WO2023013710A1 - Préimprégné, stratifié revêtu d'une feuille métallique, et carte de circuit imprimé - Google Patents
Préimprégné, stratifié revêtu d'une feuille métallique, et carte de circuit imprimé Download PDFInfo
- Publication number
- WO2023013710A1 WO2023013710A1 PCT/JP2022/029870 JP2022029870W WO2023013710A1 WO 2023013710 A1 WO2023013710 A1 WO 2023013710A1 JP 2022029870 W JP2022029870 W JP 2022029870W WO 2023013710 A1 WO2023013710 A1 WO 2023013710A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- epoxy
- group
- compound
- mass
- prepreg
- Prior art date
Links
- 229910052751 metal Inorganic materials 0.000 title claims description 37
- 239000002184 metal Substances 0.000 title claims description 37
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 119
- 239000011342 resin composition Substances 0.000 claims abstract description 118
- 238000011156 evaluation Methods 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 55
- 239000000463 material Substances 0.000 claims abstract description 14
- 239000004593 Epoxy Substances 0.000 claims description 130
- 150000001875 compounds Chemical class 0.000 claims description 126
- 229920001296 polysiloxane Polymers 0.000 claims description 122
- -1 aromatic phosphorus compound Chemical class 0.000 claims description 110
- 125000004432 carbon atom Chemical group C* 0.000 claims description 75
- 229920000642 polymer Polymers 0.000 claims description 74
- 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 description 69
- 239000003822 epoxy resin Substances 0.000 claims description 68
- 229920000647 polyepoxide Polymers 0.000 claims description 68
- 229920005989 resin Polymers 0.000 claims description 55
- 239000011347 resin Substances 0.000 claims description 55
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 49
- 125000000217 alkyl group Chemical group 0.000 claims description 45
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 34
- 239000007787 solid Substances 0.000 claims description 34
- 239000004643 cyanate ester Substances 0.000 claims description 32
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 30
- 229920003986 novolac Polymers 0.000 claims description 28
- 229930185605 Bisphenol Natural products 0.000 claims description 27
- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical compound N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 claims description 23
- 229910052698 phosphorus Inorganic materials 0.000 claims description 23
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 22
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 21
- 239000011574 phosphorus Substances 0.000 claims description 21
- 229940126062 Compound A Drugs 0.000 claims description 20
- 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 20
- 239000011888 foil Substances 0.000 claims description 19
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 16
- 239000011256 inorganic filler Substances 0.000 claims description 16
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 16
- 125000002947 alkylene group Chemical group 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 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 claims description 13
- 239000004020 conductor Substances 0.000 claims description 13
- 229930003836 cresol Natural products 0.000 claims description 13
- 125000000732 arylene group Chemical group 0.000 claims description 10
- 150000003923 2,5-pyrrolediones Chemical class 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- XAZPKEBWNIUCKF-UHFFFAOYSA-N 1-[4-[4-[2-[4-[4-(2,5-dioxopyrrol-1-yl)phenoxy]phenyl]propan-2-yl]phenoxy]phenyl]pyrrole-2,5-dione Chemical compound C=1C=C(OC=2C=CC(=CC=2)N2C(C=CC2=O)=O)C=CC=1C(C)(C)C(C=C1)=CC=C1OC(C=C1)=CC=C1N1C(=O)C=CC1=O XAZPKEBWNIUCKF-UHFFFAOYSA-N 0.000 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
- 229910001593 boehmite Inorganic materials 0.000 claims description 4
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 description 87
- 239000000126 substance Substances 0.000 description 53
- 239000011521 glass Substances 0.000 description 44
- 239000000203 mixture Substances 0.000 description 42
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 32
- 239000010410 layer Substances 0.000 description 31
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 30
- 239000011889 copper foil Substances 0.000 description 28
- 125000003118 aryl group Chemical group 0.000 description 27
- 125000003342 alkenyl group Chemical group 0.000 description 25
- 238000004519 manufacturing process Methods 0.000 description 25
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 23
- 125000003700 epoxy group Chemical group 0.000 description 23
- 125000001424 substituent group Chemical group 0.000 description 21
- 239000000758 substrate Substances 0.000 description 21
- 239000000945 filler Substances 0.000 description 20
- 239000002904 solvent Substances 0.000 description 20
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 18
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 17
- 125000000524 functional group Chemical group 0.000 description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 17
- 239000004305 biphenyl Substances 0.000 description 16
- 235000010290 biphenyl Nutrition 0.000 description 16
- 238000000465 moulding Methods 0.000 description 16
- 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 15
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 15
- 238000009413 insulation Methods 0.000 description 14
- 125000001624 naphthyl group Chemical group 0.000 description 14
- 239000002966 varnish Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 239000005011 phenolic resin Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 11
- 230000001588 bifunctional effect Effects 0.000 description 11
- 229920001568 phenolic resin Polymers 0.000 description 11
- 239000006087 Silane Coupling Agent Substances 0.000 description 10
- 125000004093 cyano group Chemical group *C#N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 150000002989 phenols Chemical class 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 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
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 8
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 8
- 125000003545 alkoxy group Chemical group 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 230000001747 exhibiting effect Effects 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 7
- 239000002356 single layer Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-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
- 239000002270 dispersing agent Substances 0.000 description 6
- 238000005530 etching Methods 0.000 description 6
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 125000004957 naphthylene group Chemical group 0.000 description 6
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- QQOWHRYOXYEMTL-UHFFFAOYSA-N triazin-4-amine Chemical compound N=C1C=CN=NN1 QQOWHRYOXYEMTL-UHFFFAOYSA-N 0.000 description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 238000009736 wetting Methods 0.000 description 5
- 239000000080 wetting agent Substances 0.000 description 5
- 239000002759 woven fabric Substances 0.000 description 5
- 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 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N Bisphenol F Natural products C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 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
- 238000000576 coating method Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 4
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 4
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 4
- 239000002685 polymerization catalyst Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000005350 fused silica glass Substances 0.000 description 3
- 125000006038 hexenyl group Chemical group 0.000 description 3
- 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 3
- 150000002576 ketones Chemical class 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- RNIPJYFZGXJSDD-UHFFFAOYSA-N 2,4,5-triphenyl-1h-imidazole Chemical compound C1=CC=CC=C1C1=NC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 RNIPJYFZGXJSDD-UHFFFAOYSA-N 0.000 description 2
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 2
- 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 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 125000006165 cyclic alkyl group Chemical group 0.000 description 2
- 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
- 229940116333 ethyl lactate Drugs 0.000 description 2
- LJJQENSFXLXPIV-UHFFFAOYSA-N fluorenylidene Chemical group C1=CC=C2[C]C3=CC=CC=C3C2=C1 LJJQENSFXLXPIV-UHFFFAOYSA-N 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 description 2
- 239000012454 non-polar solvent Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- UFKLQICEQCIWNE-UHFFFAOYSA-N (3,5-dicyanatophenyl) cyanate Chemical compound N#COC1=CC(OC#N)=CC(OC#N)=C1 UFKLQICEQCIWNE-UHFFFAOYSA-N 0.000 description 1
- YDCUTCGACVVRIQ-UHFFFAOYSA-N (3,6-dicyanatonaphthalen-1-yl) cyanate Chemical compound N#COC1=CC(OC#N)=CC2=CC(OC#N)=CC=C21 YDCUTCGACVVRIQ-UHFFFAOYSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- UMDBGQBQDICTJC-UHFFFAOYSA-N (3-cyanatonaphthalen-1-yl) cyanate Chemical compound C1=CC=CC2=CC(OC#N)=CC(OC#N)=C21 UMDBGQBQDICTJC-UHFFFAOYSA-N 0.000 description 1
- QQZZMAPJAKOSNG-UHFFFAOYSA-N (3-cyanatophenyl) cyanate Chemical compound N#COC1=CC=CC(OC#N)=C1 QQZZMAPJAKOSNG-UHFFFAOYSA-N 0.000 description 1
- UNMJLQGKEDTEKJ-UHFFFAOYSA-N (3-ethyloxetan-3-yl)methanol Chemical compound CCC1(CO)COC1 UNMJLQGKEDTEKJ-UHFFFAOYSA-N 0.000 description 1
- KUYRCFRAGLLTPO-UHFFFAOYSA-N (4-cyanatonaphthalen-1-yl) cyanate Chemical compound C1=CC=C2C(OC#N)=CC=C(OC#N)C2=C1 KUYRCFRAGLLTPO-UHFFFAOYSA-N 0.000 description 1
- GUGZCSAPOLLKNG-UHFFFAOYSA-N (4-cyanatophenyl) cyanate Chemical compound N#COC1=CC=C(OC#N)C=C1 GUGZCSAPOLLKNG-UHFFFAOYSA-N 0.000 description 1
- CQXJSKSVSXZXRU-UHFFFAOYSA-N (5-cyanatonaphthalen-2-yl) cyanate Chemical compound N#COC1=CC=CC2=CC(OC#N)=CC=C21 CQXJSKSVSXZXRU-UHFFFAOYSA-N 0.000 description 1
- RUEBPOOTFCZRBC-UHFFFAOYSA-N (5-methyl-2-phenyl-1h-imidazol-4-yl)methanol Chemical compound OCC1=C(C)NC(C=2C=CC=CC=2)=N1 RUEBPOOTFCZRBC-UHFFFAOYSA-N 0.000 description 1
- IRMQZYWARKKEQH-UHFFFAOYSA-N (6-cyanatonaphthalen-2-yl) cyanate Chemical compound C1=C(OC#N)C=CC2=CC(OC#N)=CC=C21 IRMQZYWARKKEQH-UHFFFAOYSA-N 0.000 description 1
- OFIWROJVVHYHLQ-UHFFFAOYSA-N (7-cyanatonaphthalen-2-yl) cyanate Chemical compound C1=CC(OC#N)=CC2=CC(OC#N)=CC=C21 OFIWROJVVHYHLQ-UHFFFAOYSA-N 0.000 description 1
- ZJKWUUSAPDIPQQ-UHFFFAOYSA-N (8-cyanatonaphthalen-1-yl) cyanate Chemical compound C1=CC(OC#N)=C2C(OC#N)=CC=CC2=C1 ZJKWUUSAPDIPQQ-UHFFFAOYSA-N 0.000 description 1
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 description 1
- NHWYMYDMYCNUKI-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)-3,5-diethylphenyl]methyl]-2,6-diethylphenyl]pyrrole-2,5-dione Chemical compound C=1C(CC)=C(N2C(C=CC2=O)=O)C(CC)=CC=1CC(C=C1CC)=CC(CC)=C1N1C(=O)C=CC1=O NHWYMYDMYCNUKI-UHFFFAOYSA-N 0.000 description 1
- RUORVEVRVBXRIO-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)-3,5-dimethylphenyl]methyl]-2,6-dimethylphenyl]pyrrole-2,5-dione Chemical compound C=1C(C)=C(N2C(C=CC2=O)=O)C(C)=CC=1CC(C=C1C)=CC(C)=C1N1C(=O)C=CC1=O RUORVEVRVBXRIO-UHFFFAOYSA-N 0.000 description 1
- IYSVFZBXZVPIFA-UHFFFAOYSA-N 1-ethenyl-4-(4-ethenylphenyl)benzene Chemical group C1=CC(C=C)=CC=C1C1=CC=C(C=C)C=C1 IYSVFZBXZVPIFA-UHFFFAOYSA-N 0.000 description 1
- HDYFAPRLDWYIBU-UHFFFAOYSA-N 1-silylprop-2-en-1-one Chemical class [SiH3]C(=O)C=C HDYFAPRLDWYIBU-UHFFFAOYSA-N 0.000 description 1
- XHYFCIYCSYEDCP-UHFFFAOYSA-N 2,2-dimethyloxetane Chemical compound CC1(C)CCO1 XHYFCIYCSYEDCP-UHFFFAOYSA-N 0.000 description 1
- RUFZNDNBXKOZQV-UHFFFAOYSA-N 2,3-dihydro-1h-pyrrolo[1,2-a]benzimidazole Chemical compound C1=CC=C2N(CCC3)C3=NC2=C1 RUFZNDNBXKOZQV-UHFFFAOYSA-N 0.000 description 1
- MTJUELTVQKBEPR-UHFFFAOYSA-N 2-(chloromethyl)oxetane Chemical compound ClCC1CCO1 MTJUELTVQKBEPR-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- FZIIBDOXPQOKBP-UHFFFAOYSA-N 2-methyloxetane Chemical compound CC1CCO1 FZIIBDOXPQOKBP-UHFFFAOYSA-N 0.000 description 1
- CXURGFRDGROIKG-UHFFFAOYSA-N 3,3-bis(chloromethyl)oxetane Chemical compound ClCC1(CCl)COC1 CXURGFRDGROIKG-UHFFFAOYSA-N 0.000 description 1
- RVGLUKRYMXEQAH-UHFFFAOYSA-N 3,3-dimethyloxetane Chemical compound CC1(C)COC1 RVGLUKRYMXEQAH-UHFFFAOYSA-N 0.000 description 1
- BGDOLELXXPTPFX-UHFFFAOYSA-N 3,4-dihydro-2h-1,2-benzoxazine Chemical group C1=CC=C2ONCCC2=C1 BGDOLELXXPTPFX-UHFFFAOYSA-N 0.000 description 1
- MOSSLXZUUKTULI-UHFFFAOYSA-N 3-[3-(2,5-dioxopyrrol-3-yl)-4-methylphenyl]pyrrole-2,5-dione Chemical compound CC1=CC=C(C=2C(NC(=O)C=2)=O)C=C1C1=CC(=O)NC1=O MOSSLXZUUKTULI-UHFFFAOYSA-N 0.000 description 1
- LMIOYAVXLAOXJI-UHFFFAOYSA-N 3-ethyl-3-[[4-[(3-ethyloxetan-3-yl)methoxymethyl]phenyl]methoxymethyl]oxetane Chemical compound C=1C=C(COCC2(CC)COC2)C=CC=1COCC1(CC)COC1 LMIOYAVXLAOXJI-UHFFFAOYSA-N 0.000 description 1
- SNGWZCGFOZYQTR-UHFFFAOYSA-N 3-methoxy-2,3-dimethyloxetane Chemical compound COC1(C)COC1C SNGWZCGFOZYQTR-UHFFFAOYSA-N 0.000 description 1
- VJQHJNIGWOABDZ-UHFFFAOYSA-N 3-methyloxetane Chemical compound CC1COC1 VJQHJNIGWOABDZ-UHFFFAOYSA-N 0.000 description 1
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 1
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 description 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- XYVQFUJDGOBPQI-UHFFFAOYSA-N Methyl-2-hydoxyisobutyric acid Chemical compound COC(=O)C(C)(C)O XYVQFUJDGOBPQI-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- SNYVZKMCGVGTKN-UHFFFAOYSA-N [4-(4-cyanatophenoxy)phenyl] cyanate Chemical compound C1=CC(OC#N)=CC=C1OC1=CC=C(OC#N)C=C1 SNYVZKMCGVGTKN-UHFFFAOYSA-N 0.000 description 1
- HEJGXMCFSSDPOA-UHFFFAOYSA-N [4-(4-cyanatophenyl)phenyl] cyanate Chemical group C1=CC(OC#N)=CC=C1C1=CC=C(OC#N)C=C1 HEJGXMCFSSDPOA-UHFFFAOYSA-N 0.000 description 1
