JP6408752B2 - Compatibilized resin, and prepreg and laminate using the same - Google Patents
Compatibilized resin, and prepreg and laminate using the same Download PDFInfo
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- JP6408752B2 JP6408752B2 JP2012058020A JP2012058020A JP6408752B2 JP 6408752 B2 JP6408752 B2 JP 6408752B2 JP 2012058020 A JP2012058020 A JP 2012058020A JP 2012058020 A JP2012058020 A JP 2012058020A JP 6408752 B2 JP6408752 B2 JP 6408752B2
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- 229920005989 resin Polymers 0.000 title claims description 167
- 239000011347 resin Substances 0.000 title claims description 167
- 238000006243 chemical reaction Methods 0.000 claims description 72
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate group Chemical group [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims description 59
- 150000001875 compounds Chemical class 0.000 claims description 30
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 21
- 125000003700 epoxy group Chemical group 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 20
- 125000001424 substituent group Chemical group 0.000 claims description 18
- 125000003277 amino group Chemical group 0.000 claims description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 8
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims 1
- 238000003475 lamination Methods 0.000 claims 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 43
- 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 40
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- 229920001187 thermosetting polymer Polymers 0.000 description 33
- 239000000047 product Substances 0.000 description 31
- 229920000647 polyepoxide Polymers 0.000 description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 26
- 239000003822 epoxy resin Substances 0.000 description 25
- 239000011889 copper foil Substances 0.000 description 22
- 229910052802 copper Inorganic materials 0.000 description 20
- 239000010949 copper Substances 0.000 description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 18
- -1 cyanate compound Chemical class 0.000 description 18
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 18
- 238000011156 evaluation Methods 0.000 description 18
- 239000005350 fused silica glass Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 14
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 238000005259 measurement Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 239000000758 substrate Substances 0.000 description 12
- 230000008034 disappearance Effects 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 239000004593 Epoxy Substances 0.000 description 10
- 239000004793 Polystyrene Substances 0.000 description 10
- 239000004305 biphenyl Substances 0.000 description 10
- 235000010290 biphenyl Nutrition 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 229920002223 polystyrene Polymers 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
- 229910052500 inorganic mineral Inorganic materials 0.000 description 9
- 239000011707 mineral Substances 0.000 description 9
- 150000002989 phenols Chemical class 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- 239000003480 eluent Substances 0.000 description 8
- 238000010828 elution Methods 0.000 description 8
- 239000011256 inorganic filler Substances 0.000 description 8
- 229910003475 inorganic filler Inorganic materials 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000001723 curing Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 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
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 6
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 6
- 229930185605 Bisphenol Natural products 0.000 description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 238000005530 etching Methods 0.000 description 6
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 239000011342 resin composition Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 5
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229930003836 cresol Natural products 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 229910000679 solder Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005979 thermal decomposition reaction Methods 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- 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 4
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 4
- 238000007259 addition reaction Methods 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- 239000003849 aromatic solvent Substances 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 239000012796 inorganic flame retardant Substances 0.000 description 4
- 239000011810 insulating material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 150000004780 naphthols Chemical class 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 125000002524 organometallic group Chemical group 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000007363 ring formation reaction Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- 239000002966 varnish Substances 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
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 239000002635 aromatic organic solvent Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 150000004677 hydrates Chemical class 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 230000009257 reactivity Effects 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
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 3
- 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
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- 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 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-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
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 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
- 230000001070 adhesive effect Effects 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 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
- 229910001593 boehmite Inorganic materials 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000011362 coarse particle Substances 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
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 230000007613 environmental effect Effects 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
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000012774 insulation material Substances 0.000 description 2
- 239000010410 layer 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
- 239000000203 mixture Substances 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
- OVAZZMXASSWARN-UHFFFAOYSA-N naphthalen-1-ylmethanediol Chemical compound C1=CC=C2C(C(O)O)=CC=CC2=C1 OVAZZMXASSWARN-UHFFFAOYSA-N 0.000 description 2
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
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- 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
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- 239000013557 residual solvent Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 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
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 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
- ICGQLNMKJVHCIR-UHFFFAOYSA-N 1,3,2-dioxazetidin-4-one Chemical compound O=C1ONO1 ICGQLNMKJVHCIR-UHFFFAOYSA-N 0.000 description 1
- OHBQPCCCRFSCAX-UHFFFAOYSA-N 1,4-Dimethoxybenzene Chemical compound COC1=CC=C(OC)C=C1 OHBQPCCCRFSCAX-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
- AUFZRCJENRSRLY-UHFFFAOYSA-N 2,3,5-trimethylhydroquinone Chemical compound CC1=CC(O)=C(C)C(C)=C1O AUFZRCJENRSRLY-UHFFFAOYSA-N 0.000 description 1
- 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 1
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- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- XRCRJFOGPCJKPF-UHFFFAOYSA-N 2-butylbenzene-1,4-diol Chemical compound CCCCC1=CC(O)=CC=C1O XRCRJFOGPCJKPF-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
- ZTMADXFOCUXMJE-UHFFFAOYSA-N 2-methylbenzene-1,3-diol Chemical compound CC1=C(O)C=CC=C1O ZTMADXFOCUXMJE-UHFFFAOYSA-N 0.000 description 1
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 1
- MEEKGULDSDXFCN-UHFFFAOYSA-N 2-pentylphenol Chemical compound CCCCCC1=CC=CC=C1O MEEKGULDSDXFCN-UHFFFAOYSA-N 0.000 description 1
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-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
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
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- 239000006185 dispersion Substances 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
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- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
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- 238000006460 hydrolysis reaction Methods 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
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- 239000002648 laminated material Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 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
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- ASHGTJPOSUFTGB-UHFFFAOYSA-N methyl resorcinol Natural products COC1=CC=CC(O)=C1 ASHGTJPOSUFTGB-UHFFFAOYSA-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
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- 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
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- 229920006287 phenoxy resin Polymers 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
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- ZWLUXSQADUDCSB-UHFFFAOYSA-N phthalaldehyde Chemical compound O=CC1=CC=CC=C1C=O ZWLUXSQADUDCSB-UHFFFAOYSA-N 0.000 description 1
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- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
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- 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
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Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
Description
本発明は、特に優れた低熱膨張性、銅箔接着性、耐熱性、耐湿性、難燃性、銅付き耐熱性、低誘電特性、低誘電正接を示し、また、毒性が低く安全性や作業環境に優れる、電子部品等に好適な熱硬化性の相溶化樹脂に関する。また、この相溶化樹脂を用いたプリプレグ、および積層板に関する。 The present invention exhibits particularly low thermal expansion, copper foil adhesion, heat resistance, moisture resistance, flame resistance, heat resistance with copper, low dielectric properties, and low dielectric loss tangent, and has low toxicity and safety and workability. excellent environmental concerns compatible resin suitable thermosetting electronic parts. Further, a prepreg using the compatible resin, and a laminate.
熱硬化性樹脂は、熱硬化性樹脂に特有な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、特に銅張積層板や層間絶縁材料においては、近年の高密度化や高信頼性への要求から、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ている。また、近年の環境問題から、鉛フリーはんだによる電子部品の搭載やハロゲンフリーによる難燃化が要求され、そのため従来のものよりも高い耐熱性及び難燃性が必要とされる。さらに、製品の安全性や作業環境の向上化のため、毒性の低い成分のみで構成され、毒性ガス等が発生しない熱硬化性樹脂組成物が望まれている。 Thermosetting resins are widely used in the field of electronic components, etc., because the cross-linked structure unique to thermosetting resins expresses high heat resistance and dimensional stability, especially in copper-clad laminates and interlayer insulation materials, Due to recent demands for higher density and higher reliability, high copper foil adhesion, heat resistance, good low thermal expansion, and the like are required. Moreover, due to recent environmental problems, mounting of electronic parts using lead-free solder and flame resistance using halogen-free are required, and therefore higher heat resistance and flame resistance than conventional ones are required. Furthermore, in order to improve the safety of the product and the working environment, there is a demand for a thermosetting resin composition that is composed only of low-toxic components and does not generate toxic gases.
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が、エポキシ硬化系の熱硬化性樹脂にそのまま使用した場合、耐熱性や強靭性が不足する問題があった。また次世代に対応する低熱膨張性が不足である。特許文献１、２および３等に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使用量が多く、銅張積層板や層間絶縁材料として使用した場合、ドリル加工性や成形性が不足する。また、特許文献４、特許文献５等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が、必須成分であるシアネート樹脂が靭性や硬化反応性に劣る樹脂であるため、この熱硬化性樹脂の硬化反応性や強靭性の改良が依然不足であり、これらを銅張積層板や層間絶縁材料として使用した場合も、耐熱性や信頼性、加工性等が不足しているという問題があった。 The cyanate compound, a thermosetting resin, is a resin with low dielectric properties and excellent flame retardancy, but when used as it is in an epoxy curable thermosetting resin, there is a problem of insufficient heat resistance and toughness. . Moreover, the low thermal expansion property corresponding to the next generation is insufficient. Patent Documents 1, 2, 3 and the like disclose resin compositions comprising a cyanate compound and an inorganic filler and exhibiting low thermal expansion. However, since these exhibit low thermal expansion, the amount of inorganic filler used is limited. In many cases, when used as a copper clad laminate or an interlayer insulating material, drillability and formability are insufficient. Moreover, although the example regarding the thermosetting resin which contains cyanate resin and an aralkyl modified epoxy resin as an essential component is indicated by patent document 4, patent document 5, etc., cyanate resin which is an essential component is toughness and hardening reactivity. Because it is an inferior resin, the improvement in curing reactivity and toughness of this thermosetting resin is still insufficient, and even when these are used as copper-clad laminates or interlayer insulation materials, heat resistance, reliability, workability There was a problem of lacking.
