JP6221203B2 - Resin composition, prepreg and laminate using the same - Google Patents
Resin composition, prepreg and laminate using the same Download PDFInfo
- Publication number
- JP6221203B2 JP6221203B2 JP2012058018A JP2012058018A JP6221203B2 JP 6221203 B2 JP6221203 B2 JP 6221203B2 JP 2012058018 A JP2012058018 A JP 2012058018A JP 2012058018 A JP2012058018 A JP 2012058018A JP 6221203 B2 JP6221203 B2 JP 6221203B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- compound
- mass
- parts
- thermosetting resin
- 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.)
- Expired - Fee Related
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- 239000011342 resin composition Substances 0.000 title claims description 34
- 229920005989 resin Polymers 0.000 claims description 140
- 239000011347 resin Substances 0.000 claims description 140
- 150000001875 compounds Chemical class 0.000 claims description 67
- 229920001187 thermosetting polymer Polymers 0.000 claims description 53
- 238000006243 chemical reaction Methods 0.000 claims description 50
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate group Chemical group [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims description 43
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 36
- 238000004519 manufacturing process Methods 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 17
- 125000003700 epoxy group Chemical group 0.000 claims description 12
- 239000011256 inorganic filler Substances 0.000 claims description 12
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 7
- 238000010030 laminating Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 125000002524 organometallic group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 4
- 230000003796 beauty Effects 0.000 claims 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 125000005395 methacrylic acid group Chemical group 0.000 claims 2
- 125000001424 substituent group Chemical group 0.000 claims 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 45
- 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 45
- 229920000647 polyepoxide Polymers 0.000 description 28
- 239000011889 copper foil Substances 0.000 description 25
- 239000003822 epoxy resin Substances 0.000 description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 238000011156 evaluation Methods 0.000 description 20
- 229910052802 copper Inorganic materials 0.000 description 18
- 239000010949 copper Substances 0.000 description 18
- -1 cyanate compound Chemical class 0.000 description 18
- 239000005350 fused silica glass Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 125000000524 functional group Chemical group 0.000 description 14
- 238000005259 measurement Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 150000002989 phenols Chemical class 0.000 description 10
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 239000004593 Epoxy Substances 0.000 description 9
- 239000004793 Polystyrene Substances 0.000 description 9
- 239000004305 biphenyl Substances 0.000 description 9
- 235000010290 biphenyl Nutrition 0.000 description 9
- 230000008034 disappearance Effects 0.000 description 9
- 229920002223 polystyrene Polymers 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000003063 flame retardant Substances 0.000 description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 description 8
- 239000011707 mineral Substances 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 229910000679 solder Inorganic materials 0.000 description 8
- 238000013329 compounding Methods 0.000 description 7
- 239000003480 eluent Substances 0.000 description 7
- 238000010828 elution Methods 0.000 description 7
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 7
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 6
- 238000005530 etching Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229930185605 Bisphenol Natural products 0.000 description 5
- 150000001299 aldehydes Chemical class 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000005979 thermal decomposition reaction Methods 0.000 description 5
- 239000002966 varnish Substances 0.000 description 5
- 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 4
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 4
- 125000002723 alicyclic group Chemical group 0.000 description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 125000005641 methacryl group Chemical group 0.000 description 4
- 150000004780 naphthols Chemical class 0.000 description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 4
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 4
- ALNBMSFIZFUDMD-UHFFFAOYSA-N 3,4-dimethylnaphthalene-1,2-diol Chemical compound C1=CC=C2C(O)=C(O)C(C)=C(C)C2=C1 ALNBMSFIZFUDMD-UHFFFAOYSA-N 0.000 description 3
- 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 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 239000003849 aromatic solvent Substances 0.000 description 3
- 229910001593 boehmite Inorganic materials 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 229930003836 cresol Natural products 0.000 description 3
- 150000004677 hydrates Chemical class 0.000 description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000012796 inorganic flame retardant Substances 0.000 description 3
- 239000011810 insulating material Substances 0.000 description 3
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 3
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- OVAZZMXASSWARN-UHFFFAOYSA-N naphthalen-1-ylmethanediol Chemical compound C1=CC=C2C(C(O)O)=CC=CC2=C1 OVAZZMXASSWARN-UHFFFAOYSA-N 0.000 description 3
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- OHBQPCCCRFSCAX-UHFFFAOYSA-N 1,4-Dimethoxybenzene Chemical compound COC1=CC=C(OC)C=C1 OHBQPCCCRFSCAX-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
- 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 2
- AUFZRCJENRSRLY-UHFFFAOYSA-N 2,3,5-trimethylhydroquinone Chemical compound CC1=CC(O)=C(C)C(C)=C1O AUFZRCJENRSRLY-UHFFFAOYSA-N 0.000 description 2
- CZAZXHQSSWRBHT-UHFFFAOYSA-N 2-(2-hydroxyphenyl)-3,4,5,6-tetramethylphenol Chemical compound OC1=C(C)C(C)=C(C)C(C)=C1C1=CC=CC=C1O CZAZXHQSSWRBHT-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- ZTMADXFOCUXMJE-UHFFFAOYSA-N 2-methylbenzene-1,3-diol Chemical compound CC1=C(O)C=CC=C1O ZTMADXFOCUXMJE-UHFFFAOYSA-N 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
- CNGYZEMWVAWWOB-VAWYXSNFSA-N 5-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-[(e)-2-[4-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound N=1C(NC=2C=C(C(\C=C\C=3C(=CC(NC=4N=C(N=C(NC=5C=CC=CC=5)N=4)N(CCO)CCO)=CC=3)S(O)(=O)=O)=CC=2)S(O)(=O)=O)=NC(N(CCO)CCO)=NC=1NC1=CC=CC=C1 CNGYZEMWVAWWOB-VAWYXSNFSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- 229910002706 AlOOH Inorganic materials 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 229950011260 betanaphthol Drugs 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- BXJGUBZTZWCMEX-UHFFFAOYSA-N dimethylhydroquinone Natural products CC1=C(C)C(O)=CC=C1O BXJGUBZTZWCMEX-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 2
- 229960001867 guaiacol Drugs 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- ASHGTJPOSUFTGB-UHFFFAOYSA-N methyl resorcinol Natural products COC1=CC=CC(O)=C1 ASHGTJPOSUFTGB-UHFFFAOYSA-N 0.000 description 2
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 1
- MODAACUAXYPNJH-UHFFFAOYSA-N 1-(methoxymethyl)-4-[4-(methoxymethyl)phenyl]benzene Chemical group C1=CC(COC)=CC=C1C1=CC=C(COC)C=C1 MODAACUAXYPNJH-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- BBBUAWSVILPJLL-UHFFFAOYSA-N 2-(2-ethylhexoxymethyl)oxirane Chemical compound CCCCC(CC)COCC1CO1 BBBUAWSVILPJLL-UHFFFAOYSA-N 0.000 description 1
- HHRACYLRBOUBKM-UHFFFAOYSA-N 2-[(4-tert-butylphenoxy)methyl]oxirane Chemical compound C1=CC(C(C)(C)C)=CC=C1OCC1OC1 HHRACYLRBOUBKM-UHFFFAOYSA-N 0.000 description 1
- NDOPHXWIAZIXPR-UHFFFAOYSA-N 2-bromobenzaldehyde Chemical compound BrC1=CC=CC=C1C=O NDOPHXWIAZIXPR-UHFFFAOYSA-N 0.000 description 1
- FPYUJUBAXZAQNL-UHFFFAOYSA-N 2-chlorobenzaldehyde Chemical compound ClC1=CC=CC=C1C=O FPYUJUBAXZAQNL-UHFFFAOYSA-N 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
- MEEKGULDSDXFCN-UHFFFAOYSA-N 2-pentylphenol Chemical compound CCCCCC1=CC=CC=C1O MEEKGULDSDXFCN-UHFFFAOYSA-N 0.000 description 1
- DOYKFSOCSXVQAN-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C(C)=C DOYKFSOCSXVQAN-UHFFFAOYSA-N 0.000 description 1
- FKSAYGREWVVCIZ-UHFFFAOYSA-N 3-methyl-1-phenylbut-3-en-1-one Chemical compound CC(=C)CC(=O)C1=CC=CC=C1 FKSAYGREWVVCIZ-UHFFFAOYSA-N 0.000 description 1
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- 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 1
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
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- WSMYVTOQOOLQHP-UHFFFAOYSA-N Malondialdehyde Chemical compound O=CCC=O WSMYVTOQOOLQHP-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 241000796522 Olene Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 1
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- XMUZQOKACOLCSS-UHFFFAOYSA-N [2-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=CC=C1CO XMUZQOKACOLCSS-UHFFFAOYSA-N 0.000 description 1
- NOHQTLHHNIKWBA-UHFFFAOYSA-N [SiH4].NC(=O)N Chemical compound [SiH4].NC(=O)N NOHQTLHHNIKWBA-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000002635 aromatic organic solvent Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 239000012965 benzophenone Chemical class 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical class [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
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- 239000013065 commercial product Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
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- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
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- 238000001035 drying Methods 0.000 description 1
- 239000012772 electrical insulation material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical group FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- 239000012784 inorganic fiber Substances 0.000 description 1
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- 150000002576 ketones Chemical class 0.000 description 1
- SGGOJYZMTYGPCH-UHFFFAOYSA-L manganese(2+);naphthalene-2-carboxylate Chemical compound [Mn+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 SGGOJYZMTYGPCH-UHFFFAOYSA-L 0.000 description 1
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- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- NCIAGQNZQHYKGR-UHFFFAOYSA-N naphthalene-1,2,3-triol Chemical compound C1=CC=C2C(O)=C(O)C(O)=CC2=C1 NCIAGQNZQHYKGR-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- QBDSZLJBMIMQRS-UHFFFAOYSA-N p-Cumylphenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=CC=C1 QBDSZLJBMIMQRS-UHFFFAOYSA-N 0.000 description 1
- NKTOLZVEWDHZMU-UHFFFAOYSA-N p-cumyl phenol Natural products CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- ZWLUXSQADUDCSB-UHFFFAOYSA-N phthalaldehyde Chemical compound O=CC1=CC=CC=C1C=O ZWLUXSQADUDCSB-UHFFFAOYSA-N 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
Description
本発明は、熱硬化性樹脂を含む樹脂組成物、及びこれを用いたプリプレグ及び積層板に関する。 The present invention relates to a resin composition containing a thermosetting resin, and a prepreg and a laminate using the same.
熱硬化性樹脂は、特有の架橋構造を有しており、この架橋構造が高い耐熱性や寸法安定性を発現するため、電子部品等の分野において広く使われている。特に、近年、電子機器の小型化、軽量化、動作周波数の高速化が一段と進み、プリント配線及び回路パターンの高密度化や高信頼性が要求されている。
銅張積層板では、プリント配線及び回路パターンが高密度化に伴い、プリント配線及び回路パターンを構成する導体層である銅箔との接着性や、耐熱性、良好な低熱膨張性等が必要とされている。
Thermosetting resins have a specific cross-linked structure, and since this cross-linked structure exhibits high heat resistance and dimensional stability, it is widely used in the field of electronic components and the like. In particular, in recent years, electronic devices have become smaller, lighter, and faster in operating frequency, and high density and high reliability of printed wiring and circuit patterns are required.
With copper-clad laminates, as printed wiring and circuit patterns increase in density, adhesiveness with copper foil, which is a conductor layer constituting printed wiring and circuit patterns, heat resistance, good low thermal expansion, etc. are required. Has been.
また、近年、環境問題への関心の高まりから、鉛フリーはんだやハロゲンフリー基板のニーズが高まっている。しかし、鉛フリーはんだプロセスに要求されるリフロー温度は、通常のはんだの温度条件よりも高い。また、ハロゲンフリー基板は、通常のハロゲン含有基板に比べて難燃性に劣る。このため、鉛フリーはんだやハロゲンフリー基板であって、高い耐熱性及び難燃性を有する基板が必要とされる。 In recent years, the need for lead-free solders and halogen-free substrates has increased due to increased interest in environmental issues. However, the reflow temperature required for the lead-free solder process is higher than the normal solder temperature condition. Further, the halogen-free substrate is inferior in flame retardancy as compared with a normal halogen-containing substrate. Therefore, a lead-free solder or halogen-free substrate that has high heat resistance and flame resistance is required.
熱硬化性樹脂であるシアネート化合物は、低誘電特性、難燃性に優れる樹脂である。しかし、シアネート化合物は、エポキシ硬化系の熱硬化性樹脂にそのまま使用された場合、耐熱性や強靭性が不足する問題があった。また、薄型化されたプリプレグは、反りやすくなるため、熱処理時におけるプリプレグの反りを低減するための低熱膨張性が得られないことがあった。
特許文献１、２および３には、シアネート化合物と無機充填剤からなり、低熱膨張性を発現させる樹脂組成物が開示されているが、これらは低熱膨張性を発現させるため無機充填剤の配合量が多く、銅張積層板や層間絶縁材料として使用した場合、成形性が不足する。
The cyanate compound which is a thermosetting resin is a resin having low dielectric properties and excellent flame retardancy. However, when the cyanate compound is used as it is for an epoxy curable thermosetting resin, there is a problem that heat resistance and toughness are insufficient. Further, since the thinned prepreg is easily warped, low thermal expansion for reducing the warpage of the prepreg during heat treatment may not be obtained.