- CNUHQZDDTLOZRY-UHFFFAOYSA-N [4-(4-cyanatophenyl)sulfanylphenyl] cyanate Chemical compound C1=CC(OC#N)=CC=C1SC1=CC=C(OC#N)C=C1 CNUHQZDDTLOZRY-UHFFFAOYSA-N 0.000 description 1
- BUPOATPDNYBPMR-UHFFFAOYSA-N [4-(4-cyanatophenyl)sulfonylphenyl] cyanate Chemical compound C=1C=C(OC#N)C=CC=1S(=O)(=O)C1=CC=C(OC#N)C=C1 BUPOATPDNYBPMR-UHFFFAOYSA-N 0.000 description 1
- UUQQGGWZVKUCBD-UHFFFAOYSA-N [4-(hydroxymethyl)-2-phenyl-1h-imidazol-5-yl]methanol Chemical compound N1C(CO)=C(CO)N=C1C1=CC=CC=C1 UUQQGGWZVKUCBD-UHFFFAOYSA-N 0.000 description 1
- VKUAGWJIYUEPHC-UHFFFAOYSA-N [4-[(4-cyanato-5,5-dimethylcyclohexa-1,3-dien-1-yl)methyl]-6,6-dimethylcyclohexa-1,3-dien-1-yl] cyanate Chemical compound CC1(CC(=CC=C1OC#N)CC=1CC(C(=CC=1)OC#N)(C)C)C VKUAGWJIYUEPHC-UHFFFAOYSA-N 0.000 description 1
- AUYQDAWLRQFANO-UHFFFAOYSA-N [4-[(4-cyanatophenyl)methyl]phenyl] cyanate Chemical compound C1=CC(OC#N)=CC=C1CC1=CC=C(OC#N)C=C1 AUYQDAWLRQFANO-UHFFFAOYSA-N 0.000 description 1
- AHZMUXQJTGRNHT-UHFFFAOYSA-N [4-[2-(4-cyanatophenyl)propan-2-yl]phenyl] cyanate Chemical compound C=1C=C(OC#N)C=CC=1C(C)(C)C1=CC=C(OC#N)C=C1 AHZMUXQJTGRNHT-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- IYABWNGZIDDRAK-UHFFFAOYSA-N allene Chemical group C=C=C IYABWNGZIDDRAK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004653 anthracenylene group Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- JYZIHLWOWKMNNX-UHFFFAOYSA-N benzimidazole Chemical compound C1=C[CH]C2=NC=NC2=C1 JYZIHLWOWKMNNX-UHFFFAOYSA-N 0.000 description 1
- LJUXFZKADKLISH-UHFFFAOYSA-N benzo[f]phosphinoline Chemical class C1=CC=C2C3=CC=CC=C3C=CC2=P1 LJUXFZKADKLISH-UHFFFAOYSA-N 0.000 description 1
- UMIVXZPTRXBADB-UHFFFAOYSA-N benzocyclobutene Chemical compound C1=CC=C2CCC2=C1 UMIVXZPTRXBADB-UHFFFAOYSA-N 0.000 description 1
- 150000005130 benzoxazines Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 150000001913 cyanates Chemical class 0.000 description 1
- QPJDMGCKMHUXFD-UHFFFAOYSA-N cyanogen chloride Chemical compound ClC#N QPJDMGCKMHUXFD-UHFFFAOYSA-N 0.000 description 1
- 125000006841 cyclic skeleton Chemical group 0.000 description 1
- 125000002993 cycloalkylene group Chemical group 0.000 description 1
- 125000005832 cyclohexylphenylene group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1[*:2])C1([H])C([H])([H])C([H])([H])C([H])([*:1])C([H])([H])C1([H])[H] 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000005567 fluorenylene group Chemical group 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 229940117955 isoamyl acetate Drugs 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical compound COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical group C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical class [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000005548 pyrenylene group Chemical group 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000011345 viscous material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 238000010947 wet-dispersion method Methods 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 1
- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/092—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G59/306—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G59/4014—Nitrogen containing compounds
- C08G59/4028—Isocyanates; Thioisocyanates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G59/4014—Nitrogen containing compounds
- C08G59/4042—Imines; Imides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- 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
- H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2363/00—Epoxy resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
Definitions
- the present invention relates to prepregs, metal foil-clad laminates and printed wiring boards.
- Patent Document 1 discloses a curable composition containing an alkenylphenol, an epoxy-modified silicone, and an epoxy compound other than the epoxy-modified silicone, or a curable composition containing a polymer having these as structural units. is applied to prepregs, resin sheets, metal foil-clad laminates and printed wiring boards.
- the present invention has been made in view of the above problems, and aims to provide a prepreg, a metal foil-clad laminate, and a printed wiring board that are excellent in low thermal expansion.
- the inventors have made extensive studies to solve the above problems.
- the loss elastic modulus at 100° C., 150° C. and 200° C. and the loss elastic modulus at the maximum point obtained by subjecting the prepreg to the loss elastic modulus measurement by the DMA method if the prepreg satisfies a predetermined relationship, the above We have found that the problem can be solved, and have completed the present invention.
- a prepreg comprising a base material and a thermosetting resin composition impregnated or applied to the base material
- a cured product for evaluation obtained by thermally curing the prepreg under the conditions of 230° C./100 minutes is a prepreg that satisfies the following conditions (1) to (4).
- the loss elastic modulus of the cured product for evaluation measured by the DMA method according to JIS C6481 (1996) has a maximum point at 200°C or higher.
- the ratio of the loss elastic modulus L (150) of the cured product for evaluation at 150 ° C. measured by the DMA method and the L (max) is 0 as L (150) / L (max) .60 or higher.
- the ratio of the loss elastic modulus L (200) of the cured product for evaluation at 200 ° C. measured by the DMA method and the L (max) is 0 as L (200) / L (max) .70 or higher.
- thermosetting resin composition contains alkenylphenol A, epoxy-modified silicone B, and epoxy compound C other than epoxy-modified silicone B.
- the thermosetting resin composition contains a polymer D containing structural units derived from alkenylphenol A, structural units derived from epoxy-modified silicone B, and structural units derived from epoxy compound C, [1 ] The prepreg described in . [4] [3], wherein the thermosetting resin composition further contains at least one selected from the group consisting of alkenylphenol A, epoxy-modified silicone B, and an epoxy compound C other than the epoxy-modified silicone B. prepreg.
- the maleimide compounds include bis(4-maleimidophenyl)methane, 2,2-bis ⁇ 4-(4-maleimidophenoxy)-phenyl ⁇ propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane,
- each R 5 independently represents a hydrogen atom or a methyl group, and n 1 represents an integer of 1 or more.
- each R 13 independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and n 4 represents an integer of 1 or more and 10 or less.
- the content of the polymer D in the thermosetting resin composition is 5 to 60% by mass with respect to the total 100% by mass of the polymer D and the compound E [7] to [9]
- the prepreg according to any one of [11] The prepreg according to any one of [2] to [10], wherein the epoxy-modified silicone B contains an epoxy-modified silicone represented by the following formula (1).
- each R 1 independently represents a single bond, an alkylene group, an arylene group or an aralkylene group, and each R 2 independently represents an alkyl group having 1 to 10 carbon atoms or a phenyl group. and n is an integer from 0 to 100.
- the epoxy-modified silicone B contains an epoxy-modified silicone having an epoxy equivalent of 140-250 g/mol.
- the alkenylphenol A contains diallyl bisphenol and/or dipropenyl bisphenol.
- thermosetting resin composition contains an inorganic filler, The prepreg according to any one of [1] to [18], wherein the content of the inorganic filler is 50 to 1000 parts by mass with respect to 100 parts by mass of the resin solid content.
- the present invention it is possible to provide a prepreg, a metal foil-clad laminate, and a printed wiring board that are excellent in low thermal expansion.
- this embodiment a mode for carrying out the present invention (hereinafter referred to as “this embodiment") will be described in detail, but the present invention is not limited to this, and various modifications can be made without departing from the scope of the invention. It is possible.
- the term "resin solid content” refers to the components excluding the solvent and filler in the thermosetting resin composition of the present embodiment, unless otherwise specified, and the resin solid content is 100 parts by mass. means that the total of the components excluding the solvent and filler in the thermosetting resin composition is 100 parts by mass. Moreover, 100 mass % of resin solid content means that the sum total of the component except a solvent and a filler in a thermosetting resin composition is 100 mass %.
- the prepreg of the present embodiment is a prepreg containing a substrate and a thermosetting resin composition impregnated or applied to the substrate, and the prepreg is thermally cured under conditions of 230 ° C./100 minutes.
- the obtained cured product for evaluation satisfies the following conditions (1) to (4).
- the loss elastic modulus of the cured product for evaluation measured by the DMA method according to JIS C6481 (1996) has a maximum point at 200°C or higher.
- the ratio of the loss elastic modulus L (150) of the cured product for evaluation at 150 ° C. measured by the DMA method and the L (max) is 0 as L (150) / L (max) .60 or higher.
- the ratio of the loss elastic modulus L (200) of the cured product for evaluation at 200 ° C. measured by the DMA method and the L (max) is 0 as L (200) / L (max) .70 or higher. Since the prepreg of the present embodiment is configured as described above, it is excellent in low thermal expansion.
- the prepreg of this embodiment includes a base material and a thermosetting resin composition impregnated or applied to the base material.
- the prepreg of the present embodiment is not particularly limited in its production method as long as it satisfies the above-described configuration. It can be obtained by semi-curing (to B stage) by heating and drying at a temperature of 200°C.
- the cured product of the prepreg of the present embodiment is not particularly limited as long as it is obtained by curing the prepreg of the present embodiment.
- the heating conditions for such curing are not particularly limited, and can be, for example, 180 to 230° C./60 to 180 minutes.
- the cured products of the prepreg of the present embodiment those obtained by curing the prepreg of the present embodiment under the conditions of 230° C./100 minutes are used for loss elastic modulus evaluation in the present embodiment. Yes, and it is specifically referred to as "evaluation cured product".
- the content of the thermosetting resin composition in the prepreg of the present embodiment is preferably 30 to 90% by volume, more preferably 35 to 90% by volume, based on the total amount of the prepreg, in terms of the thermosetting resin composition solid content. 85% by volume, more preferably 40 to 80% by volume.
- the content of the thermosetting resin composition is within the above range, moldability tends to be further improved.
- the thermosetting resin composition solid content as used herein means a component obtained by removing the solvent from the thermosetting resin composition.
- the filler described later is included in the thermosetting resin composition solid content. .
- the substrate is not particularly limited, and examples thereof include known substrates used as materials for various printed wiring boards.
- Specific examples of the substrate include glass substrates, inorganic substrates other than glass (for example, inorganic substrates composed of inorganic fibers other than glass such as quartz), organic substrates (for example, wholly aromatic polyamide, polyester , polyparaphenylenebenzoxazole, and organic base materials composed of organic fibers such as polyimide). These substrates are used singly or in combination of two or more.
- a glass substrate is preferable from the viewpoint of being more excellent in dimensional stability under heating.
- Fibers constituting the glass substrate include, for example, E glass, D glass, S glass, T glass, Q glass, L glass, NE glass, HME glass, and the like.
- the fibers constituting the glass substrate are the group consisting of E glass, D glass, S glass, T glass, Q glass, L glass, NE glass and HME glass, from the viewpoint of being more excellent in strength and low water absorption.
- One or more selected fibers are preferred.
- the form of the substrate is not particularly limited, but examples include forms such as woven fabric, nonwoven fabric, roving, chopped strand mat, and surfacing mat.
- the weaving method of the woven fabric is not particularly limited, but for example, plain weave, Nanako weave, twill weave, etc. are known, and it is possible to appropriately select and use from these known ones depending on the intended use and performance. .
- glass woven fabrics surface-treated with a silane coupling agent or the like are preferably used.
- the thickness of the base material is not particularly limited, a thickness of about 0.01 to 0.1 mm is usually suitably used.
- the cured product for evaluation obtained by thermally curing the prepreg of the present embodiment under conditions of 230° C./100 minutes has (1) loss of the cured product for evaluation measured by the DMA method in accordance with JIS C6481 (1996). Since the elastic modulus has a maximum point at 200° C. or higher, it has excellent heat resistance. From the same viewpoint as above, the loss elastic modulus of the cured product for evaluation preferably has a maximum point at 240 ° C. or higher, more preferably has a maximum point at 250 ° C. or higher, and has a maximum point at 260 ° C. or higher. More preferably, it may have a maximum point at 270° C. or higher.
- the temperature of the maximum point of the loss elastic modulus may be a higher value, and is not particularly limited. For example, the loss elastic modulus may have a maximum point at 290° C. or higher.