本発明の目的は、低熱膨張性、銅箔接着性、耐熱性、耐湿性、難燃性、銅付き耐熱性、低誘電特性、低誘電正接の全てに優れる熱硬化性の相溶化樹脂、及びその使用、例えばプリプレグ及び積層板等を提供するものである。 An object of the present invention, the low thermal expansion property, a copper foil adhesive property, heat resistance, moisture resistance, flame retardancy, copper with heat resistance, low dielectric properties, low dielectric all excellent thermosetting compatible resin tangent, And uses thereof, for example, prepregs and laminates.
本発明者らは、上記課題を解決するために検討を進めた結果、側鎖に反応性置換基を有するシロキサン樹脂と、シアネート基を有する化合物と、エポキシ基を有する化合物とを有機金属触媒の存在下で反応させることにより、上記のすべての特性に優れる熱硬化性の相溶化樹脂が得られることを見いだし、本発明を完成させた。 As a result of investigations to solve the above problems, the present inventors have determined that an organometallic catalyst comprises a siloxane resin having a reactive substituent in the side chain, a compound having a cyanate group, and a compound having an epoxy group. by reacting in the presence, it found that the above thermosetting compatible resin which is excellent in all the characteristics can be obtained, thereby completing the present invention.
すなわち、本発明は、（ａ）下記式（Ｉ）で示される構造と、側鎖に少なくとも2個の反応性置換基を有するシロキサン樹脂、（ｂ）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、（ｃ）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、（ｄ）反応触媒として有機金属塩を用い、芳香族系有機溶媒中で（ａ）の反応性置換基とシアネート基の付加反応、及びトリアジン環化反応させることにより得られる相溶化樹脂に関するものであり、この相溶化樹脂は、好ましくは、（ａ）と（ｂ）と（ｃ）とを、（ｄ）の有機金属塩触媒の存在下で反応させる際に、（ｂ）のシアネート基を有する化合物の反応率（消失率）が３０〜７０ｍｏｌ％となるように反応させたものである。
また、本発明は、この相溶化樹脂を用いて形成されたプリプレグおよびこのプリプレグを用いて積層形成された積層板に関するものである。
That is, the present invention comprises (a) a structure represented by the following formula (I), a siloxane resin having at least two reactive substituents in the side chain, and (b) at least two cyanate groups in one molecule. And (c) a compound having at least two epoxy groups in one molecule, (d) a reactive substituent of (a) in an aromatic organic solvent using an organometallic salt as a reaction catalyst and addition reaction of cyanate groups, and relates compatible resin obtained by triazine cyclization reaction, the compatible resin is preferably a (a) and (b) (c), When the reaction is carried out in the presence of the organometallic salt catalyst (d), the reaction is carried out so that the reaction rate (disappearance rate) of the compound (b) having a cyanate group is 30 to 70 mol%.
Further, the present invention relates to laminates which are laminated with a prepreg and the prepreg formed by using the compatible resin.
本発明の熱硬化性の相溶化樹脂は高いＴｇを有し、これを基材に含浸、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、低熱膨張性、銅箔接着性、耐熱性、耐湿性、難燃性、銅付き耐熱性（Ｔ−３００）、低誘電特性、低誘電正接性に優れ、電子機器用プリント配線板として有用である。 Thermosetting compatible resin of the present invention has a high Tg, which impregnating a base material, or prepreg obtained by coating, and laminate was prepared by laminating molding the prepreg, a low thermal It has excellent expandability, copper foil adhesion, heat resistance, moisture resistance, flame resistance, heat resistance with copper (T-300), low dielectric properties, and low dielectric loss tangent, and is useful as a printed wiring board for electronic devices.
以下、本発明について詳細に説明する。 Hereinafter, the present invention will be described in detail.
積層板材料には近年の高密度化や高信頼性への要求から、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が、微細配線形成のため銅箔接着性は、銅箔引き剥がし強さが１．０ｋＮ／ｍ以上であることが望ましく、１．２ｋＮ／ｍ以上であることがより望ましい。
また、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も必要であり、高いリフロー耐熱性が必要であるが、リフロー耐熱性評価の指針となる銅付き耐熱性（Ｔ−３００）は、３０分以上ふくれ等が生じないことが望ましい。
さらに、高密度化に伴い基材はより薄型化される方向にあり、熱処理時における基材のそりが小さいことが必要となる。低そり化のためには基材の面方向が低熱膨張性であることが有効であり、その熱膨張係数は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。
さらに、高速応答性の要求も増え続けており、基材の比誘電率は４．７以下、更には４．５以下であること、また誘電正接は０．０１０以下が、好ましくは０．００９以下、更には０．００８以下であることが望ましい。
このような状況の中、鋭意研究により以下に説明する発明に至った。
Laminate materials require high copper foil adhesion, heat resistance, good low thermal expansion, etc. due to recent demands for higher density and higher reliability. The peel strength of the copper foil is desirably 1.0 kN / m or more, and more desirably 1.2 kN / m or more.
In addition, it is necessary to increase the number of layers using a build-up material or the like for high density, and high reflow heat resistance is required. However, heat resistance with copper (T- 300) is preferably free from blistering for 30 minutes or more.
Furthermore, as the density increases, the base material tends to be thinner, and it is necessary for the base material to be less warped during heat treatment. In order to reduce warpage, it is effective that the surface direction of the base material has low thermal expansion, and the thermal expansion coefficient is preferably 7 ppm / ° C. or less, more preferably 5 ppm / ° C. or less.
Furthermore, the demand for high-speed response continues to increase, and the relative dielectric constant of the substrate is 4.7 or less, further 4.5 or less, and the dielectric loss tangent is 0.010 or less, preferably 0.009. Hereinafter, it is further desirably 0.008 or less.
Under such circumstances, the present invention described below has been made through intensive research.
本発明は、（ａ）上記の式（Ｉ）で示される構造と、側鎖に少なくとも２個の反応性置換基を有するシロキサン樹脂と、（ｂ）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、（ｃ）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、（ｄ）反応触媒として有機金属塩を用いて、芳香族系有機溶媒中で（ａ）の反応性置換基とシアネート基の付加反応、及びトリアジン環化反応させることにより得られる熱硬化性の相溶化樹脂である。以下、この相溶化樹脂について詳細に説明する。 The present invention comprises (a) a structure represented by the above formula (I), a siloxane resin having at least two reactive substituents in the side chain, and (b) at least two cyanate groups in one molecule. (C) a compound having at least two epoxy groups in one molecule, (d) reactive substitution of (a) in an aromatic organic solvent using an organometallic salt as a reaction catalyst addition reaction of groups and cyanate groups, and a thermosetting compatible resin obtained by triazine cyclization reaction. Hereinafter, the compatible resin is described in detail.
本発明の相溶化樹脂を製造する際に用いる成分（ａ）のシロキサン樹脂は、下記式（Ｉ）で示される構造と、側鎖に少なくとも２個の反応性置換基を有するものであれば特に限定されない。なお、ここでいう反応性置換基とは、水酸基、アミノ基、カルボキシル基、メタクリロイル基、アクリロイル基、エポキシ基、シクロアルキルエポキシ基およびメルカプト基から選ばれる基を意味する。
このように側鎖に少なくとも２個以上の反応性置換基を有するシロキサン樹脂のうち、各々の置換基が同一または隣接したケイ素原子と結合していないシロキサン樹脂は反応点が近接しないために、熱硬化後に反応性置換基が残りにくく吸水性や誘電特性が良好となる。また、側鎖に反応性基を有すると、反応点が嵩高くなり加水分解を受けにくくなり、シロキサン樹脂の分離を抑制することができる。 Thus, among the siloxane resins having at least two or more reactive substituents in the side chain, the siloxane resin in which each substituent is not bonded to the same or adjacent silicon atom is not close to the reaction point. Reactive substituents hardly remain after curing, and water absorption and dielectric properties are improved. Moreover, when it has a reactive group in a side chain, a reactive site becomes bulky and it becomes difficult to receive a hydrolysis, and can isolate | separate isolation | separation of a siloxane resin.
