JP6890123B2 - Resin composition for printed wiring board and resin sheet for printed wiring board using it - Google Patents
Resin composition for printed wiring board and resin sheet for printed wiring board using it Download PDFInfo
- Publication number
- JP6890123B2 JP6890123B2 JP2018520909A JP2018520909A JP6890123B2 JP 6890123 B2 JP6890123 B2 JP 6890123B2 JP 2018520909 A JP2018520909 A JP 2018520909A JP 2018520909 A JP2018520909 A JP 2018520909A JP 6890123 B2 JP6890123 B2 JP 6890123B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- printed wiring
- wiring board
- mass
- resin composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920005989 resin Polymers 0.000 title claims description 99
- 239000011347 resin Substances 0.000 title claims description 99
- 239000011342 resin composition Substances 0.000 title claims description 77
- -1 Maleimide compound Chemical class 0.000 claims description 40
- 239000003822 epoxy resin Substances 0.000 claims description 40
- 229920000647 polyepoxide Polymers 0.000 claims description 40
- 239000004925 Acrylic resin Substances 0.000 claims description 32
- 229920000178 Acrylic resin Polymers 0.000 claims description 32
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- 239000011888 foil Substances 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- 239000011256 inorganic filler Substances 0.000 claims description 17
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 17
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 9
- 235000010290 biphenyl Nutrition 0.000 claims description 7
- 239000004305 biphenyl Substances 0.000 claims description 7
- 125000003700 epoxy group Chemical group 0.000 claims description 6
- 239000004744 fabric Substances 0.000 claims description 5
- 230000001588 bifunctional effect Effects 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 61
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 30
- 239000011889 copper foil Substances 0.000 description 30
- 239000006087 Silane Coupling Agent Substances 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- 238000000034 method Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical group CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 238000010030 laminating Methods 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
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- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
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- 230000002265 prevention Effects 0.000 description 4
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- 230000003746 surface roughness Effects 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-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
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 239000011354 acetal resin Substances 0.000 description 3
- 239000004760 aramid Substances 0.000 description 3
- 229920003235 aromatic polyamide Polymers 0.000 description 3
- 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 3
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 3
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- 238000009826 distribution Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 229920006324 polyoxymethylene Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000002759 woven fabric Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical group C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 101001134276 Homo sapiens S-methyl-5'-thioadenosine phosphorylase Proteins 0.000 description 2
- 229920000106 Liquid crystal polymer Polymers 0.000 description 2
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 2
- 102100022050 Protein canopy homolog 2 Human genes 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides 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
- 125000003277 amino 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
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 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 2
- 238000009413 insulation Methods 0.000 description 2
- 229920006284 nylon film Polymers 0.000 description 2
- 239000011112 polyethylene naphthalate Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
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- 239000010935 stainless steel Substances 0.000 description 2
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- 239000002335 surface treatment layer Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 1
- POFFJVRXOKDESI-UHFFFAOYSA-N 1,3,5,7-tetraoxa-4-silaspiro[3.3]heptane-2,6-dione Chemical compound O1C(=O)O[Si]21OC(=O)O2 POFFJVRXOKDESI-UHFFFAOYSA-N 0.000 description 1
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- FBHPRUXJQNWTEW-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=CN1CC1=CC=CC=C1 FBHPRUXJQNWTEW-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
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- 230000002159 abnormal effect Effects 0.000 description 1
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- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
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- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
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- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
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- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate group Chemical group [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
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- 150000004985 diamines Chemical class 0.000 description 1
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- 125000002897 diene group Chemical group 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical group C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
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- 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
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- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
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- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
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- 239000004014 plasticizer Substances 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
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- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000002966 varnish Substances 0.000 description 1
- 238000004804 winding Methods 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
Classifications
-
- 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
-
- 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
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
-
- 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
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
-
- 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
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- 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
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3415—Five-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/062—Copolymers with monomers not covered by C08L33/06
- C08L33/068—Copolymers with monomers not covered by C08L33/06 containing glycidyl groups
-
- 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
-
- 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
-
- 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
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
Description
本発明は、プリント配線板の製造に用いられる樹脂組成物及びそれを用いたプリント配線板用樹脂シートに関する。 The present invention relates to a resin composition used for producing a printed wiring board and a resin sheet for a printed wiring board using the same.
電気部品や電子部品を搭載するプリント配線板は、その利用分野が拡大するに連れて要求される特性が高度化している。例えばパーソナルコンピュータや携帯通信機器等の情報処理用機器は一層の小型化に伴い、パッケージの薄型化、モジュール化、ＰｏＰ（Ｐａｃｋａｇｅ ｏｎ Ｐａｃａｋｇｅ）構造などによる三次元化が求められており、そのことに起因してプリント配線板の半導体素子等実装時における寸法安定性の要求がより一層高くなっている。このような要求を達成するためには、プリント配線板を構成する絶縁層に、従来にも増して熱に対する寸法安定性や低そり化が要求されるとともに絶縁樹脂自体の高耐熱化も一層要求される。 Printed wiring boards on which electrical and electronic components are mounted have more sophisticated characteristics as their fields of use expand. For example, information processing devices such as personal computers and mobile communication devices are required to be thinner, modularized, and three-dimensionalized by a PoP (Package on Package) structure as the size of the device is further reduced. As a result, the demand for dimensional stability at the time of mounting a semiconductor element or the like of a printed wiring board is further increased. In order to achieve such requirements, the insulating layer constituting the printed wiring board is required to have more dimensional stability against heat and lower warpage than before, and further to increase the heat resistance of the insulating resin itself. Will be done.
熱に対する寸法安定性を高めることを目的として、特許文献１には、エポキシ樹脂を含む熱硬化性樹脂と、硬化剤と、無機フィラーと、アクリル樹脂とを含有するプリント配線板用樹脂組成物が記載されている。同文献には、熱硬化性樹脂として前記のエポキシ樹脂の他に多官能性マレイミド樹脂を含有させてもよいことが記載されている。またアクリル樹脂がエポキシ基を有していてもよいことが記載されている。 For the purpose of improving dimensional stability with respect to heat, Patent Document 1 describes a resin composition for a printed wiring board containing a thermosetting resin containing an epoxy resin, a curing agent, an inorganic filler, and an acrylic resin. Are listed. The document describes that a polyfunctional maleimide resin may be contained as the thermosetting resin in addition to the above-mentioned epoxy resin. It is also described that the acrylic resin may have an epoxy group.
マレイミド樹脂を含むプリント配線板用の樹脂組成物は特許文献２にも記載されている。同文献に記載の樹脂組成物は、マレイミド樹脂及び該マレイミド樹脂と架橋反応が可能な化合物を含有している。マレイミド樹脂と架橋反応可能な化合物としては、アミノ基、シアネート基、フェノール性水酸基、アルコール性水酸基、アリル基、アクリル基、メタクリル基、ビニル基、共役ジエン基を有する化合物が挙げられている。 A resin composition for a printed wiring board containing a maleimide resin is also described in Patent Document 2. The resin composition described in the same document contains a maleimide resin and a compound capable of a cross-linking reaction with the maleimide resin. Examples of the compound capable of cross-linking with the maleimide resin include compounds having an amino group, a cyanate group, a phenolic hydroxyl group, an alcoholic hydroxyl group, an allyl group, an acrylic group, a methacryl group, a vinyl group, and a conjugated diene group.
しかし、上述した各文献に記載のプリント配線板用の樹脂組成物は、Ｂステージの状態で可とう性が十分でなく、外力が加わったときにクラックが発生したり、それに起因して発生する破断片の落下が生じたりすることがあった。また、可とう性を高めようとすると、樹脂組成物の流動性が低下することが多い。可とう性を高めるために例えばポリビニルアセタール樹脂等のポリマーを配合することが知られているが、その場合には硬化体の熱膨張が大きくなり寸法安定性に欠けることがあった。 However, the resin compositions for printed wiring boards described in the above-mentioned documents are not sufficiently flexible in the B stage state, and cracks occur when an external force is applied, or the resin compositions are generated due to the cracks. Fragments may fall. Further, when trying to increase the flexibility, the fluidity of the resin composition often decreases. It is known that a polymer such as a polyvinyl acetal resin is blended in order to improve the flexibility, but in that case, the thermal expansion of the cured product becomes large and the dimensional stability may be lacking.
したがって本発明の課題は、前述した従来技術が有する種々の欠点を解消し得るプリント配線板用樹脂組成物を提供することにある。 Therefore, an object of the present invention is to provide a resin composition for a printed wiring board that can eliminate various drawbacks of the above-mentioned prior art.
本発明者は鋭意検討した結果、特定の成分を特定の配合割合で含む樹脂組成物によって前記の課題が解決されることを知見した。
本発明は前記の知見に基づきなされたものであり、
マレイミド化合物と、
重量平均分子量が５万以上の（メタ）アクリル樹脂と、
硬化促進剤と、
無機フィラーと、を含有し、
前記マレイミド化合物と、前記（メタ）アクリル樹脂と、前記硬化促進剤との合計１００質量部に対して、
前記マレイミド化合物が２５質量部以上９３質量部以下含まれ、
前記（メタ）アクリル樹脂が７質量部以上７０質量部以下含まれ、
前記無機フィラーが１００質量部以上４００質量部以下含まれる、プリント配線板用樹脂組成物を提供することによって前記の課題を解決したものである。As a result of diligent studies, the present inventor has found that the above-mentioned problems can be solved by a resin composition containing a specific component in a specific blending ratio.