Patent Documents 1, 2 and 3 disclose resin compositions comprising a cyanate compound and an inorganic filler and exhibiting a low thermal expansion property. However, since these exhibit a low thermal expansion property, the blending amount of the inorganic filler is disclosed. In many cases, when used as a copper clad laminate or an interlayer insulating material, formability is insufficient.
また、特許文献４，５にシアネート樹脂とアラルキル変性エポキシ樹脂を必須成分として含有する熱硬化性樹脂に関する事例が開示されている。しかし、必須成分であるシアネート樹脂は、靱性や硬化反応性に劣る樹脂である。このため、この熱硬化性樹脂の硬化反応性や強靱性の改良が必要であり、銅張積層板や層間絶縁層材料として使用した場合、耐熱性、信頼性、加工性等が十分ではなかった。
さらに、製品の安全性や作業環境の向上のため、毒性の低い成分のみで構成され、製造工程において有毒ガス等が発生しない熱硬化性樹脂が望まれている。
Patent Documents 4 and 5 disclose examples relating to thermosetting resins containing a cyanate resin and an aralkyl-modified epoxy resin as essential components. However, the cyanate resin which is an essential component is a resin inferior in toughness and curing reactivity. For this reason, it is necessary to improve the curing reactivity and toughness of this thermosetting resin, and when used as a copper clad laminate or interlayer insulation layer material, heat resistance, reliability, workability, etc. were not sufficient. .
Furthermore, in order to improve the safety of the product and the working environment, there is a demand for a thermosetting resin that includes only low-toxic components and does not generate toxic gases or the like in the manufacturing process.
このように、多層プリント配線板などの回路基板に用いられる樹脂組成物であって、低熱膨張性、銅箔接着性、耐熱性、誘電特性に優れる樹脂組成物を得ることが困難であった。 As described above, it is difficult to obtain a resin composition used for a circuit board such as a multilayer printed wiring board, which is excellent in low thermal expansion, copper foil adhesion, heat resistance, and dielectric properties.
本発明は、低熱膨張性、銅箔接着性、耐熱性、誘電特性に優れる樹脂組成物、これを用いたプリプレグ及び積層板を提供することを目的とする。 An object of this invention is to provide the resin composition which is excellent in low thermal expansion property, copper foil adhesiveness, heat resistance, and a dielectric characteristic, a prepreg using this, and a laminated board.
本発明者らは、上記の課題を解決すべく検討を進めた結果、特定構造を有するシロキサン樹脂と、１分子中に少なくとも２個のシアネート基を有する化合物と、１分子中に少なくとも２個のエポキシ基を有する化合物とを特定量用いて反応させて得られる熱硬化性樹脂を含む樹脂組成物が、低熱膨張性、銅箔接着性、耐熱性、誘電特性に優れることを見出した。本発明は、かかる知見に基づいて完成したものである。 As a result of investigations to solve the above problems, the present inventors have determined that a siloxane resin having a specific structure, a compound having at least two cyanate groups in one molecule, and at least two in one molecule It has been found that a resin composition containing a thermosetting resin obtained by reacting with a specific amount of a compound having an epoxy group is excellent in low thermal expansion, copper foil adhesion, heat resistance and dielectric properties. The present invention has been completed based on such findings.
本発明は、以下のものに関する。
［１］下記一般式（１）で示されるシロキサン樹脂（ａ）と、
１分子中に少なくとも２個のシアネート基を有する化合物（ｂ）と、
１分子中に少なくとも２個のエポキシ基を有する化合物（ｃ）とを、
シロキサン樹脂（ａ）、化合物（ｂ）及び化合物（ｃ）の総和１００質量部あたり、シロキサン樹脂（ａ）１０〜５０質量部、該化合物（ｂ）４０〜８０質量部、及び該化合物（ｃ）１０〜５０質量部の割合で用いて、有機溶媒中で、該化合物（ｂ）の反応率が３０〜７０ｍｏｌ％となるように反応させて得られた熱硬化性樹脂を含有する樹脂組成物、
［２］反応触媒として有機金属塩（ｄ）を含む前記溶媒中で反応させて得られた上記［１］の樹脂組成物、
［３］上記［１］又は［２］の樹脂組成物が基材に含浸又は塗布されたプリプレグ、
及び［４］上記［３］のプリプレグを複数枚積層して形成された積層板。
The present invention relates to the following.
[1] A siloxane resin (a) represented by the following general formula (1):
A compound (b) having at least two cyanate groups in one molecule;
A compound (c) having at least two epoxy groups in one molecule;
10-100 parts by mass of the siloxane resin (a), 40-80 parts by mass of the compound (b), and the compound (c) per 100 parts by mass of the total of the siloxane resin (a), the compound (b), and the compound (c). A resin composition containing a thermosetting resin obtained by reacting the compound (b) so as to have a reaction rate of 30 to 70 mol% in an organic solvent at a ratio of 10 to 50 parts by mass;
[2] The resin composition of the above-mentioned [1] obtained by reacting in the solvent containing the organometallic salt (d) as a reaction catalyst,
[3] A prepreg in which a base material is impregnated or coated with the resin composition of [1] or [2],
And [4] A laminate formed by laminating a plurality of the prepregs of [3] above.
本発明によれば、低熱膨張性、銅箔接着性、耐熱性、誘電特性に優れる樹脂組成物、これを用いたプリプレグ及び積層板を提供することができる。 According to the present invention, it is possible to provide a resin composition excellent in low thermal expansion, copper foil adhesion, heat resistance, and dielectric properties, and a prepreg and a laminate using the resin composition.
以下、本発明の実施形態について詳細に説明する。
［熱硬化性樹脂］
本発明に係る熱硬化性樹脂は、下記一般式（１）で示されるシロキサン樹脂（ａ）と、１分子中に少なくとも２個のシアネート基を有する化合物（ｂ）と、１分子中に少なくとも２個のエポキシ基を有する化合物（ｃ）とを、シロキサン樹脂（ａ）、化合物（ｂ）及び化合物（ｃ）の総和１００質量部あたり、シロキサン樹脂（ａ）１０〜５０質量部、該化合物（ｂ）４０〜８０質量部、及び該化合物（ｃ）１０〜５０質量部の割合で用いて、有機溶媒中で、該化合物（ｂ）の反応率が３０〜７０ｍｏｌ％となるように反応させて得られる。
Hereinafter, embodiments of the present invention will be described in detail.
[Thermosetting resin]
The thermosetting resin according to the present invention includes a siloxane resin (a) represented by the following general formula (1), a compound (b) having at least two cyanate groups in one molecule, and at least 2 in one molecule. 10 to 50 parts by mass of the siloxane resin (a), the compound (b), and the compound (c) are added to 10 to 50 parts by mass of the compound (b). ) 40-80 parts by mass and 10-50 parts by mass of the compound (c), and obtained by reacting in an organic solvent so that the reaction rate of the compound (b) is 30-70 mol%. It is done.
＜シロキサン樹脂（ａ）＞
本発明の熱硬化性樹脂を構成するシロキサン樹脂（ａ）は、上記一般式（１）で表される構造を有していれば、特に限定されない。
両末端にカルボキシ基を有するシロキサン樹脂（ａ）の市販品としては、例えば、信越化学工業株式会社製、商品名Ｘ−２２−１６２Ｃ（官能基当量：２３３０ｇ／ｍｏｌ）が挙げられる。
両末端にメタクリル基を有するシロキサン樹脂（ａ）の市販品としては、例えば、信越化学工業株式会社製、商品名Ｘ−２２−１６４Ａ（官能基当量：９５０ｇ／ｍｏｌ）、商品名Ｘ−２２−１６４Ｂ（官能基当量：１６３０ｇ／ｍｏｌ）、商品名Ｘ−２２−１６４Ｃ（官能基当量：２３７０ｇ／ｍｏｌ）等が挙げられる。
両末端にグリシジル基を有するシロキサン樹脂（ａ）の市販品としては、例えば、信越化学工業株式会社製、商品名ＫＦ−１０５（官能基当量：４９０ｇ／ｍｏｌ）、商品名Ｘ−２２−１６３Ａ（官能基当量：９５０ｇ／ｍｏｌ）、商品名Ｘ−２２−１６３Ｂ（官能基当量：１７６０ｇ／ｍｏｌ）、商品名Ｘ−２２−１６３Ｃ（官能基当量：２７９０ｇ／ｍｏｌ）が挙げられる。
両末端に脂環式エポキシ基を有するシロキサン樹脂（ａ）の市販品としては、例えば、信越化学工業株式会社製、商品名Ｘ−２２−１６９ＡＳ（官能基当量：５３０ｇ／ｍｏｌ）、商品名Ｘ−２２−１６９Ｂ（官能基当量：１６７０ｇ／ｍｏｌ）が挙げられる。
両末端にメルカプト基を有するシロキサン樹脂（ａ）の市販品としては、例えば、信越化学工業株式会社製、商品名Ｘ−２２−１６７Ｂ（官能基当量：１６７０ｇ／ｍｏｌ）が挙げられる。
<Siloxane resin (a)>
The siloxane resin (a) constituting the thermosetting resin of the present invention is not particularly limited as long as it has the structure represented by the general formula (1).
As a commercial item of the siloxane resin (a) having a carboxy group at both ends, for example, trade name X-22-162C (functional group equivalent: 2330 g / mol) manufactured by Shin-Etsu Chemical Co., Ltd. may be mentioned.
As a commercial item of the siloxane resin (a) having a methacryl group at both ends, for example, trade name X-22-164A (functional group equivalent: 950 g / mol) manufactured by Shin-Etsu Chemical Co., Ltd., trade name X-22 164B (functional group equivalent: 1630 g / mol), trade name X-22-164C (functional group equivalent: 2370 g / mol), and the like.
As a commercial item of the siloxane resin (a) having a glycidyl group at both ends, for example, trade name KF-105 (functional group equivalent: 490 g / mol), trade name X-22-163A (manufactured by Shin-Etsu Chemical Co., Ltd.) Functional group equivalent: 950 g / mol), trade name X-22-163B (functional group equivalent: 1760 g / mol), trade name X-22-163C (functional group equivalent: 2790 g / mol).
As a commercial item of the siloxane resin (a) having an alicyclic epoxy group at both ends, for example, trade name X-22-169AS (functional group equivalent: 530 g / mol) manufactured by Shin-Etsu Chemical Co., Ltd., trade name X -22-169B (functional group equivalent: 1670 g / mol).
As a commercial item of the siloxane resin (a) having a mercapto group at both ends, for example, trade name X-22-167B (functional group equivalent: 1670 g / mol) manufactured by Shin-Etsu Chemical Co., Ltd. may be mentioned.
＜化合物（ｂ）＞
本発明の熱硬化性樹脂を構成する化合物（ｂ）は、１分子中に少なくとも２個のシアネート基を有する。化合物（ｂ）としては、例えば、ノボラック型シアネート樹脂、ビスフェノールＡ型シアネート樹脂、ビスフェノールＥ型シアネート樹脂、ビスフェノールＦ型シアネート樹脂、テトラメチルビスフェノールＦ型シアネート樹脂等が挙げられ、これらのうち１種又は２種以上を混合して使用することができる。これらの中で、誘電特性、耐熱性、難燃性、低熱膨張性、及び安価である点から、ビスフェノールＡ型シアネート樹脂、又は下記一般式（２）に示すノボラック型シアネート樹脂が好ましい。
<Compound (b)>
The compound (b) constituting the thermosetting resin of the present invention has at least two cyanate groups in one molecule. Examples of the compound (b) include novolak type cyanate resin, bisphenol A type cyanate resin, bisphenol E type cyanate resin, bisphenol F type cyanate resin, tetramethylbisphenol F type cyanate resin, etc. Two or more kinds can be mixed and used. Among these, bisphenol A type cyanate resin or novolak type cyanate resin represented by the following general formula (2) is preferable from the viewpoints of dielectric properties, heat resistance, flame retardancy, low thermal expansion, and low cost.
化合物（ｂ）として使用可能なビスフェノールＡ型シアネート樹脂の市販品としては、ロンザジャパン株式会社製、商品名Ａｒｏｃｙ Ｂ−１０が挙げられる。また、ノボラック型シアネート樹脂の市販品としては、ロンザジャパン株式会社製、商品名プリマセットＰＴ−３０（重量平均分子量５００〜１，０００）、商品名プリマセットＰＴ−６０（重量平均分子量２，０００〜３，０００）等が挙げられる。
As a commercial product of bisphenol A type cyanate resin that can be used as the compound (b), Lonza Japan Co., Ltd., trade name Arocy B-10 can be mentioned. Moreover, as a commercial item of a novolak-type cyanate resin, Lonza Japan Co., Ltd. make, brand name Primaset PT-30 (weight average molecular weight 500-1,000), brand name Primaset PT-60 (weight average molecular weight 2,000) ~ 3,000).