このようなシロキサン樹脂としては、例えば水酸基で置換された化合物は信越化学工業（株）製、商品名Ｘ−２２−４０３９（水酸基当量：９５０ｇ／ｍｏｌ）、商品名Ｘ−２２−４０１５（水酸基価：１９００ｇ／ｍｏｌ）等が挙げられ、アミノ基で置換された化合物は信越化学工業（株）製、商品名ＫＦ−８６８（アミノ基当量：８８００ｇ／ｍｏｌ）、商品名ＫＦ−８６５（アミノ基当量：５０００ｇ／ｍｏｌ）、商品名ＫＦ−８６４（アミノ基当量：３８００ｇ／ｍｏｌ）、商品名ＫＦ−８５９（アミノ基当量：６０００ｇ／ｍｏｌ）、商品名ＫＦ−８００４（アミノ基当量：１５００ｇ／ｍｏｌ）、東レ・ダウコーニング（株）製、商品名ＦＺ−３７０５（アミノ基当量：４０００ｇ／ｍｏｌ）、商品名ＢＹ１６−８４９（アミノ基当量：６００ｇ／ｍｏｌ）商品名ＢＹ１６−８９０（アミノ基当量：１８００ｇ／ｍｏｌ）、商品名ＢＹ１６−２０８（アミノ基当量：３６００ｇ／ｍｏｌ）等が挙げられ、エポキシ基で置換された化合物は信越化学工業（製）Ｘ−２２−３４３（エポキシ基当量：５２５ｇ／ｍｏｌ）、ＫＦ−１００１（エポキシ基当量：３５００）、東レ・ダウコーニング（株）製、商品名ＳＦ８４１１（エポキシ基当量：３２００ｇ／ｍｏｌ）等が挙げられ、エポキシシクロヘキシル基で置換された化合物は信越化学工業（製）、商品名ＫＦ−１０２（エポキシ基当量：３６００ｇ／ｍｏｌ）、商品名Ｘ−２２−２０４６（トルエン５０％カット品、エポキシ基当量：６００ｇ／ｍｏｌ）、東レ・ダウコーニング（株）製、商品名ＢＹ１６−８３９（エポキシ基当量：３７００ｇ／ｍｏｌ）、等が挙げられ、メルカプト基で置換された化合物は信越化学工業（製）、商品名ＫＦ−２００１（メルカプト基当量：１９００ｇ／ｍｏｌ）、商品名ＫＦ−２００４（メルカプト基当量：３００００ｇ／ｍｏｌ）等が挙げられ、カルボキシル基で置換された化合物は信越化学工業（製）、商品名Ｘ−２２−３７０１Ｅ（カルボキシル基当量：４０００ｇ／ｍｏｌ）、東レ・ダウコーニング（株）製、商品名ＢＹ１６−８８０（カルボキシル基当量：３５００ｇ／ｍｏｌ）、等が挙げられる。これらの中で、反応性に優れる点から、水酸基とアミノ基が好ましい。また、置換基の位置は側鎖のみに限定されず、末端置換基を有するシロキサン樹脂を用いることもできる。 As such a siloxane resin, for example, a compound substituted with a hydroxyl group is manufactured by Shin-Etsu Chemical Co., Ltd., trade name X-22-4039 (hydroxyl equivalent: 950 g / mol), trade name X-22-4015 (hydroxyl value). 1900 g / mol) and the like. Compounds substituted with an amino group are manufactured by Shin-Etsu Chemical Co., Ltd., trade name KF-868 (amino group equivalent: 8800 g / mol), trade name KF-865 (amino group equivalent). : Trade name KF-864 (amino group equivalent: 3800 g / mol), trade name KF-859 (amino group equivalent: 6000 g / mol), trade name KF-8004 (amino group equivalent: 1500 g / mol) Manufactured by Toray Dow Corning Co., Ltd., trade name FZ-3705 (amino group equivalent: 4000 g / mol), trade name BY16-849 (amino) Equivalent: 600 g / mol) Trade name BY16-890 (amino group equivalent: 1800 g / mol), trade name BY16-208 (amino group equivalent: 3600 g / mol), and the like. The compound substituted with an epoxy group is Shin-Etsu Chemical. Industrial (product) X-22-343 (epoxy group equivalent: 525 g / mol), KF-1001 (epoxy group equivalent: 3500), manufactured by Toray Dow Corning Co., Ltd., trade name SF8411 (epoxy group equivalent: 3200 g / mol) The compounds substituted with an epoxycyclohexyl group are Shin-Etsu Chemical Co., Ltd., trade name KF-102 (epoxy group equivalent: 3600 g / mol), trade name X-22-2046 (toluene 50% cut product) , Epoxy group equivalent: 600 g / mol), manufactured by Toray Dow Corning Co., Ltd., trade name BY16-839 ( The compound substituted with a mercapto group is Shin-Etsu Chemical Co., Ltd. (trade name), trade name KF-2001 (mercapto group equivalent: 1900 g / mol), trade name KF-2004 ( Mercapto group equivalent: 30000 g / mol) and the like. Compounds substituted with a carboxyl group are Shin-Etsu Chemical Co., Ltd. (trade name), trade name X-22-3701E (carboxyl group equivalent: 4000 g / mol), Toray Dow Corning ( Product name BY16-880 (carboxyl group equivalent: 3500 g / mol), etc. are mentioned. Among these, a hydroxyl group and an amino group are preferable from the viewpoint of excellent reactivity. The position of the substituent is not limited to the side chain alone, and a siloxane resin having a terminal substituent can also be used.
本発明の相溶化樹脂を製造する際に用いる成分（ｂ）の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、ジシクロペンタジエン型シアネート樹脂等が挙げられ、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、ジシクロペンタジエン型シアネート樹脂、下記式（II）に示すノボラック型シアネート樹脂が特に好ましい。
（ｍは正の数）
一般式（II）で示されるノボラック型シアネート樹脂の平均繰り返し数：ｍは、特に限定されないが、０．１〜３０が好ましい。０．１より多いと結晶化が抑制され取り扱いが容易となり、３０より少ないと硬化物が脆くなりにくい。
Compounds having at least two cyanate groups per molecule of component (b) to be used in producing a compatible resin of the present invention, for example, a novolac type cyanate resin, bisphenol A type cyanate resin, bisphenol E type cyanate Resins, bisphenol F-type cyanate resins, tetramethylbisphenol F-type cyanate resins, dicyclopentadiene-type cyanate resins and the like can be mentioned, and one kind or a mixture of two or more kinds can be used. Among these, bisphenol A-type cyanate resin, dicyclopentadiene-type cyanate resin, and novolak-type cyanate resin represented by the following formula (II) from the viewpoints of dielectric properties, heat resistance, flame retardancy, low thermal expansion, and low cost. Is particularly preferred.
(M is a positive number)
Although the average repeating number: m of the novolak-type cyanate resin represented by the general formula (II) is not particularly limited, it is preferably 0.1 to 30. When it is more than 0.1, crystallization is suppressed and handling is easy, and when it is less than 30, the cured product is hardly brittle.
本発明の相溶化樹脂を製造する際に用いる成分（ｃ）の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等のエポキシ樹脂が挙げられ、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、高剛性、誘電特性、耐熱性、難燃性、耐湿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く、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く、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、下記式（III）に示すビフェニル型エポキシ樹脂が特に好ましい。
本発明の相溶性樹脂の製造に用いる成分（ｄ）の反応触媒の有機金属塩は、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が挙げられる。 Examples of the organic catalyst salt of the reaction catalyst of the component (d) used for the production of the compatible resin of the present invention include zinc naphthenate, manganese naphthenate, cobalt naphthenate, tin octylate, and cobalt octylate.
反応に際しては、上記の（ａ）と（ｂ）と（ｃ）の総和１００重量部あたりの（ａ）の使用量を１０〜５０重量部の範囲とし、（ｂ）の使用量を４０〜８０重量部の範囲とし、（ｃ）の使用量を１０〜５０重量部の範囲とし、これらを例えば予めトルエン、キシレン、メシチレンから選ばれる溶媒中に均一に溶解し、８０℃〜１２０℃程度の反応温度で（ａ）の反応性置換基とシアネート基の付加反応、及びトリアジン環化反応させ、（ｂ）のシアネート基を有する化合物の反応率（消失率）を好ましくは３０〜７０ｍｏｌ％となるように反応を行う必要がある。ここで、反応溶媒にはトルエン、キシレン、メシチレンから選ばれる芳香族系溶媒が好適であり、必要により少量の他の溶剤を用いてもよいが、所望の反応が遅くなり、耐熱性等が低下する。また、ベンゼンは毒性が強く、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塗工時に残溶剤となりやすいので好ましくない。 In the reaction, the amount of (a) used per 100 parts by weight of the sum of (a), (b) and (c) is in the range of 10 to 50 parts by weight, and the amount of (b) is 40 to 80 parts by weight. The amount of (c) used is in the range of 10 to 50 parts by weight, and these are uniformly dissolved in, for example, a solvent selected beforehand from toluene, xylene and mesitylene, and reacted at about 80 ° C to 120 ° C. The reaction rate (disappearance rate) of the compound having the cyanate group (b) is preferably 30 to 70 mol% by the addition reaction of the reactive substituent and cyanate group (a) and the triazine cyclization reaction at temperature. It is necessary to perform the reaction. Here, the reaction solvent is preferably an aromatic solvent selected from toluene, xylene, and mesitylene, and if necessary, a small amount of other solvent may be used, but the desired reaction is slowed down, and heat resistance and the like are reduced. To do. In addition, benzene is highly toxic, and an aromatic solvent having a molecular weight larger than that of mesitylene is not preferable because it tends to be a residual solvent during prepreg production coating.