The present invention has been made based on the above findings.
Maleimide compound and
(Meta) acrylic resin with a weight average molecular weight of 50,000 or more,
Curing accelerator and
Contains inorganic filler,
With respect to a total of 100 parts by mass of the maleimide compound, the (meth) acrylic resin, and the curing accelerator.
The maleimide compound is contained in an amount of 25 parts by mass or more and 93 parts by mass or less.
The (meth) acrylic resin is contained in an amount of 7 parts by mass or more and 70 parts by mass or less.
The above problem is solved by providing a resin composition for a printed wiring board containing 100 parts by mass or more and 400 parts by mass or less of the inorganic filler.
以下本発明を、その好ましい実施形態に基づき説明する。本発明の樹脂組成物は、プリント配線板の製造に用いられるものである。つまり本発明はプリント配線板用樹脂組成物に係るものである。本発明の樹脂組成物は、その構成成分として、マレイミド化合物と、（メタ）アクリル樹脂と、硬化促進剤と、無機フィラーとを含有している。以下、これらの成分についてそれぞれ詳述する。 Hereinafter, the present invention will be described based on its preferred embodiment. The resin composition of the present invention is used for producing a printed wiring board. That is, the present invention relates to a resin composition for a printed wiring board. The resin composition of the present invention contains a maleimide compound, a (meth) acrylic resin, a curing accelerator, and an inorganic filler as constituent components thereof. Hereinafter, each of these components will be described in detail.
マレイミド化合物は、少なくとも一つのマレイミド部位を有する化合物である。特にマレイミド部位が２つであるマレイミド化合物（いわゆるビスマレイミド化合物）やマレイミド部位が３つ以上であるポリマレイミド化合物を用いることが、樹脂組成物の低そり化を高め、且つ耐熱性を向上させる観点から好ましい。 A maleimide compound is a compound having at least one maleimide moiety. In particular, the use of a maleimide compound having two maleimide moieties (so-called bismaleimide compound) or a polymaleimide compound having three or more maleimide moieties has a viewpoint of increasing the warpage of the resin composition and improving the heat resistance. Is preferable.
マレイミド化合物を構成する分子骨格としては、例えばビフェニル骨格、４，４’−ジフェニルメタン骨格、フェニルメタン骨格、フェニレン骨格及びジフェニルエーテル骨格並びにこれらの組み合わせが挙げられる。これらの中でもビフェニル骨格、４，４’−ジフェニルメタン骨格又はフェニルメタン骨格を有するマレイミド化合物を用いることが、十分な耐熱性を保持するとともに、樹脂組成物の可とう性を一層高め、且つ流動性を一層高める観点から好ましい。これらのマレイミド化合物は、一種を単独で又は二種以上を組み合わせて用いることができる。これらの中でも、ビフェニル骨格からなるマレイミド化合物が、耐熱性及びＢステージにおけるクラック耐性が一層高い点から最も好ましい。 Examples of the molecular skeleton constituting the maleimide compound include a biphenyl skeleton, a 4,4'-diphenylmethane skeleton, a phenylmethane skeleton, a phenylene skeleton, a diphenyl ether skeleton, and a combination thereof. Among these, using a maleimide compound having a biphenyl skeleton, a 4,4'-diphenylmethane skeleton or a phenylmethane skeleton maintains sufficient heat resistance, further enhances the flexibility of the resin composition, and improves the fluidity. It is preferable from the viewpoint of further enhancing. These maleimide compounds may be used alone or in combination of two or more. Among these, the maleimide compound having a biphenyl skeleton is most preferable because it has higher heat resistance and crack resistance at the B stage.
マレイミド化合物は、そのマレイミド当量が１００〜１０００であることが好ましく、より好ましくは１５０〜８００、更に好ましくは２００〜４００である。マレイミド当量をこの範囲内に設定することで、十分な耐熱性を保持できるとともに、樹脂組成物の可とう性が一層高まり、且つ流動性が一層高まる。 The maleimide compound preferably has a maleimide equivalent of 100 to 1000, more preferably 150 to 800, and even more preferably 200 to 400. By setting the maleimide equivalent within this range, sufficient heat resistance can be maintained, the flexibility of the resin composition is further enhanced, and the fluidity is further enhanced.
本発明の樹脂組成物において、マレイミド化合物は、マレイミド化合物と、（メタ）アクリル樹脂と、硬化促進剤との合計１００質量部に対して、２５質量部以上９３質量部以下含まれることが好ましく、２８質量部以上７０質量部以下含まれることが更に好ましく、３０質量部以上５０質量部以下含まれることが一層好ましい。マレイミド化合物の配合量をこの範囲内に設定することで、樹脂組成物の可とう性が一層高まり、且つ流動性が一層高まる。 In the resin composition of the present invention, the maleimide compound is preferably contained in an amount of 25 parts by mass or more and 93 parts by mass or less with respect to a total of 100 parts by mass of the maleimide compound, the (meth) acrylic resin, and the curing accelerator. It is more preferably contained in an amount of 28 parts by mass or more and 70 parts by mass or less, and further preferably contained in an amount of 30 parts by mass or more and 50 parts by mass or less. By setting the blending amount of the maleimide compound within this range, the flexibility of the resin composition is further enhanced and the fluidity is further enhanced.
本発明の樹脂組成物に含まれる（メタ）アクリル樹脂は、主として樹脂組成物の可とう性を高めることを目的として配合される。また、上述したマレイミド化合物との併用によって、樹脂組成物の可とう性を高めることを目的としても配合される。（メタ）アクリル樹脂とは、アクリル樹脂及びメタクリル樹脂の総称である。（メタ）アクリル樹脂は、アクリル酸又はその誘導体を重合性単量体の一つとして重合された樹脂であるか、メタクリル酸又はその誘導体を重合性単量体の一つとして重合された樹脂であるか、アクリル酸又はその誘導体及びメタクリル酸又はその誘導体を重合性単量体として重合された樹脂である。アクリル酸及びメタクリル酸誘導体としては、これらの酸のエステルやそのエポキシ変性物、ヒドロキシル変性物、カルボシキル変性物、アミノ変性物、アミド変性物などが挙げられる。 The (meth) acrylic resin contained in the resin composition of the present invention is blended mainly for the purpose of increasing the flexibility of the resin composition. It is also blended for the purpose of increasing the flexibility of the resin composition by using it in combination with the above-mentioned maleimide compound. (Meta) Acrylic resin is a general term for acrylic resin and methacrylic resin. The (meth) acrylic resin is a resin obtained by polymerizing acrylic acid or a derivative thereof as one of the polymerizable monomers, or a resin obtained by polymerizing methacrylic acid or a derivative thereof as one of the polymerizable monomers. Or, it is a resin polymerized using acrylic acid or a derivative thereof and methacrylic acid or a derivative thereof as a polymerizable monomer. Examples of the acrylic acid and the methacrylic acid derivative include esters of these acids, epoxy-modified products, hydroxyl-modified products, carbosilyl-modified products, amino-modified products, amide-modified products, and the like.
（メタ）アクリル樹脂が二種以上の繰り返し単位を含む共重合体である場合、該共重合体における繰り返し単位の配置は、ランダムであってもよく、ブロックであってもよく、グラフトであってもよい。共重合体中に、共重合成分として、（メタ）アクリル酸又はその誘導体以外の繰り返し単位が含まれている場合、該繰り返し単位としては、例えばアクリロニトリル由来の繰り返し単位や、ブタジエン由来の繰り返し単位、及びスチレン由来の繰り返し単位などが挙げられる。 When the (meth) acrylic resin is a copolymer containing two or more kinds of repeating units, the arrangement of the repeating units in the copolymer may be random, may be a block, or may be a graft. May be good. When the copolymer contains a repeating unit other than (meth) acrylic acid or a derivative thereof as the copolymerization component, the repeating unit includes, for example, a repeating unit derived from acrylonitrile, a repeating unit derived from butadiene, and the like. And repeating units derived from styrene.
（メタ）アクリル樹脂は、高分子鎖の末端、側鎖又は主鎖に、各種の官能基を有していてもよい。そのような官能基としては、例えばエポキシ樹脂及び硬化剤の少なくともいずれかと反応性を有する基が挙げられる。具体的には、例えば、エポキシ基、ヒドロキシル基、カルボキシル基、アミノ基及びアミド基などが挙げられる。これらの官能基が（メタ）アクリル樹脂中に含まれていることで、例えば、樹脂組成物中に含まれている他の成分と反応することが可能になり、それによって樹脂組成物の耐熱性、熱に対する寸法安定性、及び吸湿耐性（はんだ耐熱性）等の向上を図ることが期待できる。上述の各種の官能基のうち、エポキシ基が特に好ましい。官能基は（メタ）アクリル樹脂１分子につき、複数含まれていてもよい。 The (meth) acrylic resin may have various functional groups at the end, side chain or main chain of the polymer chain. Examples of such a functional group include a group having reactivity with at least one of an epoxy resin and a curing agent. Specific examples thereof include an epoxy group, a hydroxyl group, a carboxyl group, an amino group and an amide group. The inclusion of these functional groups in the (meth) acrylic resin allows, for example, to react with other components contained in the resin composition, thereby making the resin composition heat resistant. , Dimensional stability against heat, moisture absorption resistance (solder heat resistance), etc. can be expected to be improved. Of the various functional groups described above, epoxy groups are particularly preferred. A plurality of functional groups may be contained in one molecule of the (meth) acrylic resin.