- the cured product for evaluation obtained by thermally curing the prepreg of the present embodiment under the conditions of 230° C./100 minutes has (2) loss elastic modulus L of the cured product for evaluation at 100° C. measured by the DMA method ( 100) and the loss elastic modulus L (max) of the cured product for evaluation at the maximum point is 0.70 or more as L (100) / L (max), so it is excellent in low thermal expansion. .
- L(100)/L(max) is preferably 0.71 or more, more preferably 0.73 or more.
- the L(100)/L(max) may be a higher value and is not particularly limited. It may be 95.
- the cured product for evaluation obtained by thermally curing the prepreg of the present embodiment under conditions of 230° C./100 minutes has (3) loss elastic modulus L of the cured product for evaluation at 150° C. measured by the DMA method ( 150) and the L(max) is 0.60 or more as L(150)/L(max), so the low thermal expansion property is excellent.
- L(150)/L(max) is preferably 0.65 or more, more preferably 0.68 or more.
- the L(150)/L(max) may be a higher value, and is not particularly limited. It may be 90.
- the cured product for evaluation obtained by thermally curing the prepreg of the present embodiment under the conditions of 230° C./100 minutes has (4) loss elastic modulus L of the cured product for evaluation at 200° C. measured by the DMA method ( 200) and the L(max) is 0.70 or more as L(200)/L(max), so that the low thermal expansion property is excellent.
- L(200)/L(max) is preferably 0.71 or more, more preferably 0.75 or more.
- the above L(200)/L(max) may be a higher value and is not particularly limited, but for example, the above L(200)/L(max) may be 0.95.
- the loss elastic modulus L (max), the loss elastic modulus L (100), the loss elastic modulus L (150), and the loss elastic modulus L (200) in the present embodiment are described in Examples below. method.
- the components of the thermosetting resin composition include, but are not limited to, aromatic phosphorus compound P, alkenylphenol A, epoxy-modified silicone B, other than the epoxy-modified silicone B, which will be described later.
- loss elastic modulus L(max), loss elastic modulus L(100), loss elastic modulus L(150), and loss elastic modulus L(200) can be preferably adjusted within the ranges described above.
- the value of cyanate equivalent/epoxy equivalent is preferably less than 0.8.
- thermosetting resin composition As long as the prepreg of the present embodiment satisfies the above configuration, the thermosetting resin composition of the present embodiment is not particularly limited. On the other hand, from the viewpoint of excellent low thermal expansion properties, the thermosetting resin composition in the present embodiment may contain alkenylphenol A, epoxy-modified silicone B, and an epoxy compound C other than the epoxy-modified silicone B. preferable.
- first composition the thermosetting resin composition containing alkenylphenol A, epoxy-modified silicone B, and epoxy compound C other than epoxy-modified silicone B is also referred to as "first composition".
- thermosetting resin composition in the present embodiment comprises structural units derived from alkenylphenol A, structural units derived from epoxy-modified silicone B, and an epoxy compound C other than the epoxy-modified silicone B. It is also preferable to include a polymer D containing a structural unit derived from.
- a thermosetting polymer D containing a structural unit derived from alkenylphenol A, a structural unit derived from epoxy-modified silicone B, and a structural unit derived from an epoxy compound C other than the epoxy-modified silicone B The resin composition is also called “second composition”.
- first composition and “second composition shall include both “things”.
- Alkenylphenol A is not particularly limited as long as it is a compound having a structure in which one or more alkenyl groups are directly bonded to a phenolic aromatic ring.
- the thermosetting resin composition in the present embodiment tends to be excellent in low thermal expansion properties due to the inclusion of alkenylphenol A.
- the alkenyl group is not particularly limited, but examples thereof include alkenyl groups having 2 to 30 carbon atoms such as vinyl group, allyl group, propenyl group, butenyl group and hexenyl group. Among them, the alkenyl group is preferably an allyl group and/or a propenyl group, more preferably an allyl group, from the viewpoint of more effectively and reliably exhibiting the effects of the present embodiment.
- the number of alkenyl groups directly bonded to one phenolic aromatic ring is not particularly limited, and is, for example, 1-4.
- the number of alkenyl groups directly bonded to one phenolic aromatic ring is preferably 1 to 2, more preferably 1, from the viewpoint of more effectively and reliably exhibiting the effects of the present embodiment.
- the bonding position of the alkenyl group to the phenolic aromatic ring is not particularly limited, but the ortho positions (2,6 positions) are preferable.
- a phenolic aromatic ring is one in which one or more hydroxyl groups are directly bonded to an aromatic ring, and includes phenol rings and naphthol rings.
- the number of hydroxyl groups directly bonded to one phenolic aromatic ring is not particularly limited, and is, for example, 1 to 2, preferably 1.
- the phenolic aromatic ring may have substituents other than alkenyl groups.
- substituents include linear alkyl groups having 1 to 10 carbon atoms, branched alkyl groups having 3 to 10 carbon atoms, cyclic alkyl groups having 3 to 10 carbon atoms, linear alkyl groups having 1 to 10 carbon atoms, A chain alkoxy group, a branched alkoxy group having 3 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, and a halogen atom.
- the number of such substituents directly bonded to one phenolic aromatic ring is not particularly limited, and is, for example, 1-2.
- the bonding position of the substituent to the phenolic aromatic ring is not particularly limited.
- Alkenylphenol A may have one or more structures in which one or more alkenyl groups are directly bonded to a phenolic aromatic ring. From the viewpoint of achieving the effects of the present embodiment more effectively and reliably, alkenylphenol A preferably has one or two structures in which one or more alkenyl groups are directly bonded to a phenolic aromatic ring. It is preferable to have
- Alkenylphenol A may be, for example, a compound represented by the following formula (1A) or the following formula (1B).
- 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 form a fused structure with a benzene ring
- Rxc may or may not be present
- A is 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).
- 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 is , represents an aromatic ring having 4 to 12 carbon atoms
- Rxf may form a fused structure with a benzene ring
- Rxf may or may not exist
- one benzene ring may have two or more Rxd and/or Rxe groups.
- the alkenyl group having 2 to 8 carbon atoms represented by Rxa and Rxd is not particularly limited, and examples thereof include vinyl group, allyl group, propenyl group, butenyl group and hexenyl group. etc.
- the alkyl group having 1 to 10 carbon atoms represented by Rxb and Rxe is not particularly limited, and examples thereof include methyl group, ethyl group, propyl group, butyl group, and pentyl group. , straight-chain alkyl groups such as hexyl group, branched alkyl groups such as isopropyl group, isobutyl group and tert-butyl group.
- the alkylene group having 1 to 6 carbon atoms represented by A is not particularly limited, and examples thereof include methylene group, ethylene group, trimethylene group and propylene group.
- the aralkylene group having 7 to 16 carbon atoms represented by A is not particularly limited, for example, the formulas: -CH 2 -Ar-CH 2 -, -CH 2 -CH 2 -Ar-CH 2 -CH 2 - , or a group represented by the formula: —CH 2 —Ar—CH 2 —CH 2 — (wherein Ar represents a phenylene group, a naphthylene group, or a biphenylene group).
- the arylene group having 6 to 10 carbon atoms represented by A is not particularly limited, but includes, for example, a phenylene ring.
- Rxf is preferably a benzene ring (compound containing a dihydroxynaphthalene skeleton) from the viewpoint of more effectively and reliably exhibiting the effects of the present embodiment.
- alkenylphenol A is preferably an alkenylbisphenol in which one alkenyl group is bonded to each of two phenolic aromatic rings of a bisphenol.
- alkenyl bisphenol is diallyl bisphenol in which two phenolic aromatic rings of bisphenols are respectively bonded to one allyl group, and/or bisphenols in which two phenolic aromatic rings are respectively bonded to one propenyl group. Dipropenyl bisphenol is preferred.
- diallyl bisphenol examples include, but are not limited to, o, o'-diallyl bisphenol A ("DABPA", a product of Daiwa Kasei Kogyo Co., Ltd.), o, o'-diallyl bisphenol F, and o, o'-diallyl bisphenol S. , o,o'-diallylbisphenol fluorene.
- DABPA o, o'-diallyl bisphenol A
- F a product of Daiwa Kasei Kogyo Co., Ltd.
- o, o'-diallyl bisphenol F examples include, but are not limited to, o, o'-diallyl bisphenol F, and o, o'-diallyl bisphenol S. , o,o'-diallylbisphenol fluorene.
- dipropenyl bisphenol examples include, but are not limited to, o,o'-dipropenylbisphenol A ("PBA01" available from Gunei Chemical Industry Co., Ltd.), o,o'-dipropenylbisphenol F, o,o'- Dipropenyl bisphenol S, o,o'-dipropenyl bisphenol fluorene.
- PBA01 available from Gunei Chemical Industry Co., Ltd.
- o,o'-dipropenylbisphenol F o,o'- Dipropenyl bisphenol S
- o,o'-dipropenyl bisphenol fluorene examples include, but are not limited to, o,o'-dipropenylbisphenol A ("PBA01" available from Gunei Chemical Industry Co., Ltd.), o,o'-dipropenylbisphenol F, o,o'- Dipropenyl bisphenol S, o,o'-dipropenyl bisphenol
- the average number of phenol groups per molecule of alkenylphenol A is preferably 1 or more and less than 3, and 1.5 or more and 2.5 or less, from the viewpoint of more effectively and reliably exhibiting the effects of the present embodiment. is more preferred.
- the average number of phenol groups is calculated by the following formula.
- A represents the number of phenol groups of alkenylphenol having i phenol groups in the molecule
- Xi represents the ratio of alkenylphenol having i phenol groups in the molecule to the total alkenylphenol
- X 1 +X 2 + . . . X n 1.
- 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 thermosetting resin composition in the present embodiment tends to exhibit excellent low thermal expansion and chemical resistance 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 in which siloxane bonds are repeatedly formed.
- the polysiloxane skeleton may be a linear skeleton, a cyclic skeleton, or a network skeleton. Among these, a linear skeleton is preferred from the viewpoint of more effectively and reliably exhibiting the effects of the present embodiment.
- Examples of the epoxy group-containing group include, but are not particularly limited to, groups represented by the following formula (a1).
- R 0 represents an alkylene group (for example, a methylene group, an ethylene group, an alkylene group having 1 to 5 carbon atoms such as a propylene group)
- X is represented by the following formula (a2). represents a monovalent group or a monovalent group represented by the following formula (a3).
- Epoxy-modified silicone B preferably contains an epoxy-modified silicone having an epoxy equivalent of 140 to 250 g/mol. By containing an epoxy-modified silicone having an epoxy equivalent within the above range, epoxy-modified silicone B tends to further improve low thermal expansion and chemical resistance in a well-balanced manner. From the same viewpoint, the epoxy equivalent is more preferably 145 to 245 g/mol, still more preferably 150 to 240 g/mol.
- Epoxy-modified silicone B preferably contains two or more epoxy-modified silicones from the viewpoint of further improving the balance between heat resistance and low thermal expansion.
- the two or more epoxy-modified silicones preferably have different epoxy equivalents, and an epoxy-modified silicone having an epoxy equivalent of 50 to 350 g/mol (hereinafter also referred to as "low equivalent epoxy-modified silicone B1"). and an epoxy-modified silicone having an epoxy equivalent of 400 to 4000 g/mol (hereinafter also referred to as "high equivalent epoxy-modified silicone B2”), and an epoxy having an epoxy equivalent of 140 to 250 g/mol. More preferably, it contains a modified silicone (low-equivalent epoxy-modified silicone B1′) and an epoxy-modified silicone having an epoxy equivalent of 450 to 3000 g/mol (high-equivalent epoxy-modified silicone B2′).
- the average epoxy equivalent of the epoxy-modified silicone B is preferably 140 to 3000 g/mol, more preferably 250 to 2000 g/mol. More preferably 300 to 1000 g/mol.
- Epoxy-modified silicone B preferably contains an epoxy-modified silicone represented by the following formula (1) from the viewpoint of further improving low thermal expansion and chemical resistance in a well-balanced manner.
- each R 1 independently represents a single bond, an alkylene group, an arylene group or an aralkylene group, and each R 2 independently represents an alkyl group having 1 to 10 carbon atoms or a phenyl group.
- n represents an integer from 0 to 100.
- the alkylene group represented by R 1 may be linear, branched or cyclic.
- the number of carbon atoms in the alkylene group is preferably 1-12, more preferably 1-4.
- alkylene groups include, but are not limited to, methylene, ethylene, and propylene groups.
- R 1 is preferably a propylene group.
- the arylene group represented by R 1 may have a substituent.
- the number of carbon atoms in the arylene group is preferably 6-40, more preferably 6-20.
- the arylene group includes, for example, a phenylene group, a cyclohexylphenylene group, a hydroxyphenylene group, a cyanophenylene group, a nitrophenylene group, a naphthylene group, a biphenylene group, an anthrylene group, a pyrenylene group, a fluorenylene group and the like. These groups may contain an ether bond, a ketone bond or an ester bond.
- the aralkylene group represented by R 1 preferably has 7 to 30 carbon atoms, more preferably 7 to 13 carbon atoms.
- the aralkylene group is not particularly limited, but includes, for example, groups represented by the following formula (XI). (In formula (XI), * represents a bond.)
- the group represented by R 1 may further have a substituent.
- substituents include linear alkyl groups having 1 to 10 carbon atoms, branched alkyl groups, cyclic alkyl groups having 3 to 10 carbon atoms, linear alkoxy groups having 1 to 10 carbon atoms, branched alkoxy groups having 3 to 10 carbon atoms, and cyclic alkoxy groups having 3 to 10 carbon atoms. be done.
- R 1 is particularly preferably a propylene group.
- each R 2 independently represents an alkyl group having 1 to 10 carbon atoms or a phenyl group.
- the above alkyl group and phenyl group may have a substituent.
- the alkyl group having 1 to 10 carbon atoms may be linear, branched or cyclic.
- Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, and cyclohexyl groups.