＜化合物（ｃ）＞
本発明の熱硬化性樹脂組成物を構成する化合物（ｃ）は、１分子中に少なくとも２個のエポキシ基を有する。化合物（ｃ）としては、例えば、ビスフェノールＡ系、ビスフェノールＦ系、テトラメチルビスフェノールＦ系、ビスフェノールＳ系、ビスフェノールＫ系、ビフェノール系、テトラメチルビフェノールビフェニル系、ノボラック系、多官能フェノール系、ナフタレン系、脂環式系及びアルコール系等のグリシジルエーテル、グリシジルアミン系並びにグリシジルエステル系が挙げられ、これらのうち１種又は２種以上を混合して使用することができる。
上述した化合物（ｃ）の中では、高剛性、誘電特性、耐熱性、難燃性、及び低熱膨張性の点から、ナフタレン型エポキシ樹脂、ナフトールアラルキル型エポキシ樹脂、ジヒドロキシナフタレンアラルキル型エポキシ樹脂、ナフトールアラルキル・クレゾール共重合型エポキシ樹脂等のナフタレン環含有エポキシ樹脂、ビフェニル型エポキシ樹脂、ビフェニルアラルキル型エポキシ樹脂等のビフェニル基含有エポキシ樹脂が好ましい。
さらに、芳香族系有機溶剤への溶解性の点から、ナフトールアラルキル型エポキシ樹脂、ナフトールアラルキル・クレゾール共重合型エポキシ樹脂、ビフェニル型エポキシ樹脂がより好ましい。さらに、安価であることやエポキシ当量が小さく少量の配合でよいことから、一般式（３）で表されるビフェニル型エポキシ樹脂を使用することが、特に好ましい。
<Compound (c)>
The compound (c) constituting the thermosetting resin composition of the present invention has at least two epoxy groups in one molecule. Examples of the compound (c) include bisphenol A, bisphenol F, tetramethylbisphenol F, bisphenol S, bisphenol K, biphenol, tetramethylbiphenol biphenyl, novolac, polyfunctional phenol, and naphthalene. And glycidyl ethers such as alicyclic type and alcohol type, glycidyl amine type and glycidyl ester type. Among these, one kind or a mixture of two or more kinds can be used.
Among the above-mentioned compounds (c), naphthalene type epoxy resin, naphthol aralkyl type epoxy resin, dihydroxynaphthalene aralkyl type epoxy resin, naphthol are used in terms of high rigidity, dielectric properties, heat resistance, flame retardancy, and low thermal expansion. A naphthalene ring-containing epoxy resin such as an aralkyl / cresol copolymerized epoxy resin, or a biphenyl group-containing epoxy resin such as a biphenyl type epoxy resin or a biphenyl aralkyl type epoxy resin is preferred.
Furthermore, from the viewpoint of solubility in an aromatic organic solvent, a naphthol aralkyl type epoxy resin, a naphthol aralkyl / cresol copolymer type epoxy resin, and a biphenyl type epoxy resin are more preferable. Furthermore, it is particularly preferable to use a biphenyl type epoxy resin represented by the general formula (3) because it is inexpensive and has a small epoxy equivalent and may contain a small amount.
＜熱硬化性樹脂の製造＞
本発明に係る熱硬化性樹脂は、シロキサン樹脂（ａ）、化合物（ｂ）及び化合物（ｃ）は、反応溶媒中で反応して得られる。熱硬化性樹脂を製造する際のシロキサン樹脂（ａ）、化合物（ｂ）及び化合物（ｃ）の配合量は、シロキサン樹脂（ａ）、化合物（ｂ）及び化合物（ｃ）の総和１００質量部あたり、シロキサン樹脂（ａ）１０〜５０質量部、化合物（ｂ）４０〜８０質量部、及び化合物（ｃ）１０〜５０質量部である。
シロキサン樹脂（ａ）の配合量が１０質量部未満であると、得られる基材の面方向の低熱膨張性が低下する場合があり、シロキサン樹脂（ａ）の配合量が５０質量部を超えると、耐熱性及び耐薬品性が低下する場合がある。また、化合物（ｂ）の配合量が４０質量部未満であると、得られる樹脂の相溶性が低下する場合があり、化合物（ｂ）の配合量が８０質量部を超えると、得られる基材の面方向の低熱膨張性が低下する場合がある。
また、化合物（ｃ）の配合量が１０質量部未満であると、耐湿耐熱性が低下する場合があり、化合物（ｃ）の配合量が５０質量部を超えると、銅箔接着性や誘電特性が低下する場合がある。
反応溶媒は、トルエン、キシレン、メシチレンから選択される溶媒、すなわち、芳香族系溶媒である。これら以外の溶剤を用いると、所望の反応が進行せず、耐熱性等が低下する。メシチレンよりも分子量の大きい芳香族系溶媒は、プリプレグの製造時に残溶剤となり易いため、好ましくない。また、芳香族系溶媒であっても、ベンゼンは、毒性が強いため、好ましくない。
<Manufacture of thermosetting resin>
The thermosetting resin according to the present invention is obtained by reacting the siloxane resin (a), the compound (b) and the compound (c) in a reaction solvent. The blending amount of the siloxane resin (a), the compound (b) and the compound (c) at the time of producing the thermosetting resin is about 100 parts by mass of the total of the siloxane resin (a), the compound (b) and the compound (c). Siloxane resin (a) 10-50 parts by mass, compound (b) 40-80 parts by mass, and compound (c) 10-50 parts by mass.
When the compounding amount of the siloxane resin (a) is less than 10 parts by mass, the low thermal expansion property in the surface direction of the obtained base material may be lowered, and when the compounding amount of the siloxane resin (a) exceeds 50 parts by mass. , Heat resistance and chemical resistance may decrease. Moreover, when the compounding quantity of a compound (b) is less than 40 mass parts, the compatibility of resin obtained may fall, and when the compounding quantity of a compound (b) exceeds 80 mass parts, the base material obtained will be obtained. In some cases, the low thermal expansibility in the surface direction of the film may decrease.
Moreover, when the compounding amount of the compound (c) is less than 10 parts by mass, the moisture and heat resistance may be lowered. When the compounding amount of the compound (c) is more than 50 parts by mass, the copper foil adhesion and dielectric properties are reduced. May decrease.
The reaction solvent is a solvent selected from toluene, xylene, and mesitylene, that is, an aromatic solvent. When a solvent other than these is used, the desired reaction does not proceed and heat resistance and the like are reduced. An aromatic solvent having a molecular weight larger than that of mesitylene is not preferable because it tends to become a residual solvent during the production of the prepreg. Even if it is an aromatic solvent, benzene is not preferred because it is highly toxic.
シロキサン樹脂（ａ）、化合物（ｂ）及び化合物（ｃ）は、上記溶媒に均一に溶解されて、８０℃〜１２０℃の反応温度で、化合物（ｂ）の反応率（消失率ともいう）が３０〜７０ｍｏｌ％となるように反応させられることが好ましい。
ここで、化合物（ｂ）の反応率は、ＧＰＣ測定により求められる。すなわち、化合物（ｂ）の反応開始時のピーク面積と、所定時間反応した後のピーク面積とを比較し、ピーク面積の消失率から求められる。
反応率が３０ｍｏｌ％以上であると、得られる樹脂が相容化され、白濁もしないため、Ｂステージの塗布工程が容易に行える。反応率が７０ｍｏｌ％以下であると、得られる熱硬化性樹脂が溶剤に可溶となり、Ａステージのワニス（熱硬化性樹脂組成物）を製造可能になり、プリプレグのゲルタイムが長くなるためにプレスの際に成形性が良好になる。
化合物（ｂ）のシアネート基は、活性水素を有するカルボキシ基やエポキシ基と付加反応する、或いは、シアネート基同士で３量化しトリアジン環を形成する。シアネート基が３量化しトリアジン環を形成する反応によって３次元網目構造化が進行するが、１分子中に少なくとも２個のエポキシ基を有する化合物（ｃ）が３次元網目構造中に均一に分散されて、シロキサン樹脂（ａ）と化合物（ｂ）と化合物（ｃ）とが均一に分散された熱硬化性樹脂が形成される。
The siloxane resin (a), the compound (b) and the compound (c) are uniformly dissolved in the above solvent, and the reaction rate (also referred to as the disappearance rate) of the compound (b) at a reaction temperature of 80 ° C. to 120 ° C. It is preferable to make it react so that it may become 30-70 mol%.
Here, the reaction rate of the compound (b) is determined by GPC measurement. That is, the peak area at the start of the reaction of the compound (b) is compared with the peak area after reacting for a predetermined time, and is obtained from the disappearance rate of the peak area.
When the reaction rate is 30 mol% or more, the obtained resin is compatibilized and does not become cloudy, so that the B-stage coating process can be easily performed. When the reaction rate is 70 mol% or less, the resulting thermosetting resin becomes soluble in the solvent, and it becomes possible to produce an A-stage varnish (thermosetting resin composition), and the gel time of the prepreg is increased. In this case, the moldability is improved.
The cyanate group of the compound (b) undergoes an addition reaction with a carboxy group or an epoxy group having active hydrogen, or trimerizes with each other to form a triazine ring. A three-dimensional network structure is formed by a reaction in which a cyanate group is trimerized to form a triazine ring, but the compound (c) having at least two epoxy groups in one molecule is uniformly dispersed in the three-dimensional network structure. Thus, a thermosetting resin in which the siloxane resin (a), the compound (b), and the compound (c) are uniformly dispersed is formed.
＜有機金属塩（ｄ）＞
本発明に係る熱硬化性樹脂を製造する際には、反応溶媒中に、反応触媒として有機金属塩（ｄ）が含まれていてもよい。有機金属塩（ｄ）としては、例えば、ナフテン酸亜鉛、ナフテン酸マンガン、ナフテン酸コバルト、オクチル酸錫、オクチル酸コバルト等の有機酸の金属塩が挙げられる。
有機金属塩（ｄ）の配合量は、シロキサン樹脂（ａ）と化合物（ｂ）と化合物（ｃ）の総和１００質量部に対して、０．０００１〜０．００４質量部であることが好ましい。０．０００１質量部以上であると、反応時間を適切に調整でき、所望の反応率に達し易い。また、０．００４質量部以下であると、反応終点の管理が容易にできる。
<Organic metal salt (d)>
When producing the thermosetting resin according to the present invention, an organic metal salt (d) may be contained as a reaction catalyst in the reaction solvent. Examples of the organic metal salt (d) include metal salts of organic acids such as zinc naphthenate, manganese naphthenate, cobalt naphthenate, tin octylate, and cobalt octylate.
The compounding amount of the organometallic salt (d) is preferably 0.0001 to 0.004 parts by mass with respect to 100 parts by mass of the total of the siloxane resin (a), the compound (b) and the compound (c). When it is 0.0001 part by mass or more, the reaction time can be appropriately adjusted, and a desired reaction rate is easily achieved. Moreover, management of the reaction end point can be easily performed as it is 0.004 mass part or less.
［樹脂組成物］
本発明の樹脂組成物は、上記一般式（１）で示されるシロキサン樹脂（ａ）と、１分子中に少なくとも２個のシアネート基を有する化合物（ｂ）と、１分子中に少なくとも２個のエポキシ基を有する化合物（ｃ）とを反応して得られる熱硬化性樹脂と、以下に示すその他の成分とを用いることで得られる。
＜フェノール樹脂、エポキシ樹脂＞
本発明の樹脂組成物には、熱硬化後に残存するシアネート基を減少させる目的で、フェノール樹脂やエポキシ樹脂を添加することができる。
フェノール樹脂としては、例えば、フェノール、クレゾール、キシレノール、ブチルフェノール、アミルフェノール、ノニルフェノール、ｐ−クミルフェノール、１−ナフトール、２−ナフトール等の単官能フェノール化合物や、ビスフェノールＡ、テトラメチルビスフェノールＦ、ビスフェノールＦ、ビスフェノールＳ、ビスフェノールＫ、ビフェノール、テトラメチルビフェノール、ハイドロキノン、メチルハイドロキノン、ジメチルハイドロキノン、トリメチルハイドロキノン、ジ−ｔｅｒ−ブチルハイドロキノン、レゾルシノール、メチルレゾルシノール、カテコール、メチルカテコール、ジヒドロキシナフタレン、ジヒドロキシメチルナフタレン、ジヒドロキシジメチルナフタレン、ビスフェノールフルオレン、ビスクレゾールフルオレン等の２官能フェノール化合物、フェノール類、又はナフトール類とアルデヒド類との縮合物、フェノール類又はナフトール類とキシリレングリコールとの縮合物、フェノール類又はナフトール類とビスメトキシメチルビフェニルとの縮合物、フェノール類とイソプロペニルアセトフェノンとの縮合物、フェノール類とジシクロペンタジエンの反応物が挙げられる。これらは、公知の方法により得ることができる。
[Resin composition]
The resin composition of the present invention comprises a siloxane resin (a) represented by the general formula (1), a compound (b) having at least two cyanate groups in one molecule, and at least two in one molecule. It can be obtained by using a thermosetting resin obtained by reacting the compound (c) having an epoxy group and other components shown below.