（メタ）アクリル樹脂は、その重量平均分子量（以下「ＭＷ」とも言う。）が５万以上であることが好ましく、７万以上であることが更に好ましく、１０万以上であることが一層好ましい。重量平均分子量の上限値に関しては、１００万以下であることが好ましく、９０万以下であることが更に好ましく、７０万以下であることが一層好ましい。この範囲の分子量を有する（メタ）アクリル樹脂を用いることで、本発明の樹脂組成物に十分な可とう性が付与され、Ｂステージ状態である樹脂シートを形成した場合においてもクラック等の発生を防止することが可能となる。（メタ）アクリル樹脂の重量平均分子量は、例えばＪＩＳ Ｋ７２５２−１：２００８で規定されるサイズ排除クロマトグラフィー（ＳＥＣ）、又はゲル浸透クロマトグラフィー分析（ＧＰＣ）で測定される。 The weight average molecular weight (hereinafter, also referred to as “MW”) of the (meth) acrylic resin is preferably 50,000 or more, more preferably 70,000 or more, and further preferably 100,000 or more. The upper limit of the weight average molecular weight is preferably 1 million or less, more preferably 900,000 or less, and even more preferably 700,000 or less. By using a (meth) acrylic resin having a molecular weight in this range, sufficient flexibility is imparted to the resin composition of the present invention, and cracks and the like are generated even when a resin sheet in the B stage state is formed. It becomes possible to prevent it. The weight average molecular weight of the (meth) acrylic resin is measured by, for example, size exclusion chromatography (SEC) defined by JIS K7252-1: 2008 or gel permeation chromatography analysis (GPC).
本発明の樹脂組成物において、（メタ）アクリル樹脂は、マレイミド化合物と、（メタ）アクリル樹脂と、硬化促進剤との合計１００質量部に対して、７質量部以上７０質量部以下含まれることが好ましく、１０質量部以上６０質量部以下含まれることが更に好ましく、１５質量部以上５０質量部以下含まれることが一層好ましい。（メタ）アクリル樹脂の配合量をこの範囲内に設定することで、樹脂組成物の可とう性及び流動性が一層高まり、且つ耐熱性にも優れたものとなる。 In the resin composition of the present invention, the (meth) acrylic resin is contained in an amount of 7 parts by mass or more and 70 parts by mass or less with respect to a total of 100 parts by mass of the maleimide compound, the (meth) acrylic resin, and the curing accelerator. It is more preferable that it is contained in an amount of 10 parts by mass or more and 60 parts by mass or less, and more preferably 15 parts by mass or more and 50 parts by mass or less. By setting the blending amount of the (meth) acrylic resin within this range, the flexibility and fluidity of the resin composition are further enhanced, and the heat resistance is also excellent.
本発明の樹脂組成物に含まれる硬化促進剤は、該樹脂組成物中に含まれるマレイミド化合物の硬化を促進するために用いられる。硬化促進剤は特に、重合性反応性基の一種であるエポキシ基の重合反応（架橋反応）も促進する化合物であることが好ましい。そのような硬化促進剤としては例えば、アミン系化合物、及びりん化合物などが挙げられる。これらの硬化促進剤は一種を単独で又は二種以上を組み合わせて用いることができる。その中でも、保存安定性と硬化反応促進の両立の観点から、硬化促進剤は複素環に窒素原子を含む複素環式芳香族アミンであることが好ましい。 The curing accelerator contained in the resin composition of the present invention is used to accelerate the curing of the maleimide compound contained in the resin composition. The curing accelerator is particularly preferably a compound that also promotes the polymerization reaction (crosslinking reaction) of an epoxy group, which is a kind of polymerizable reactive group. Examples of such a curing accelerator include amine compounds and phosphorus compounds. These curing accelerators can be used alone or in combination of two or more. Among them, from the viewpoint of achieving both storage stability and promotion of curing reaction, the curing accelerator is preferably a heterocyclic aromatic amine containing a nitrogen atom in the heterocycle.
これらの中でも、硬化物の耐熱性及び絶縁信頼性の観点から、硬化促進剤はイミダゾール系化合物であることが特に好ましい。イミダゾール系化合物の例としては、２−メチルイミダゾール、２−エチル−４−メチルイミダゾール、２−フェニルイミダゾール、２−フェニル−４−メチルイミダゾール、１−ベンジル−２−メチルイミダゾール、１−ベンジル−２−フェニルイミダゾール、１，２−ジメチルイミダゾールなどが挙げられる。 Among these, from the viewpoint of heat resistance and insulation reliability of the cured product, the curing accelerator is particularly preferably an imidazole compound. Examples of imidazole compounds include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2. -Phenylimidazole, 1,2-dimethylimidazole and the like can be mentioned.
本発明の樹脂組成物において、硬化促進剤は、マレイミド化合物と、（メタ）アクリル樹脂と、硬化促進剤との合計１００質量部に対して、０．０１質量部以上１０質量部以下含まれることが好ましく、０．１０質量部以上５質量部以下含まれることが更に好ましく、０．１５質量部以上３質量部以下含まれることが一層好ましい。硬化促進剤の配合量をこの範囲内に設定することで、樹脂組成物を十分に硬化させることができる。 In the resin composition of the present invention, the curing accelerator is contained in an amount of 0.01 part by mass or more and 10 parts by mass or less with respect to a total of 100 parts by mass of the maleimide compound, the (meth) acrylic resin, and the curing accelerator. It is more preferable that it is contained in an amount of 0.10 parts by mass or more and 5 parts by mass or less, and more preferably 0.15 parts by mass or more and 3 parts by mass or less. By setting the blending amount of the curing accelerator within this range, the resin composition can be sufficiently cured.
本発明の樹脂組成物は、上述した各成分に加えて無機フィラーを含んでいる。無機フィラーは、本発明の樹脂組成物から生じる硬化体に、熱に対する寸法安定性を付与する目的で配合される。あるいは、本発明の樹脂組成物に適度な流動性や可とう性を付与する目的で配合される。更に、本発明の樹脂組成物にブロッキングが発生することを防止する目的で配合される。無機フィラーは、その種類に特に制限はなく、例えばシリカ、硫酸バリウム、焼成タルク、モリブデン酸亜鉛処理タルク、チタン酸バリウム、酸化チタン、クレー、アルミナ、マイカ、ベーマイト、ホウ酸亜鉛、スズ酸亜鉛、水酸化アルミニウム、炭酸カルシウム、水酸化マグネシウム、ケイ酸マグネシウム、ガラス短繊維、ホウ酸アルミニウムウィスカ及び炭酸ケイ素ウィスカ等が挙げられる。これらの無機フィラーは一種を単独で用いてもよく、あるいは二種以上を組み合わせて用いてもよい。 The resin composition of the present invention contains an inorganic filler in addition to the above-mentioned components. The inorganic filler is added to the cured product obtained from the resin composition of the present invention for the purpose of imparting dimensional stability to heat. Alternatively, it is blended for the purpose of imparting appropriate fluidity and flexibility to the resin composition of the present invention. Further, it is blended for the purpose of preventing blocking from occurring in the resin composition of the present invention. The type of inorganic filler is not particularly limited, and for example, silica, barium sulfate, calcined talc, zinc molybdate treated talc, barium titanate, titanium oxide, clay, alumina, mica, borate, zinc borate, zinc nitrate, etc. Examples thereof include aluminum hydroxide, calcium carbonate, magnesium hydroxide, magnesium silicate, short glass fiber, aluminum borate whisker and silicon carbonate whisker. These inorganic fillers may be used alone or in combination of two or more.
これらの中でも樹脂組成物から生じる硬化体に、熱に対する寸法安定性を付与するとともに、入手のしやすさ、硬化体の耐熱性及び絶縁信頼性等を付与する観点から、無機フィラーはシリカであることが好ましい。シリカとしては、無定形シリカ、溶融シリカ、結晶シリカ、合成シリカ、中空シリカ等のシリカが知られているところ、樹脂組成物中に高充填で添加でき、Ｂステージ状態の樹脂シートの熱を加えたときの流動性（レジンフロー）の良好さの観点から、球状のものが特に好ましい。 Among these, the inorganic filler is silica from the viewpoint of imparting dimensional stability to heat to the cured product produced from the resin composition, as well as imparting availability, heat resistance of the cured product, insulation reliability, and the like. Is preferable. As silica, silica such as amorphous silica, molten silica, crystalline silica, synthetic silica, and hollow silica is known, and can be added to the resin composition with high filling, and the heat of the resin sheet in the B stage state is applied. From the viewpoint of good fluidity (resin flow) at the time, a spherical one is particularly preferable.