- R 2 is preferably a methyl group or a phenyl group.
- n represents an integer of 0 or more, for example, 0 to 100. From the viewpoint of further improving low thermal expansion and chemical resistance in a well-balanced manner, n is preferably 50 or less, more preferably 30 or less, and even more preferably 20 or less.
- Epoxy-modified silicone B preferably contains two or more types of epoxy-modified silicone represented by formula (1) from the viewpoint of further improving low thermal expansion and chemical resistance in a well-balanced manner.
- two or more types of epoxy-modified silicones preferably have different values of n. It is more preferable to contain a certain epoxy-modified silicone.
- the average number of epoxy groups per molecule of the epoxy-modified silicone B is preferably 1 or more and less than 3, and is 1.5 or more and 2.5 or less, from the viewpoint of more effectively and reliably exhibiting the effects of the present embodiment. is more preferable.
- the content of the epoxy-modified silicone B is 5 to 95% by mass with respect to the total 100% by mass of the epoxy-modified silicone B and the epoxy compound C, from the viewpoint of expressing even better low thermal expansion and chemical resistance. , more preferably 10 to 90% by mass, even more preferably 40 to 85% by mass, even more preferably 50 to 80% by mass.
- epoxy-modified silicone B a commercially available product may be used, or a product manufactured by a known method may be used. Examples of commercially available products include “X-22-163" and “KF-105" manufactured by Shin-Etsu Chemical Co., Ltd.
- Epoxy compound C is an epoxy compound other than epoxy-modified silicone B, more specifically, an epoxy compound that does not have a polysiloxane skeleton. By containing the epoxy compound C, the thermosetting resin composition in the present embodiment tends to exhibit excellent heat resistance, chemical resistance, copper foil adhesion 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.
- the epoxy compound C in the thermosetting resin composition typically, a bifunctional epoxy compound having two epoxy groups in one molecule or a polyfunctional epoxy compound having three or more epoxy groups in one molecule is used. can do.
- Epoxy compound C preferably contains a bifunctional epoxy compound and/or a polyfunctional epoxy compound from the viewpoint of being able to exhibit even better heat resistance, chemical resistance, copper foil adhesion and insulation reliability.
- the epoxy compound C in the thermosetting resin composition is not particularly limited, but a compound represented by the following formula (3a) can be used.
- Ar 3 each independently represents a benzene ring or naphthalene ring
- Ar 4 represents a benzene ring, naphthalene ring or biphenyl ring
- R 3a each independently represents a hydrogen atom.
- the benzene ring or naphthalene ring in Ar 3 may further have one or more substituents, and the substituent may be a glycidyloxy group (not shown), or other substituents such as It may be an alkyl group having 1 to 5 carbon atoms, a phenyl group, etc.
- the benzene ring, naphthalene ring or biphenyl ring in Ar 4 may further have one or more substituents, which may be a glycidyloxy group, other substituents such as carbon number It may be an alkyl group of 1 to 5, a phenyl group, or the like.
- examples of bifunctional epoxy compounds include compounds represented by the following formula (b1).
- each Ar 3 independently represents a benzene ring or naphthalene ring
- each Ar 4 represents a benzene ring, naphthalene ring or biphenyl ring
- each R 3a independently represents a hydrogen atom or represents a methyl group
- the benzene ring or naphthalene ring in Ar 3 may further have one or more substituents, and the substituents are, for example, a glycidyloxy group such as an alkyl group having 1 to 5 carbon atoms or a phenyl group.
- the benzene ring, naphthalene ring or biphenyl ring in Ar 4 may further have one or more substituents, and the substituents are, for example, a glycidyloxy group such as an alkyl group having 1 to 5 carbon atoms or a phenyl group. It may be a substituent other than )
- the compound represented by formula (3a) is preferably a phenolic novolac type epoxy resin in which Ar 4 in formula (3a) is at least substituted with a glycidyloxy group.
- the phenolic novolak-type epoxy resin is not particularly limited. Epoxy resins may be mentioned.
- each Ar 31 independently represents a benzene ring or a naphthalene ring
- each Ar 41 independently represents a benzene ring, a naphthalene ring or a biphenyl ring
- each R 31a independently represents represents represents a hydrogen atom or a methyl group
- p represents 1
- kz represents an integer of 1 to 50
- each ring represents a substituent other than a glycidyloxy group (for example, an alkyl group having 1 to 5 carbon atoms, a 1 to 5 alkoxy groups or phenyl groups)
- at least one of Ar 31 and Ar 41 represents a naphthalene ring.
- Compounds having a structure represented by formula (3-1) include compounds having a structure represented by formula (3-2). (Wherein, R represents a methyl group, and kz is synonymous with kz in the above formula (3-1).)
- the naphthalene cresol novolak type epoxy resin is not particularly limited, but for example, a cresol/naphthol novolak type epoxy resin represented by the following formula (NE) is preferable.
- the compound represented by the following formula (NE) is a random copolymer of a cresol novolak epoxy structural unit and a naphthol novolak epoxy structural unit, and both cresol epoxy and naphthol epoxy can be terminals.
- n and n in the formula (NE) each represent an integer of 1 or more.
- naphthalene cresol novolac type epoxy resin a commercially available product or a product manufactured by a known method may be used.
- commercially available products include "NC-7000", “NC-7300” and “NC-7300L” manufactured by Nippon Kayaku Co., Ltd., and "HP-9540” and “HP-9500” manufactured by DIC Corporation. and "HP-9540" is particularly preferred.
- the compound represented by formula (3a) may be a compound (hereinafter also referred to as "aralkyl epoxy resin") that does not correspond to the phenolic novolac epoxy resins described above.
- Aralkyl-type epoxy resins include compounds in which Ar 3 is a naphthalene ring and Ar 4 is a benzene ring in the formula (3a) (also referred to as a "naphthol aralkyl- type epoxy resin”); It is preferably a compound in which it is a benzene ring and Ar 4 is a biphenyl ring (also referred to as a "biphenylaralkyl-type epoxy resin”), and more preferably a biphenylaralkyl-type epoxy resin.
- naphthol aralkyl type epoxy resin a commercially available product or a product manufactured by a known method may be used.
- Examples of commercially available products include “HP-5000” and “HP-9900” manufactured by DIC Corporation, and “ESN-375” and “ESN-475" manufactured by Nippon Steel Chemical & Materials Co., Ltd.
- the biphenyl aralkyl type epoxy resin is preferably a compound represented by the following formula (3b). (Wherein, ka represents an integer of 1 or more, preferably 1 to 20, more preferably 1 to 6.)
- bifunctional epoxy compounds include, for example, compounds in which ka is 1 in formula (3b).
- biphenyl aralkyl type epoxy resin a commercially available product or a product manufactured by a known method may be used.
- commercially available products include “NC-3000”, “NC-3000L”, and “NC-3000FH” manufactured by Nippon Kayaku Co., Ltd.
- the epoxy compound C in the thermosetting resin composition it is preferable to use a naphthalene-type epoxy resin (excluding those corresponding to the compounds represented by formula (3a)).
- the naphthalene-type epoxy resin is preferably a naphthylene ether-type epoxy resin from the viewpoint of further improving heat resistance, chemical resistance, copper foil adhesion, and insulation reliability.
- the naphthylene ether type epoxy resin is a bifunctional epoxy compound represented by the following formula (3-3) or the following formula (3 -4) is preferably a polyfunctional epoxy compound or a mixture thereof.
- each R 13 is independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (eg, methyl group or ethyl group), or an alkenyl group having 2 to 3 carbon atoms (eg, vinyl group, allyl group or propenyl group).
- each R 14 is independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (e.g., methyl group or ethyl group), or an alkenyl group having 2 to 3 carbon atoms (e.g., vinyl group, allyl group or propenyl group).)
- a commercially available product or a product manufactured by a known method may be used as the naphthylene ether type epoxy resin.
- Commercially available naphthylene ether type epoxy resins include, for example, DIC Corporation products "HP-6000", “EXA-7300”, “EXA-7310", “EXA-7311”, “EXA-7311L”, “ EXA7311-G3", “EXA7311-G4", “EXA-7311G4S”, “EXA-7311G5", etc., and HP-6000 is particularly preferred.
- each R 3b is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms (e.g., methyl group or ethyl group), an aralkyl group, a benzyl group, a naphthyl group, at least one glycidyl represents a naphthyl group containing an oxy group or a naphthylmethyl group containing at least one glycidyloxy group, and n represents an integer of 0 or more (eg, 0 to 2).)
- each Ra independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom.
- the alkyl group having 1 to 10 carbon atoms may be linear, branched or cyclic.
- alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, and cyclohexyl groups.
- the biphenyl-type epoxy resin may be in the form of a mixture of compounds b2 having different numbers of Ra as alkyl groups. Specifically, it is preferably a mixture of biphenyl-type epoxy resins having different numbers of Ra as alkyl groups. It is more preferred to be a mixture of compounds b2 which are
- a dicyclopentadiene type epoxy resin (excluding those corresponding to the epoxy compound C described above) can be used.
- the dicyclopentadiene-type epoxy resin is not particularly limited, but includes, for example, compounds represented by the following formula (3-5). (In the formula, each R 3c independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and k2 represents an integer of 0 to 10.)
- each R 3c independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms (eg, methyl group or ethyl group).)
- dicyclopentadiene type epoxy resin A commercially available product or a product manufactured by a known method may be used as the dicyclopentadiene type epoxy resin.
- Commercial products of dicyclopentadiene type epoxy resin include "EPICRON HP-7200L”, “EPICRON HP-7200”, “EPICRON HP-7200H” and "EPICRON HP-7000HH” manufactured by Dainippon Ink and Chemicals. mentioned.
- the epoxy compound C is an epoxy compound represented by the formula (3a), a naphthalene-type epoxy resin and a biphenyl, from the viewpoint of being able to exhibit even better heat resistance, chemical resistance, copper foil adhesion and insulation reliability.
- Epoxy compound C may contain other epoxy compounds that do not correspond to the epoxy compounds described above.
- other epoxy compounds include, but are not limited to, bisphenol-type epoxy resins, trisphenolmethane-type epoxy resins, anthracene-type epoxy resins, glycidyl ester-type epoxy resins, polyol-type epoxy resins, isocyanurate ring-containing epoxy resins, and fluorene-type epoxy resins.
- examples thereof include resins, epoxy resins composed of bisphenol A structural units and hydrocarbon structural units, and the like.
- bisphenol-type epoxy resins can be included.
- bisphenol-type epoxy resins examples include diallyl Bisphenol type epoxy resins (for example, diallyl bisphenol A type epoxy resin, diallyl bisphenol E type epoxy resin, diallyl bisphenol F type epoxy resin, diallyl bisphenol S type epoxy resin, etc.) and the like can be used.
- epoxy compound C one of the above-described epoxy compounds and epoxy resins may be used alone, or two or more thereof may be used in combination.
- the average number of epoxy groups per molecule of the epoxy compound C is preferably 1 or more and less than 3, and 1.5 or more and 2.5 or less, from the viewpoint of more effectively and reliably exhibiting the effects of the present embodiment. is more preferred.
- the content of the epoxy compound C is, from the viewpoint of being able to exhibit even better heat resistance, chemical resistance, copper foil adhesion and insulation reliability, the total amount of the epoxy-modified silicone B and the epoxy compound C being 100% by mass, It 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.
- thermosetting resin composition in the present embodiment contains a maleimide compound, a cyanate ester compound, and a phenol other than the alkenylphenol A. It is preferable to further include at least one compound E selected from the group consisting of compound A' and alkenyl-substituted nadimide compounds.
- compound E is not particularly limited, it is preferably bifunctional or higher, and may be trifunctional or higher polyfunctional.
- the content of compound E in the thermosetting resin composition of the present embodiment is preferably 10 to 80% by mass, preferably 20 to 60% by mass, relative to 100% by mass of the resin solid content. is more preferable, and 30 to 50% by mass is even more preferable.
- the thermosetting resin composition in the present embodiment preferably contains a maleimide compound from the viewpoint of further improving heat resistance, low thermal expansion and chemical resistance.
- the maleimide compound is not particularly limited as long as it is a compound having one or more maleimide groups in one molecule.
- each R 5 independently represents a hydrogen atom or a
- n 1 is 1 or more, preferably 1-100, more preferably 1-10.
- the maleimide compound is preferably a compound having two or more maleimide groups in one molecule, and bis(4-maleimidophenyl)methane , 2,2-bis ⁇ 4-(4-maleimidophenoxy)-phenyl ⁇ propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, a maleimide compound represented by formula (3), and the following More preferably, it contains at least one selected from the group consisting of maleimide compounds represented by formula (3′).
- each R 13 independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and n 4 represents an integer of 1 or more and 10 or less.
- maleimide compound a commercially available product or a product manufactured by a known method may be used.
- Commercially available maleimide compounds include "BMI-70", “BMI-80” and “BMI-1000P” manufactured by K.I. -4000”, “BMI-5100”, “BMI-7000”, “BMI-2300”, Nippon Kayaku Co., Ltd. product “MIR-3000-70MT” (R 13 in formula (3′) are all hydrogen atoms and n4 is a mixture of 1 to 10.) and the like.
- the content of the maleimide compound is preferably 1 to 50 parts by mass, preferably 5 to 40 parts by mass, relative to 100 parts by mass of the resin solid content. More preferably, 10 to 40 parts by mass is even more preferable.
- thermosetting resin composition in the present embodiment preferably contains a cyanate ester compound from the viewpoint of further improving heat resistance, low thermal expansion properties and chemical resistance.
- the cyanate ester compound is not particularly limited as long as it is a compound having two or more cyanate groups (cyanate ester groups) in one molecule.
- the cyanate ester compound is a polyfunctional cyanate ester compound such as a naphthol aralkyl-type cyanate ester compound and/or a novolac-type cyanate ester compound. and more preferably a naphthol aralkyl-type cyanate ester compound and/or a novolac-type cyanate ester compound.