<Phenolic resin, epoxy resin>
To the resin composition of the present invention, a phenol resin or an epoxy resin can be added for the purpose of reducing the cyanate group remaining after thermosetting.
Examples of the phenol resin include monofunctional phenol compounds such as phenol, cresol, xylenol, butylphenol, amylphenol, nonylphenol, p-cumylphenol, 1-naphthol, and 2-naphthol, bisphenol A, tetramethylbisphenol F, and bisphenol. F, bisphenol S, bisphenol K, biphenol, tetramethylbiphenol, hydroquinone, methylhydroquinone, dimethylhydroquinone, trimethylhydroquinone, di-ter-butylhydroquinone, resorcinol, methylresorcinol, catechol, methylcatechol, dihydroxynaphthalene, dihydroxymethylnaphthalene, dihydroxy Dimethylnaphthalene, bisphenolfluorene, biscresol Bifunctional phenolic compounds such as olene, phenols or condensates of naphthols and aldehydes, condensates of phenols or naphthols and xylylene glycol, condensates of phenols or naphthols and bismethoxymethylbiphenyl And a condensate of phenols and isopropenyl acetophenone, and a reaction product of phenols and dicyclopentadiene. These can be obtained by known methods.
上記例示したフェノール類のなかでは、ビスフェノールＡ、テトラメチルビスフェノールＦ、ビスフェノールＦ、ビスフェノールＳ、ビスフェノールＫ、ビフェノール、テトラメチルビフェノール、ハイドロキノン、メチルハイドロキノン、ジメチルハイドロキノン、トリメチルハイドロキノン、ジ−ｔｅｒ−ブチルハイドロキノン、レゾルシノール、メチルレゾルシノール、カテコール、メチルカテコール、ジヒドロキシナフタレン、ジヒドロキシメチルナフタレン、ジヒドロキシジメチルナフタレン、ビスフェノールフルオレン、ビスクレゾールフルオレン等を好ましく用いることができる。 Among the phenols exemplified above, bisphenol A, tetramethylbisphenol F, bisphenol F, bisphenol S, bisphenol K, biphenol, tetramethylbiphenol, hydroquinone, methylhydroquinone, dimethylhydroquinone, trimethylhydroquinone, di-ter-butylhydroquinone, Resorcinol, methylresorcinol, catechol, methylcatechol, dihydroxynaphthalene, dihydroxymethylnaphthalene, dihydroxydimethylnaphthalene, bisphenolfluorene, biscresolfluorene and the like can be preferably used.
ナフトール類としては、１−ナフトール、２−ナフトール、ジヒドロキシナフタレン、ジヒドロキシメチルナフタレン、ジヒドロキシジメチルナフタレン、トリヒドロキシナフタレン等が挙げられる。 Examples of naphthols include 1-naphthol, 2-naphthol, dihydroxynaphthalene, dihydroxymethylnaphthalene, dihydroxydimethylnaphthalene, trihydroxynaphthalene and the like.
更に、アルデヒド類としては、ホルムアルデヒド、アセトアルデヒド、プロピルアルデヒド、ブチルアルデヒド、バレルアルデヒド、カプロンアルデヒド、ベンズアルデヒド、クロルベンズアルデヒド、ブロムベンズアルデヒド、グリオキザール、マロンアルデヒド、スクシンアルデヒド、グルタルアルデヒド、アジピンアルデヒド、ピメリンアルデヒド、セバシンアルデヒド、アクロレイン、クロトンアルデヒド、サリチルアルデヒド、フタルアルデヒド、ヒドロキシベンズアルデヒド等が挙げられる。 Furthermore, as aldehydes, formaldehyde, acetaldehyde, propyl aldehyde, butyraldehyde, valeraldehyde, capronaldehyde, benzaldehyde, chlorbenzaldehyde, bromobenzaldehyde, glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde, adipine aldehyde, pimelin aldehyde, Examples include sebacic aldehyde, acrolein, crotonaldehyde, salicylaldehyde, phthalaldehyde, and hydroxybenzaldehyde.
エポキシ樹脂としては、化合物（ｃ）として用いられるエポキシ樹脂のほか、アリルグリシジルエーテル、２−エチルヘキシルグリシジルエーテル、フェニルグリシジルエーテル、ｐ−ｔｅｒｔ−ブチルフェニルグリシジルエーテル、ラウリルアルコールグリシジルエーテル等の一分子中に１個しかフェノール性水酸基をもたないエポキシ基を有する化合物が挙げられる。 As an epoxy resin, in addition to the epoxy resin used as the compound (c), in one molecule such as allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, lauryl alcohol glycidyl ether, etc. Examples thereof include compounds having an epoxy group having only one phenolic hydroxyl group.
＜無機充填剤＞
本発明に係る樹脂組成物には、低熱膨張性や耐熱性、難燃性等の向上化のために無機充填材が配合されてもよい。
無機充填材としては、特に、溶融シリカを用いることが好ましく、中でも官能基を有するシラン化合物で表面を処理した溶融シリカを用いることが好ましい。
官能基を有するシラン化合物には、官能基とアルコキシル基を有するシラン化合物であればどのようなものでもよく、ビニルトリエトキシシラン、３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルメチルジエトキシシラン、３−メタクリロキシプロピルメチルジエトキシシラン、３−メタクリロキシプロピルトリメトキシシラン、３−グリシドキシプロピルメチルジメトキシシラン、３−メタクリロキシプロピルトリエトキシシラン、Ｎ−２−（アミノエチル）−３−アミノプロピルメチルジメトキシシラン、Ｎ−２−（アミノエチル）−３−アミノプロピルトリメトキシシラン、Ｎ−２−（アミノエチル）−３−アミノプロピルトリエトキシシラン、３−アミノプロピルトリメトキシシラン、３−アミノプロピルトリエトキシシラン、Ｎ−フェニル−３−アミノプロピルトリメトキシシランなどが上げられる。
これらの中でも特に、一般式（４）で示されるＮ−フェニル−３−アミノプロピルトリメトキシシランが特に好ましい。
<Inorganic filler>
In the resin composition according to the present invention, an inorganic filler may be blended for improving low thermal expansion, heat resistance, flame retardancy, and the like.
As the inorganic filler, it is particularly preferable to use fused silica, and it is particularly preferable to use fused silica whose surface is treated with a silane compound having a functional group.
The silane compound having a functional group may be any silane compound having a functional group and an alkoxyl group, such as vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropylmethyl. Diethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane , 3-aminopropyl Triethoxysilane, etc. N- phenyl-3-aminopropyltrimethoxysilane, and the like.
Among these, N-phenyl-3-aminopropyltrimethoxysilane represented by the general formula (4) is particularly preferable.
無機充填材への表面処理方法の例としては、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系有機溶剤やエチレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテル等のアルコール系有機溶剤に、溶融シリカを添加して混合した後、上記一般式（４）で示されるトリメトキシシラン化合物を添加して、６０℃〜１２０℃で、０．５〜５時間程度撹拌する方法が挙げられる。この方法により、所望の表面状態を有する溶融シリカが得られる。
また、このような表面処理が施された溶融シリカの市販品としては、例えば、アドマテックス社製、商品名ＳＣ−２０５０ＫＮＫ、ＳＣ−２０５０ＨＮＫ等が挙げられる。
これら溶融シリカの使用量は、固形分換算の該樹脂組成物１００質量部に対し、１０〜３００質量部とすることが好ましく、１００〜２５０質量部とすることがより好ましく、１５０〜２５０質量部とすることが特に好ましい。
１０質量部以上であると、基材の剛性や、耐湿耐熱性、難燃性が十分であり、また、３００質量部以下であると成形性や耐めっき液性等の耐薬品性が向上する。
Examples of surface treatment methods for inorganic fillers include adding fused silica to ketone organic solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, and alcohol organic solvents such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether. After mixing, the method of adding the trimethoxysilane compound shown by the said General formula (4) and stirring at 60 to 120 degreeC for about 0.5 to 5 hours is mentioned. By this method, fused silica having a desired surface state is obtained.
Moreover, as a commercial item of the fused silica in which such surface treatment was performed, the product name SC-2050KNK, SC-2050HNK, etc. made from Admatex are mentioned, for example.
The amount of these fused silica used is preferably 10 to 300 parts by weight, more preferably 100 to 250 parts by weight, and more preferably 150 to 250 parts by weight with respect to 100 parts by weight of the resin composition in terms of solid content. It is particularly preferable that
If it is 10 parts by mass or more, the rigidity, heat resistance, and flame resistance of the substrate are sufficient, and if it is 300 parts by mass or less, chemical resistance such as moldability and plating solution resistance is improved. .
本発明に係る樹脂組成物に配合可能なこの他の無機充填材としては、例えば、破砕シリカ、マイカ、タルク、ガラス短繊維又は微粉末及び中空ガラス、炭酸カルシウム、石英粉末、金属水和物等が挙げられる。
これらの中でも、低熱膨張性や高弾性、耐熱性、難燃性の点から、水酸化アルミニウム、水酸化マグネシウム等の金属水和物が好ましく、さらに金属水和物の中でも、高い耐熱性と難燃性が両立する点から熱分解温度が３００℃以上である金属水和物、例えばベーマイト型水酸化アルミニウム（ＡｌＯＯＨ）、あるいはギブサイト型水酸化アルミニウム（Ａｌ（ＯＨ）3）を熱処理によりその熱分解温度を３００℃以上に調整した化合物、水酸化マグネシウム等がより好ましい。特に、安価であり、３５０℃以上の特に高い熱分解温度と、高い耐薬品性を有するベーマイト型水酸化アルミニウム（ＡｌＯＯＨ）を用いることが好ましい。
これらの無機充填材の使用量は、固形分換算の該樹脂組成物１００質量部に対し、０〜２００質量部とすることが好ましく、１０〜１５０質量部とすることがより好ましく、５０〜１５０質量部とすることが特に好ましい。１０質量部を超えると難燃性が十分となり、２００質量部未満であると耐めっき液性等の耐薬品性や成形性が低下せず、良好となる。
Other inorganic fillers that can be blended in the resin composition according to the present invention include, for example, crushed silica, mica, talc, short glass fiber or fine powder, hollow glass, calcium carbonate, quartz powder, metal hydrate, and the like. Is mentioned.
Among these, metal hydrates such as aluminum hydroxide and magnesium hydroxide are preferable from the viewpoint of low thermal expansion, high elasticity, heat resistance, and flame retardancy, and among the metal hydrates, high heat resistance and difficulty are also obtained. Thermal decomposition of metal hydrates with a thermal decomposition temperature of 300 ° C or higher, such as boehmite type aluminum hydroxide (AlOOH), or gibbsite type aluminum hydroxide (Al (OH) 3 ) by heat treatment from the point of achieving both flammability More preferred are compounds whose temperature is adjusted to 300 ° C. or higher, magnesium hydroxide, and the like. In particular, it is preferable to use boehmite type aluminum hydroxide (AlOOH) which is inexpensive and has a particularly high thermal decomposition temperature of 350 ° C. or higher and high chemical resistance.
The amount of these inorganic fillers used is preferably 0 to 200 parts by mass, more preferably 10 to 150 parts by mass, and more preferably 50 to 150 parts per 100 parts by mass of the resin composition in terms of solid content. It is particularly preferable to use parts by mass. If it exceeds 10 parts by mass, the flame retardancy will be sufficient, and if it is less than 200 parts by mass, chemical resistance such as plating solution resistance and moldability will not be deteriorated, and it will be good.
＜硬化促進剤＞
本発明に係る樹脂組成物には、耐熱性や難燃性、銅箔接着性等の向上化のため、硬化促進剤を配合してもよい。硬化促進剤の一例としては、ナフテン酸亜鉛、ナフテン酸コバルト、オクチル酸錫、オクチル酸コバルト等の有機金属塩、イミダゾール類及びその誘導体、第三級アミン類及び第四級アンモニウム塩等が挙げられる。硬化促進剤を使用することによって、耐熱性や難燃性、銅箔接着性等を、より高めることができる。
<Curing accelerator>
The resin composition according to the present invention may contain a curing accelerator for improving heat resistance, flame retardancy, copper foil adhesion, and the like. Examples of curing accelerators include organometallic salts such as zinc naphthenate, cobalt naphthenate, tin octylate and cobalt octylate, imidazoles and their derivatives, tertiary amines and quaternary ammonium salts. . By using a curing accelerator, heat resistance, flame retardancy, copper foil adhesion, and the like can be further enhanced.