無機フィラーの形状や大きさに特に制限はない。形状に関しては、例えば球状、多面体状、針状、紡錘状、不定形などを採用することができる。これらの形状の２種以上の組み合わせを用いてもよい。大きさに関しては、平均粒径が０．００１μｍ以上２０μｍ以下であることが好ましく、０．０１μｍ以上１０μｍ以下であることが更に好ましく、０．０５μｍ以上５μｍ以下であることが一層好ましい。平均粒径が異なる二種以上の無機フィラーを組み合わせて用い、粒度分布に複数のピークが観察されるようにしてもよい。平均粒径は、レーザー回折・散乱式の粒子径分布測定装置を用いた粒度分布曲線から求められるメジアン径（Ｄ５０）で測定される。粒子の長径と短径の比であるアスペクト比は特に制限されない。尤も本発明の製品の製造にあたって、レジンフローや、可とう性を付与する際の制御のしやすさの観点から、アスペクト比は１．０以上１０以下が好ましく、１．０以上５．０以下がより好ましく、１．０以上２．０以下が最も好ましい。There is no particular limitation on the shape and size of the inorganic filler. As for the shape, for example, a spherical shape, a polyhedral shape, a needle shape, a spindle shape, an amorphous shape, or the like can be adopted. A combination of two or more of these shapes may be used. Regarding the size, the average particle size is preferably 0.001 μm or more and 20 μm or less, more preferably 0.01 μm or more and 10 μm or less, and further preferably 0.05 μm or more and 5 μm or less. Two or more kinds of inorganic fillers having different average particle sizes may be used in combination so that a plurality of peaks can be observed in the particle size distribution. The average particle size is measured by the median diameter (D 50 ) obtained from the particle size distribution curve using a laser diffraction / scattering type particle size distribution measuring device. The aspect ratio, which is the ratio of the major axis to the minor axis of the particles, is not particularly limited. However, in the production of the product of the present invention, the aspect ratio is preferably 1.0 or more and 10 or less, and 1.0 or more and 5.0 or less, from the viewpoint of resin flow and ease of control when imparting flexibility. Is more preferable, and 1.0 or more and 2.0 or less is most preferable.
樹脂成分と無機フィラーの密着性を向上させる点、及び樹脂組成物の吸湿耐性を向上させる点等から無機フィラーの表面は、シランカップリング剤による表面処理が施されていことが好ましい。シランカップリング剤としては、例えばアミノ官能性シランカップリング剤、アクリル官能性シランカップリング剤、メタクリル官能性シランカップリング剤、エポキシ官能性シランカップリング剤、オレフィン官能性シランカップリング剤、メルカプト官能性シランカップリング剤、及びビニル官能性シランカップリング剤等が挙げられる。これらの中でも、エポキシ官能性シランカップリング剤、アミノ官能性シランカップリング剤、アクリル官能性シランカップリング剤、メタクリル官能性シランカップリング剤、及びビニル官能性シランカップリング剤等がより好ましい。 The surface of the inorganic filler is preferably surface-treated with a silane coupling agent from the viewpoint of improving the adhesion between the resin component and the inorganic filler and improving the moisture absorption resistance of the resin composition. Examples of the silane coupling agent include an amino-functional silane coupling agent, an acrylic-functional silane coupling agent, a methacryl-functional silane coupling agent, an epoxy-functional silane coupling agent, an olefin-functional silane coupling agent, and a mercapto-functional agent. Examples thereof include a sex silane coupling agent and a vinyl functional silane coupling agent. Among these, epoxy-functional silane coupling agents, amino-functional silane coupling agents, acrylic-functional silane coupling agents, methacryl-functional silane coupling agents, vinyl-functional silane coupling agents and the like are more preferable.
本発明の樹脂組成物において、無機フィラーは、マレイミド化合物と、（メタ）アクリル樹脂と、硬化促進剤との合計１００質量部に対して、１００質量部以上４００質量部以下含まれることが好ましく、１００質量部以上３５０質量部以下含まれることが更に好ましく、１５０質量部以上３００質量部以下含まれることが一層好ましい。無機フィラーの配合量をこの範囲内に設定することで、Ｂステージ状態の樹脂シートに熱を加えたときの流動性（レジンフロー）が良好になり、また、熱に対する硬化体の寸法安定性、及び耐熱性の良好な特性を得ることができる。 In the resin composition of the present invention, the inorganic filler is preferably contained in an amount of 100 parts by mass or more and 400 parts by mass or less with respect to a total of 100 parts by mass of the maleimide compound, the (meth) acrylic resin, and the curing accelerator. It is more preferably contained in an amount of 100 parts by mass or more and 350 parts by mass or less, and further preferably contained in an amount of 150 parts by mass or more and 300 parts by mass or less. By setting the blending amount of the inorganic filler within this range, the fluidity (resin flow) when heat is applied to the resin sheet in the B stage state is improved, and the dimensional stability of the cured product against heat is improved. And good heat resistance can be obtained.
本発明の樹脂組成物は、これまでに説明してきた成分に加え、必要に応じて他の成分を含んでいてもよい。他の成分としては、例えばエポキシ樹脂、難燃剤、難燃助剤、カップリング剤、密着付与剤、着色剤、レーザー加工性向上剤、酸化防止剤、紫外線劣化防止剤、離型剤、ＰＨ調整剤、イオン捕捉剤、消泡剤、レベリング剤、アンチブロッキング剤、増粘剤、揺変性付与剤及び上述した樹脂以外の他の樹脂などが挙げられる。特に本発明の樹脂組成物がエポキシ樹脂を含んでいると、硬化体の耐熱性が向上し、熱に対する寸法安定性が一層向上し、更には吸湿耐性も一層向上する点から有利である。 The resin composition of the present invention may contain other components, if necessary, in addition to the components described so far. Other components include, for example, epoxy resin, flame retardant, flame retardant aid, coupling agent, adhesion imparting agent, colorant, laser processability improver, antioxidant, ultraviolet deterioration inhibitor, mold release agent, PH adjustment. Examples thereof include agents, ion trapping agents, defoaming agents, leveling agents, antiblocking agents, thickeners, rocking denaturing agents, and resins other than the above-mentioned resins. In particular, when the resin composition of the present invention contains an epoxy resin, it is advantageous in that the heat resistance of the cured product is improved, the dimensional stability against heat is further improved, and the moisture absorption resistance is further improved.
エポキシ樹脂としては、当該技術分野においてこれまで用いられてきたものを特に制限なく用いることができる。例えばナフタレン型エポキシ樹脂、ビフェニルアラルキル型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、脂環式エポキシ樹脂、脂肪族鎖状エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、アルキルフェノールノボラック型エポキシ樹脂、アラルキル型エポキシ樹脂、ビフェノール型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、トリスヒドロキシフェニルメタン型エポキシ化合物、フェノール類とフェノール性水酸基を有する芳香族アルデヒドとの縮合物のエポキシ化物、ビスフェノールのジグリシジルエーテル化物、ナフタレンジオールのジグリシジルエーテル化物、フェノール類のグリシジルエーテル化物、アルコール類のジグリシジルエーテル化物、トリグリシジルイソシアヌレート等が挙げられる。これらのエポキシ樹脂は一種を単独で、又は二種以上を組み合わせて用いることができる。 As the epoxy resin, those that have been used so far in the technical field can be used without particular limitation. For example, naphthalene type epoxy resin, biphenyl aralkyl type epoxy resin, cresol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, cresol It has novolac type epoxy resin, phenol novolac type epoxy resin, alkylphenol novolac type epoxy resin, aralkyl type epoxy resin, biphenol type epoxy resin, dicyclopentadiene type epoxy resin, trishydroxyphenylmethane type epoxy compound, phenols and phenolic hydroxyl group. Examples thereof include an epoxy product of a condensate with an aromatic aldehyde, a diglycidyl ether product of bisphenol, a diglycidyl ether product of naphthalene diol, a glycidyl ether product of phenols, a diglycidyl ether product of alcohols, and triglycidyl isocyanurate. These epoxy resins can be used alone or in combination of two or more.
特に、前記のエポキシ樹脂はナフタレン型エポキシ樹脂及び／又はビフェニルアラルキル型エポキシ樹脂であることが好ましい。これらのエポキシ樹脂を用いることで、硬化体の耐熱性が一層向上し、熱に対する寸法安定性が更に一層向上し、更には吸湿耐性も更に一層向上する。この効果を一層顕著なものとする観点から、エポキシ樹脂としてナフタレン型エポキシ樹脂を用いることが好ましい。 In particular, the epoxy resin is preferably a naphthalene type epoxy resin and / or a biphenyl aralkyl type epoxy resin. By using these epoxy resins, the heat resistance of the cured product is further improved, the dimensional stability against heat is further improved, and the moisture absorption resistance is further improved. From the viewpoint of making this effect more remarkable, it is preferable to use a naphthalene type epoxy resin as the epoxy resin.
ナフタレン型エポキシ樹脂やビフェニルアラルキル型エポキシ樹脂を始めとする前記のエポキシ樹脂は、本発明の樹脂組成物中に、マレイミド化合物と、（メタ）アクリル樹脂と、硬化促進剤と、該エポキシ樹脂との合計１００質量部に対して、１０質量部以上４０質量部以下含まれることが好ましく、１０質量部以上３０質量部以下含まれることが更に好ましく、１５質量部以上２５質量部以下含まれることが一層好ましい。 The above-mentioned epoxy resin such as a naphthalene type epoxy resin and a biphenyl aralkyl type epoxy resin contains a maleimide compound, a (meth) acrylic resin, a curing accelerator, and the epoxy resin in the resin composition of the present invention. It is preferably contained in an amount of 10 parts by mass or more and 40 parts by mass or less, more preferably 10 parts by mass or more and 30 parts by mass or less, and further preferably 15 parts by mass or more and 25 parts by mass or less based on 100 parts by mass in total. preferable.