反応率が３０ｍｏｌ％以上であると、得られる樹脂が相溶化され、樹脂が分離、白濁するようなことがない。また、反応率が７０ｍｏｌ％以下であると、得られる熱硬化性の樹脂が溶剤に不溶化するようなことがなく、Ａステージのワニス（熱硬化性樹脂組成物）が製造できなくなったり、プリプレグのゲルタイムが短くなり過ぎ、プレスの際に成形性が低下するようなこともない。なお、イミノカーボネート化反応に代表される付加反応とは、水酸基またはカルボキシル基とシアネート基ではイミノカーボネ−ト結合（−Ｏ−（Ｃ＝ＮＨ）−Ｏ−）が生成され、アミノ基とシアネート基ではイミノカルバメート結合（−Ｏ−（Ｃ＝ＮＨ）−ＮＨ−）が生成され、エポキシ基とシアネート基ではオキサゾリン環が生成され、メルカプト基とシアネート基ではイミノチオカーボネート結合（−Ｏ−（Ｃ＝ＮＨ）−Ｓ−）が生成される反応を示す。トリアジン環化反応は、シアネート基が３量化しトリアジン環を形成する反応である。 When the reaction rate is at least 30 mol%, the resin is compatible of the resulting resin is separated, there is no such thing as clouded. If the reaction rate is 70 mol% or less, the resulting thermosetting resin will not be insolubilized in the solvent, and the A-stage varnish (thermosetting resin composition) cannot be produced. The gel time becomes too short, and the moldability does not deteriorate during pressing. The addition reaction represented by the imino carbonate reaction is an imino carbonate bond (—O— (C═NH) —O—) formed by a hydroxyl group or a carboxyl group and a cyanate group, and an amino group and a cyanate group. An iminocarbamate bond (—O— (C═NH) —NH—) is formed, an oxazoline ring is formed between the epoxy group and the cyanate group, and an iminothiocarbonate bond (—O— (C═NH) is formed between the mercapto group and the cyanate group. ) -S-) is produced. The triazine cyclization reaction is a reaction in which a cyanate group is trimerized to form a triazine ring.
また、このシアネート基が３量化しトリアジン環を形成する反応により３次元網目構造化が進行するが、この時（ｃ）である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が３次元網目構造中に均一に分散され、これによって（ａ）成分と（ｂ）成分と（ｃ）成分と（ｄ）成分が均一に分散された熱硬化性の相溶化樹脂が製造される。ここで、（ａ）の使用量が１０重量部を超えると、得られる基材の面方向の低熱膨張性が得られ、また（ａ）の使用量が５０重量部未満であると、耐熱性や耐薬品性が低下せず良好である。（ｂ）の使用量が４０重量部を超えると得られる樹脂の相溶性が良好となり、また（ｂ）の使用量が８０重量部を未満であると、得られる基材の面方向の低熱膨張性が得られ良好である。（ｃ）の使用量が１０重量部を超えると、耐湿耐熱性が低下せず良好であり、また（ｃ）の使用量が５０重量部を未満であると、銅箔接着性や誘電特性が低下せず良好となる。 In addition, a three-dimensional network structure is formed by a reaction in which the cyanate group is trimerized to form a triazine ring. At this time, a compound having at least two epoxy groups per molecule (c) is formed in the three-dimensional network. It is uniformly dispersed in the structure, whereby the component (a) and component (b) and (c) component and the component (d) is uniformly dispersed thermosetting compatible resin is produced. Here, when the amount of use of (a) exceeds 10 parts by weight, low thermal expansion in the surface direction of the obtained substrate is obtained, and when the amount of use of (a) is less than 50 parts by weight, heat resistance is obtained. And chemical resistance does not decrease. Compatible resin usage can be obtained with more than 40 parts by weight of (b) is improved, also when the amount of (b) is less than 80 parts by weight, the low heat in the planar direction of the resulting substrate Good expandability. When the amount of use of (c) exceeds 10 parts by weight, the moisture resistance and heat resistance is good without decreasing, and when the amount of use of (c) is less than 50 parts by weight, the copper foil adhesion and dielectric properties are improved. It does not decrease and becomes good.
反応触媒の（ｄ）成分の使用量は、（ａ）と（ｂ）と（ｃ）の各成分の総和１００重量部に対して、０．０００１〜０．００４重量部が好ましい。この範囲であると、反応に長時間を要したり、反応速度が速すぎて終点管理が難しくなるようなこともない。ここで、（ｂ）のシアネート基を有する化合物の反応率は、ＧＰＣ測定により反応開始時の（ｂ）のシアネート基を有する化合物のピーク面積と、所定時間反応後のピーク面積を比較し、ピーク面積の消失率から求められる。 The amount of component (d) used in the reaction catalyst is preferably 0.0001 to 0.004 parts by weight with respect to 100 parts by weight as the sum of the components (a), (b) and (c). Within this range, the reaction does not take a long time, and the reaction rate is not so high that the end point management becomes difficult. Here, the reaction rate of the compound having the cyanate group (b) is determined by comparing the peak area of the compound having the cyanate group (b) at the start of the reaction with the peak area after the reaction for a predetermined time by GPC measurement. It is obtained from the disappearance rate of the area.
本発明で言う相溶化樹脂とは、構成成分が相互に分離せずに均一に混合された樹脂のことである。シロキサン樹脂は低極性のため、シアネート樹脂やエポキシ樹脂とは分離しやすいが、本発明の手法を用いて反応させることで相互に混合された相溶化樹脂となり、シロキサン樹脂の有する低熱膨張性が発現する。得られた樹脂溶液を加熱乾燥させて目視で確認し、均一で透明な樹脂硬化物になっていることが相溶化の判断基準である。 The compatible resin in the present invention is that the resin components are uniformly mixed without being separated from each other. Since the siloxane resin having a low polarity, tends to separate from the cyanate resin or epoxy resin, but become compatible resin which is mixed with one another by reaction with the technique of the present invention, the low thermal expansion properties possessed by the siloxane resin To express. The resulting resin solution is dried by heating was confirmed by visual observation, a uniform and transparent criteria it is compatible of which is the cured resin.
また、本発明の相溶化樹脂を合成する際、反応には有機溶媒を使用することが好ましい。この反応で使用される有機溶媒は特に制限されないが、例えばエタノール、プロパノール、ブタノール、メチルセロソルブ、ブチルセロソルブ、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溶剤、アセトン、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溶剤、酢酸エチルエステルやγ−ブチロラクトン等のエステル系溶剤、テトラヒドロフラン等のエーテル系溶剤、トルエン、キシレン、メシチレン等の芳香族系溶剤、ジメチルホルムアミド、ジメチルアセトアミド、Ｎ−メチルピロリドン、ジメチルスルホキシド等の非プロトン性極性溶媒等が挙げられ、１種又は２種以上を混合して使用できる。
これらの中で、溶解性が良好であることや、揮発性が高く残溶剤として残りにくい点、反応触媒の作用を阻害しにくい点からトルエン、キシレン、メシチレン等の芳香族系溶剤の使用が好ましい。
Furthermore, the synthesis of the compatible resin of the present invention, it is preferable to use the organic solvent in the reaction. The organic solvent used in this reaction is not particularly limited, but alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, and ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. , Ester solvents such as ethyl acetate and γ-butyrolactone, ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene and mesitylene, aprotic compounds such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone and dimethylsulfoxide May be used, and one or two or more may be used in combination.
Of these, aromatic solvents such as toluene, xylene and mesitylene are preferably used because of their good solubility, high volatility and difficulty in remaining as a residual solvent, and difficulty in inhibiting the reaction catalyst. .
本発明の熱硬化性の相溶化樹脂には、熱硬化後の残存シアネート基を減らす目的でフェノール樹脂やフェノール類などの化合物を更に添加することができる。フェノール類などの化合物としては、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化合物が挙げられる。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二官能化合物があげられる。 The thermosetting compatible resin of the present invention, a compound such as a phenol resin and phenol for the purpose of reducing the residual cyanate group after thermal curing may be further added. Examples of compounds such as phenols include monofunctional compounds such as phenol, cresol, xylenol, butylphenol, amylphenol, nonylphenol, p-cumylphenol, 1-naphthol, and 2-naphthol. Bisphenol A, tetramethylbisphenol F, bisphenol F, bisphenol S, bisphenol K, biphenol, tetramethylbiphenol, hydroquinone, methylhydroquinone, dimethylhydroquinone, trimethylhydroquinone, di-ter. Bifunctional compounds such as butylhydroquinone, resorcinol, methylresorcinol, catechol, methylcatechol, dihydroxynaphthalene, dihydroxymethylnaphthalene, dihydroxydimethylnaphthalene, bisphenolfluorene, biscresolfluorene and the like can be mentioned.
また、フェノール樹脂としては、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等が挙げられる。これらは、公知の方法により得ることが出来る。 In addition, as the phenol resin, phenols, or a condensate of naphthols and aldehydes, a condensate of phenols or naphthols and xylylene glycol, a condensate of phenols or naphthols and bismethoxymethylbiphenyl, Examples include condensates of phenols and isopropenyl acetophenone, and reaction products of phenols and dicyclopentadiene. These can be obtained by known methods.