＜難燃剤、難燃助剤＞
本発明に係る樹脂組成物には、任意に他の難燃剤を配合することもできる。配合可能な難燃剤の一例としては、トリフェニルホスフェート、トリクレジルホスフェート、トリスジクロロプロピルホスフェート、リン酸エステル系化合物、ホスファゼン、赤リン等のリン系難燃剤、三酸化アンチモン、モリブデン酸亜鉛等の無機難燃助剤等が挙げられる。特に、モリブデン酸亜鉛をタルク等の無機充填材に担持した無機難燃助剤は、難燃性のみならずドリル加工性をも著しく向上することができるため、特に好ましい。モリブデン酸亜鉛を使用する場合には、本発明の熱硬化性樹脂組成物１００質量部に対し、５〜２０質量部とすることが好ましい。５質量部以上であると難燃性が向上し、また２０質量部未満であるとワニスのゲルタイムが短くなり過ぎず、プレスにより積層板を成形する際に成形性が満足できる。なお、臭素や塩素を含有する含ハロゲン系難燃剤や熱分解温度が３００℃未満である金属水酸化物等は、本発明の目的に合わないため、不用いることは好ましくない。
<Flame retardant, flame retardant aid>
Another flame retardant can also be arbitrarily mix | blended with the resin composition which concerns on this invention. Examples of flame retardants that can be incorporated include triphenyl phosphate, tricresyl phosphate, trisdichloropropyl phosphate, phosphoric ester compounds, phosphazenes, phosphorous flame retardants such as red phosphorus, antimony trioxide, zinc molybdate, etc. Examples include inorganic flame retardant aids. In particular, an inorganic flame retardant aid in which zinc molybdate is supported on an inorganic filler such as talc is particularly preferable because not only flame retardancy but also drill workability can be remarkably improved. When using zinc molybdate, it is preferable to set it as 5-20 mass parts with respect to 100 mass parts of thermosetting resin compositions of this invention. When it is 5 parts by mass or more, flame retardancy is improved, and when it is less than 20 parts by mass, the gel time of the varnish does not become too short, and the moldability can be satisfied when the laminate is molded by pressing. Note that halogen-containing flame retardants containing bromine and chlorine, metal hydroxides having a thermal decomposition temperature of less than 300 ° C., and the like do not meet the purpose of the present invention, and thus it is not preferable to not use them.
＜その他の配合剤＞
本発明に係る樹脂組成物は、公知の熱可塑性樹脂、エラストマー、有機充填材等と併用できる。熱可塑性樹脂の例としては、テトラフルオロエチレン、ポリエチレン、ポリプロピレン、ポリスチレン、ポリフェニレンエーテル樹脂、フェノキシ樹脂、ポリカーボネート樹脂、ポリエステル樹脂、ポリアミド樹脂、ポリイミド樹脂、キシレン樹脂、石油樹脂及びシリコーン樹脂が挙げられる。
エラストマーの例としては、ポリブタジエン、アクリロニトリル、エポキシ変性ポリブタジエン、無水マレイン酸変性ポリブタジエン、フェノール変性ポリブタジエン及びカルボキシ変性アクリロニトリルが挙げられる。
有機充填材の例としては、シリコーンパウダー、テトラフルオロエチレン、ポリエチレン、ポリプロピレン、ポリスチレン、並びにポリフェニレンエーテル等の有機物粉末が挙げられる。
<Other ingredients>
The resin composition according to the present invention can be used in combination with known thermoplastic resins, elastomers, organic fillers and the like. Examples of the thermoplastic resin include tetrafluoroethylene, polyethylene, polypropylene, polystyrene, polyphenylene ether resin, phenoxy resin, polycarbonate resin, polyester resin, polyamide resin, polyimide resin, xylene resin, petroleum resin, and silicone resin.
Examples of elastomers include polybutadiene, acrylonitrile, epoxy-modified polybutadiene, maleic anhydride-modified polybutadiene, phenol-modified polybutadiene, and carboxy-modified acrylonitrile.
Examples of organic fillers include organic powders such as silicone powder, tetrafluoroethylene, polyethylene, polypropylene, polystyrene, and polyphenylene ether.
本発明に係る樹脂組成物には、任意に、紫外線吸収剤、酸化防止剤、光重合開始剤、蛍光増白剤及び密着性向上剤等を配合することも可能である。通常、紫外線吸収剤、酸化防止剤、光重合開始剤、蛍光増白剤及び密着性向上剤として使用可能な化合物であれば、特に限定されない。
紫外線吸収剤の一例としては、ベンゾトリアゾール系等の紫外線吸収剤、ヒンダードフェノール系やスチレン化フェノール等の酸化防止剤、ベンゾフェノン類、ベンジルケタール類、チオキサントン系等の光重合開始剤、スチルベン誘導体等の蛍光増白剤、尿素シラン等の尿素化合物やシランカップリング剤等の密着性向上剤等が挙げられる。
The resin composition according to the present invention can optionally contain an ultraviolet absorber, an antioxidant, a photopolymerization initiator, a fluorescent brightener, an adhesion improver, and the like. In general, the compound is not particularly limited as long as it is a compound that can be used as an ultraviolet absorber, an antioxidant, a photopolymerization initiator, a fluorescent brightener, and an adhesion improver.
Examples of UV absorbers include UV absorbers such as benzotriazoles, antioxidants such as hindered phenols and styrenated phenols, benzophenones, benzyl ketals, photopolymerization initiators such as thioxanthones, stilbene derivatives, etc. Fluorescent brighteners, urea compounds such as urea silane, and adhesion improvers such as silane coupling agents.
［プリプレグ］
以下、本発明のプリプレグについて詳述する。
本発明のプリプレグは、上述の熱硬化性樹脂組成物が基材に含浸又は塗布されてなる。
本発明のプリプレグは、本発明の熱硬化性樹脂組成物を、基材に含浸又は塗工し、加熱等により半硬化（Ｂステージ化）して本発明のプリプレグを製造することができる。基材としては、各種の電気絶縁材料用積層板に用いられている周知のものが使用でき、一例としては、Ｅガラス、Ｄガラス、Ｓガラス及びＱガラス等の無機物繊維、ポリイミド、ポリエステル及びテトラフルオロエチレン等の有機繊維、並びにそれらの混合物等が挙げられる。
これらの基材は、例えば、織布、不織布、ロービンク、チョップドストランドマット及びサーフェシングマット等の形状を有するが、材質及び形状は、目的とする成形物の用途や性能により選択され、必要により、単独又は２種類以上の材質及び形状を組み合わせることができる。基材の厚さは、特に制限されず、例えば、約０．０３〜０．５ｍｍを使用することができ、シランカップリング剤等で表面処理したもの又は機械的に開繊処理を施したものが、耐熱性、加工性の面から好適である。該基材に対する樹脂組成物の付着量が、乾燥後のプリプレグの樹脂含有率で、２０〜９０質量％となるように、基材に含浸又は塗工した後、通常、１００〜２００℃の温度で１〜３０分加熱乾燥し、半硬化（Ｂステージ化）させる。
以上の工程により、本発明のプリプレグを得ることができる。
[Prepreg]
Hereinafter, the prepreg of the present invention will be described in detail.
The prepreg of the present invention is obtained by impregnating or applying the above-mentioned thermosetting resin composition to a substrate.
The prepreg of the present invention can be produced by impregnating or coating the base material with the thermosetting resin composition of the present invention and semi-curing (B-stage) by heating or the like. As a base material, the well-known thing used for the laminated board for various electrical insulation materials can be used, As an example, inorganic fiber, such as E glass, D glass, S glass, and Q glass, polyimide, polyester, and tetra Examples thereof include organic fibers such as fluoroethylene, and mixtures thereof.
These base materials have, for example, shapes such as woven fabric, non-woven fabric, robink, chopped strand mat, and surfacing mat, but the material and shape are selected depending on the intended use and performance of the molded product, and if necessary, A single material or two or more materials and shapes can be combined. The thickness of the base material is not particularly limited, and for example, about 0.03 to 0.5 mm can be used, and the surface is treated with a silane coupling agent or the like or mechanically subjected to a fiber opening treatment. Is preferable from the viewpoint of heat resistance and workability. After impregnating or coating the base material so that the amount of the resin composition attached to the base material is 20 to 90% by mass in terms of the resin content of the prepreg after drying, the temperature is usually 100 to 200 ° C. And dried for 1 to 30 minutes and semi-cured (B-stage).
Through the above steps, the prepreg of the present invention can be obtained.
［積層板］
本発明の積層板は、前述の本発明のプリプレグを用いて、所定の枚数を積層成形して、製造することができる。本発明のプリプレグを、例えば、１〜２０枚重ね、その片面又は両面に銅及びアルミニウム等の金属箔を配置した構成で積層成形することにより製造することができる。金属箔は、電気絶縁材料用途で用いるものであれば特に制限されない。また、成形条件は、例えば、電気絶縁材料用積層板及び多層板の手法が適用でき、例えば多段プレス、多段真空プレス、連続成形、オートクレーブ成形機等を使用し、温度１００〜２５０℃、圧力０．２〜１０ＭＰａ、加熱時間０．１〜５時間の範囲で成形することができる。また、本発明のプリプレグと内層用配線板とを組合せ、積層成形して、多層板を製造することもできる。
[Laminated board]
The laminate of the present invention can be produced by laminating a predetermined number of sheets using the prepreg of the present invention described above. The prepreg of the present invention can be produced, for example, by laminating 1 to 20 sheets and laminating and forming a metal foil such as copper and aluminum on one or both sides thereof. The metal foil is not particularly limited as long as it is used for electrical insulating material applications. The molding conditions may be, for example, a laminated plate for an electrical insulating material and a multilayer plate. For example, a multistage press, a multistage vacuum press, continuous molding, an autoclave molding machine or the like is used, and the temperature is 100 to 250 ° C. and the pressure is 0. It can be molded in a range of 2 to 10 MPa and a heating time of 0.1 to 5 hours. Further, the prepreg of the present invention and the inner layer wiring board can be combined and laminated to produce a multilayer board.
近年の高密度化や高信頼性への要求から、積層板の材料には、高い銅箔接着性や耐熱性、良好な低熱膨張性等が必要とされる。微細配線形成のため銅箔接着性は、銅箔引き剥がし強さ（ピール強度）が１．０ｋＮ／ｍ以上であることが望まれ、１．２ｋＮ／ｍ以上であることがより望まれる。
また、積層板は、高密度化のため、ビルドアップ材等を用いてより高多層化することが求められる。この場合、リフローはんだの温度条件（〜２５０℃程度）に対する耐性を考慮すると、銅張積層板のガラス転移温度は、２５０℃以上であることが好ましい。
リフロー耐熱性評価の指針となる銅付き耐熱性（Ｔ−３００）試験では、基板のふくれ等が３０分以上生じないことが望ましい。
さらに、銅張積層板は、さらなる薄型化が望まれており、これに併せて銅張積層板を構成するプリプレグの薄型化も検討されている。薄型化されたプリプレグは、反りやすくなるため、熱処理時におけるプリプレグの反りが小さいことが望まれる。すなわち、熱膨張係数の値が７ｐｐｍ／℃以下であることが望ましく、５ｐｐｍ／℃以下であることがより望ましい。
Due to demands for higher density and higher reliability in recent years, materials for laminates are required to have high copper foil adhesion, heat resistance, good low thermal expansion, and the like. For the formation of fine wiring, the copper foil adhesiveness is preferably such that the copper foil peel strength (peel strength) is 1.0 kN / m or more, and more preferably 1.2 kN / m or more.
In addition, the laminated board is required to have a higher number of layers using a build-up material or the like in order to increase the density. In this case, considering the resistance to the temperature condition (about 250 ° C.) of the reflow solder, the glass transition temperature of the copper clad laminate is preferably 250 ° C. or higher.
In the heat resistance test with copper (T-300) test, which is a guideline for evaluation of reflow heat resistance, it is desirable that no blistering of the substrate occurs for 30 minutes or more.
Furthermore, the copper-clad laminate is desired to be further reduced in thickness, and in conjunction with this, the prepreg constituting the copper-clad laminate is also being considered to be thinner. Since the thinned prepreg is likely to warp, it is desired that the prepreg warp during heat treatment be small. That is, the value of the thermal expansion coefficient is preferably 7 ppm / ° C. or less, and more preferably 5 ppm / ° C. or less.
次に、下記の実施例により本発明を更に詳しく説明するが、これらの実施例は本発明を制限するものではない。 Next, the present invention will be described in more detail with reference to the following examples, but these examples do not limit the present invention.
［評価方法］
＜銅箔接着性（銅箔ピール強度）の評価＞
銅箔の接着性は、ピール強度によって評価した。銅張積層板を銅エッチング液に浸漬することにより１ｃｍ幅の銅箔を形成して評価基板を作製し、引張り試験機を用いて銅箔のピール強度を測定した。
[Evaluation method]
<Evaluation of copper foil adhesion (copper foil peel strength)>
The adhesiveness of the copper foil was evaluated by peel strength. A 1 cm wide copper foil was formed by immersing the copper clad laminate in a copper etching solution to produce an evaluation substrate, and the peel strength of the copper foil was measured using a tensile tester.