上述したエポキシ樹脂の架橋反応をより緻密にし、硬化体の耐熱性を向上させる点で、樹脂組成物にはエポキシ基と反応性のある硬化剤を含有させることがより好ましい。そのような硬化剤としては例えば、第一級アミンや第二級アミンなどのジアミン系硬化剤、２官能以上のフェノール化合物、酸無水物系硬化剤、ジシアンジアミドなどが挙げられる。これらの硬化剤は一種を単独で又は二種以上を組み合わせて用いることができる。これらの硬化剤は、先に述べたマレイミド化合物の硬化促進剤として機能する場合がある。そのような場合には、該硬化剤は硬化促進剤として位置づける。 It is more preferable that the resin composition contains a curing agent that is reactive with the epoxy group, in order to make the above-mentioned cross-linking reaction of the epoxy resin more dense and improve the heat resistance of the cured product. Examples of such a curing agent include diamine-based curing agents such as primary amines and secondary amines, bifunctional or higher-functional phenol compounds, acid anhydride-based curing agents, and dicyandiamide. These curing agents may be used alone or in combination of two or more. These curing agents may function as curing accelerators for the maleimide compounds described above. In such a case, the curing agent is positioned as a curing accelerator.
これらの中でも、フェノール化合物、酸無水物系硬化剤の単独又はこれらの組み合わせによる硬化剤は、本発明の樹脂組成物における全体の熱硬化反応速度を制御しやすい点からより好ましい。その理由は、これらの化合物はエポキシ樹脂との硬化反応にのみ寄与し、マレイミド化合物の硬化反応には寄与しない化合物であるため、全体の熱硬化反応速度が急激に進行することを防止できるからである。その結果、得られる絶縁層中のマレイミド硬化物やエポキシ樹脂硬化物の異常凝集を防ぐことができるため、系内均一性を保つことができる。 Among these, a curing agent using a phenol compound or an acid anhydride-based curing agent alone or in combination thereof is more preferable because it is easy to control the overall thermosetting reaction rate in the resin composition of the present invention. The reason is that since these compounds contribute only to the curing reaction with the epoxy resin and do not contribute to the curing reaction of the maleimide compound, it is possible to prevent the entire thermosetting reaction rate from rapidly progressing. is there. As a result, it is possible to prevent abnormal aggregation of the maleimide cured product and the epoxy resin cured product in the obtained insulating layer, so that the uniformity in the system can be maintained.
本発明の樹脂組成物は、上述の各成分を有機溶媒中で混合し撹拌することで得ることができる。有機溶媒としては、この種の樹脂組成物の調製に従来用いられているものと同様のものを用いることができる。そのような有機溶媒の例としては、例えばメタノール、エタノール、メチルエチルケトン、トルエン、プロピレングリコールモノメチルエーテル、ジメチルホルムアミド、ジメチルアセトアミド、シクロヘキサノン、シクロペンタノン、エチルセロソルブ、１,３−ジオキソランなどが挙げられる。 The resin composition of the present invention can be obtained by mixing and stirring each of the above-mentioned components in an organic solvent. As the organic solvent, the same solvent as that conventionally used for preparing this kind of resin composition can be used. Examples of such organic solvents include, for example, methanol, ethanol, methyl ethyl ketone, toluene, propylene glycol monomethyl ether, dimethylformamide, dimethylacetamide, cyclohexanone, cyclopentanone, ethyl cellosolve, 1,3-dioxolane and the like.
このようにして得られた樹脂組成物は、先に述べたとおり、プリント配線板の製造に用いられる。例えば本発明の樹脂組成物をシート状に成形し、Ｂステージの半硬化状態になるまで加熱乾燥することで、該樹脂組成物を含むプリント配線板用樹脂シートとすることができる。この樹脂シートを積層することで、プリント配線板を製造することができる。 As described above, the resin composition thus obtained is used for manufacturing a printed wiring board. For example, the resin composition of the present invention is formed into a sheet and dried by heating until the B stage is in a semi-cured state, whereby a resin sheet for a printed wiring board containing the resin composition can be obtained. A printed wiring board can be manufactured by laminating these resin sheets.
本発明の樹脂組成物でプリント配線板を製造する一つの例として、樹脂シートを硬化して得られる樹脂層を単独で絶縁層とすることが可能である。樹脂層を単独で絶縁層とする場合、樹脂層の厚みは、０．５μｍ以上２００μｍ以下の範囲内であることが好ましく、０．５μｍ以上１５０μｍ以下の範囲内であることが更に好ましい。樹脂層の厚みをこの範囲とすることで、絶縁性に十分な厚みを確保することができ、Ｂステージの樹脂シートに高い可とう性を付与することができる。 As an example of manufacturing a printed wiring board with the resin composition of the present invention, the resin layer obtained by curing the resin sheet can be used alone as an insulating layer. When the resin layer is used alone as an insulating layer, the thickness of the resin layer is preferably in the range of 0.5 μm or more and 200 μm or less, and more preferably in the range of 0.5 μm or more and 150 μm or less. By setting the thickness of the resin layer within this range, it is possible to secure a sufficient thickness for insulating properties, and it is possible to impart high flexibility to the resin sheet of the B stage.
あるいは本発明の樹脂組成物を織布等の繊維基材（クロス）に含浸させ、それによって得られた含浸体をＢステージの半硬化状態になるまで加熱乾燥することで、該樹脂組成物を含むプリント配線板用プリプレグとすることができる。このプリプレグを積層することで、プリント配線板を製造することができる。 Alternatively, the resin composition of the present invention is impregnated into a fiber base material (cloth) such as a woven fabric, and the impregnated body obtained thereby is heated and dried until it reaches a semi-cured state of the B stage to obtain the resin composition. It can be a prepreg for a printed wiring board including. By laminating these prepregs, a printed wiring board can be manufactured.
前記の繊維基材としては、特に限定されないが、平織等のように縦糸及び横糸がほぼ直交するように織られた基材を使用することができる。例えば、ガラスクロス等のような無機繊維の織布を用いることができる。あるいは、アラミドクロス、ポリエステルクロス等のような有機繊維の織布を用いることができる。繊維基材の厚みは特に制限はなく、例えば好ましくは１０μｍ以上２００μｍ以下とすることができる。 The fiber base material is not particularly limited, but a base material woven so that the warp threads and the weft threads are substantially orthogonal to each other, such as a plain weave, can be used. For example, an inorganic fiber woven fabric such as glass cloth can be used. Alternatively, organic fiber woven fabrics such as aramid cloth and polyester cloth can be used. The thickness of the fiber base material is not particularly limited, and can be, for example, preferably 10 μm or more and 200 μm or less.
本発明の樹脂組成物は、上述したシートやプリプレグの他に、支持体付プリント配線板用樹脂シートとして用いることもできる。この樹脂シートは、支持体と、該支持体の一面に配置された本発明の樹脂組成物の層とを有するものであることが好ましい。支持体としては、種々のフィルム状ないし箔状のものを用いることができる。例えば支持体として樹脂製フィルムを用いることができる。あるいは支持体として金属箔を用いることもできる。支持体の厚さは、５．０μｍ以上１００μｍ以下であることがハンドリングのしやすさの点から好ましい。 The resin composition of the present invention can also be used as a resin sheet for a printed wiring board with a support, in addition to the above-mentioned sheet and prepreg. This resin sheet preferably has a support and a layer of the resin composition of the present invention arranged on one surface of the support. As the support, various film-like or foil-like ones can be used. For example, a resin film can be used as the support. Alternatively, a metal foil can be used as the support. The thickness of the support is preferably 5.0 μm or more and 100 μm or less from the viewpoint of ease of handling.
前記の樹脂製フィルムとしては、例えばポリエチレンテレフタレート（ＰＥＴ）フィルム、ポリエチレンナフタレート（ＰＥＮ）フィルム、アラミドフィルム、ポリイミドフィルム、ナイロンフィルム、液晶ポリマー等の樹脂フィルムなどが挙げられる。これらの樹脂フィルム上に金属層コート層を備える金属コート樹脂フィルムを用いてもよい。金属箔としては、例えば銅箔、アルミニウム箔、ステンレス箔、ニッケル箔、チタン箔、又はこれらのいずれかが複数積層された箔などが挙げられる。特に、プリント配線板を形成する際の配線パターン加工法として、ＭＳＡＰ法、ＳＡＰ法、又はサブトラクティブ法等を採用する場合、樹脂組成物を硬化させた層と配線との密着性を確保する点と、金属箔のエッチング加工性との両立の点から、とりわけ支持体は金属箔であること好ましく、より好ましくは銅箔である。 Examples of the resin film include a polyethylene terephthalate (PET) film, a polyethylene naphthalate (PEN) film, an aramid film, a polyimide film, a nylon film, a resin film such as a liquid crystal polymer, and the like. A metal-coated resin film having a metal layer-coated layer on these resin films may be used. Examples of the metal foil include copper foil, aluminum foil, stainless steel foil, nickel foil, titanium foil, or a foil in which a plurality of any of these is laminated. In particular, when the MSAP method, the SAP method, the subtractive method, or the like is adopted as the wiring pattern processing method when forming the printed wiring board, the point of ensuring the adhesion between the layer obtained by curing the resin composition and the wiring. In particular, the support is preferably a metal foil, and more preferably a copper foil, from the viewpoint of compatibility with the etching processability of the metal foil.