- each R 6 independently represents a hydrogen atom or a methyl group, and n 2 represents an integer of 1 or more.
- each Rya independently represents an alkenyl group having 2 to 8 carbon atoms or a hydrogen atom
- each Ryb 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 or a hydrogen atom, Ryc may form a condensed structure with a benzene ring, Ryc may be present or may be present
- 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, and an oxygen atom.
- one benzene ring may have two or more Rya and/or Ryb groups.n is 1 to represents an integer of 20.
- the cyanate ester compound preferably contains a compound represented by formula (4) and/or formula (5) from the viewpoint of further improving heat resistance and low thermal expansion in a well-balanced manner, and formula (4 ) is more preferably included.
- n2 represents an integer of 1 or more, preferably an integer of 1-20, more preferably an integer of 1-10.
- the alkenyl group having 2 to 8 carbon atoms represented by Rya is not particularly limited, and examples thereof include vinyl group, allyl group, propenyl group, butenyl group, and hexenyl group.
- the alkyl group having 1 to 10 carbon atoms represented by Ryb is not particularly limited. branched alkyl groups such as isopropyl group, isobutyl group and tert-butyl group;
- the alkylene group having 1 to 6 carbon atoms represented by A 1a is not particularly limited, but includes methylene group, ethylene group, trimethylene group and propylene group.
- the aralkylene group having 7 to 16 carbon atoms represented by A 1a is not particularly limited, and examples thereof include formulas: —CH 2 —Ar—CH 2 — and —CH 2 —CH 2 . -Ar-CH 2 -CH 2 -, or a group represented by the formula: -CH 2 -Ar-CH 2 -CH 2 - (wherein Ar represents a phenylene group, a naphthylene group, or a biphenylene group) is mentioned.
- the arylene group having 6 to 10 carbon atoms represented by A 1a is not particularly limited, but includes, for example, a phenylene ring.
- n represents an integer of 1-20, preferably an integer of 1-15, more preferably an integer of 1-10.
- the compound represented by Formula (5) is preferably a compound represented by Formula (c1) below.
- each Rx independently represents a hydrogen atom or a methyl group
- each R independently represents an alkenyl group having 2 to 8 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or hydrogen represents an atom
- n represents an integer from 1 to 10.
- cyanate ester compounds may be produced according to known methods. Specific production methods include, for example, the method described in JP-A-2017-195334 (particularly paragraphs 0052 to 0057).
- the content of the cyanate ester compound is preferably 5 to 70 parts by mass with respect to 100 parts by mass of the resin solid content. It is more preferably from 10 to 40 parts by mass, more preferably from 10 to 40 parts by mass.
- the thermosetting resin composition in the present embodiment can contain a phenol compound A' other than alkenylphenol A from the viewpoint of being able to exhibit even better chemical resistance.
- the phenolic compound A′ is not particularly limited, but may be a bisphenol-type phenol resin (eg, bisphenol A-type resin, bisphenol E-type resin, bisphenol F-type resin, bisphenol S-type resin, etc.), phenolic novolac resin (e.g., phenol novolac resins, naphthol novolak resins, cresol novolac resins, aminotriazine novolak resins described later, etc.), glycidyl ester type phenolic resins, naphthalene type phenolic resins, anthracene type phenolic resins, dicyclopentadiene type phenolic resins, biphenyl type phenolic resins, alicyclic Phenolic resins, polyol-type phenolic
- the phenolic compound A' preferably contains a bifunctional phenolic compound having two phenolic hydroxyl groups in one molecule or an aminotriazine novolac resin, from the viewpoint of being able to exhibit even better chemical resistance.
- bifunctional phenol compound examples include, but are not limited to, bisphenol, biscresol, bisphenols having a fluorene skeleton (e.g., bisphenol having a fluorene skeleton, biscresol having a fluorene skeleton, etc.), biphenols (e.g., p, p'- biphenol, etc.), dihydroxydiphenyl ether (e.g., 4,4'-dihydroxydiphenyl ether, etc.), dihydroxydiphenyl ketone (e.g., 4,4'-dihydroxydiphenyl ketone, etc.), dihydroxydiphenyl sulfide (e.g., 4,4'-dihydroxydiphenyl sulfide) etc.), and dihydroxyarene (eg, hydroquinone, etc.).
- bisphenol biscresol
- bisphenols having a fluorene skeleton e.g., bisphenol having a fluorene skeleton, biscre
- bifunctional phenol compounds are used singly or in combination of two or more.
- the bifunctional phenol compound preferably contains at least one selected from the group consisting of bisphenol, biscresol, and bisphenols having a fluorene skeleton, from the viewpoint of being able to exhibit even better chemical resistance. It is more preferable to contain bisphenols having a fluorene skeleton. From the same viewpoint as above, bis-cresol fluorene is preferable as the bisphenols having a fluorene skeleton.
- the thermosetting resin composition in this embodiment may contain an aminotriazine novolak resin as the phenol compound A'.
- the aminotriazine novolak resin When the aminotriazine novolak resin is contained, the terminal hydroxyl group or epoxy group generated by the reaction of the alkenylphenol A, the epoxy-modified silicone B, and the epoxy compound C other than the epoxy-modified silicone B, and the aminotriazine novolac resin are further combined. It tends to react and increase terminal functional groups such as hydroxyl groups and amino groups. As a result, a large number of terminal functional groups having high reactivity with the thermosetting resin are present, so that the compatibility and crosslink density are improved, and the peel strength of the copper foil tends to be improved.
- the aminotriazine novolac resin is not particularly limited, but from the viewpoint of improving copper foil peel strength, it is preferably a novolac resin having 2 to 20 phenolic hydroxyl groups per triazine skeleton in the molecule. More preferably, it is a novolac resin having 2 to 15 phenolic hydroxyl groups for one triazine skeleton in the molecule, and a novolak resin having 2 to 10 phenolic hydroxyl groups for one triazine skeleton in the molecule. is more preferred.
- the content of alkenylphenol A in the thermosetting resin composition is the total amount of alkenylphenol A, epoxy-modified silicone B, epoxy compound C and phenol compound A' from the viewpoint of further improving the balance between heat resistance and low thermal expansion. It 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 with respect to 100 parts by mass.
- the content of the epoxy-modified silicone B in the thermosetting resin composition is set to alkenylphenol A, epoxy-modified silicone B, epoxy compound C, and phenol compound A from the viewpoint of achieving better balance between low thermal expansion and chemical resistance. It 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 with respect to 100 parts by mass of the total amount of '.
- the content of the epoxy compound C in the thermosetting resin composition is, from the viewpoint of being able to express even better chemical resistance, copper foil adhesion and insulation reliability, alkenylphenol A, epoxy-modified silicone B, epoxy compound C and phenol It is preferably 5 to 50 parts by mass, more preferably 10 to 30 parts by mass, even more preferably 15 to 25 parts by mass, relative to 100 parts by mass of the total amount of compound A'.
- the content of the phenolic compound A' in the thermosetting resin composition is 100 parts by mass in total of the alkenylphenol A, the epoxy-modified silicone B, the epoxy compound C and the phenolic compound A', from the viewpoint of expressing even better chemical resistance.
- the amount 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.
- thermosetting resin composition does not contain the phenol compound A′
- contents of the alkenylphenol A, the epoxy-modified silicone B, and the epoxy compound C are the same as those of the alkenylphenol A, the epoxy-modified silicone B, and the epoxy compound. It represents the content per 100 parts by mass of the total amount of C.
- the thermosetting resin composition in the present embodiment preferably contains an alkenyl-substituted nadimide compound.
- the alkenyl-substituted nadimide compound is not particularly limited as long as it is a compound having one or more alkenyl-substituted nadimide groups in one molecule, and examples thereof include compounds represented by the following formula (2d).
- each R 1 independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (e.g., a methyl group or an ethyl group); represents an alkylene group, a phenylene group, a biphenylene group, a naphthylene group, or a group represented by the following formula (6) or (7).
- R3 represents a methylene group, an isopropylidene group, CO, O, S or SO2 .
- each R 4 independently represents an alkylene group having 1 to 4 carbon atoms or a cycloalkylene group having 5 to 8 carbon atoms.
- alkenyl-substituted nadimide compound represented by formula (2d) a commercially available product or a product manufactured according to a known method may be used.
- Commercially available products include “BANI-M” and “BANI-X” manufactured by Maruzen Petrochemical Co., Ltd.
- the content of the alkenyl-substituted nadimide compound is preferably 1 to 40 parts by mass, more preferably 5 to 35 parts by mass, based on 100 parts by mass of the resin solid content. , more preferably 10 to 30 parts by mass.
- the second composition contains polymer D containing structural units derived from alkenylphenol A, structural units derived from epoxy-modified silicone B, and structural units derived from epoxy compound C. Moreover, the polymer D may further contain a structural unit derived from a phenol compound A' other than the alkenylphenol A.
- structural units derived from alkenylphenol A "structural units derived from epoxy-modified silicone B,””structural units derived from epoxy compound C,” and "phenol compounds A other than alkenylphenol A
- the description to the effect that it contains a 'structural unit derived from' is a structure in which each component of alkenylphenol A, epoxy-modified silicone B, epoxy compound C and, if necessary, phenol compound A' is polymerized in polymer D. It includes the case of containing a unit and the case of containing a structural unit formed by a reaction or the like that can give a similar structural unit.
- Alkenylphenol A, epoxy-modified silicone B, epoxy compound C, and phenol compound A' are as described above.
- the second composition can exhibit excellent heat resistance, low thermal expansion, chemical resistance, copper foil adhesion, and insulation reliability in a well-balanced manner.
- a structural unit derived from alkenylphenol A a structural unit derived from epoxy-modified silicone B, a structural unit derived from epoxy compound C, and a structural unit derived from phenol compound A' other than alkenylphenol A, respectively. Also referred to as units A, B, C, and A'.
- the second composition in addition to the polymer D, is optionally selected from the group consisting of the above-described maleimide compounds, cyanate ester compounds, phenol compounds A' other than the alkenylphenol A, and alkenyl-substituted nadimide compounds.
- the compound E may be an unreacted component remaining after polymerization of the polymer D, or may be a component newly added to the synthesized polymer D.
- the second composition may contain at least one selected from the group consisting of alkenylphenol A, epoxy-modified silicone B and epoxy compound C described above.
- the alkenylphenol A, the epoxy-modified silicone B, or the epoxy compound C contained in the second composition may be an unreacted component remaining after the polymerization of the polymer D, or Alternatively, it may be a component added anew.
- the weight-average molecular weight of polymer D is preferably 3.0 ⁇ 10 3 to 5.0 ⁇ 10 4 , more preferably 3.0 ⁇ 10 3 to 2.0 ⁇ 10 in terms of polystyrene in gel permeation chromatography. 4 is more preferred.
- a weight average molecular weight of 3.0 ⁇ 10 3 or more the second composition tends to exhibit even better copper foil adhesion and chemical resistance.
- a weight average molecular weight of 5.0 ⁇ 10 4 or less tends to further improve the balance between heat resistance and low thermal expansion.
- the content of the structural unit A in the polymer D is preferably 5-50% by mass with respect to the total mass of the polymer D.
- the second composition tends to further improve the balance between heat resistance and low thermal expansion.
- the content of structural unit A is more preferably 10 to 45% by mass, even more preferably 10 to 40% by mass.
- the content of the structural unit B in the polymer D is preferably 20-60% by mass with respect to the total mass of the polymer D.
- the content of the structural unit B is within the above range, the second composition tends to exhibit even better low thermal expansion and chemical resistance in a well-balanced manner.
- the content of the structural unit B is more preferably 25 to 55% by mass, even more preferably 30 to 55% by mass.
- Structural unit B is an epoxy-modified silicone having an epoxy equivalent of 50 to 350 g/mol (low equivalent epoxy-modified silicone B1) and an epoxy-modified silicone having an epoxy equivalent of 400 to 4000 g/mol (high equivalent epoxy-modified silicone B2). It preferably contains a structural unit derived from. Low-equivalent epoxy-modified silicone B1 and high-equivalent epoxy-modified silicone B2 have an epoxy equivalent of 140-250 g/mol (low-equivalent epoxy-modified silicone B1′) and 450-3000 g/mol, respectively. Epoxy-modified silicone (high-equivalent epoxy-modified silicone B2') is more preferable.
- the content of the structural unit B1 derived from the low-equivalent epoxy-modified silicone B1 in the polymer D is preferably 5 to 25% by mass, more preferably 7.5 to 20% by mass, relative to the total mass of the polymer D. is more preferable, and 10 to 17% by mass is even more preferable.
- the content of the structural unit B2 derived from the high-equivalent epoxy-modified silicone B2 in the polymer D is preferably 15 to 55% by mass, more preferably 20 to 52.5% by mass, relative to the total mass of the polymer D. and more preferably 25 to 50% by mass.
- 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 1.5 to 3.5, and 1.5 to 3.3. is more preferable.
- the contents of the structural unit B1 and the structural unit B2 have the above relationship, the copper foil adhesion and chemical resistance tend to be further improved.
- the compound represented by the above formula (b1), the compound represented by the above formula (b2), the compound represented by the above formula (b3), and the above formula (b4) It is preferably a unit derived from at least one selected from the group consisting of the compounds represented.
- the structural unit C in the polymer D is more preferably a unit derived from the compound represented by the above formula (b2).
- the content of the structural unit C in the polymer D is preferably 5-40% by mass with respect to the total mass of the polymer D.
- the content of the structural unit C is within the above range, the second composition tends to exhibit even better heat resistance, chemical resistance, copper foil adhesion and insulation reliability.
- the content of structural unit C is preferably 10 to 30% by mass, more preferably 15 to 25% by mass.
- the content of the structural unit C is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, relative to the total mass of the structural unit B and the structural unit C, and 15 to 60% by mass. % by mass is more preferred, and 20 to 50% by mass is particularly preferred.
- the content of the structural unit A' in the polymer D is preferably 5-30% by mass with respect to the total mass of the polymer D.