＜ガラス転移温度（Ｔｇ）の測定＞
銅張積層板を銅エッチング液に浸漬することにより銅箔を取り除いた５ｍｍ角の評価基板を作製し、ＴＭＡ試験装置「ＴＭＡ２９４０」（デュポン株式会社製）を用い、評価基板の面方向の熱膨張特性を観察することにより評価した。
<Measurement of glass transition temperature (Tg)>
A 5-mm square evaluation board from which the copper foil has been removed by immersing the copper-clad laminate in a copper etching solution is prepared, and thermal expansion in the surface direction of the evaluation board is performed using a TMA test apparatus “TMA2940” (manufactured by DuPont). Evaluation was made by observing the characteristics.
＜線熱膨張係数の測定＞
銅張積層板を銅エッチング液に浸漬することにより銅箔を取り除いた５ｍｍ角の評価基板を作製し、ＴＭＡ試験装置「ＴＭＡ２９４０」（デュポン株式会社製）を用い、評価基板の面方向の３０℃〜１００℃の線熱膨張率を測定した。
<Measurement of linear thermal expansion coefficient>
A 5 mm square evaluation board from which the copper foil was removed by immersing the copper-clad laminate in a copper etching solution was prepared, and the TMA test apparatus “TMA2940” (manufactured by DuPont Co., Ltd.) was used. The linear thermal expansion coefficient at ˜100 ° C. was measured.
＜はんだ耐熱性の評価＞
銅張積層板を銅エッチング液に浸漬することにより銅箔を取り除いた５ｃｍ角の評価基板を作製し、プレッシャー・クッカー試験装置（平山製作所株式会社製）を用いて、１２１℃、２ａｔｍの条件で４時間までプレッシャー・クッカー処理を行った後、温度２８８℃のはんだ浴に、評価基板を２０秒間浸漬した後、外観を観察することにより、リフローはんだの温度条件に対する耐熱性（はんだ耐熱性という）を評価した。
<Evaluation of solder heat resistance>
A copper-clad laminate is immersed in a copper etching solution to produce a 5 cm square evaluation substrate from which the copper foil has been removed. Using a pressure cooker test apparatus (manufactured by Hirayama Seisakusho Co., Ltd.), the conditions are 121 ° C. and 2 atm. After pressure cooker treatment for up to 4 hours, the evaluation board is immersed in a solder bath at a temperature of 288 ° C. for 20 seconds, and then the appearance is observed, whereby the heat resistance against the temperature conditions of reflow soldering (referred to as solder heat resistance) Evaluated.
＜銅付き耐熱性（Ｔ−３００）の評価＞
銅張積層板から５ｍｍ角の評価基板を作製し、ＴＭＡ試験装置「ＴＭＡ２９４０」（デュポン株式会社製）を用い、３００℃で評価基板の膨れが発生するまでの時間を測定することにより評価した。
<Evaluation of heat resistance with copper (T-300)>
A 5 mm square evaluation board was prepared from the copper clad laminate, and evaluation was performed by measuring the time until the evaluation board swells at 300 ° C. using a TMA test apparatus “TMA2940” (manufactured by DuPont).
＜難燃性の評価＞
銅張積層板を銅エッチング液に浸漬することにより銅箔を取り除いた評価基板から、長さ１２７ｍｍ、幅１２．７ｍｍに切り出した試験片を作製し、ＵＬ９４の試験法（Ｖ法）に準じて評価した。
<Evaluation of flame retardancy>
A test piece cut out to a length of 127 mm and a width of 12.7 mm was prepared from an evaluation board from which the copper foil was removed by immersing the copper-clad laminate in a copper etching solution, and in accordance with the UL94 test method (Method V). evaluated.
＜比誘電率及び誘電正接の測定＞
得られた銅張積層板を銅エッチング液に浸漬することにより銅箔を取り除いた評価基板を作製し、比誘電率測定装置「ＨＰ４２９１Ｂ」（Ｈｅｗｌｌｅｔ Ｐａｃｋｅｒｄ株式会社製）を用いて、周波数１ＧＨｚでの比誘電率及び誘電正接を測定した。
<Measurement of relative dielectric constant and dielectric loss tangent>
The obtained copper-clad laminate was immersed in a copper etching solution to prepare an evaluation substrate from which the copper foil was removed, and using a relative dielectric constant measuring device “HP4291B” (manufactured by Hewlett Packard Co., Ltd.) at a frequency of 1 GHz. The relative dielectric constant and dielectric loss tangent were measured.
［熱硬化性樹脂の製造］
＜製造例１：熱硬化性樹脂（１−１）の製造＞
温度計、攪拌装置、還流冷却管の付いた加熱及び冷却可能な容積３リットルの反応容器に、ビスフェノールＡ型シアネート樹脂（ロンザジャパン社製：商品名Ｐｒｉｍａｓｅｔ ＢＡＤＣｙ）：６００．０ｇと、下記一般式（５）に示すシロキサン樹脂（信越化学社製：商品名Ｘ−２２−１６３Ｂ、グリシジル基当量：１，７６０）：２００．０ｇと、ビフェニル型エポキシ樹脂（ジャパンエポキシレジン社製：商品名ＹＸ−４０００、エポキシ当量：１８６）：２００．０ｇと、トルエン：１０００．０ｇを投入した。
次いで、攪拌しながら１２０℃に昇温し、樹脂固形分が溶解し均一な溶液になっていることを確認した後、ナフテン酸亜鉛の８質量％ミネラルスピリット溶液を０．０１ｇ添加し、約１１０℃で４時間反応を行った。その後、室温に冷却し、熱硬化性樹脂（１−１）の溶液を得た。
この反応溶液を少量取り出し、ＧＰＣ測定（ポリスチレン換算、溶離液：テトラヒドロフラン）を行ったところ、溶出時間が約１２．４分付近に出現する合成原料のビスフェノールＡ型シアネート樹脂のピーク面積が、反応開始時のビスフェノールＡ型シアネート樹脂のピーク面積と比較し、ピーク面積の消失率が６８％であった。また、約１０．９分付近、及び８．０〜１０．０分付近に出現する熱硬化性樹脂の生成物のピークが確認でき、熱硬化性樹脂（１−１）が製造されていることを確認した。
[Manufacture of thermosetting resin]
<Production Example 1: Production of thermosetting resin (1-1)>
In a reaction vessel with a capacity of 3 liters, which can be heated and cooled, equipped with a thermometer, a stirrer, and a reflux condenser, bisphenol A type cyanate resin (product name: Primaset BADCy): 600.0 g and the following general formula (5) Siloxane resin (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name X-22-163B, glycidyl group equivalent: 1,760): 200.0 g, biphenyl type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd .: trade name YX- 4000, epoxy equivalent: 186): 200.0 g and toluene: 1000.0 g were added.
Next, the temperature was raised to 120 ° C. with stirring, and after confirming that the resin solids had dissolved and became a uniform solution, 0.01 g of an 8% by mass mineral spirit solution of zinc naphthenate was added, and about 110 The reaction was carried out at 4 ° C. for 4 hours. Then, it cooled to room temperature and obtained the solution of the thermosetting resin (1-1).
A small amount of this reaction solution was taken out and subjected to GPC measurement (polystyrene conversion, eluent: tetrahydrofuran). As a result, the peak area of the bisphenol A type cyanate resin, which is a synthetic raw material and the elution time appears around 12.4 minutes, is the start of the reaction. Compared to the peak area of the bisphenol A type cyanate resin at the time, the disappearance rate of the peak area was 68%. Moreover, the peak of the product of the thermosetting resin which appears in the vicinity of about 10.9 minutes and 8.0-10.0 minutes can be confirmed, and the thermosetting resin (1-1) is manufactured. It was confirmed.
＜製造例２：熱硬化性樹脂（１−２）の製造＞
温度計、攪拌装置、還流冷却管の付いた加熱及び冷却可能な容積３リットルの反応容器に、ノボラック型シアネート樹脂（ロンザジャパン社製：商品名Ｐｒｉｍａｓｅｔ ＰＴ−１５，重量平均分子量５００〜１，０００）：８００．０ｇと、下記一般式（６）に示すシロキサン樹脂（信越化学社製：商品名Ｘ−２２−１６７Ｂ、メルカプト基当量：１６７０）：１００．０ｇと、ナフトールアラルキル・クレゾール共重合型エポキシ樹脂（日本化薬社製：商品名ＮＣ−７０００Ｌ、エポキシ当量：２３０）：１００．０ｇと、トルエン：１０００．０ｇを投入した。次いで、攪拌しながら１２０℃に昇温し、樹脂固形分が溶解し均一な溶液になっていることを確認した後、ナフテン酸亜鉛の８質量％ミネラルスピリット溶液を０．０１ｇ添加し、約１１０℃で４時間反応を行った。その後、室温に冷却し熱硬化性樹脂（１−２）の溶液を得た。
この反応溶液を少量取り出し、ＧＰＣ測定（ポリスチレン換算、溶離液：テトラヒドロフラン）を行ったところ、溶出時間が約１２．１分付近に出現する合成原料のノボラック型シアネート樹脂のピーク面積が、反応開始時のノボラック型シアネート樹脂のピーク面積と比較し、ピーク面積の消失率が４３％であった。また、約１０．９分付近、及び８．０〜１０．０分付近に出現する熱硬化性樹脂の生成物のピークが確認でき、熱硬化性樹脂（１−２）が製造されていることを確認した。
<Production Example 2: Production of thermosetting resin (1-2)>
A novolak-type cyanate resin (Lonza Japan Co., Ltd .: trade name Primaset PT-15, weight average molecular weight 500 to 1,000) was added to a reaction vessel having a volume of 3 liters that can be heated and cooled with a thermometer, a stirrer, and a reflux condenser. ): 800.0 g and a siloxane resin represented by the following general formula (6) (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name X-22-167B, mercapto group equivalent: 1670): 100.0 g, naphthol aralkyl-cresol copolymer type Epoxy resin (manufactured by Nippon Kayaku Co., Ltd .: trade name NC-7000L, epoxy equivalent: 230): 100.0 g and toluene: 1000.0 g were charged. Next, the temperature was raised to 120 ° C. with stirring, and after confirming that the resin solids had dissolved and became a uniform solution, 0.01 g of an 8% by mass mineral spirit solution of zinc naphthenate was added, and about 110 The reaction was carried out at 4 ° C. for 4 hours. Then, it cooled to room temperature and obtained the solution of the thermosetting resin (1-2).
A small amount of this reaction solution was taken out and subjected to GPC measurement (polystyrene conversion, eluent: tetrahydrofuran). As a result, the peak area of the novolac-type cyanate resin, which is a synthetic raw material with an elution time of about 12.1 minutes, The disappearance rate of the peak area was 43% as compared with the peak area of the novolak-type cyanate resin. Moreover, the peak of the product of the thermosetting resin which appears in the vicinity of about 10.9 minutes and 8.0-10.0 minutes can be confirmed, and the thermosetting resin (1-2) is manufactured. It was confirmed.
＜製造例３：熱硬化性樹脂（１−３）の製造＞
温度計、攪拌装置、還流冷却管の付いた加熱及び冷却可能な容積３リットルの反応容器に、ジシクロペンタジエン型シアネート樹脂（ロンザジャパン社製：商品名Ｐｒｉｍａｓｅｔ ＤＴ−４０００，重量平均分子量５００〜１，０００）：４００．０ｇと、下記一般式（７）に示すシロキサン樹脂（信越化学社製：商品名Ｘ−２２−１６４Ａ、メタクリル基当量：９５０）：１００．０ｇと、ビフェニルアラルキル型エポキシ樹脂（日本化薬社製：商品名ＮＣ−３０００Ｈ、エポキシ当量：２８０）：５００．０ｇと、メシチレン：１０００．０ｇを投入した。次いで、攪拌しながら１２０℃に昇温し、樹脂固形分が溶解し均一な溶液になっていることを確認した後、ナフテン酸亜鉛の８質量％ミネラルスピリット溶液を０．３０ｇ添加し、約１１０℃で４時間反応を行った。その後、室温に冷却し、熱硬化性樹脂（１−３）の溶液を得た。
この反応溶液を少量取り出し、ＧＰＣ測定（ポリスチレン換算、溶離液：テトラヒドロフラン）を行ったところ、溶出時間が約１２．０分付近に出現する合成原料のジシクロペンタジエン型シアネート樹脂のピーク面積が、反応開始時のジシクロペンタジエン型シアネート樹脂のピーク面積と比較し、ピーク面積の消失率が４３％であった。また、約１０．９分付近、及び８．０〜１０．０分付近に出現する熱硬化性樹脂の生成物のピークが確認でき、熱硬化性樹脂（１−３）が製造されていることを確認した。
<Production Example 3: Production of thermosetting resin (1-3)>
A dicyclopentadiene type cyanate resin (manufactured by Lonza Japan Co., Ltd., trade name: Primaset DT-4000, weight average molecular weight: 500 to 1) was added to a reaction vessel having a volume of 3 liters that can be heated and cooled with a thermometer, a stirrer, and a reflux condenser. , 000): 400.0 g, and a siloxane resin represented by the following general formula (7) (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name X-22-164A, methacryl group equivalent: 950): 100.0 g, biphenyl aralkyl type epoxy resin (Nippon Kayaku Co., Ltd. product name: NC-3000H, epoxy equivalent: 280): 500.0 g and mesitylene: 1000.0 g were added. Next, the temperature was raised to 120 ° C. while stirring, and after confirming that the resin solids had dissolved and became a uniform solution, 0.30 g of an 8% by mass mineral spirit solution of zinc naphthenate was added, and about 110 The reaction was carried out at 4 ° C. for 4 hours. Then, it cooled to room temperature and obtained the solution of the thermosetting resin (1-3).