支持体としての金属箔の厚さが例えば５．０μｍ未満である場合には、樹脂層付金属箔のハンドリング性を向上させる目的で、特に樹脂層付金属箔としてのプリント配線板を製造する際のハンドリング性を向上させる目的で、支持体は金属箔の他面に、いわゆる剥離層及びキャリアを設け、キャリア付金属箔の形態で用いてもよい。キャリアの例としては、銅箔、ニッケル箔、ステンレス箔、アルミニウム箔等の金属箔に加えて、ＰＥＴフィルム、ＰＥＮフィルム、アラミドフィルム、ポリイミドフィルム、ナイロンフィルム、液晶ポリマー等の樹脂フィルム、樹脂フィルム上に金属層コート層を備える金属コート樹脂フィルム等が挙げられるが、典型的には銅箔である。剥離層は、有機剥離層及び無機剥離層などが挙げられる。有機剥離層に用いられる有機成分の例としては、窒素含有有機化合物、硫黄含有有機化合物、カルボン酸等が挙げられる。一方、無機剥離層に用いられる無機成分の例としては、Ｎｉ、Ｍｏ、Ｃｏ、Ｃｒ、Ｆｅ、Ｔｉ、Ｗ、Ｐ、Ｚｎ、クロメート処理膜等が挙げられる。 When the thickness of the metal foil as a support is, for example, less than 5.0 μm, for the purpose of improving the handleability of the metal foil with a resin layer, particularly when manufacturing a printed wiring board as a metal foil with a resin layer. The support may be used in the form of a metal foil with a carrier by providing a so-called release layer and a carrier on the other surface of the metal foil for the purpose of improving the handleability of the support. Examples of carriers include, in addition to metal foils such as copper foil, nickel foil, stainless steel foil, and aluminum foil, PET film, PEN film, aramid film, polyimide film, nylon film, resin film such as liquid crystal polymer, and resin film. Examples thereof include a metal-coated resin film provided with a metal layer-coated layer, which is typically a copper foil. Examples of the release layer include an organic release layer and an inorganic release layer. Examples of the organic component used in the organic exfoliation layer include nitrogen-containing organic compounds, sulfur-containing organic compounds, and carboxylic acids. On the other hand, examples of the inorganic component used in the inorganic release layer include Ni, Mo, Co, Cr, Fe, Ti, W, P, Zn, and a chromate-treated film.
前記金属箔における樹脂組成物層との接着面は、ＪＩＳ Ｂ０６１０−１９９４による表面粗さ（Ｒｚｊｉｓ）が４．０μｍ以下であることが好ましく、より好ましくは３．５μｍ以下であり、更に好ましくは３．０μｍ以下である。表面粗さ（Ｒｚｊｉｓ）をこの範囲とすることで、金属箔をエッチングした後の樹脂層表面の凹凸を微細にすることができるので、樹脂層の表面に形成される上部導体層の寸法精度を高いものとすることが可能となる。また、上部導体層と樹脂層との密着性保持の観点から、金属箔の表面粗さ（Ｒｚｊｉｓ）は０．００５μｍ以上が好ましく、より好ましくは０．０１μｍ以上であり、更に好ましくは０．０５μｍ以上である。 The surface roughness (Rzjis) of the metal foil with the resin composition layer according to JIS B0610-1994 is preferably 4.0 μm or less, more preferably 3.5 μm or less, still more preferably 3. It is 0.0 μm or less. By setting the surface roughness (Rzjis) in this range, the unevenness of the surface of the resin layer after etching the metal foil can be made fine, so that the dimensional accuracy of the upper conductor layer formed on the surface of the resin layer can be improved. It can be expensive. Further, from the viewpoint of maintaining the adhesion between the upper conductor layer and the resin layer, the surface roughness (Rzjis) of the metal foil is preferably 0.005 μm or more, more preferably 0.01 μm or more, still more preferably 0.05 μm. That is all.
更に、金属箔の表面には、防錆被膜処理などによる表面処理層が形成されてもよい。防錆被膜としては、亜鉛、ニッケル及びコバルト等を用いた無機防錆被膜、クロム酸塩を用いたクロメート被膜、並びにベンゾトリアゾール及びイミダゾール等の有機剤を用いた有機防錆被膜等が挙げられる。 Further, a surface treatment layer may be formed on the surface of the metal foil by a rust preventive coating treatment or the like. Examples of the rust preventive film include an inorganic rust preventive film using zinc, nickel, cobalt and the like, a chromate film using chromate, and an organic rust preventive film using an organic agent such as benzotriazole and imidazole.
また、前記表面処理層の表面には、シラン層が形成されていてもよい。シラン層を設けることにより、金属箔の表面と樹脂層との密着性をより良好なものとすることができる。シラン層を構成する材料としては、例えばテトラアルコキシシランや、シランカップリング剤などが挙げられる。 Further, a silane layer may be formed on the surface of the surface treatment layer. By providing the silane layer, the adhesion between the surface of the metal foil and the resin layer can be improved. Examples of the material constituting the silane layer include tetraalkoxysilane and a silane coupling agent.
支持体がどのような材質の場合であっても、前記のプリント配線板用積層体は、例えば、本発明の樹脂組成物から得られたＢステージの状態のシート状物を、支持体と重ね合わせ、それらを一体に加熱加圧することで得ることができる。加熱加圧には真空プレス法や真空ラミネート法を採用することができる。あるいは、支持体の少なくとも一面に本発明の樹脂組成物を塗工し、得られた塗膜をＢステージの半硬化状態になるまで加熱乾燥することで得ることができる。 Regardless of the material of the support, in the above-mentioned laminated body for printed wiring boards, for example, a sheet-like material in a B stage state obtained from the resin composition of the present invention is superposed on the support. It can be obtained by combining them and heating and pressurizing them integrally. A vacuum press method or a vacuum laminating method can be adopted for heating and pressurizing. Alternatively, it can be obtained by applying the resin composition of the present invention to at least one surface of the support and heating and drying the obtained coating film until the B stage is in a semi-cured state.
これらの支持体付プリント配線板用樹脂シートは、上述したように樹脂シート層を硬化して絶縁層として採用できる他、プリプレグと支持体（例えば金属箔）との密着性を向上させるためのプライマー樹脂層として採用することも可能である。プライマー樹脂層として採用する場合、支持体付プリント配線板用樹脂シート厚さは０．４μｍ以上１５μｍ以下であることが好ましく、０．５μｍ以上１０μｍ以下とすることがより好ましい。この範囲とすることで、層間密着性の十分な向上のための厚みを確保することができるとともに、プリント配線板のビア加工（例えばレーザー加工等）において、微細加工に適した厚さとすることができる。 These resin sheets for printed wiring boards with a support can be used as an insulating layer by curing the resin sheet layer as described above, and also have a primer for improving the adhesion between the prepreg and the support (for example, metal leaf). It can also be used as a resin layer. When used as a primer resin layer, the thickness of the resin sheet for a printed wiring board with a support is preferably 0.4 μm or more and 15 μm or less, and more preferably 0.5 μm or more and 10 μm or less. By setting this range, it is possible to secure a thickness for sufficiently improving the interlayer adhesion, and it is possible to make the thickness suitable for fine processing in via processing (for example, laser processing) of a printed wiring board. it can.
支持体と樹脂組成物の層との間には、必要に応じて両者の接合強度を高める目的で別の樹脂組成物からなるプライマー層を形成してもよい。このようにして得られた積層体の厚みは、例えば１０μｍ以上１５０μｍ以下であることが好ましい。 If necessary, a primer layer made of another resin composition may be formed between the support and the layer of the resin composition for the purpose of increasing the bonding strength between the two. The thickness of the laminate thus obtained is preferably, for example, 10 μm or more and 150 μm or less.
このようにして得られたプリント配線板用樹脂シートやプリプレグや積層体は、本発明の樹脂組成物を使用して形成されているので、熱に対する寸法安定性が高く、また外力を加えたときにクラックの発生が抑制されたものとなる。したがって、これらのプリント配線板用樹脂シートやプリプレグや積層体は、高性能のプリント配線板を製造するための原料として特に好適なものとなる。プリント配線板の工法としては、例えばＭＳＡＰ法やＳＡＰ法、サブトラクティブ法等が好適に使用される。そして、これらのプリント配線板用樹脂シートやプリプレグや積層体を用いた製造されたプリント配線板は、熱に対する寸法安定性が高く、高周波特性が良好なものとなる。 Since the resin sheet, prepreg, and laminate for the printed wiring board thus obtained are formed by using the resin composition of the present invention, they have high dimensional stability against heat and when an external force is applied. The occurrence of cracks is suppressed. Therefore, these resin sheets for printed wiring boards, prepregs, and laminates are particularly suitable as raw materials for producing high-performance printed wiring boards. As the method of constructing the printed wiring board, for example, the MSAP method, the SAP method, the subtractive method and the like are preferably used. The printed wiring board manufactured by using these resin sheets for printed wiring boards, prepregs, and laminates has high dimensional stability against heat and good high-frequency characteristics.