縮合物を得るため縮合に用いるフェノール類としては、上記において例示したようなフェノールやクレゾールなどの各種化合物があげられ、同様にナフトール類としては、１−ナフトール、２−ナフトールの他、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あげられる。
更に、縮合に用いる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。
Examples of the phenols used for the condensation in order to obtain a condensate include various compounds such as phenol and cresol as exemplified above. Similarly, naphthols include 1-naphthol and 2-naphthol, dihydroxynaphthalene, Examples thereof include dihydroxymethylnaphthalene, dihydroxydimethylnaphthalene and trihydroxynaphthalene.
Further, the aldehydes used for the condensation include formaldehyde, acetaldehyde, propyl aldehyde, butyraldehyde, valeraldehyde, capronaldehyde, benzaldehyde, chlorbenzaldehyde, bromobenzaldehyde, glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde, adipine aldehyde, picine aldehyde. Examples include melinaldehyde, sebacinaldehyde, acrolein, crotonaldehyde, salicylaldehyde, phthalaldehyde, and hydroxybenzaldehyde.
本発明の熱硬化性の相溶化樹脂には、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を用いるのが望ましく、特に溶融シリカを用いるのが好ましく、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のがより好ましい。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良く、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。この中でも特に、下記式（IV）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分散性の点で好ましい。
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、例えば、上記構造式（IV）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時間程度攪拌しながら反応（表面処理）させることにより得られる。また、アドマテックス社等から商業的にも入手でき、例えば、アドマテックス社製の商品名ＳＣ−２０５０ＫＮＫや、ＳＣ−２０５０ＨＮＫ等がある。 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, for example, the trimethoxysilane compound represented by the above structural formula (IV) is added and reacted (surface treatment) with stirring at 60 ° C. to 120 ° C. for about 0.5 to 5 hours. . Also, commercially available from Admatechs, Inc., for example, trade names SC-2050KNK and SC-2050HNK manufactured by Admatechs are available.
また、シリカの形状は低熱膨張性及び樹脂に充填した際の高流動性から球状が好ましい。
その平均粒子径は０．１〜１０μｍであることが好ましく、０．３〜８μｍであることがより好ましい。該溶融球状シリカの平均粒子径を０．１μｍ以上にすることで、樹脂に高充填した際の流動性を良好に保つことができ、さらに１０μｍ以下にすることで、粗大粒子の混入確率を減らし粗大粒子起因の不良の発生を抑えることができる。ここで、平均粒子径とは、粒子の全体積を１００％として粒子径による累積度数分布曲線を求めた時、ちょうど体積５０％に相当する点の粒子径のことであり、レーザ回折散乱法を用いた粒度分布測定装置等で測定することができる。
The shape of silica is preferably spherical because of its low thermal expansibility and high fluidity when filled in a resin.
The average particle diameter is preferably from 0.1 to 10 μm, more preferably from 0.3 to 8 μm. By setting the average particle diameter of the fused spherical silica to 0.1 μm or more, the fluidity when the resin is highly filled can be kept good, and by setting it to 10 μm or less, the mixing probability of coarse particles is reduced. Generation of defects due to coarse particles can be suppressed. Here, the average particle size is a particle size at a point corresponding to a volume of 50% when a cumulative frequency distribution curve based on the particle size is obtained with the total volume of the particles being 100%, and the laser diffraction scattering method is used. It can be measured with the used particle size distribution measuring device or the like.
これら溶融シリカの使用量は、固形分換算の該相溶性樹脂１００重量部に対し、１０〜３００重量部とすることが好ましく、１００〜２５０重量部とすることがより好ましく、１５０〜２５０重量部とすることが特に好ましい。１０重量部以上であると、基材の剛性や、耐湿耐熱性、難燃性が十分であり、また、３００重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。 The amount of the 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 compatible resin in terms of solid content. It is particularly preferable that If it is 10 parts by weight or more, the rigidity, moisture heat resistance, and flame resistance of the substrate are sufficient, and if it is 300 parts by weight or less, chemical resistance such as moldability and plating solution resistance is improved. .
本発明の熱硬化性の相溶化樹脂には、他の無機充填剤を使用してもよく、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、これらの中で、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く、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）が特に好ましい。これらの無機充填剤使用量は、固形分換算の該相溶性樹脂１００重量部に対し、０〜２００重量部とすることが好ましく、１０〜１５０重量部とすることがより好ましく、５０〜１５０重量部とすることが特に好ましい。１０重量部を超えると難燃性が十分となり、２００重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。 The thermosetting compatible resin of the present invention may be used with other inorganic fillers, for example, crushed silica, mica, talc, glass short fiber or powder and hollow glass, calcium carbonate, quartz powder 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 metal Among the hydrates, metal hydrates having a thermal decomposition temperature of 300 ° C. or higher, such as boehmite type aluminum hydroxide (AlOOH), or gibbsite type aluminum hydroxide (Al A compound in which the thermal decomposition temperature of (OH) 3) is adjusted to 300 ° C. or higher by heat treatment, magnesium hydroxide, and the like are more preferable, particularly inexpensive and a particularly high thermal decomposition temperature of 350 ° C. or higher. If, boehmite-type aluminum hydroxide having a high chemical resistance (AlOOH) is particularly preferred. The amount of these inorganic fillers used is preferably 0 to 200 parts by weight, more preferably 10 to 150 parts by weight, and more preferably 50 to 150 parts by weight with respect to 100 parts by weight of the compatible resin in terms of solid content. It is particularly preferable to use parts. If it exceeds 10 parts by weight, the flame retardancy will be sufficient, and if it is less than 200 parts by weight, the chemical resistance such as the plating solution resistance and the moldability will not be deteriorated and it will be good.
本発明の熱硬化性の相溶化樹脂には、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用いることが望ましく、硬化促進剤の例としては、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。硬化促進剤を使用しないと、耐熱性や難燃性、銅箔接着性等が不足する場合がある。 The thermosetting compatible resin of the present invention, it is desirable to use heat resistance and flame retardancy, a curing accelerator for improving of the copper foil adhesive property, etc., as examples of curing accelerators, naphthenic acid Examples thereof include organic metal salts such as zinc, cobalt naphthenate, tin octylate and cobalt octylate, imidazoles and derivatives thereof, tertiary amines and quaternary ammonium salts. If a curing accelerator is not used, heat resistance, flame retardancy, copper foil adhesion, etc. may be insufficient.
本発明の熱硬化性の相溶化樹脂には、任意に他の難燃剤の併用ができるが、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そぐわない。他の難燃剤の併用の例としては、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剤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化させるので、特に好ましい無機難燃助剤である。モリブデン酸亜鉛の使用量は本発明の相溶化樹脂１００重量部に対し、５〜２０重量部とすることが好ましい。５重量部未満であると難燃性やドリル加工性の向上効果がみられなかったり、また２０重量部を超えるとワニスのゲルタイムが短くなり過ぎ、プレスにより積層板を成形する際に成形性が低下する場合がある。 Metal hydroxide thermosetting compatible resin of the present invention may be used in combination of other flame retardants optionally halogen-containing flame retardant and thermal decomposition temperature containing bromine or chlorine is less than 300 ° C. Things are not suitable for the purpose of the present invention. Examples of other flame retardant combinations include triphenyl phosphate, tricresyl phosphate, trisdichloropropyl phosphate, phosphoric ester compounds, phosphazenes, phosphorous flame retardants such as red phosphorus, antimony trioxide, zinc molybdate, etc. Inorganic flame retardant aids and the like. In particular, an inorganic flame retardant aid in which zinc molybdate is supported on an inorganic filler such as talc is a particularly preferred inorganic flame retardant aid because it significantly improves not only the flame retardancy but also the drill workability. The amount of zinc molybdate whereas compatible resin 100 parts by weight of the present invention, preferably 5 to 20 parts by weight. If the amount is less than 5 parts by weight, flame retardancy and drilling workability are not improved. If the amount exceeds 20 parts by weight, the gel time of the varnish becomes too short. May decrease.
本発明の相溶化樹脂には、靭性や流動性を改善するため、任意に公知の熱可塑性樹脂、エラストマー、有機充填剤等の併用ができる。
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等が挙げられる。
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等が挙げられる。
有機充填剤の例としては、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等が挙げられる。
The compatible resin of the present invention in order to improve the toughness and fluidity, any known thermoplastic resins, elastomers, combinations of such organic fillers.
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 the elastomer 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.
また、本発明の相溶化樹脂においては、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の添加も可能であり、特に限定されない。これらの例としては、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。 In the compatible resin of the present invention, optionally a UV absorber, an antioxidant, a photopolymerization initiator, additives such as fluorescent whitening agent and an adhesion improver is also possible, not particularly limited. Examples of these include UV absorbers such as benzotriazoles, antioxidants such as hindered phenols and styrenated phenols, photopolymerization initiators such as benzophenones, benzyl ketals, and thioxanthones, and fluorescence such as stilbene derivatives. Examples include brighteners, urea compounds such as urea silane, and adhesion improvers such as silane coupling agents.