A small amount of this reaction solution was taken out and subjected to GPC measurement (polystyrene conversion, eluent: tetrahydrofuran). As a result, the peak area of the synthetic raw material dicyclopentadiene-type cyanate resin, whose elution time appears around 12.0 minutes, Compared with the peak area of the dicyclopentadiene-type cyanate resin at the start, the disappearance rate of the peak area was 43%. Moreover, the peak of the product of the thermosetting resin which appears in the vicinity of about 10.9 minutes and 8.0-10.0 minutes can be confirmed, and the thermosetting resin (1-3) is manufactured. It was confirmed.
＜製造例４：熱硬化性樹脂（１−４）の製造＞
温度計、攪拌装置、還流冷却管の付いた加熱及び冷却可能な容積３リットルの反応容器に、ビスフェノールＡ型シアネート樹脂（ロンザジャパン社製：商品名Ｐｒｉｍａｓｅｔ ＢＡＤＣｙ）：４００．０ｇと、下記一般式（８）に示すシロキサン樹脂（信越化学社製：商品名Ｘ−２２−１６２Ｃ、カルボキシル基当量：２，３３０）：５００．０ｇと、ナフタレン型エポキシ樹脂（大日本インキ化学社製：商品名エピクロンＨＰ−４０３２、エポキシ当量：１５０）：１００．０ｇと、トルエン：１０００．０ｇを投入した。次いで、攪拌しながら１２０℃に昇温し、樹脂固形分が溶解し均一な溶液になっていることを確認した後、ナフテン酸亜鉛の８質量％ミネラルスピリット溶液を０．０１ｇ添加し、約１１０℃で４時間反応を行った。その後、室温に冷却し熱硬化性樹脂（１−４）の溶液を得た。
この反応溶液を少量取り出し、ＧＰＣ測定（ポリスチレン換算、溶離液：テトラヒドロフラン）を行ったところ、溶出時間が約１２．４分付近に出現する合成原料のビスフェノールＡ型シアネート樹脂のピーク面積が、反応開始時のビスフェノールＡ型シアネート樹脂のピーク面積と比較し、ピーク面積の消失率が５５％であった。また、約１０．９分付近、及び８．０〜１０．０分付近に出現する熱硬化性樹脂の生成物のピークが確認でき、熱硬化性樹脂（１−４）が製造されていることを確認した。
<Production Example 4: Production of thermosetting resin (1-4)>
In a reaction vessel with a capacity of 3 liters, which can be heated and cooled, equipped with a thermometer, a stirrer, and a reflux condenser, bisphenol A type cyanate resin (product name: Primaset BADCy): 400.0 g and the following general formula (8) Siloxane resin (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name X-22-162C, carboxyl group equivalent: 2,330): 500.0 g and naphthalene type epoxy resin (manufactured by Dainippon Ink and Chemicals, Inc .: trade name Epicron) HP-4032, epoxy equivalent: 150): 100.0 g and toluene: 1000.0 g were added. Next, the temperature was raised to 120 ° C. with stirring, and after confirming that the resin solids had dissolved and became a uniform solution, 0.01 g of an 8% by mass mineral spirit solution of zinc naphthenate was added, and about 110 The reaction was carried out at 4 ° C. for 4 hours. Then, it cooled to room temperature and obtained the solution of the thermosetting resin (1-4).
A small amount of this reaction solution was taken out and subjected to GPC measurement (polystyrene conversion, eluent: tetrahydrofuran). As a result, the peak area of the bisphenol A type cyanate resin, which is a synthetic raw material and the elution time appears around 12.4 minutes, is the start of the reaction. Compared with the peak area of the bisphenol A type cyanate resin at the time, the disappearance rate of the peak area was 55%. Moreover, the peak of the product of the thermosetting resin which appears in the vicinity of about 10.9 minutes and 8.0-10.0 minutes can be confirmed, and the thermosetting resin (1-4) is manufactured. It was confirmed.
＜製造例５：トリメトキシシラン化合物により表面処理（湿式処理）された溶融シリカ（２−１）の製造＞
温度計、攪拌装置、還流冷却管の付いた加熱及び冷却可能な容積３リットルの反応容器に、溶融シリカ（アドマテックス社製：商品名ＳＯ−２５Ｒ）：７００．０ｇと、プロピレングリコールモノメチルエーテル：１０００．０ｇを配合し、攪拌しながらＮ−フェニル−３−アミノプロピルトリメトキシシラン（信越化学社製：商品名ＫＢＭ−５７３）：７．０ｇを添加した。次いで８０℃に昇温し、８０℃で１時間反応を行い溶融シリカの表面処理（湿式処理）を行った後、室温に冷却し、Ｎ−フェニル−３−アミノプロピルトリメトキシシランにより表面処理（湿式処理）された溶融シリカ（２−１）の溶液を得た。
<Production Example 5: Production of fused silica (2-1) surface-treated (wet treatment) with a trimethoxysilane compound>
In a reaction vessel having a volume of 3 liters that can be heated and cooled, equipped with a thermometer, a stirrer, and a reflux condenser, fused silica (manufactured by Admatechs: trade name SO-25R): 700.0 g and propylene glycol monomethyl ether: 1000.0 g was mixed, and 7.0 g of N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name KBM-573) was added with stirring. Next, the temperature was raised to 80 ° C., reacted at 80 ° C. for 1 hour to perform surface treatment of the fused silica (wet treatment), then cooled to room temperature, and surface treatment with N-phenyl-3-aminopropyltrimethoxysilane ( A solution of fused silica (2-1) that was wet-treated was obtained.
＜比較製造例１：（比較樹脂１）の製造＞
温度計、攪拌装置、還流冷却管の付いた加熱及び冷却可能な容積３リットルの反応容器に、ビスフェノールＡ型シアネート樹脂（ロンザジャパン社製：商品名Ｐｒｉｍａｓｅｔ ＢＡＤＣｙ）：６００．０ｇと、上記一般式（５）に示すシロキサン樹脂（信越化学社製：商品名Ｘ−２２−１６３Ｂ、グリシジル基当量：１，７６０）：２００．０ｇと、ビフェニル型エポキシ樹脂（ジャパンエポキシレジン社製：商品名ＹＸ−４０００、エポキシ当量：１８６）：２００．０ｇと、トルエン：１０００．０ｇを投入した。次いで、攪拌しながら１２０℃に昇温し、樹脂固形分が溶解し均一な溶液になっていることを確認した後、ナフテン酸亜鉛の８質量％ミネラルスピリット溶液を０．０１ｇ添加し、約１１０℃で１時間反応を行った。その後、室温に冷却し（比較樹脂１）の溶液を得た。この反応溶液を少量取り出し、ＧＰＣ測定（ポリスチレン換算、溶離液：テトラヒドロフラン）を行ったところ、溶出時間が約１２．４分付近に出現する合成原料のビスフェノールＡ型シアネート樹脂のピーク面積が、反応開始時のビスフェノールＡ型シアネート樹脂のピーク面積と比較し、ピーク面積の消失率が１５％であった。また、この溶液は翌日結晶化により沈殿物が生じた。
<Comparative Production Example 1: Production of (Comparative Resin 1)>
In a reaction vessel with a capacity of 3 liters, which can be heated and cooled, equipped with a thermometer, a stirrer, and a reflux condenser, bisphenol A type cyanate resin (Lonza Japan Co., Ltd .: trade name Primaset BADCy): 600.0 g and the above general formula (5) Siloxane resin (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name X-22-163B, glycidyl group equivalent: 1,760): 200.0 g, biphenyl type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd .: trade name YX- 4000, epoxy equivalent: 186): 200.0 g and toluene: 1000.0 g were added. Next, the temperature was raised to 120 ° C. with stirring, and after confirming that the resin solids had dissolved and became a uniform solution, 0.01 g of an 8% by mass mineral spirit solution of zinc naphthenate was added, and about 110 The reaction was carried out at 1 ° C. for 1 hour. Then, it cooled to room temperature and obtained the solution of (Comparative Resin 1). A small amount of this reaction solution was taken out and subjected to GPC measurement (polystyrene conversion, eluent: tetrahydrofuran). As a result, the peak area of the bisphenol A type cyanate resin, which is a synthetic raw material and the elution time appears around 12.4 minutes, is the start of the reaction. Compared with the peak area of the bisphenol A type cyanate resin at the time, the disappearance rate of the peak area was 15%. In addition, a precipitate was formed in the solution by crystallization the next day.
＜比較製造例２：（比較樹脂２）の製造＞
温度計、攪拌装置、還流冷却管の付いた加熱及び冷却可能な容積３リットルの反応容器に、ビスフェノールＡ型シアネート樹脂（ロンザジャパン社製：商品名Ｐｒｉｍａｓｅｔ ＢＡＤＣｙ）：６００．０ｇと、上記一般式（５）に示すシロキサン樹脂（信越化学社製：商品名Ｘ−２２−１６３Ｂ、グリシジル基当量：１，７６０）：２００．０ｇと、ビフェニル型エポキシ樹脂（ジャパンエポキシレジン社製：商品名ＹＸ−４０００、エポキシ当量：１８６）：２００．０ｇと、トルエン：１０００．０ｇを投入した。次いで、攪拌しながら１２０℃に昇温し、樹脂固形分が溶解し均一な溶液になっていることを確認した後、ナフテン酸亜鉛の８質量％ミネラルスピリット溶液を０．０１ｇ添加し、約１２０℃で６時間反応を行った。その後、室温に冷却し（比較樹脂２）の溶液を得た。この反応溶液を少量取り出し、ＧＰＣ測定（ポリスチレン換算、溶離液：テトラヒドロフラン）を行ったところ、溶出時間が約１２．４分付近に出現する合成原料のビスフェノールＡ型シアネート樹脂のピーク面積が、反応開始時のビスフェノールＡ型シアネート樹脂のピーク面積と比較し、ピーク面積の消失率が７６％であった。
<Comparative Production Example 2: Production of (Comparative Resin 2)>
In a reaction vessel with a capacity of 3 liters, which can be heated and cooled, equipped with a thermometer, a stirrer, and a reflux condenser, bisphenol A type cyanate resin (Lonza Japan Co., Ltd .: trade name Primaset BADCy): 600.0 g and the above general formula (5) Siloxane resin (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name X-22-163B, glycidyl group equivalent: 1,760): 200.0 g, biphenyl type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd .: trade name YX- 4000, epoxy equivalent: 186): 200.0 g and toluene: 1000.0 g were added. Next, the temperature was raised to 120 ° C. while stirring, and after confirming that the resin solids had dissolved and became a uniform solution, 0.01 g of an 8% by mass mineral spirit solution of zinc naphthenate was added, and about 120 The reaction was carried out at 6 ° C. for 6 hours. Then, it cooled to room temperature and obtained the solution of (comparative resin 2). A small amount of this reaction solution was taken out and subjected to GPC measurement (polystyrene conversion, eluent: tetrahydrofuran). As a result, the peak area of the bisphenol A type cyanate resin, which is a synthetic raw material and the elution time appears around 12.4 minutes, is the start of the reaction. Compared with the peak area of the bisphenol A type cyanate resin at the time, the disappearance rate of the peak area was 76%.
