents a hydrogen atom, a C1-3 alkyl group or a C2-3 alkenyl group,
wherein R is 14 Each independently represents a hydrogen atom, a C1-3 alkyl group or a C2-3 alkenyl group.
21. The curable composition according to claim 1 or 9, further comprising at least 1 compound F selected from the group consisting of a maleimide compound, a cyanate ester compound, a phenol compound a' other than alkenyl phenol a, and an alkenyl-substituted nadic imide compound.
22. The curable composition according to claim 21, wherein the maleimide compound comprises at least 1 selected from the group consisting of bis (4-maleimidophenyl) methane, 2-bis {4- (4-maleimidophenoxy) -phenyl } propane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, a maleimide compound represented by the following formula (3) and a maleimide compound represented by the following formula (3'),
wherein R is 5 Each independently represents a hydrogen atom or a methyl group, n 1 Represents an integer of 1 or more,
in the formula (3'), R 13 Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a phenyl group, n 4 And represents an integer of 1 to 10 inclusive.
23. The curable composition according to claim 21, wherein the cyanate ester compound comprises a compound represented by the following formula (4) and/or a compound represented by the following formula (5) other than the compound represented by the following formula (4),
wherein R is 6 Each independently represents a hydrogen atom or a methyl group, n 2 Represents an integer of 1 or more,
wherein R is ya Each independently represents an alkenyl group having 2 to 8 carbon atoms or a hydrogen atom, R yb Each independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom, R yc Each independently represents an aromatic ring having 4 to 12 carbon atoms, R yc Optionally forming a condensed structure with the benzene ring, R yc Optionally present or absent, A 1a Each independently represents an alkylene group having 1 to 6 carbon atoms, an aralkylene group having 7 to 16 carbon atoms, an arylene group having 6 to 10 carbon atoms, a fluorenylidene group, a sulfonyl group, an oxygen atom, a sulfur atom or a single bond, R yc In the absence, 1 benzene ring may have more than 2R ya And/or R yb N represents an integer of 1 to 20.
24. The curable composition according to claim 21, wherein the phenol compound A' comprises a compound represented by the following formula (8),
wherein R is 7 Each independently represents a hydrogen atom or a methyl group, n 3 And represents an integer of 1 or more.
25. The curable composition according to claim 1 or 9, further comprising an inorganic filler, wherein the content of the inorganic filler is 50 to 1000 parts by mass per 100 parts by mass of the resin solid content.
26. The curable composition according to claim 25, wherein the inorganic filler comprises 1 or more selected from the group consisting of silica, boehmite, and alumina.
27. The curable composition according to claim 1 or 9, which is a curable composition for a printed circuit board.
28. A prepreg comprising a substrate and the curable composition of claim 1 or 9 impregnated or coated on the substrate.
29. A resin sheet comprising a support and the curable composition according to claim 1 or 9 disposed on the surface of the support.
30. A metal foil-clad laminate comprising:
a laminate formed using the prepreg according to claim 28, and
and a metal foil disposed on one or both sides of the laminate.
31. A metal foil-clad laminate comprising:
a laminate formed by using the resin sheet according to claim 29, and
and a metal foil disposed on one or both sides of the laminate.
32. A printed circuit board, having:
an insulating layer formed using the prepreg of claim 28, and
and a conductor layer formed on the surface of the insulating layer.
33. A printed circuit board, having:
an insulating layer formed using the resin sheet according to claim 29, and
and a conductor layer formed on the surface of the insulating layer.
34. A method for producing the curable composition according to claim 1 or 9, comprising:
a step of polymerizing an alkenylphenol A, an epoxy-modified silicone B, and an epoxy compound C to obtain a prepolymer; and
and a step of reacting the acid anhydride D with the prepolymer.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021128743 | 2021-08-05 | ||
| JP2021-128743 | 2021-08-05 | ||
| PCT/JP2022/029878 WO2023013715A1 (en) | 2021-08-05 | 2022-08-04 | Curable composition, prepreg, resin sheet, metal foil–clad laminate, and printed wiring board |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117836370A true CN117836370A (en) | 2024-04-05 |
Family
ID=85155808
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202280054529.4A Pending CN117836370A (en) | 2021-08-05 | 2022-08-04 | Curable composition, prepreg, resin sheet, metal foil-clad laminate, and printed wiring board |
Country Status (5)
| Country | Link |
|---|---|
| JP (2) | JP7411170B2 (en) |
| KR (1) | KR20240021990A (en) |
| CN (1) | CN117836370A (en) |
| TW (1) | TW202313755A (en) |
| WO (1) | WO2023013715A1 (en) |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH044213A (en) * | 1990-04-23 | 1992-01-08 | Sumitomo Bakelite Co Ltd | Production of resin for sealing semiconductor |
| JPH06136093A (en) * | 1992-09-08 | 1994-05-17 | Fujitsu Ltd | Epoxy resin composition |
| JP2809885B2 (en) * | 1990-12-25 | 1998-10-15 | 住友ベークライト株式会社 | Resin composition for semiconductor encapsulation |
| JPH04314723A (en) * | 1991-04-15 | 1992-11-05 | Fujitsu Ltd | Epoxy resin composition |
| JP2005097448A (en) * | 2003-09-25 | 2005-04-14 | Matsushita Electric Works Ltd | Liquid epoxy resin composition for sealing semiconductor and semiconductor apparatus |
| JP2009007467A (en) * | 2007-06-28 | 2009-01-15 | Shin Etsu Chem Co Ltd | Flame-retardant sidefill material for mounting and semiconductor device |
| JP5527816B2 (en) * | 2010-06-22 | 2014-06-25 | 信越化学工業株式会社 | Die bond agent composition and semiconductor device. |
| JP5633382B2 (en) | 2011-01-18 | 2014-12-03 | 日立化成株式会社 | Thermosetting resin composition and prepreg, laminate and multilayer printed wiring board using the same |
| WO2018124164A1 (en) * | 2016-12-28 | 2018-07-05 | 三菱瓦斯化学株式会社 | Resin composition, prepreg, laminate, metal foil clad laminate, printed wiring board, and multilayer printed wiring board |
| KR20210037606A (en) * | 2018-07-26 | 2021-04-06 | 미츠비시 가스 가가쿠 가부시키가이샤 | Curable composition, prepreg, resin sheet, metal foil clad laminate and printed wiring board |
-
2022
- 2022-08-04 CN CN202280054529.4A patent/CN117836370A/en active Pending
- 2022-08-04 WO PCT/JP2022/029878 patent/WO2023013715A1/en active Application Filing
- 2022-08-04 JP JP2022571828A patent/JP7411170B2/en active Active
- 2022-08-04 KR KR1020247004066A patent/KR20240021990A/en active IP Right Grant
- 2022-08-05 TW TW111129449A patent/TW202313755A/en unknown
-
2023
- 2023-10-13 JP JP2023177242A patent/JP2024016043A/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| KR20240021990A (en) | 2024-02-19 |
| WO2023013715A1 (en) | 2023-02-09 |
| TW202313755A (en) | 2023-04-01 |
| JP7411170B2 (en) | 2024-01-11 |
| JPWO2023013715A1 (en) | 2023-02-09 |
| JP2024016043A (en) | 2024-02-06 |
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