本発明のプリプレグは、前記した本発明の熱硬化性の相溶化樹脂、あるいは必要に応じて他の成分を添加した熱硬化性の相溶化樹脂組成物を、基材に含浸又は塗工してなるものである。以下、本発明のプリプレグについて詳述する。 The prepreg of the present invention, a thermosetting compatible resin, or thermosetting compatible resin composition obtained by adding other ingredients as needed for the present invention described above, impregnated in the substrate or coating It is made. Hereinafter, the prepreg of the present invention will be described in detail.
本発明のプリプレグは、本発明の熱硬化性の相溶化樹脂あるいは相溶化樹脂組成物を、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。本発明の基材として、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る。その材質の例としては、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、耐熱性や耐湿性、加工性の面から好適である。該基材に対する相溶化樹脂あるいは相溶化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重量％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）させて、本発明のプリプレグを得ることができる。 Of the present invention prepreg, the thermosetting compatible resin or a compatible resin composition of the present invention, by impregnating or coating a base material, by heating or the like of the semi-cured (B-stage) the present invention A prepreg can be manufactured. As the base material of the present invention, known materials used for various types of laminates for electrical insulating materials can be used. Examples of the material include inorganic fibers such as E glass, D glass, S glass, and Q glass, organic fibers such as polyimide, polyester, and tetrafluoroethylene, 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. However, it is suitable from the aspects of heat resistance, moisture resistance, and workability. Adhesion amount of incompatible resin or a compatible resin composition to the substrate is a resin content of the prepreg after drying, so that 20 to 90% by weight, after impregnating or coating a base Usually, the prepreg of the present invention can be obtained by heating and drying at a temperature of 100 to 200 ° C. for 1 to 30 minutes and semi-curing (B-stage).
本発明の積層板は、前述の本発明のプリプレグを用いて、積層成形して、形成することができる。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２〜１００ｋｇ／ｃｍ２、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。 The laminate of the present invention can be formed by laminate molding 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. In addition, as the molding conditions, for example, a method of a laminated plate for an electrical insulating material and a multilayer plate can be applied. For example, a multistage press, a multistage vacuum press, continuous molding, an autoclave molding machine, etc. are used, and a temperature of 100 to 250 ° C. It can be molded in a range of ˜100 kg / cm 2 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.
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いかなる意味においても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 in any way.
製造例１：相溶化樹脂（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、アルコール変性シロキサン樹脂（信越化学社製；商品名Ｘ−２２−４０３９、水酸基当量；９５０）：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８ｗｔ％ミネラルスピリット溶液を０．０１ｇ添加し、約１１０℃で６時間反応を行った。その後、室温に冷却し熱硬化性の相溶化樹脂（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６０％であった。また、約１０．９分付近、及び８．０〜１０．０付近に出現する熱硬化性の樹脂の生成物のピークが確認された。この反応溶液を、熱風乾燥機で１７０℃、１５分乾燥させることで得られる樹脂硬化物を目視で評価し、樹脂硬化物が透明であり分離が生じなかったため相溶化樹脂であることが確認された。
Preparation Example 1: incompatible resin (1-1) with a thermometer, stirrer, the reaction vessel of the heating and cooling capacity capable of 3 liters equipped with a reflux condenser, a bisphenol A type cyanate resin (Lonza Japan Ltd. Trade name: Primaset BADCy): 600.0 g, alcohol-modified siloxane resin (manufactured by Shin-Etsu Chemical Co., Ltd .; trade name: X-22-4039, hydroxyl group equivalent; 950): 200.0 g, biphenyl type epoxy resin (Japan Epoxy Resin Co., Ltd.) Product 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 wt% mineral spirit solution of zinc naphthenate was added, and the temperature was about 110 ° C. The reaction was carried out for 6 hours. Then, to obtain a solution was cooled to room temperature thermosetting compatible 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 with the peak area of the bisphenol A type cyanate resin at the time, the disappearance rate of the peak area was 60%. Moreover, the peak of the product of the thermosetting resin which appears in about 10.9 minutes vicinity and 8.0-10.0 vicinity was confirmed. The reaction solution, 170 ° C. with a hot air dryer, the resin cured product obtained by drying 15 minutes and rated visually confirmed that the resin cured product is transparent separation is compatible resin for not occur It was done.
製造例２：相溶化樹脂（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、アミン変性シロキサン樹脂（信越化学社製；商品名ＫＦ−８６４、アミノ基当量；３，８００）：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８ｗｔ％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の相溶化樹脂（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付近に出現する熱硬化性の樹脂の生成物のピークが確認された。この反応溶液を、熱風乾燥機で１７０℃、１５分乾燥させることで得られる樹脂硬化物を目視で評価し、樹脂硬化物が透明であり分離が生じなかったため相溶化樹脂であることが確認された。
Production Example 2: Production thermometer compatible resin (1-2), a stirring device and a reaction vessel heating and cooling capacity capable of 3 liters equipped with a reflux condenser, a novolac type cyanate resin (Lonza Japan Ltd.; Brand name Primaset PT-15, weight average molecular weight 500 to 1,000): 800.0 g, and amine-modified siloxane resin (manufactured by Shin-Etsu Chemical; trade name KF-864, amino group equivalent; 3,800): 100.0 g Then, naphthol aralkyl-cresol copolymerization 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 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 wt% mineral spirit solution of zinc naphthenate was added, and the temperature was about 110 ° C. The reaction was carried out for 4 hours. Then, to obtain a solution was cooled to room temperature thermosetting compatible 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 about 10.9 minutes vicinity and 8.0-10.0 vicinity was confirmed. The reaction solution, 170 ° C. with a hot air dryer, the resin cured product obtained by drying 15 minutes and rated visually confirmed that the resin cured product is transparent separation is compatible resin for not occur It was done.
製造例３：相溶化樹脂（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、カルボキシル変性シロキサン樹脂（信越化学社製；商品名Ｘ−２２−３７０１Ｅ、カルボキシル基当量；４，０００）：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８ｗｔ％ミネラルスピリット溶液を０．３０ｇ添加し、約１１０℃で３時間反応を行った。その後、室温に冷却し、熱硬化性の相溶化樹脂（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付近に出現する熱硬化性の樹脂の生成物のピークが確認された。この反応溶液を、熱風乾燥機で１７０℃、１５分乾燥させることで得られる樹脂硬化物を目視で評価し、樹脂硬化物が透明であり分離が生じなかったため相溶化樹脂であることが確認された。
Production Example 3: Production thermometer compatible resin (1-3), a stirring device and a reaction vessel heating and cooling capacity capable of 3 liters equipped with a reflux condenser, dicyclopentadiene type cyanate resin (Lonza Japan Ltd. Product name: Primaset DT-4000, weight average molecular weight 500-1,000): 400.0 g, carboxyl-modified siloxane resin (manufactured by Shin-Etsu Chemical Co., Ltd .; product name X-22-3701E, carboxyl group equivalent: 4,000) : 100.0 g, biphenyl aralkyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd .; trade name NC-3000H, epoxy equivalent: 280): 500.0 g and mesitylene: 1000.0 g were charged. 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 wt% mineral spirit solution of zinc naphthenate was added, and the temperature was about 110 ° C. The reaction was carried out for 3 hours. Then cooled to room temperature to obtain a solution of a thermosetting compatible 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 about 10.9 minutes vicinity and 8.0-10.0 vicinity was confirmed. The reaction solution, 170 ° C. with a hot air dryer, the resin cured product obtained by drying 15 minutes and rated visually confirmed that the resin cured product is transparent separation is compatible resin for not occur It was done.
製造例４：相溶化樹脂（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、エポキシ変性シロキサン樹脂（信越化学社製；商品名ＫＦ−１００１、エポキシ基当量；３，５００）：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８ｗｔ％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の相溶化樹脂（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付近に出現する熱硬化性の樹脂の生成物のピークが確認された。この反応溶液を、熱風乾燥機で１７０℃、１５分乾燥させることで得られる樹脂硬化物を目視で評価し、樹脂硬化物が透明であり分離が生じなかったため相溶化樹脂であることが確認された。
Production Example 4: incompatible resin (1-4) with a thermometer, stirrer, the reaction vessel of the heating and cooling capacity capable of 3 liters equipped with a reflux condenser, a bisphenol A type cyanate resin (Lonza Japan Ltd. Trade name: Primaset BADCy): 400.0 g, epoxy-modified siloxane resin (manufactured by Shin-Etsu Chemical; trade name: KF-1001, epoxy group equivalent: 3,500): 500.0 g, naphthalene type epoxy resin (Dainippon Ink) Chemical company make; brand name Epicron HP-4032, epoxy equivalent; 150): 100.0g and toluene: 1000.0g were supplied. 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 wt% mineral spirit solution of zinc naphthenate was added, and the temperature was about 110 ° C. The reaction was carried out for 4 hours. Then, to obtain a solution was cooled to room temperature thermosetting compatible 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 about 10.9 minutes vicinity and 8.0-10.0 vicinity was confirmed. The reaction solution, 170 ° C. with a hot air dryer, the resin cured product obtained by drying 15 minutes and rated visually confirmed that the resin cured product is transparent separation is compatible resin for not occur It was done.