- the content of the structural unit A' is preferably 10 to 27.5% by mass, more preferably 10 to 25% by mass, relative to the total mass of the polymer D.
- the alkenyl group equivalent weight of polymer D is preferably 300 to 1500 g/mol.
- the alkenyl group equivalent is 300 g/mol or more, the cured product of the second composition tends to have a further decreased elastic modulus, and as a result, the thermal expansion coefficient of the substrate obtained using the cured product decreases. It tends to be even lower.
- the alkenyl group equivalent is 1500 g/mol or less, the chemical resistance and insulation reliability of the second composition tend to be further improved.
- the alkenyl group equivalent is preferably 350-1200 g/mol, more preferably 400-1000 g/mol.
- the content of the polymer D in the second composition is preferably 5 to 50% by mass, more preferably 10 to 45% by mass, relative to 100% by mass of the resin solid content, and 15 to 40% by mass. % by mass is more preferred.
- the second composition tends to exhibit even better heat resistance, low thermal expansion, chemical resistance, copper foil adhesion and insulation reliability in a well-balanced manner.
- the second composition may further contain compound E in addition to polymer D, if necessary.
- the second composition tends to be further improved in heat resistance, low thermal expansion and chemical resistance.
- the content of the polymer D in the second composition is 5 to 60% by mass with respect to the total 100% by mass of the polymer D and the compound E. %, more preferably 10 to 55% by mass, even more preferably 20 to 50% by mass.
- the second composition tends to exhibit even better heat resistance, low thermal expansion, chemical resistance, copper foil adhesion and insulation reliability in a well-balanced manner.
- the content of the compound E in the second composition is preferably 20 to 80 with respect to the total 100% by mass of the polymer D and the compound E. % by mass is preferable, 35 to 75% by mass is more preferable, and 45 to 65% by mass is even more preferable.
- Polymer D is obtained, for example, by a step of reacting alkenylphenol A, epoxy-modified silicone B, epoxy compound C, and optionally phenol compound A' in the presence of polymerization catalyst G.
- the reaction may be performed in the presence of an organic solvent. More specifically, in the above steps, the addition reaction between the epoxy group of the epoxy-modified silicone B and the epoxy compound C and the hydroxyl group of the alkenylphenol A, and the hydroxyl group of the resulting addition reaction product and the epoxy-modified silicone B and
- the polymer D can be obtained by the progress of an addition reaction with the epoxy group of the epoxy compound C.
- the polymerization catalyst G is not particularly limited, and includes, for example, imidazole catalysts and phosphorus-based catalysts. These catalysts are used individually by 1 type or in combination of 2 or more types. Among these, imidazole catalysts are preferred.
- the imidazole catalyst is not particularly limited. -cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1, imidazoles such as 2-a]benzimidazole ("TBZ", a product of Shikoku Kasei Kogyo Co., Ltd.) and 2,4,5-triphenylimidazole ("TPIZ”, a product of Tokyo Kasei Kogyo Co., Ltd.);
- TZ a product of Shikoku Kasei Kogyo Co., Ltd.
- TPIZ 2,4,5-triphenylimidazole
- TPIZ a product of Tokyo Kasei Kogyo Co., Ltd.
- the amount of polymerization catalyst G (preferably imidazole catalyst) to be used is not particularly limited, and is, for example, 0.5 parts per 100 parts by mass of alkenylphenol A, epoxy-modified silicone B, epoxy compound C, and phenol compound A′. It is preferably 1 to 10 parts by mass, and from the viewpoint of increasing the weight average molecular weight of the polymer D, the amount of the polymerization catalyst G used is preferably 0.5 parts by mass or more and 4.0 parts by mass or less. is more preferable.
- the organic solvent is not particularly limited, and for example, a polar solvent or a non-polar solvent can be used.
- Polar solvents include, but are not limited to, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; cellosolve solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; ethyl lactate, methyl acetate, ethyl acetate, and acetic acid; Ester solvents such as butyl, isoamyl acetate, ethyl lactate, methyl methoxypropionate and methyl hydroxyisobutyrate; and amides such as dimethylacetamide and dimethylformamide.
- the nonpolar solvent is not particularly limited, but examples thereof include aromatic hydrocarbons such as toluene and xylene. These solvents are used singly or in combination of two or more.
- the amount of the organic solvent used is not particularly limited, and is, for example, 50 to 150 parts by mass with respect to 100 parts by mass of the total amount of alkenylphenol A, epoxy-modified silicone B, epoxy compound C, and phenol compound A'.
- the reaction temperature is not particularly limited, and may be, for example, 100-170°C.
- the reaction time is also not particularly limited, and may be, for example, 3 to 8 hours.
- polymer D may be separated and purified from the reaction mixture by a conventional method.
- thermosetting resin composition of the present embodiment may further contain other resins as long as the effects of the present embodiment are not impaired.
- Other resins include, for example, oxetane resins, benzoxazine compounds, compounds having polymerizable unsaturated groups, and the like. These resins are used singly or in combination of two or more.
- oxetane resin examples include, but are not limited to, oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, alkyloxetane such as 3,3-dimethyloxetane, 3-methyl-3-methoxy Methyloxetane, 3,3'-di(trifluoromethyl)perfluoxetane, 2-chloromethyloxetane, 3,3-bis(chloromethyl)oxetane, biphenyl type oxetane, "OXT-101" manufactured by Toagosei Co., Ltd. , “OXT-121” and the like.
- benzoxazine compound refers to a compound having two or more dihydrobenzoxazine rings in one molecule.
- benzoxazine compound examples include, but are not limited to, "Bisphenol F-type benzoxazine BF-BXZ” and "Bisphenol S-type benzoxazine BS-BXZ” manufactured by Konishi Chemical Co., Ltd., and the like.
- Examples of compounds having a polymerizable unsaturated group include, but are not limited to, vinyl compounds such as ethylene, propylene, styrene, divinylbenzene, and divinylbiphenyl; methyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate; , 2-hydroxypropyl (meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate ) monohydric or polyhydric alcohol (meth)acrylates such as acrylate; epoxy (meth)acrylates such as bisphenol A type epoxy (meth)acrylate and bisphenol F type epoxy (meth)acrylate; benzocyclobutene resin, etc. be done.
- vinyl compounds such as ethylene,
- the thermosetting resin composition in the present embodiment preferably further contains an aromatic phosphorus compound P from the viewpoint of further improving low thermal expansion properties.
- the aromatic phosphorus compound P is not particularly limited as long as it contains a phosphorus atom in its molecule and exhibits aromaticity.
- the aromatic phosphorus compound P is at least selected from the group consisting of cyclic phosphazene compounds, phosphate ester compounds, phosphite ester compounds and phosphaphenanthrene compounds. It is preferred that one species is included.
- the aromatic phosphorus compound P more preferably contains at least one selected from the group consisting of a cyclic phosphazene compound, a phosphate ester compound, and a phosphite ester compound from the viewpoint of further improving low thermal expansion properties. , a cyclic phosphazene compound and a phosphate ester compound.
- the aromatic phosphorus compound P is represented by the following formulas (P1) and (P2) , (P3) or (P4).
- P1 and P2 represent a substituted or unsubstituted aryl group
- Ph1, Ph2 and Ph3 may be the same or different.
- P2 Ph1 and Ph2 represent a substituted or unsubstituted aryl group
- the Ph1 and Ph2 may be the same or different
- R is an alkyl group having 1 to 30 carbon atoms. or represents an aryl group having 6 to 30 carbon atoms.
- A is each independently a hydrogen atom, a methyl group, a hydroxyl group, a cyano group, an amino group, a carboxyl group, a glycidyloxy group, a parahydroxyphenyldimethyl group, a paraglycidyloxyphenyldimethyl group.
- R represents a hydrogen atom, an alkyl group having 2 to 30 carbon atoms, or a substituted or unsubstituted aryl group.
- the aromatic phosphorus compound P is an aromatic phosphorus compound P′ represented by the following formula (P5). ' is preferably included.
- the content of the aromatic phosphorus compound P in the thermosetting resin composition in the present embodiment is 3 to 15 parts by mass with respect to 100 parts by mass of the resin solid content, from the viewpoint of achieving well-balanced heat resistance and low thermal expansion. parts, more preferably 3 to 12 parts by mass, even more preferably 4 to 10 parts by mass.
- the thermosetting resin composition in the present embodiment preferably further contains an inorganic filler from the viewpoint of further improving the low thermal expansion property.
- the inorganic filler is not particularly limited, and examples thereof include silicas, silicon compounds (e.g., white carbon, etc.), metal oxides (e.g., alumina, titanium white, zinc oxide, magnesium oxide, zirconium oxide, etc.), metal nitrides.
- boron nitride aggregated boron nitride, silicon nitride, aluminum nitride, etc.
- metal sulfates e.g., barium sulfate, etc.
- metal hydroxides e.g., aluminum hydroxide, aluminum hydroxide heat-treated products (e.g., aluminum hydroxide heat-treated to reduce a portion of the water of crystallization), boehmite, magnesium hydroxide, etc.
- molybdenum compounds e.g., molybdenum oxide, zinc molybdate, etc.
- zinc compounds e.g., zinc borate, zinc stannate, etc.
- the inorganic filler is preferably at least one selected from the group consisting of silicas, metal hydroxides and metal oxides, from the viewpoint of further improving low thermal expansion properties. Silicas, boehmite and alumina, and more preferably silicas.
- silicas examples include natural silica, fused silica, synthetic silica, aerosil, and hollow silica. These silicas are used individually by 1 type or in combination of 2 or more types. Among these, fused silica is preferable from the viewpoint of dispersibility, and two or more types of fused silica having different particle sizes are more preferable from the viewpoint of filling properties and fluidity.
- the content of the inorganic filler is preferably 50 to 1000 parts by mass, more preferably 70 to 500 parts by mass, based on 100 parts by mass of the resin solid content, from the viewpoint of further improving the low thermal expansion property. , more preferably 100 to 300 parts by mass.
- thermosetting resin composition in this embodiment may further contain a silane coupling agent.
- a silane coupling agent By containing a silane coupling agent, the thermosetting resin composition further improves the dispersibility of the inorganic filler, and further increases the adhesive strength between the components of the thermosetting resin composition and the substrate described later. It tends to improve.
- the silane coupling agent is not particularly limited, and includes silane coupling agents generally used for surface treatment of inorganic substances, aminosilane compounds (eg, ⁇ -aminopropyltriethoxysilane, N- ⁇ -(aminoethyl) - ⁇ -aminopropyltrimethoxysilane, etc.), epoxysilane compounds (eg, ⁇ -glycidoxypropyltrimethoxysilane, etc.), acrylsilane compounds (eg, ⁇ -acryloxypropyltrimethoxysilane, etc.), cationic Examples include silane compounds (eg, N- ⁇ -(N-vinylbenzylaminoethyl)- ⁇ -aminopropyltrimethoxysilane hydrochloride), styrylsilane compounds, phenylsilane compounds, and the like.
- aminosilane compounds eg, ⁇ -aminopropyltriethoxysilane, N-
- a silane coupling agent is used individually by 1 type or in combination of 2 or more types.
- the silane coupling agent is preferably an epoxysilane compound.
- epoxysilane compounds include Shin-Etsu Chemical Co., Ltd. products "KBM-403", “KBM-303", “KBM-402”, and "KBE-403".
- the content of the silane coupling agent is not particularly limited, but may be 0.1 to 5.0 parts by mass with respect to 100 parts by mass of the resin solid content.
- thermosetting resin composition in this embodiment may further contain a wetting and dispersing agent.
- the thermosetting resin composition tends to further improve the dispersibility of the filler by containing a wetting and dispersing agent.
- any known dispersing agent used to disperse the filler may be used. 161, BYK-W996, W9010, W903 and the like.
- the content of the wetting and dispersing agent is not particularly limited, it is preferably 0.5 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the resin solid content.
- thermosetting resin composition in this embodiment may further contain a solvent.
- a solvent By containing a solvent, the thermosetting resin composition has a lower viscosity during preparation of the thermosetting resin composition, further improving the handling property (handleability), and further improving the impregnating property into the substrate. tend to fall.
- the solvent is not particularly limited as long as it can dissolve some or all of the components in the thermosetting resin composition, but examples include ketones (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbons (e.g., toluene, xylene, etc.), amides (eg, dimethylformaldehyde, etc.), propylene glycol monomethyl ether and its acetate, and the like. These solvents are used singly or in combination of two or more.
- the method for producing the thermosetting resin composition in the present embodiment is not particularly limited, and includes, for example, a method of collectively or sequentially blending each component with a solvent and stirring the mixture. At this time, in order to uniformly dissolve or disperse each component, known treatments such as stirring, mixing, and kneading are used.
- thermosetting resin composition a contains the epoxy compound C, the compound E and the inorganic filler (such a thermosetting resin composition is hereinafter also referred to as “thermosetting resin composition a”).
- the thermosetting resin composition a preferably has the following physical properties. That is, a thermosetting resin composition a containing an epoxy compound C, a compound E and an inorganic filler, and a cured product a for evaluation obtained by subjecting the thermosetting resin composition a to the following test, It is preferable to satisfy the conditions (1a) to (4a).
- thermosetting resin composition a A composite of the thermosetting resin composition a and an S glass woven fabric as a base material, wherein the content of the thermosetting resin composition in the composite is 40 to 80% by volume. prepare. This mixture is thermally cured at 155-165° C. for 5 minutes to obtain a composite. Next, two sheets of this composite were stacked, and further electrodeposited copper foils having a thickness of 12 ⁇ m were arranged above and below, and lamination molding was performed at a pressure of 30 kgf/cm 2 and a temperature of 230° C. for 100 minutes to obtain a thickness of 0.22 mm. A test copper foil clad laminate is obtained, which includes an insulating layer having a thickness.
- Condition (1a) The loss elastic modulus of the cured product a for evaluation measured by the DMA method according to JIS C6481 (1996) has a maximum point at 200° C. or higher.