＜比較製造例３：（比較樹脂３）の製造＞
温度計、攪拌装置、還流冷却管の付いた加熱及び冷却可能な容積２リットルの反応容器に、ビスフェノールＡ型シアネート樹脂（ロンザジャパン社製：商品名Ｐｒｉｍａｓｅｔ ＢＡＤＣｙ）：６００．０ｇと、上記一般式（５）に示すシロキサン樹脂（信越化学社製：商品名Ｘ−２２−１６３Ｂ、グリシジル基当量：１，７６０）：２００．０ｇと、トルエン：８００．０ｇを投入した。次いで、攪拌しながら１２０℃に昇温し、樹脂固形分が溶解し均一な溶液になっていることを確認した後、ナフテン酸亜鉛の８質量％ミネラルスピリット溶液を０．０１ｇ添加し、約１１０℃で４時間反応を行った。その後、室温に冷却し（比較樹脂３）の溶液を得た。この反応溶液を少量取り出し、ＧＰＣ測定（ポリスチレン換算、溶離液：テトラヒドロフラン）を行ったところ、溶出時間が約１２．４分付近に出現する合成原料のビスフェノールＡ型シアネート樹脂のピーク面積が、反応開始時のビスフェノールＡ型シアネート樹脂のピーク面積と比較し、ピーク面積の消失率が５３％であった。
<Comparative Production Example 3: Production of (Comparative Resin 3)>
In a reaction vessel with a capacity of 2 liters that can be heated and cooled with a thermometer, a stirrer, and a reflux condenser, bisphenol A type cyanate resin (Lonza Japan Co., Ltd., trade name: Primaset BADCy): 600.0 g and the above general formula The siloxane resin shown in (5) (trade name X-22-163B, manufactured by Shin-Etsu Chemical Co., Ltd., glycidyl group equivalent: 1,760): 200.0 g and toluene: 800.0 g were added. Next, the temperature was raised to 120 ° C. with stirring, and after confirming that the resin solids had dissolved and became a uniform solution, 0.01 g of an 8% by mass mineral spirit solution of zinc naphthenate was added, and about 110 The reaction was carried out at 4 ° C. for 4 hours. Then, it cooled to room temperature and obtained the solution of (comparative resin 3). A small amount of this reaction solution was taken out and subjected to GPC measurement (polystyrene conversion, eluent: tetrahydrofuran). As a result, the peak area of the bisphenol A type cyanate resin, which is a synthetic raw material and the elution time appears around 12.4 minutes, is the start of the reaction. Compared to the peak area of the bisphenol A-type cyanate resin at the time, the disappearance rate of the peak area was 53%.
［実施例１〜６、比較例１〜５］
製造例１〜４により得られた熱硬化性樹脂、及び比較製造例１〜３で得られた樹脂、及び、製造例５又は商業的に入手した無機充填材、また、難燃剤又は難燃助剤、硬化促進剤を、表１と表２に示した配合割合（質量部）で混合して、希釈溶剤にメチルエチルケトンを使用して樹脂分６０質量％の均一なワニスを得た。
次に、ワニスを厚さ０．２ｍｍのＳガラスクロスに含浸させた。これを１６０℃で１０分加熱することにより乾燥させて、樹脂含有量５５質量％のプリプレグを得た。
続いて、プリプレグを４枚重ねて積層体を形成し、積層体の一方の表面と他方の表面とに配線幅が１８μｍの電解銅箔を配置し、圧力２５ｋｇ／ｃｍ2、温度１８５℃の条件で９０分間プレスを行って、銅張積層板を得た。
[Examples 1-6, Comparative Examples 1-5]
Thermosetting resins obtained in Production Examples 1 to 4, and resins obtained in Comparative Production Examples 1 to 3, and inorganic fillers obtained in Production Example 5 or commercially available, and flame retardants or flame retardant aids Agents and curing accelerators were mixed in the mixing ratios (parts by mass) shown in Tables 1 and 2, and methyl ethyl ketone was used as a diluent solvent to obtain a uniform varnish having a resin content of 60% by mass.
Next, an S glass cloth having a thickness of 0.2 mm was impregnated with varnish. This was dried by heating at 160 ° C. for 10 minutes to obtain a prepreg having a resin content of 55% by mass.
Subsequently, four prepregs are stacked to form a laminated body, and an electrolytic copper foil having a wiring width of 18 μm is disposed on one surface and the other surface of the laminated body, under conditions of a pressure of 25 kg / cm 2 and a temperature of 185 ° C. Was pressed for 90 minutes to obtain a copper clad laminate.
表中の数字は、固形分としての質量部を示している。また、表１に示す注書きは、下記のとおりである。
＊１：溶融シリカに対して１質量％のＮ−フェニル−３−アミノプロピルトリメトキシシランにより表面処理された溶融シリカ（株式会社アドマテック製：商品名ＳＣ−２０５０ＫＮＫ，希釈溶剤：メチルイソブチルケトン）
＊２：溶融シリカに対して１質量％のＮ−フェニル−３−アミノプロピルトリメトキシシランにより表面処理された溶融シリカ（株式会社アドマテック製：商品名ＳＣ−２０５０ＨＮＫ，希釈溶剤：シクロヘキサノン）
＊３：ベーマイト型水酸化アルミニウム（河合石灰工業株式会社製：商品名ＢＭＴ−３Ｌ，熱分解温度：４００℃）
＊４：モリブデン酸亜鉛をタルクに担持した無機難燃助剤（シャーウィン・ウイリアムス社製、商品名ケムガード１１００）
＊５：ナフテン酸亜鉛の８質量％ミネラルスピリット溶液
＊６：ビフェニル型エポキシ樹脂（ジャパンエポキシレジン社製：商品名ＹＸ−４０００、エポキシ当量：１８６）
＊７：溶融シリカ（アドマテック社製：商品名ＳＯ−２５Ｒ）
＊８：溶融シリカに対し１．０質量％のγ−グリシドキシプロピルトリメトキシシラン（下記一般式（９）に示す）により表面処理された溶融シリカ（アドマテック社製：商品名ＳＣ１０３０−ＭＪＡ，希釈溶剤：メチルエチルケトン）
The numbers in the table indicate parts by mass as the solid content. The notes shown in Table 1 are as follows.
* 1: Fused silica surface-treated with 1% by mass of N-phenyl-3-aminopropyltrimethoxysilane based on fused silica (manufactured by Admatech Co., Ltd .: trade name SC-2050KNK, diluent solvent: methyl isobutyl ketone)
* 2: Fused silica surface-treated with 1% by mass of N-phenyl-3-aminopropyltrimethoxysilane based on fused silica (manufactured by Admatech Co., Ltd .: trade name SC-2050HNK, diluent solvent: cyclohexanone)
* 3: Boehmite type aluminum hydroxide (manufactured by Kawai Lime Industry Co., Ltd .: trade name BMT-3L, thermal decomposition temperature: 400 ° C.)
* 4: Inorganic flame retardant aid with zinc molybdate supported on talc (manufactured by Sherwin Williams, trade name Chemguard 1100)
* 5: 8% by mass mineral spirit solution of zinc naphthenate * 6: Biphenyl type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd .: trade name YX-4000, epoxy equivalent: 186)
* 7: Fused silica (manufactured by Admatech: trade name SO-25R)
* 8: Fused silica surface-treated with 1.0% by mass of γ-glycidoxypropyltrimethoxysilane (shown by the following general formula (9)) based on fused silica (manufactured by Admatech Co., Ltd .: trade name SC1030-MJA, Diluent: Methyl ethyl ketone)
［評価結果］
実施例１〜６、比較例１〜５の銅張積層板の評価結果を、表３と表４に示す。
[Evaluation results]
Tables 3 and 4 show the evaluation results of the copper-clad laminates of Examples 1 to 6 and Comparative Examples 1 to 5.
比較例１は、熱硬化性樹脂が析出しワニスを製造できなかった。比較例２は、成形性が不良であり積層板を作製できなかった。比較例３は、樹脂が分離し、プリプレグ及び積層板を作製できなかった。
表３及び表４から明らかなように、本発明の実施例は、Ｔｇ、銅箔ピール強度、耐熱性、低熱膨張性、難燃性、銅付き耐熱性（Ｔ−２８８）、誘電特性の全てに優れる。一方、比較例４及び５は、Ｔｇ、銅箔ピール強度、耐熱性、難燃性、銅付き耐熱性（Ｔ−３００）、誘電特性の全ての特性に劣っている。
本発明の熱硬化性樹脂組成物を基材に含浸、又は塗工して得たプリプレグ、及び該プリプレグを積層成形することにより製造した積層板は、Ｔｇ、低熱膨張性、銅箔接着性、耐熱性、難燃性、銅付き耐熱性（Ｔ−３００）、誘電特性に優れ、電子機器用プリント配線板として有用であることが判った。
In Comparative Example 1, the thermosetting resin was precipitated and the varnish could not be produced. In Comparative Example 2, the moldability was poor and a laminated plate could not be produced. In Comparative Example 3, the resin separated and a prepreg and a laminate could not be produced.
As is apparent from Tables 3 and 4, the examples of the present invention are all about Tg, copper foil peel strength, heat resistance, low thermal expansion, flame resistance, heat resistance with copper (T-288), and dielectric properties. Excellent. On the other hand, Comparative Examples 4 and 5 are inferior in all the characteristics of Tg, copper foil peel strength, heat resistance, flame retardancy, heat resistance with copper (T-300), and dielectric characteristics.
A prepreg obtained by impregnating or coating a base material with the thermosetting resin composition of the present invention, and a laminate produced by laminating the prepreg are Tg, low thermal expansion, copper foil adhesion, The heat resistance, flame retardancy, heat resistance with copper (T-300), and excellent dielectric properties were found to be useful as printed wiring boards for electronic devices.
Claims (6)
１分子中に少なくとも２個のシアネート基を有する化合物（ｂ）と、
１分子中に少なくとも２個のエポキシ基を有する化合物（ｃ）とを、
シロキサン樹脂（ａ）、化合物（ｂ）及び化合物（ｃ）の総和１００質量部あたり、シロキサン樹脂（ａ）１０〜５０質量部、該化合物（ｂ）４０〜８０質量部、及び該化合物（ｃ）１０〜５０質量部の割合で用いて、有機溶媒中で、該化合物（ｂ）の反応率が３０〜７０ｍｏｌ％となるように反応させて得られた熱硬化性樹脂と、
無機充填材とを含有する樹脂組成物。
（式中、Ｒ１はそれぞれ独立に炭素数１〜５の飽和炭化水素基であり、Ｘは、それぞれ独立にメタクリル基、及びメルカプト基から選択される置換基であり、ｍは５〜１００の整数である。） A siloxane resin (a) represented by the following general formula (1):
A compound (b) having at least two cyanate groups in one molecule;
A compound (c) having at least two epoxy groups in one molecule;
10-100 parts by mass of the siloxane resin (a), 40-80 parts by mass of the compound (b), and the compound (c) per 100 parts by mass of the total of the siloxane resin (a), the compound (b), and the compound (c). A thermosetting resin obtained by reacting in an organic solvent such that the reaction rate of the compound (b) is 30 to 70 mol%, in a proportion of 10 to 50 parts by mass;
A resin composition containing an inorganic filler.
(Wherein, R 1 is each independently a saturated hydrocarbon group having 1 to 5 carbon atoms, X is a substituent selected independently main methacrylic group, from 及 Beauty mercapto group, m is 5 to It is an integer of 100.)
１分子中に少なくとも２個のシアネート基を有する化合物（ｂ）と、
１分子中に少なくとも２個のエポキシ基を有する化合物（ｃ）とを、
シロキサン樹脂（ａ）、化合物（ｂ）及び化合物（ｃ）の総和１００質量部あたり、シロキサン樹脂（ａ）１０〜５０質量部、該化合物（ｂ）４０〜８０質量部、及び該化合物（ｃ）１０〜５０質量部の割合で用いて、有機溶媒中で、該化合物（ｂ）の反応率が３０〜７０ｍｏｌ％となるように反応させて熱硬化性樹脂を得る工程と、
得られた熱硬化性樹脂と、無機充填材とを配合する工程とを
有する樹脂組成物の製造方法。
（式中、Ｒ１はそれぞれ独立に炭素数１〜５の飽和炭化水素基であり、Ｘは、それぞれ独立にメタクリル基、及びメルカプト基から選択される置換基であり、ｍは５〜１００の整数である。） A siloxane resin (a) represented by the following general formula (1):
A compound (b) having at least two cyanate groups in one molecule;
A compound (c) having at least two epoxy groups in one molecule;
10-100 parts by mass of the siloxane resin (a), 40-80 parts by mass of the compound (b), and the compound (c) per 100 parts by mass of the total of the siloxane resin (a), the compound (b), and the compound (c). used in a proportion of 10 to 50 parts by weight, in an organic solvent, a step of reaction rate of the compound (b) to obtain a reacted with thermosetting resin so that 30～70Mol%,
The manufacturing method of the resin composition which has the process of mix | blending the obtained thermosetting resin and an inorganic filler.
(Wherein, R 1 is each independently a saturated hydrocarbon group having 1 to 5 carbon atoms, X is a substituent selected independently main methacrylic group, from 及 Beauty mercapto group, m is 5 to It is an integer of 100.)
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| JP6217280B2 (en) * | 2013-09-24 | 2017-10-25 | 日立化成株式会社 | Thermosetting resin composition and prepreg, laminate, printed wiring board, and mounting board using the same |
| JP6326986B2 (en) * | 2014-06-04 | 2018-05-23 | 日立化成株式会社 | Laminate, laminate, printed wiring board |
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| JP3186843B2 (en) * | 1992-06-18 | 2001-07-11 | 日本曹達株式会社 | Curable resin composition |
| JP5114816B2 (en) * | 2001-04-12 | 2013-01-09 | 日立化成工業株式会社 | Siloxane-modified cyanate resin composition, and adhesive film, metal foil with resin, and multilayer printed wiring board using the same |
| CN103189418B (en) * | 2010-08-06 | 2015-08-12 | 日立化成株式会社 | The manufacture method of compatible resin, hot curing resin composition, prepreg and plywood |
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