製造例５：相溶化樹脂（１−５）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）：６００．０ｇと、チオール変性シロキサン樹脂（信越化学社製；商品名ＫＦ−２００１、チオール基当量；１，９００）：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８ｗｔ％ミネラルスピリット溶液を０．０１ｇ添加し、約１１０℃で６時間反応を行った。その後、室温に冷却し熱硬化性の相溶化樹脂（１−５）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５０％であった。また、約１０．９分付近、及び８．０〜１０．０付近に出現する熱硬化性の樹脂の生成物のピークが確認された。この反応溶液を、熱風乾燥機で１７０℃、１５分乾燥させることで得られる樹脂硬化物を目視で評価し、樹脂硬化物が透明であり分離が生じなかったため相溶化樹脂であることが確認された。
Production Example 5: Production thermometer compatible resin (1-5), a stirring device and a reaction vessel heating and cooling capacity capable of 3 liters equipped with a reflux condenser, a novolac type cyanate resin (Lonza Japan Ltd.; Brand name Primaset PT-15, weight average molecular weight 500-1,000): 600.0 g, thiol-modified siloxane resin (manufactured by Shin-Etsu Chemical; trade name KF-2001, thiol group equivalent; 1,900): 200.0 g Then, biphenyl type epoxy resin (manufactured by Japan Epoxy Resin; trade name YX-4000, epoxy equivalent: 186): 200.0 g and toluene: 1000.0 g were charged. 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 wt% mineral spirit solution of zinc naphthenate was added, and the temperature was about 110 ° C. The reaction was carried out for 6 hours. Then, to obtain a solution was cooled to room temperature thermosetting compatible resin (1-5). 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 50% 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 about 10.9 minutes vicinity and 8.0-10.0 vicinity was confirmed. The reaction solution, 170 ° C. with a hot air dryer, the resin cured product obtained by drying 15 minutes and rated visually confirmed that the resin cured product is transparent separation is compatible resin for not occur It was done.
製造例６：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、粒径０．５μｍ、球状）：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）の分散液を得た。
Production Example 6: Production of fused silica (2-1) surface-treated (wet treatment) with a trimethoxysilane compound In a reaction vessel with a volume of 3 liters that can be heated and cooled with a thermometer, a stirrer, and a reflux condenser. , Fused silica (manufactured by Admatechs; trade name SO-25R, particle size 0.5 μm, spherical): 700.0 g and propylene glycol monomethyl ether: 1000.0 g were mixed and stirred with N-phenyl-3- Aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .; trade name KBM-573): 7.0 g was added. 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 dispersion of fused silica (2-1) that was wet-treated was obtained.
比較製造例１：（比較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、アミン変性シロキサン樹脂（信越化学社製；商品名ＫＦ−８６４、水酸基当量；３，８００）：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８ｗｔ％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１）の反応溶液を得た。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２０％であった。この反応溶液を、熱風乾燥機で１７０℃、１５分乾燥させることで得られる樹脂硬化物を目視で評価し、樹脂硬化物表面に分離が生じたため相溶化していないことが確認された。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 1) A bisphenol A type cyanate resin (manufactured by Lonza Japan Co., Ltd .; trade name Primaset) was added to a reaction vessel with a volume of 3 liters that can be heated and cooled with a thermometer, a stirrer, and a reflux condenser. BADCy): 600.0 g, amine-modified siloxane resin (manufactured by Shin-Etsu Chemical Co., Ltd .; trade name KF-864, hydroxyl group equivalent; 3,800): 200.0 g, biphenyl type epoxy resin (Japan Epoxy Resin Co., Ltd .; trade name) YX-4000, epoxy equivalent; 186): 200.0 g and toluene: 1000.0 g were charged. 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 wt% mineral spirit solution of zinc naphthenate was added, and the temperature was about 110 ° C. The reaction was carried out for 1 hour. Then, it cooled to room temperature and obtained the reaction solution of (Comparative 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 20%. The reaction solution, 170 ° C. with a hot air dryer, the resin cured product obtained by drying 15 minutes and rated visually, the separation in the cured resin surface is not turned into compatible for resulting was confirmed. In addition, a precipitate was formed in the solution by crystallization the next day.
比較製造例２：（比較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、エポキシ変性シロキサン樹脂（信越化学社製；商品名ＫＦ−１００１、エポキシ基当量；３，５００）：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８ｗｔ％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２）の反応溶液を得た。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。反応溶液を、熱風乾燥機で１７０℃、１５分乾燥させることで得られる樹脂硬化物を目視で評価し、樹脂硬化物が透明であり分離が生じなかったため相溶化樹脂であることが確認された。
Comparative Production Example 2: Production of (Comparative 2) A bisphenol A type cyanate resin (manufactured by Lonza Japan Co., Ltd .; trade name Primaset) was added to a reaction vessel with a volume of 3 liters that can be heated and cooled with a thermometer, a stirrer, and a reflux condenser. BADCy): 600.0 g, epoxy-modified siloxane resin (manufactured by Shin-Etsu Chemical Co., Ltd .; trade name KF-1001, epoxy group equivalent; 3,500): 200.0 g, biphenyl type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd .; product) Name YX-4000, epoxy equivalent; 186): 200.0 g and toluene: 1000.0 g were charged. 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 wt% mineral spirit solution of zinc naphthenate was added, and the temperature was about 120 ° C. The reaction was carried out for 6 hours. Thereafter, the reaction solution was cooled to room temperature (Comparative 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%. The reaction solution, 170 ° C. with a hot air dryer, the resin cured product obtained by drying 15 minutes visually evaluated, it is confirmed that the separation is a resin cured product transparency is compatible resin for not occur It was.
比較製造例３：（比較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、アミン変性シロキサン樹脂（信越化学社製；商品名ＫＦ−８６４、アミノ基当量；３，８００）：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８ｗｔ％ミネラルスピリット溶液を０．０１ｇ添加し、約１１０℃で３時間反応を行った。その後、室温に冷却し（比較３）の反応溶液を得た。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。反応溶液を、熱風乾燥機で１７０℃、１５分乾燥させることで得られる樹脂硬化物を目視で評価し、樹脂硬化物が透明であり分離が生じなかったため相溶化樹脂であることが確認された。
Comparative Production Example 3: Production of (Comparative 3) Bisphenol A type cyanate resin (manufactured by Lonza Japan Co., Ltd .; trade name Primaset) was added to a reaction vessel with a volume of 2 liters which can be heated and cooled with a thermometer, a stirrer and a reflux condenser. BADCy): 600.0 g, amine-modified siloxane resin (manufactured by Shin-Etsu Chemical Co., Ltd .; trade name KF-864, amino group equivalent; 3,800): 200.0 g and toluene: 800.0 g were charged. 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 wt% mineral spirit solution of zinc naphthenate was added, and the temperature was about 110 ° C. The reaction was carried out for 3 hours. Thereafter, the reaction solution was cooled to room temperature (Comparative 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%. The reaction solution, 170 ° C. with a hot air dryer, the resin cured product obtained by drying 15 minutes visually evaluated, it is confirmed that the separation is a resin cured product transparency is compatible resin for not occur It was.
（実施例１〜６、比較例１〜４）
製造例１〜５により得られた相溶化樹脂、及び比較製造例１〜３で得られた樹脂、及び、製造例６又は商業的に入手した溶融シリカ、また、必要により無機充填剤、難燃助剤、硬化促進剤、及び希釈溶剤にメチルエチルケトンを使用して、表１と表２に示した配合割合（重量部）で混合して樹脂分６０ｗｔ％の均一なワニスを得た。
次に、上記ワニスを厚さ０．２ｍｍのＳガラスクロスに含浸塗工し、１６０℃で１０分加熱乾燥して樹脂含有量５５重量％のプリプレグを得た。次に、このプリプレグを４枚重ね、１８μｍの電解銅箔を上下に配置し、圧力２５ｋｇ／ｃｍ２、温度２３０℃で６０分間プレスを行って、銅張積層板を得た。このようにして得られた銅張積層板を用いて、銅箔接着性（銅箔ピール強度）、ガラス転移温度、はんだ耐熱性、線熱膨張係数、難燃性、ドリル加工性、比誘電率（１ＧＨｚ）、誘電正接（１ＧＨｚ）について以下の方法で測定・評価し、表３と表４に評価結果を示した。
(Examples 1-6, Comparative Examples 1-4)
Compatible resin obtained in Production Example 1-5, and Comparative Preparation Examples 1 to 3 obtained in resin, and Production Examples 6 or commercially available molten silica, also inorganic fillers if necessary, a flame Using methyl ethyl ketone as a combustion aid, a curing accelerator, and a diluent solvent, mixing was performed at a blending ratio (parts by weight) shown in Tables 1 and 2 to obtain a uniform varnish having a resin content of 60 wt%.
Next, the varnish was impregnated and applied to an S glass cloth having a thickness of 0.2 mm and dried by heating at 160 ° C. for 10 minutes to obtain a prepreg having a resin content of 55% by weight. Next, four sheets of this prepreg were stacked, 18 μm electrolytic copper foils were placed one above the other, and pressed at a pressure of 25 kg / cm 2 and a temperature of 230 ° C. for 60 minutes to obtain a copper clad laminate. Using the copper-clad laminate thus obtained, copper foil adhesion (copper foil peel strength), glass transition temperature, solder heat resistance, linear thermal expansion coefficient, flame retardancy, drill workability, relative dielectric constant (1 GHz) and dielectric loss tangent (1 GHz) were measured and evaluated by the following methods. Tables 3 and 4 show the evaluation results.