- Condition (3a) The ratio of the loss elastic modulus L′(150) of the cured product a for evaluation at 150° C. measured by the DMA method to the L′(max) is L′(150)/L′ (max) is 0.60 or more.
- Condition (4a) The ratio of the loss elastic modulus L'(200) of the cured product a for evaluation at 200°C measured by the DMA method to the L'(max) is L'(200)/L' (max) is 0.70 or more.
- thermosetting resin composition a can be said to be one aspect of the thermosetting resin composition in the above-described present embodiment, and includes the epoxy compound C, the compound E, and the inorganic filler as essential, except that the above-described present A configuration similar to that of the thermosetting resin composition in the embodiment can be adopted.
- the cured product for evaluation a has (1a) excellent heat resistance because the loss elastic modulus of the cured product for evaluation a measured by the DMA method in accordance with JIS C6481 (1996) has a maximum point at 200°C or higher.
- the loss elastic modulus of the cured product a for evaluation preferably has a maximum point at 240 ° C. or higher, more preferably has a maximum point at 250 ° C. or higher, and has a maximum point at 260 ° C. or higher. More preferably, it may have a maximum point at 270° C. or higher.
- the temperature of the maximum point of the loss elastic modulus may be a higher value, and is not particularly limited. For example, the loss elastic modulus may have a maximum point at 290° C. or higher.
- the cured product for evaluation a has (2a) a loss elastic modulus L′ (100) of the cured product for evaluation at 100° C. measured by the DMA method, and a loss elastic modulus L of the cured product for evaluation at the maximum point.
- '(max) is 0.70 or more as L'(100)/L'(max), so it is excellent in low thermal expansion.
- L'(100)/L'(max) is preferably 0.71 or more, more preferably 0.73 or more.
- the L'(100)/L'(max) may be a higher value, and is not particularly limited.
- the L'(100)/L'(max) is 0.90, 0.95 There may be.
- L' ( 150)/L'(max) the ratio of the loss elastic modulus L' (150) of the evaluation cured product a at 150 ° C. measured by the DMA method to the L' (max) is L' ( 150)/L'(max) is 0.60 or more, so it is excellent in low thermal expansion.
- L'(150)/L'(max) is preferably 0.65 or more, more preferably 0.68 or more.
- the L'(150)/L'(max) may be a higher value, and is not particularly limited. For example, the L'(150)/L'(max) is 0.85, 0.90 There may be.
- the ratio of the loss elastic modulus L '(200) of the evaluation cured product a at 200 ° C. measured by the DMA method and the L ' (max) is L ' ( 200)/L'(max) is 0.70 or more, so it is excellent in low thermal expansion.
- L'(200)/L'(max) is preferably 0.71 or more, more preferably 0.75 or more.
- the L'(200)/L'(max) may be a higher value, and is not particularly limited. For example, the L'(200)/L'(max) may be 0.95. .
- the loss elastic modulus L'(max), the loss elastic modulus L'(100), the loss elastic modulus L'(150), and the loss elastic modulus L'(200) in the present embodiment are described later. It can be measured by the method described in the examples.
- the above-described aromatic phosphorus compound P, alkenylphenol A, epoxy-modified silicone B, and epoxy other than the epoxy-modified silicone B are used as components of the evaluation cured product a.
- the polymer D and / or the compound E especially by reducing the functional group equivalent ratio (cyanate equivalent / epoxy equivalent) of the cyanate group and the epoxy group in the cured product for evaluation a, loss elasticity
- the modulus L'(max), the loss modulus L'(100), the loss modulus L'(150) and the loss modulus L'(200) can be preferably adjusted within the ranges described above. From the above viewpoint, in the present embodiment, the value of cyanate equivalent/epoxy equivalent is preferably less than 0.8.
- the loss elastic modulus L' (max), the loss elastic modulus L' (100), the loss elastic modulus L' (150) and the loss elastic modulus L' (200) can be controlled, and Without adjusting the value of cyanate equivalent/epoxy equivalent, for example, an aromatic phosphorus compound P, alkenylphenol A, epoxy-modified silicone B, an epoxy compound C other than the epoxy-modified silicone B, polymer D and compound E can be combined appropriately.
- loss elastic modulus L'(max), loss elastic modulus L'(100), loss elastic modulus L'(150) and loss elastic modulus L'(200) can be controlled.
- thermosetting resin composition in the present embodiment can exhibit excellent low thermal expansion properties as described above. Therefore, by using the thermosetting resin composition of the present embodiment, it is possible to obtain the prepreg of the present embodiment having excellent low thermal expansion properties.
- the thermosetting resin composition of the present embodiment can also be applied to uses other than prepreg, taking advantage of its excellent low thermal expansion properties. Specific examples thereof include a resin sheet containing the above-described thermosetting resin composition a.
- a metal foil-clad laminate or a printed wiring board can be obtained by performing predetermined processing using the prepreg and resin sheet of the present embodiment. That is, the thermosetting resin composition in the present embodiment is also suitably used as a metal foil-clad laminate and a printed wiring board.
- the second composition contains, in addition to the polymer D and the aromatic phosphorus compound P, at least an epoxy compound C (polymer It preferably contains an epoxy compound C) which is present separately from the constituent unit C in D.
- the polymer D preferably has units derived from the bifunctional epoxy compound described above as units derived from the epoxy compound C, and more preferably has units derived from the biphenyl type epoxy resin described above.
- the epoxy compound C present separately from the structural unit C in the polymer D the above-mentioned naphthylene ether type epoxy resin (commercially available products, for example, "HP-6000” manufactured by DIC Corporation) and / Or naphthalene cresol novolak type epoxy resin (commercially available, for example, "HP-9540" manufactured by DIC Corporation) is preferably included.
- the cyanate equivalent/epoxy equivalent value in the second composition is less than 0.8.
- the cyanate equivalent/epoxy equivalent (functional group equivalent ratio) is the equivalent of the cyanate group in the cyanate ester compound that may be contained in the second composition, and the "polymer D It is the equivalent ratio of the epoxy group in the epoxy compound C that exists separately from the structural unit C in the inside, and is calculated by the following formula (1). In the present embodiment, it is possible to use two or more types of either the cyanate ester compound or the epoxy compound.
- the number of functional groups (that is, the equivalent weight of cyanate groups and the equivalent weight of epoxy groups) is calculated, and these values are summed up to calculate the equivalent weight of all cyanate groups and the equivalent weight of all epoxy groups.
- the functional group equivalent ratio is a value obtained by dividing the equivalent weight of all cyanate groups by the equivalent weight of all epoxy groups.
- the number of functional groups is a value obtained by dividing the parts by mass of a component by the functional group equivalent of the component.
- the resin sheet of the present embodiment contains the thermosetting resin composition a, and may be a laminated resin sheet having a support or a single-layer resin sheet having no support.
- the laminated resin sheet of this embodiment has a support and a thermosetting resin composition a disposed on one side or both sides of the support.
- the method for producing the laminated resin sheet is not particularly limited, and for example, it can be produced by coating a support with a solution obtained by diluting the thermosetting resin composition a with a solvent and drying the sheet.
- Examples of the support used here include polyethylene film, polypropylene film, polycarbonate film, polyethylene terephthalate film, ethylene tetrafluoroethylene copolymer film, and a release film obtained by applying a release agent to the surface of these films,
- Examples include organic film substrates such as polyimide films, conductor foils such as copper foil and aluminum foil, and plate-like substrates such as glass plates, SUS plates, and FRP, but are not particularly limited thereto.
- Examples of the coating method include a method in which a solution obtained by diluting the thermosetting resin composition a with a solvent is coated on the support with a bar coater, die coater, doctor blade, baker applicator, or the like.
- the single-layer resin sheet of the present embodiment is obtained by molding the thermosetting resin composition a into a sheet. That is, the single-layer resin sheet of this embodiment contains the thermosetting resin composition a.
- the method for producing the single-layer resin sheet is not particularly limited. A method of peeling or etching the support from the resin sheet can be used.
- a solution obtained by diluting the thermosetting resin composition a with a solvent is supplied into a mold having a sheet-shaped cavity and dried to form a sheet, so that a single layer can be obtained without using a support.
- a resin sheet (resin sheet) can also be obtained.
- the drying conditions for removing the solvent are not particularly limited.
- a temperature of 20° C. to 170° C. and a time of 1 to 90 minutes are preferable because the curing of the composition proceeds.
- the thickness of the resin layer of the single layer or laminated sheet of the present embodiment can be adjusted by the concentration of the solution of the thermosetting resin composition a and the coating thickness, and is not particularly limited, but generally the coating thickness
- the thickness is preferably 0.1 to 500 ⁇ m because the solvent tends to remain during drying as the thickness increases.
- the metal foil-clad laminate of the present embodiment includes a laminate containing the prepreg of the present embodiment and/or the cured product of the present embodiment, and metal foil arranged on one side or both sides of the laminate.
- the laminate may contain one prepreg and/or cured product, or may contain a plurality of prepregs and/or cured products.
- the metal foil may be any metal foil that is used for various printed wiring board materials, and examples thereof include metal foils of copper, aluminum, and the like. Copper foil, such as foil, is mentioned.
- the thickness of the conductor layer is, for example, 1 to 70 ⁇ m, preferably 1.5 to 35 ⁇ m.
- the molding method and molding conditions for the metal foil-clad laminate are not particularly limited, and general techniques and conditions for printed wiring board laminates and multilayer boards can be applied.
- a multistage press machine, a multistage vacuum press machine, a continuous molding machine, an autoclave molding machine, or the like can be used when molding a laminate (laminate described above) or a metal foil-clad laminate.
- the temperature is 100 to 300° C.
- the pressure is 2 to 100 kgf/cm 2
- the heating time is 0.05 to 5. Time ranges are common.
- post-curing can be performed at a temperature of 150-300°C.
- the temperature is preferably 200° C. to 250° C.
- the pressure is 10 to 40 kgf/cm 2
- the heating time is 80 minutes to 130 minutes
- the temperature is 215° C. to 215° C., from the viewpoint of sufficiently accelerating the curing of the prepreg.
- the temperature is 235° C.
- the pressure is 25 to 35 kgf/cm 2
- the heating time is 90 to 120 minutes.
- the printed wiring board of this embodiment has an insulating layer containing the cured product of this embodiment, and a conductor layer formed on the surface of the insulating layer.
- the printed wiring board of the present embodiment can be formed, for example, 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.
- the printed wiring board of the present embodiment can be manufactured, for example, by the following method.
- An inner layer board having a conductor layer (inner layer circuit) is produced by etching the metal foil of the metal foil clad laminate into a predetermined wiring pattern.
- a laminate is obtained.
- the laminate molding method and molding conditions are the same as the laminate molding method and molding conditions for the laminate and the metal foil-clad laminate described above.
- the laminate is perforated for through holes and via holes, and the wall surfaces of the holes thus formed are plated with a metal film for conducting the conductor layer (internal circuit) and the metal foil for the outer layer circuit.
- the metal foil for the outer layer circuit is etched into a predetermined wiring pattern to form an outer layer substrate having a conductor layer (outer layer circuit). A printed wiring board is thus manufactured.
- a printed wiring board may be produced by forming a conductor layer that becomes a circuit on the insulating layer. At this time, an electroless plating technique can be used to form the conductor layer.
- the electrical conductivity of the wastewater after the fifth washing was 5 ⁇ S/cm, and it was confirmed that the ionic compounds that could be removed were sufficiently removed by washing with water.
- the organic phase after washing with water is concentrated under reduced pressure and finally concentrated to dryness at 90° C. for 1 hour to obtain the desired 1-naphthol aralkyl cyanate ester compound (SN495V-CN, cyanate group equivalent: 261 g/eq. ) (orange viscous substance) 331 g were obtained.
- the infrared absorption spectrum of the obtained SN495V-CN showed absorption at 2250 cm -1 (cyanate group) and no absorption of hydroxy group.
- R 2a represents a hydrogen atom and m represents an integer of 1 to 10.
- Example 1 In a three-necked flask equipped with a thermometer and a Dimroth, 5.0 parts by mass of diallyl bisphenol A (DABPA, Daiwa Kasei Kogyo Co., Ltd.), 5.4 parts by mass of biscresol fluorene (BCF, Osaka Gas Chemical Co., Ltd.), epoxy Modified silicone b1 (X-22-163, Shin-Etsu Chemical Co., Ltd., functional group equivalent 200 g / mol) 3.7 parts, epoxy-modified silicone b2 (KF-105, Shin-Etsu Chemical Co., Ltd., functional group equivalent 490 g /mol) 11.0 parts by mass, biphenyl type epoxy resin c1 (YL-6121H, Mitsubishi Chemical Corporation) 4.9 parts by mass, propylene glycol monomethyl ether acetate (DOWANOL PMA, Dow Chemical Japan Co., Ltd.) as a solvent 30 parts by mass was added, and the mixture was heated and stirred to 120° C.
- diallyl bisphenol A corresponds to "alkenylphenol A”
- epoxy-modified silicone b1 and epoxy-modified silicone b2 correspond to "epoxy-modified silicone B”
- biphenyl type epoxy resin c1 corresponds to "epoxy compound C”.
- the phenoxy polymer solution contained a polymer D containing a structural unit derived from alkenylphenol A, a structural unit derived from epoxy-modified silicone B, and a structural unit derived from epoxy compound C.
- polymer D is also referred to as phenoxy polymer.
- the content of structural unit B with respect to polymer D was 48.8% by mass.
- the content of structural unit C with respect to the total amount of structural unit B and structural unit C was 25% by mass.
- the weight average molecular weight Mw of the phenoxy polymer obtained as described above was measured as follows. Analysis was performed by injecting 20 ⁇ L of a solution obtained by dissolving 0.5 g of the phenoxy polymer solution in 2 g of THF into a high-performance liquid chromatography (manufactured by Shimadzu Corporation, pump: LC-20AD). The columns were Shodex GPC KF-804 (length 30 cm x inner diameter 8 mm) manufactured by Showa Denko, Shodex GPC KF-803 (length 30 cm x inner diameter 8 mm), Shodex GPC KF-802 (length 30 cm x inner diameter 8 mm), Shodex GPC.