以下、実施例により本発明を更に詳細に説明する。しかしながら本発明の範囲は、かかる実施例に制限されない。特に断らない限り、「％」は「質量％」を意味する。
以下の実施例及び比較例で用いた各成分は以下の表１に示すとおりである。また、以下の表２ないし表４中の各成分の配合量は、質量部で表したものである。Hereinafter, the present invention will be described in more detail with reference to Examples. However, the scope of the present invention is not limited to such examples. Unless otherwise specified, "%" means "mass%".
The components used in the following Examples and Comparative Examples are as shown in Table 1 below. The blending amount of each component in Tables 2 to 4 below is expressed in parts by mass.
〔実施例１〕
以下の表２に示す成分を、同表に示す配合比で、溶剤をメチルエチルケトンとして、固形分が６０質量部となるように秤量し、フラスコに入れ温度６０℃に昇温させ１時間プロペラ式撹拌装置で撹拌させて樹脂組成物（樹脂ワニス）を得た。この樹脂組成物を、エッジコーターを用いて、キャリア付銅箔の粗化処理面に、乾燥後の厚さが１００μｍとなるように塗布し、１２０℃、６分間の加熱条件で乾燥させ、溶剤を気散して、Ｂステージの半硬化状態の樹脂が積層された樹脂層付銅箔を得た。キャリア付銅箔は、表面粗さ（Ｒｚｊｉｓ）が１．７μｍであり、厚さが２μｍのものであった。このキャリア付銅箔は、ニッケル２１ｍｇ／ｍ２、亜鉛８ｍｇ／ｍ２、及びクロム３ｍｇ／ｍ２の防錆処理が施されているものであり、また、アミノ系シランカップリング剤の表面処理が施されているものであった。[Example 1]
The components shown in Table 2 below are weighed at the compounding ratio shown in the same table, using methyl ethyl ketone as the solvent and having a solid content of 60 parts by mass, placed in a flask, heated to a temperature of 60 ° C., and stirred with a propeller for 1 hour. The mixture was stirred with an apparatus to obtain a resin composition (resin varnish). This resin composition is applied to the roughened surface of the copper foil with a carrier using an edge coater so that the thickness after drying is 100 μm, dried at 120 ° C. for 6 minutes, and a solvent is used. Was dissipated to obtain a copper foil with a resin layer on which a semi-cured resin of the B stage was laminated. The copper foil with a carrier had a surface roughness (Rzjis) of 1.7 μm and a thickness of 2 μm. The copper foil with a carrier is intended Nickel 21 mg / m 2, zinc 8 mg / m 2, and rust chrome 3 mg / m 2 is applied, also the surface treatment of the amino-based silane coupling agent It was given.
〔実施例２〕
実施例１において、乾燥後の厚さが４０μｍとなるように樹脂層を形成した。それ以外は実施例１と同様にして、樹脂層付銅箔を得た。[Example 2]
In Example 1, the resin layer was formed so that the thickness after drying was 40 μm. A copper foil with a resin layer was obtained in the same manner as in Example 1 except for the above.
〔実施例３ないし１４〕
樹脂組成物の配合を表２及び表３に示すとおりとした以外は実施例１と同様にして樹脂層付銅箔を得た。[Examples 3 to 14]
A copper foil with a resin layer was obtained in the same manner as in Example 1 except that the composition of the resin composition was as shown in Tables 2 and 3.
〔比較例１〕
本比較例では、表４に示すとおり、（メタ）アクリル樹脂として重量平均分子量が低いものを用いた。それ以外は実施例１と同様にして樹脂層付銅箔を得た。[Comparative Example 1]
In this comparative example, as shown in Table 4, a (meth) acrylic resin having a low weight average molecular weight was used. A copper foil with a resin layer was obtained in the same manner as in Example 1 except for the above.
〔比較例２〕
本比較例ではマレイミド化合物を用いなかった。また、樹脂組成物の配合を表４に示すとおりとした。それ以外は実施例１と同様にして樹脂層付銅箔を得た。[Comparative Example 2]
No maleimide compound was used in this comparative example. The composition of the resin composition was as shown in Table 4. A copper foil with a resin layer was obtained in the same manner as in Example 1 except for the above.
〔比較例３〕
本比較例では（メタ）アクリル樹脂を用いなかった。また、樹脂組成物の配合を表４に示すとおりとした。それ以外は実施例１と同様にして樹脂層付銅箔を得た。[Comparative Example 3]
No (meth) acrylic resin was used in this comparative example. The composition of the resin composition was as shown in Table 4. A copper foil with a resin layer was obtained in the same manner as in Example 1 except for the above.
〔比較例４〕
本比較例では（メタ）アクリル樹脂を用いず、それに代えてポリビニルアセタール樹脂を用いた。それ以外は実施例１と同様にして樹脂層付銅箔を得た。ポリビニルアセタール樹脂は、当該技術分野において可塑剤として用いられてきた物質である。[Comparative Example 4]
In this comparative example, a (meth) acrylic resin was not used, and a polyvinyl acetal resin was used instead. A copper foil with a resin layer was obtained in the same manner as in Example 1 except for the above. Polyvinyl acetal resin is a substance that has been used as a plasticizer in the art.
〔評価〕
実施例及び比較例で得られた樹脂層付銅箔について、巻き取り時のクラック防止性、ブロッキング防止性、及びレジンフローを以下の方法で評価した。
また、実施例及び比較例で得られた樹脂層付銅箔を硬化させた後の、寸法安定性、ガラス転移点、吸水率及び誘電特性（Ｄｆ）を以下の方法で測定した。それらの結果を以下の表２ないし４に示す。[Evaluation]
With respect to the copper foils with a resin layer obtained in Examples and Comparative Examples, the crack prevention property, the blocking prevention property, and the resin flow at the time of winding were evaluated by the following methods.
Further, the dimensional stability, the glass transition point, the water absorption rate and the dielectric property (Df) after curing the copper foil with the resin layer obtained in Examples and Comparative Examples were measured by the following methods. The results are shown in Tables 2 to 4 below.
〔クラック防止性〕
樹脂層付銅箔を、１０ｃｍ×１０ｃｍの寸法に切断して試料片を得た。この試料片を、樹脂層側が下面側となるように机上に載置し、上面の銅箔表面の中央部に直径１０ｍｍの円柱をその外周面が銅箔表面に接触するように配置し、この円柱に沿って試料片を上方に向けて折り曲げた。このとき樹脂層に割れ（クラック）が発生する最低折り曲げ角度を測定した。この角度に応じて以下の基準で評価した。ＡＡ：１３５度以上で割れなし（最良）Ａ：９０度以上１３５度未満で割れ発生（良）Ｂ：４５度以上９０度未満で割れ発生（可）Ｃ：４５度未満で割れ発生（不良）[Crack prevention]
A copper foil with a resin layer was cut to a size of 10 cm × 10 cm to obtain a sample piece. This sample piece was placed on a desk so that the resin layer side was on the lower surface side, and a cylinder having a diameter of 10 mm was placed at the center of the copper foil surface on the upper surface so that the outer peripheral surface was in contact with the copper foil surface. The sample piece was bent upward along the cylinder. At this time, the minimum bending angle at which cracks occur in the resin layer was measured. The evaluation was made according to the following criteria according to this angle. AA: No cracking at 135 degrees or more (best) A: Cracking at 90 degrees or more and less than 135 degrees (good) B: Cracking at 45 degrees or more and less than 90 degrees (possible) C: Cracking at less than 45 degrees (defective)
〔ブロッキング防止性〕
１０ｃｍ×１０ｃｍに切断した２０μｍ厚のキャリア付銅箔の光沢面に、同じ大きさの樹脂層付銅箔を、その樹脂層面が接するように重ねて、５００ｇの荷重を乗せ、温度３０℃、湿度４０％ＲＨの恒温恒湿オーブンに４８時間保存した。その後取り出して、樹脂層面と銅箔光沢面との付着の程度を以下の基準で評価した。Ａ：付着なし（良好）Ｂ：ほぼ付着なし（可）Ｃ：付着あり（不良）[Blocking prevention]
A copper foil with a resin layer of the same size is layered on the glossy surface of a 20 μm thick copper foil with a carrier cut into 10 cm × 10 cm so that the resin layer surface is in contact with each other, and a load of 500 g is applied to the temperature at 30 ° C. and humidity. It was stored in a constant temperature and humidity oven at 40% RH for 48 hours. After that, it was taken out and the degree of adhesion between the resin layer surface and the copper foil glossy surface was evaluated according to the following criteria. A: No adhesion (good) B: Almost no adhesion (possible) C: Adhesion (defective)
〔レジンフロー〕
レジンフローとは、ＭＩＬ規格におけるＭＩＬ−Ｐ−１３９４９Ｇに準拠して、樹脂層の厚さを４０μｍとした樹脂層付銅箔から１０ｃｍ角試料を４枚サンプリングし、この４枚の試料を重ねた状態（積層体）でプレス温度１７１℃、プレス圧１．４ＭＰａ、プレス時間１０分の条件で張り合わせ、そのときの樹脂の流出質量を測定した結果から以下の式に基づいて算出した値である。この値に応じて以下の基準で評価した。レジンフロー（％）＝流出樹脂質量／（樹脂層付銅箔質量−銅箔質量）×１００Ａ：８％以上２３％未満（良好）Ｂ：５％以上８％未満、又は２３％以上４０％未満（可）Ｃ：５％未満、又は４０％以上（不良）[Resin flow]
The resin flow is based on MIL-P-13949G in the MIL standard, and four 10 cm square samples were sampled from a copper foil with a resin layer having a resin layer thickness of 40 μm, and these four samples were stacked. It is a value calculated based on the following formula from the result of laminating under the conditions of a press temperature of 171 ° C., a press pressure of 1.4 MPa, and a press time of 10 minutes in a state (laminated body) and measuring the outflow mass of the resin at that time. The evaluation was made according to the following criteria according to this value. Resin flow (%) = mass of outflow resin / (mass of copper foil with resin layer-mass of copper foil) x 100A: 8% or more and less than 23% (good) B: 5% or more and less than 8%, or 23% or more and less than 40% (Yes) C: Less than 5% or 40% or more (defective)
〔寸法安定性〕
２枚の樹脂層付銅箔を、樹脂層どうしを向かい合わせて張り合わせ、真空プレス機にてプレスした。プレス条件は２２０℃×９０分、１ＭＰａとした。更に、プレスしたサンプルから銅箔をエッチングによって除去した。これによって厚さ約１９０μｍの樹脂フィルムを作製した。
ただし実施例２については以下の方法で樹脂フィルムを作製した。
２枚の樹脂層付銅箔を、樹脂層どうしを向かい合わせて張り合わせ、真空ラミネート機にてプレスした。プレス条件は１２０℃×３０秒、０．７ＭＰａとした。更に、プレスしたサンプルを、オーブンを用いて２００℃×１２０分の条件で後硬化させた。後硬化を行ったサンプルの銅箔をエッチングによって除去した。これによって厚さ約２００μｍの樹脂フィルムを作製した。
以上の樹脂フィルムについて、ＪＩＳ Ｃ ６４８１に準拠して測定した熱膨張係数を測定し寸法安定性の尺度とした。この値に応じて以下の基準で評価した。Ａ：２０ｐｐｍ／℃未満（良）Ｂ：２０ｐｐｍ／℃以上４５ｐｐｍ／℃未満（可）Ｃ：４５ｐｐｍ／℃以上（不良）[Dimensional stability]
Two copper foils with a resin layer were laminated with the resin layers facing each other and pressed with a vacuum press. The pressing conditions were 220 ° C. x 90 minutes and 1 MPa. Further, the copper foil was removed from the pressed sample by etching. As a result, a resin film having a thickness of about 190 μm was produced.