（１）銅箔接着性（銅箔ピール強度）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接着性（９０°ピール強度）を測定した。
(1) Evaluation of copper foil adhesion (copper foil peel strength) A copper-clad laminate is dipped in a copper etching solution to form a 1 cm wide copper foil to produce an evaluation substrate, and copper is tested using a tensile tester. The adhesiveness (90 ° peel strength) of the foil was measured.
（２）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（デュポン社製、ＴＭＡ２９４０）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。
(2) Measurement of glass transition temperature (Tg) A 5-mm square evaluation board from which copper foil was removed by immersing a copper clad laminate in a copper etching solution was prepared, and a TMA test apparatus (manufactured by DuPont, TMA2940) was used. The evaluation was performed by observing the thermal expansion characteristics in the surface direction of the evaluation substrate.
（３）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（デュポン社製、ＴＭＡ２９４０）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。
(3) Measurement of coefficient of linear thermal expansion A copper-clad laminate was immersed in a copper etching solution to produce a 5 mm square evaluation substrate from which the copper foil was removed, and evaluation was performed using a TMA test apparatus (manufactured by DuPont, TMA2940). The linear thermal expansion coefficient of 30 to 100 ° C. in the surface direction of the substrate was measured.
（４）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、平山製作所（株）製プレッシャー・クッカー試験装置を用いて、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はんだ耐熱性を評価した。
(4) Evaluation of solder heat resistance A 5 cm square evaluation board from which a copper foil was removed by immersing a copper clad laminate in a copper etching solution was prepared using a pressure cooker test apparatus manufactured by Hirayama Seisakusho Co., Ltd. After performing the pressure-cooker treatment for 4 hours under the conditions of 121 ° C. and 2 atm, the evaluation substrate was immersed in a solder bath at a temperature of 288 ° C. for 20 seconds, and then the solder heat resistance was evaluated by observing the appearance.
（５）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（デュポン社製、ＴＭＡ２９４０）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。
(5) Evaluation of heat resistance with copper (T-300) A 5 mm square evaluation board was produced from a copper clad laminate, and the evaluation board swelled at 300 ° C. using a TMA test apparatus (manufactured by DuPont, TMA2940). It was evaluated by measuring the time to do.
（６）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。
(6) Flame Retardancy Evaluation A test piece cut out to 127 mm in length and 12.7 mm in width was prepared from an evaluation board from which a copper foil was removed by immersing a copper-clad laminate in a copper etching solution, and tested for UL94. Evaluation was made according to the method (Method V).
（７）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、Ｈｅｗｌｌｅｔ・Ｐａｃｋｅｒｄ社製比誘電率測定装置（製品名：ＨＰ４２９１Ｂ）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。
(7) Measurement of relative dielectric constant and dielectric loss tangent The obtained copper-clad laminate was immersed in a copper etching solution to produce an evaluation substrate from which the copper foil was removed, and a relative dielectric constant measuring device manufactured by Hewlett-Packard Company (product) Name: HP4291B), relative permittivity and dielectric loss tangent at a frequency of 1 GHz were measured.
表１および表２中の数字は、固形分の重量部により示されている。注書きは、それぞれ
＊１：溶融シリカに対し１．０ｗｔ％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（アドマテック社製；商品名ＳＣ−２０５０ＫＮＫ、粒径０．５μｍ、球状、希釈溶剤；メチルイソブチルケトン）
＊２：溶融シリカに対し１．０ｗｔ％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（アドマテック社製；商品名ＳＣ−２０５０ＨＮＫ、粒径０．５μｍ、球状など、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・ウィリアムス社製；商品名 ケムガード１１００）
＊５：ナフテン酸亜鉛の８ｗｔ％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、粒径０．５μ、球状など）
＊８：溶融シリカに対し１．０ｗｔ％のγ−グリシドキシプロピルトリメトキシシラン（下記式Ｖ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）
を意味する。
The numbers in Tables 1 and 2 are indicated by parts by weight of solid content. * 1: Fused silica surface-treated with 1.0 wt% of N-phenyl-3-aminopropyltrimethoxysilane with respect to fused silica (manufactured by Admatech; trade name SC-2050KNK, particle size 0. 5μm, spherical, diluent solvent; methyl isobutyl ketone)
* 2: Fused silica surface-treated with 1.0 wt% of N-phenyl-3-aminopropyltrimethoxysilane with respect to fused silica (manufactured by Admatech; trade name SC-2050HNK, particle size 0.5 μm, spherical shape, etc. Diluent: cyclohexanone)
* 3: Boehmite type aluminum hydroxide (manufactured by Kawai Lime 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 wt% mineral spirit solution of zinc naphthenate * 6: Biphenyl type epoxy resin (manufactured by Japan Epoxy Resin; trade name YX-4000, epoxy equivalent; 186)
* 7: Fused silica (manufactured by Admatech; trade name SO-25R, particle size 0.5 μ, spherical, etc.)
* 8: Fused silica surface-treated with 1.0 wt% γ-glycidoxypropyltrimethoxysilane (shown in the following formula V) with respect to fused silica (manufactured by Admatech; trade name SC1030-MJA, diluent solvent; methyl ethyl ketone) )
Means.
表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、低誘電特性、低誘電正接性の全てに優れている。一方、比較例は、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、低誘電特性、低誘電正接性の全てを満たすものは無く、いずれかの特性に劣っている。 As is clear from the table, the examples of the present invention are excellent in all of Tg, copper foil peel strength, heat resistance, low thermal expansion, flame resistance, heat resistance with copper, low dielectric properties, and low dielectric loss tangent. Yes. On the other hand, there is no comparative example satisfying all of Tg, copper foil peel strength, heat resistance, low thermal expansion property, flame retardancy, heat resistance with copper, low dielectric property, low dielectric loss tangent, Inferior.
Claims (4)
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、
反応触媒として有機金属塩（ｄ）とを、
（ａ）と（ｂ）と（ｃ）の総和１００重量部あたり、（ａ）の使用量が１０〜５０重量部の範囲であり、（ｂ）の使用量が４０〜８０重量部の範囲であり、（ｃ）の使用量が１０〜５０重量部の範囲として、反応させ、（ａ）と（ｂ）と（ｃ）とを反応させる際に、（ｂ）の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の反応率が３０〜７０ｍｏｌ％となるように反応させることにより得られる相溶化樹脂であって、前記反応性置換基が、水酸基、アミノ基、カルボキシル基、エポキシ基、シクロアルキルエポキシ基およびメルカプト基から選ばれる基である、相溶化樹脂。
A compound (b) having at least two cyanate groups in one molecule;
A compound (c) having at least two epoxy groups in one molecule;
An organic metal salt (d) as a reaction catalyst,
The total amount of (a), (b) and (c) is in the range of 10 to 50 parts by weight of (a), and the amount of (b) is in the range of 40 to 80 parts by weight. Yes, when the amount of (c) used is in the range of 10 to 50 parts by weight, and when (a), (b) and (c) are reacted, at least two in one molecule of (b) a compatible resin obtained reaction rate by reacting such a 30～70Mol% of compounds having a cyanate group, the reactive substituent, a hydroxyl group, an amino group, a carboxyl group, an epoxy group, A compatibilizing resin, which is a group selected from a cycloalkyl epoxy group and a mercapto group .
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、
反応触媒として有機金属塩（ｄ）とを、
（ａ）と（ｂ）と（ｃ）の総和１００重量部あたり、（ａ）の使用量が１０〜５０重量部の範囲であり、（ｂ）の使用量が４０〜８０重量部の範囲であり、（ｃ）の使用量が１０〜５０重量部の範囲として、反応させ、（ａ）と（ｂ）と（ｃ）とを反応させる際に、（ｂ）の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の反応率を３０〜７０ｍｏｌ％となるように反応させることにより相溶化樹脂を得る、相溶化樹脂の製造方法であって、前記反応性置換基が、水酸基、アミノ基、カルボキシル基、エポキシ基、シクロアルキルエポキシ基およびメルカプト基から選ばれる基である、相溶化樹脂の製造方法。
A compound (b) having at least two cyanate groups in one molecule;
A compound (c) having at least two epoxy groups in one molecule;
An organic metal salt (d) as a reaction catalyst,
The total amount of (a), (b) and (c) is in the range of 10 to 50 parts by weight of (a), and the amount of (b) is in the range of 40 to 80 parts by weight. Yes, when the amount of (c) used is in the range of 10 to 50 parts by weight, and when (a), (b) and (c) are reacted, at least two in one molecule of (b) the reaction of a compound having a cyanate group to obtain a compatible resin by reacting so that 30～70Mol%, a process for the preparation of a compatible resin, the reactive substituent, a hydroxyl group, an amino A method for producing a compatibilizing resin, which is a group selected from a group, a carboxyl group, an epoxy group, a cycloalkylepoxy group, and a mercapto group .
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