- the weight average molecular weight Mw was obtained by GPC method using standard polystyrene as a standard substance.
- the weight average molecular weight Mw of the phenoxy polymer measured as described above was 12,000.
- naphthalene cresol novolak type epoxy resin HP-9540, DIC Corporation, functional group equivalent 244 g/mol
- phenol novolak type cyanate ester compound PT-30, Lonza, functional group equivalent 127 g/mol) mol
- phosphate ester compound PX-200, Daihachi Chemical Industry Co., Ltd.
- slurry silica as filler SC-2050MB, Admatechs Co., Ltd.
- wet dispersion A varnish was obtained by mixing 1 part by mass of an agent (DISPERBYK-161, BYK-Chemie Japan Co., Ltd.) and 5 parts by mass of a silane coupling agent (KBM-403, Shin-Etsu Chemical Co., Ltd.) (varnish production step).
- thermosetting resin composition solid content (including filler) was 58.2% by volume. of prepreg was obtained (prepreg manufacturing process).
- Example 2 A prepreg having a thermosetting resin composition solid content (including filler) content of 58.2% by volume was obtained in the same manner as in Example 1, except for the following points. That is, 14 parts by mass of SN495V-CN was used instead of PT-30 in the varnish production step.
- Example 3 A prepreg having a thermosetting resin composition solid content (including filler) content of 58.2% by volume was obtained in the same manner as in Example 1, except for the following points. That is, in the varnish production step, the amount of BMI-2300 used was changed to 16.5 parts by mass, the amount of BMI-80 used was changed to 5.5 parts by mass, and 15 parts of SN495V-CN was used instead of PT-30. The amount of HP-9540 was changed to 28 parts by mass, the amount of PX-200 was changed to 5 parts by mass, and the amount of SC-2050MB was changed to 200 parts by mass. Furthermore, in the prepreg manufacturing process, the heat drying conditions were changed to 155° C. for 5 minutes.
- Example 4 A prepreg having a thermosetting resin composition solid content (including filler) content of 58.2% by volume was obtained in the same manner as in Example 2, except for the following points. That is, in the varnish production step, the amount of SC-2050MB used was changed to 200 parts by mass. Furthermore, in the prepreg manufacturing process, the heat drying conditions were changed to 155° C. for 5 minutes.
- Example 5 A prepreg having a thermosetting resin composition solid content (including filler) content of 58.2% by volume was obtained in the same manner as in Example 4, except for the following points. That is, in the varnish production step, 30 parts by mass of a naphthylene ether type epoxy resin (HP-6000, DIC Corporation, functional group equivalent: 250 g/mol) is used instead of HP-9540, and the amount of SN495V-CN used is reduced to was changed to 15 parts by mass, and the amount of PX-200 used was changed to 5 parts by mass.
- a naphthylene ether type epoxy resin HP-6000, DIC Corporation, functional group equivalent: 250 g/mol
- Example 6 A prepreg having a thermosetting resin composition solid content (including filler) content of 58.2% by volume was obtained in the same manner as in Example 3, except for the following points. That is, in the varnish production process, the amount of BMI-2300 used was changed to 16 parts by mass, the amount of HP-9540 used was changed to 32.5 parts by mass, and the amount of SN495V-CN used was changed to 16 parts by mass. , PX-200 was not used.
- thermosetting resin composition solid content (including filler) content of 58.2% by volume was obtained in the same manner as in Example 1, except for the following points. That is, in the varnish production step, the amount of HP-9540 used was changed to 32 parts by mass, the amount of PT-30 used was changed to 18 parts by mass, and PX-200 was not used.
- thermosetting resin composition solid content (including filler) content of 58.2% by volume was obtained in the same manner as in Comparative Example 1, except for the following points. That is, in the prepreg manufacturing process, the heat drying conditions were changed to 155° C. for 5 minutes.
- thermosetting resin composition solid content (including filler) content of 58.2% by volume was obtained in the same manner as in Example 1, except for the following points. That is, in the varnish production process, the phenoxy polymer solution was not used, the amount of BMI-2300 used was changed to 24.6 parts by mass, BMI-80 was not used, and HP-6000 was replaced with 38 parts of HP-9540. .6 parts by mass were used, 36.8 parts by mass of SN495V-CN was used instead of PT-30, the amount of SC-2050MB was changed to 200 parts by mass, and PX-200 was not used.
- thermosetting resin composition solid content (including filler) content of 58.2% by volume was obtained in the same manner as in Example 1, except for the following points. That is, in the varnish production step, the amount of BMI-2300 used was changed to 17 parts by mass, BMI-80 was not used, 27 parts by mass of HP-6000 was used in place of HP-9540, and PT-30 was replaced with SN495V-CN was used in an amount of 26 parts by mass, and PX-200 was not used.
- thermosetting resin composition solid content (including filler) content of 58.2% by volume was obtained in the same manner as in Comparative Example 3, except for the following points. That is, in the varnish production step, the amount of BMI-2300 used was changed to 20 parts by mass, the amount of HP-6000 used was changed to 35 parts by mass, the amount of SN495V-CN used was changed to 30 parts by mass, and SC The amount of -2050MB used was changed to 140 parts by mass, and 15 parts by mass of silicone acrylic graft (US-350, Toagosei Co., Ltd.) was used as the low-elasticity component. Furthermore, in the prepreg manufacturing process, the heat drying conditions were changed to 140° C. for 3 minutes.
- thermosetting resin composition solid content (including filler) content of 58.2% by volume was obtained in the same manner as in Comparative Example 5, except for the following points. That is, in the varnish production step, 15 parts by mass of an acrylic resin (SG-80H, Nagase ChemteX Corporation) was used as a low-elasticity component instead of US-350.
- thermosetting resin composition solid content (including filler) content of 58.2% by volume was obtained in the same manner as in Comparative Example 5, except for the following points. That is, in the varnish production step, 15 parts by mass of a silicone resin (KR-480, Shin-Etsu Chemical Co., Ltd.) was used as a low-elasticity component instead of US-350. Furthermore, in the prepreg manufacturing process, the heat drying conditions were changed to 150° C. for 3 minutes.
- the loss elastic modulus E'' is measured by the DMA method using a dynamic viscoelasticity analyzer (manufactured by TA Instruments) in accordance with JIS C6481 (1996). ' was defined as Tg (unit: °C). Also, the loss elastic modulus L (max) at the maximum point, the loss elastic modulus L (100) at 100 ° C., the loss elastic modulus L (150) at 150 ° C. and the loss elastic modulus L (200) obtained by the measurement From the values, L(100)/L(max), L(150)/L(max) and L(200)/L(max) were calculated respectively.
- the present invention has industrial applicability as prepregs, metal foil-clad laminates, printed wiring boards, and the like.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
Abstract
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202280054648.XA CN117836359A (zh) | 2021-08-05 | 2022-08-04 | 预浸料、覆金属箔层叠板及印刷电路板 |
JP2022573361A JP7276674B1 (ja) | 2021-08-05 | 2022-08-04 | プリプレグ、金属箔張積層板及びプリント配線板 |
KR1020247003101A KR20240043744A (ko) | 2021-08-05 | 2022-08-04 | 프리프레그, 금속박 피복 적층판 및 프린트 배선판 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2021128706 | 2021-08-05 | ||
JP2021-128706 | 2021-08-05 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2023013710A1 true WO2023013710A1 (fr) | 2023-02-09 |
Family
ID=85156010
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2022/029870 WO2023013710A1 (fr) | 2021-08-05 | 2022-08-04 | Préimprégné, stratifié revêtu d'une feuille métallique, et carte de circuit imprimé |
Country Status (5)
Country | Link |
---|---|
JP (1) | JP7276674B1 (fr) |
KR (1) | KR20240043744A (fr) |
CN (1) | CN117836359A (fr) |
TW (1) | TWI819735B (fr) |
WO (1) | WO2023013710A1 (fr) |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014061812A1 (fr) * | 2012-10-19 | 2014-04-24 | 三菱瓦斯化学株式会社 | Composition de résine, pré-imprégné, stratifié, et tableau de connexions imprimé |
WO2017006898A1 (fr) * | 2015-07-06 | 2017-01-12 | 三菱瓦斯化学株式会社 | Composition de résine, pré-imprégné, feuille de résine, plaque stratifiée recouverte d'une feuille métallique, et carte de circuit imprimé |
WO2018074278A1 (fr) * | 2016-10-17 | 2018-04-26 | パナソニックIpマネジメント株式会社 | Composition de résine, procédé de production d'une composition de résine, préimprégné, film avec résine, feuille métallique avec résine, stratifié à revêtement métallique, et carte de câblage |
WO2018124161A1 (fr) * | 2016-12-28 | 2018-07-05 | 三菱瓦斯化学株式会社 | Composition de résine de carte de circuit imprimé, préimprégné, feuille de résine, plaque stratifiée, plaque stratifiée avec gainage de feuille métallique, carte de circuit imprimé, et carte de circuit imprimé multicouche |
WO2019203291A1 (fr) * | 2018-04-20 | 2019-10-24 | 三菱瓦斯化学株式会社 | Composition thermodurcissable, préimprégné, stratifié, stratifié revêtu d'une feuille métallique, carte de circuit imprimé et carte de circuit imprimé multicouche |
WO2020022084A1 (fr) * | 2018-07-26 | 2020-01-30 | 三菱瓦斯化学株式会社 | Composition durcissable, préimprégné, feuille de résine, stratifié plaqué d'une feuille métallique et carte de circuit imprimé |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110121530B (zh) * | 2016-12-28 | 2022-02-11 | 三菱瓦斯化学株式会社 | 树脂组合物、预浸料、层叠板、覆金属箔层叠板、印刷电路板、及多层印刷电路板 |
US20220162408A1 (en) * | 2019-03-26 | 2022-05-26 | Toray Industries, Inc. | Fiber-reinforced resin base material |
CN115996989A (zh) * | 2020-06-24 | 2023-04-21 | 松下知识产权经营株式会社 | 树脂组合物、预浸料、具有树脂的膜、具有树脂的金属箔、覆金属层压体和印刷线路板 |
-
2022
- 2022-08-04 KR KR1020247003101A patent/KR20240043744A/ko unknown
- 2022-08-04 CN CN202280054648.XA patent/CN117836359A/zh active Pending
- 2022-08-04 JP JP2022573361A patent/JP7276674B1/ja active Active
- 2022-08-04 WO PCT/JP2022/029870 patent/WO2023013710A1/fr active Application Filing
- 2022-08-05 TW TW111129470A patent/TWI819735B/zh active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014061812A1 (fr) * | 2012-10-19 | 2014-04-24 | 三菱瓦斯化学株式会社 | Composition de résine, pré-imprégné, stratifié, et tableau de connexions imprimé |
WO2017006898A1 (fr) * | 2015-07-06 | 2017-01-12 | 三菱瓦斯化学株式会社 | Composition de résine, pré-imprégné, feuille de résine, plaque stratifiée recouverte d'une feuille métallique, et carte de circuit imprimé |
WO2018074278A1 (fr) * | 2016-10-17 | 2018-04-26 | パナソニックIpマネジメント株式会社 | Composition de résine, procédé de production d'une composition de résine, préimprégné, film avec résine, feuille métallique avec résine, stratifié à revêtement métallique, et carte de câblage |
WO2018124161A1 (fr) * | 2016-12-28 | 2018-07-05 | 三菱瓦斯化学株式会社 | Composition de résine de carte de circuit imprimé, préimprégné, feuille de résine, plaque stratifiée, plaque stratifiée avec gainage de feuille métallique, carte de circuit imprimé, et carte de circuit imprimé multicouche |
WO2019203291A1 (fr) * | 2018-04-20 | 2019-10-24 | 三菱瓦斯化学株式会社 | Composition thermodurcissable, préimprégné, stratifié, stratifié revêtu d'une feuille métallique, carte de circuit imprimé et carte de circuit imprimé multicouche |
WO2020022084A1 (fr) * | 2018-07-26 | 2020-01-30 | 三菱瓦斯化学株式会社 | Composition durcissable, préimprégné, feuille de résine, stratifié plaqué d'une feuille métallique et carte de circuit imprimé |
Also Published As
Publication number | Publication date |
---|---|
KR20240043744A (ko) | 2024-04-03 |
CN117836359A (zh) | 2024-04-05 |
JP7276674B1 (ja) | 2023-05-18 |
JPWO2023013710A1 (fr) | 2023-02-09 |
TWI819735B (zh) | 2023-10-21 |
TW202313835A (zh) | 2023-04-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP7488513B2 (ja) | 硬化性組成物、プリプレグ、レジンシート、金属箔張積層板及びプリント配線板 | |
JP7274105B2 (ja) | 熱硬化性組成物、プリプレグ、積層板、金属箔張積層板、プリント配線板及び多層プリント配線板 | |
JP7307896B2 (ja) | 熱硬化性組成物、プリプレグ、積層板、金属箔張積層板、プリント配線板及び多層プリント配線板 | |
JP7276674B1 (ja) | プリプレグ、金属箔張積層板及びプリント配線板 | |
JP7428981B2 (ja) | 硬化性組成物、プリプレグ、レジンシート、金属箔張積層板及びプリント配線板 | |
JP7411170B2 (ja) | 硬化性組成物、プリプレグ、レジンシート、金属箔張積層板及びプリント配線板 | |
JP7284945B1 (ja) | 硬化性組成物、プリプレグ、金属箔張積層板、及びプリント配線板 | |
JP7449498B2 (ja) | 硬化性組成物、プリプレグ、金属箔張積層板及びプリント配線板 | |
WO2023013711A1 (fr) | Composition de résine thermodurcissable, préimprégné, et carte de circuits imprimés |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
ENP | Entry into the national phase |
Ref document number: 2022573361 Country of ref document: JP Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 22853128 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 202280054648.X Country of ref document: CN Ref document number: 2401000738 Country of ref document: TH |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 22853128 Country of ref document: EP Kind code of ref document: A1 |