However, in Example 2, a resin film was produced by the following method.
Two copper foils with a resin layer were laminated with the resin layers facing each other and pressed by a vacuum laminating machine. The pressing conditions were 120 ° C. × 30 seconds and 0.7 MPa. Further, the pressed sample was post-cured in an oven under the conditions of 200 ° C. × 120 minutes. The copper foil of the post-cured sample was removed by etching. As a result, a resin film having a thickness of about 200 μm was produced.
For the above resin films, the coefficient of thermal expansion measured in accordance with JIS C 6481 was measured and used as a measure of dimensional stability. The evaluation was made according to the following criteria according to this value. A: Less than 20ppm / ° C (good) B: 20ppm / ° C or more and less than 45ppm / ° C (possible) C: 45ppm / ° C or more (poor)
〔ガラス転移点〕
寸法安定性の項で得た樹脂フィルムを用い、これを４０ｍｍ×５ｍｍに切り出した。これを測定試料とし、動的粘弾性測定装置（ＤＭＡ）を用いてガラス転移点測定した（測定条件：引張モード、周波数１Ｈｚ、昇温速度：５℃／ｍｉｎ）。この値に応じて以下の基準で評価した。Ａ：２６０℃以上（良）Ｂ：２００℃以上２６０℃未満（可）Ｃ：２００℃未満（不良）[Glass transition point]
Using the resin film obtained in the section of dimensional stability, this was cut out to 40 mm × 5 mm. Using this as a measurement sample, the glass transition point was measured using a dynamic viscoelasticity measuring device (DMA) (measurement conditions: tensile mode, frequency 1 Hz, heating rate: 5 ° C./min). The evaluation was made according to the following criteria according to this value. A: 260 ° C or higher (good) B: 200 ° C or higher and lower than 260 ° C (possible) C: less than 200 ° C (defective)
〔吸水率〕
ＪＩＳ Ｃ６４８１に基づき測定した。寸法安定性の項で得た樹脂フィルムを用い、これを５０ｍｍ×５０ｍｍに切り出し質量を測定した。煮沸している水中に測定試料を１時間浸漬させた。その後、水中から引き上げ、測定試料の表面に付着した水をふき取った後、その質量を測定し、浸漬前後の差から吸水量を算出した。この値に応じて以下の基準で評価した。Ａ：０．７％未満（良）Ｂ：０．７％以上１．２％未満（可）Ｃ：１．２％以上（不良）[Water absorption rate]
Measured based on JIS C6481. Using the resin film obtained in the section of dimensional stability, this was cut out to 50 mm × 50 mm and the mass was measured. The measurement sample was immersed in boiling water for 1 hour. Then, it was pulled up from the water, the water adhering to the surface of the measurement sample was wiped off, the mass was measured, and the amount of water absorption was calculated from the difference before and after immersion. The evaluation was made according to the following criteria according to this value. A: Less than 0.7% (good) B: 0.7% or more and less than 1.2% (possible) C: 1.2% or more (bad)
〔誘電特性〕
前記の〔寸法安定性〕の項で得た樹脂フィルムを用い、ネットワークアナライザー（キーサイト社製、ＰＮＡ−ｌ Ｎ５２３４Ａ）を用いてＳＰＤＲ誘電体共振器法により、３ＧＨｚにおける誘電正接を測定した。この測定はＡＳＴＭＤ２５２０（ＪＩＳ Ｃ２５６５）に準拠して行い、測定結果を誘電正接（Ｄｆ）の値とした。[Dielectric characteristics]
Using the resin film obtained in the above [Dimensional stability] section, the dielectric loss tangent at 3 GHz was measured by the SPDR dielectric resonator method using a network analyzer (PNA-l N5234A, manufactured by Keysight). This measurement was performed in accordance with ASTMD2520 (JIS C2565), and the measurement result was taken as the value of dielectric tangent (Df).
表２ないし４に示す結果から明らかなとおり、各実施例で得られた樹脂組成物を用いて得られた樹脂層付銅箔は、いずれもクラックの発生が防止され、またブロッキングの発生も防止されたものであることが判る。更に、樹脂組成物の流動性が良好である。しかも硬化体が寸法安定性に優れ、高周波での誘電特性（Ｄｆ）も低いものである。 As is clear from the results shown in Tables 2 to 4, the copper foils with the resin layer obtained by using the resin compositions obtained in each example prevent the occurrence of cracks and also prevent the occurrence of blocking. It turns out that it was done. Further, the fluidity of the resin composition is good. Moreover, the cured product has excellent dimensional stability and low dielectric properties (Df) at high frequencies.
本発明によれば、Ｂステージの状態で高い可とう性を有し、且つ硬化体が熱に対して寸法安定性が高いプリント配線板用樹脂組成物が提供される。 According to the present invention, there is provided a resin composition for a printed wiring board which has high flexibility in a B stage state and whose cured product has high dimensional stability with respect to heat.
Claims (10)
重量平均分子量が５万以上の（メタ）アクリル樹脂と、
前記マレイミド化合物の硬化促進剤と、
エポキシ樹脂と、
前記エポキシ樹脂の硬化剤と、
無機フィラーと、を含有し、
前記マレイミド化合物が、ビフェニル骨格を有するマレイミド化合物であり、
前記硬化促進剤が、イミダゾール系化合物であり、
前記硬化剤が、前記エポキシ樹脂との硬化反応に寄与し、前記マレイミド化合物の硬化反応に寄与しない化合物であり、
前記マレイミド化合物と、前記（メタ）アクリル樹脂と、前記硬化促進剤との合計１００質量部に対して、
前記マレイミド化合物が２５質量部以上８９質量部以下含まれ、
前記（メタ）アクリル樹脂が７質量部以上７０質量部以下含まれ、
前記無機フィラーが１００質量部以上４００質量部以下含まれる、プリント配線板用樹脂組成物。 Maleimide compound and
(Meta) acrylic resin with a weight average molecular weight of 50,000 or more,
With the curing accelerator of the maleimide compound,
Epoxy resin and
With the epoxy resin curing agent,
Contains inorganic filler,
The maleimide compound is a maleimide compound having a biphenyl skeleton.
The curing accelerator is an imidazole compound, and the curing accelerator is an imidazole compound.
The curing agent is a compound that contributes to the curing reaction with the epoxy resin and does not contribute to the curing reaction of the maleimide compound.
With respect to a total of 100 parts by mass of the maleimide compound, the (meth) acrylic resin, and the curing accelerator.
The maleimide compound is contained in an amount of 25 parts by mass or more and 89 parts by mass or less.
The (meth) acrylic resin is contained in an amount of 7 parts by mass or more and 70 parts by mass or less.
A resin composition for a printed wiring board containing 100 parts by mass or more and 400 parts by mass or less of the inorganic filler.
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| WO2019073891A1 (en) * | 2017-10-10 | 2019-04-18 | 三井金属鉱業株式会社 | Resin composition for printed wiring board, copper foil with resin, copper-clad laminate board, and printed wiring board |
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