JP2015063614A - Prepreg using compatibilizing resin and laminate plate and printed wiring board using the same - Google Patents
Prepreg using compatibilizing resin and laminate plate and printed wiring board using the same Download PDFInfo
- Publication number
- JP2015063614A JP2015063614A JP2013198236A JP2013198236A JP2015063614A JP 2015063614 A JP2015063614 A JP 2015063614A JP 2013198236 A JP2013198236 A JP 2013198236A JP 2013198236 A JP2013198236 A JP 2013198236A JP 2015063614 A JP2015063614 A JP 2015063614A
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- Prior art keywords
- resin
- prepreg
- reaction
- mass
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 229920005989 resin Polymers 0.000 title claims abstract description 123
- 239000011347 resin Substances 0.000 title claims abstract description 123
- 238000006243 chemical reaction Methods 0.000 claims abstract description 66
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate group Chemical group [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims abstract description 50
- 239000000463 material Substances 0.000 claims abstract description 27
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- 239000000835 fiber Substances 0.000 claims abstract description 24
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 18
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 9
- 239000007809 chemical reaction catalyst Substances 0.000 claims abstract description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- 229920000647 polyepoxide Polymers 0.000 claims description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- -1 trimethoxysilane compound Chemical class 0.000 claims description 21
- 239000005350 fused silica glass Substances 0.000 claims description 17
- 230000008034 disappearance Effects 0.000 claims description 15
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 12
- 239000004593 Epoxy Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 229920001225 polyester resin Polymers 0.000 claims description 7
- 239000004645 polyester resin Substances 0.000 claims description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 7
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims 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 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 238000007363 ring formation reaction Methods 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- 125000002524 organometallic group Chemical group 0.000 claims description 5
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 5
- 239000008096 xylene Substances 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 229920001721 polyimide Polymers 0.000 claims description 4
- 239000009719 polyimide resin Substances 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000004760 aramid Substances 0.000 claims description 3
- 229920003235 aromatic polyamide Polymers 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 28
- 239000011889 copper foil Substances 0.000 abstract description 22
- 125000003277 amino group Chemical group 0.000 abstract description 13
- 239000011248 coating agent Substances 0.000 abstract description 10
- 238000000576 coating method Methods 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 150000003839 salts Chemical class 0.000 abstract description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 35
- 239000003822 epoxy resin Substances 0.000 description 20
- 238000004519 manufacturing process Methods 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 18
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 239000011342 resin composition Substances 0.000 description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 238000005259 measurement Methods 0.000 description 14
- 239000007787 solid Substances 0.000 description 14
- 229920001187 thermosetting polymer Polymers 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000004305 biphenyl Substances 0.000 description 10
- 235000010290 biphenyl Nutrition 0.000 description 10
- 239000000047 product Substances 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
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 239000004793 Polystyrene Substances 0.000 description 9
- 229920002223 polystyrene Polymers 0.000 description 9
- 229910052500 inorganic mineral Inorganic materials 0.000 description 8
- 239000011707 mineral Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000003480 eluent Substances 0.000 description 7
- 238000010828 elution Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 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 6
- 239000002966 varnish Substances 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000011256 inorganic filler Substances 0.000 description 5
- 229910003475 inorganic filler Inorganic materials 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 5
- 238000004381 surface treatment Methods 0.000 description 5
- 238000005979 thermal decomposition reaction Methods 0.000 description 5
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 150000004677 hydrates Chemical class 0.000 description 4
- FCXSGAKSWAEXPU-UHFFFAOYSA-N iminocarbamic acid Chemical compound OC(=O)N=N FCXSGAKSWAEXPU-UHFFFAOYSA-N 0.000 description 4
- 239000012796 inorganic flame retardant Substances 0.000 description 4
- 238000010030 laminating Methods 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000126 substance 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
- 239000002635 aromatic organic solvent Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 229930003836 cresol Natural products 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000011810 insulating material Substances 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-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
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- 229910002706 AlOOH Inorganic materials 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 2
- 238000010521 absorption reaction Methods 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
- 239000003849 aromatic solvent Substances 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical group 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
- 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
- 239000012766 organic filler Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 2
- 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
- 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
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- NOHQTLHHNIKWBA-UHFFFAOYSA-N [SiH4].NC(=O)N Chemical compound [SiH4].NC(=O)N NOHQTLHHNIKWBA-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 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
- 150000002460 imidazoles Chemical class 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 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 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
- Epoxy Resins (AREA)
Abstract
Description
本発明のプリプレグは、特に優れた低熱膨張性、及び銅箔接着性、を付与し、電子部品等に好適な積層板、配線板に関する。 The prepreg of the present invention relates to a laminated board and a wiring board suitable for electronic parts and the like, which are particularly excellent in low thermal expansion and copper foil adhesiveness.
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、加工性等が不足である。 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 Etc. are insufficient.
本発明の目的は、低熱膨張性、銅箔接着性を発現するプリプレグ、及び該プリプレグを使用した積層板、配線板を提供するものである。 An object of the present invention is to provide a prepreg that exhibits low thermal expansion and copper foil adhesion, and a laminate and a wiring board using the prepreg.
本発明は、（ａ）下記一般式（Ｉ）で示される構造の末端に１級アミノ基を含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、（ｄ）反応触媒として有機金属塩を、芳香族系有機溶媒中でイミノカルバメート化反応、及びトリアジン環化反応させることにより得られる相容化樹脂を必須成分とする樹脂組成物を、有機繊維基材に塗工し、得られるプリプレグを用いた積層板及び配線板が、良好な低熱膨張性、及び銅箔接着性を発現することを見出した。
本発明は、かかる知見に基づいて完成したものである。
The present invention includes (a) a siloxane resin containing a primary amino group at the end of the structure represented by the following general formula (I), (b) a compound having at least two cyanate groups in one molecule, c) It is obtained by subjecting a compound having at least two epoxy groups in one molecule and (d) an organometallic salt as a reaction catalyst to an iminocarbamation reaction and a triazine cyclization reaction in an aromatic organic solvent. A resin composition containing a compatibilizing resin as an essential component is applied to an organic fiber substrate, and the resulting laminate and wiring board using the prepreg exhibit good low thermal expansion and copper foil adhesion. I found out.
The present invention has been completed based on such findings.
本発明は、［１］ 下記一般式（Ｉ）で示される末端に１級アミノを有するシロキサン樹脂（ａ）と、１分子中に少なくとも２個のシアネート基を有する化合物（ｂ）と、１分子中に少なくとも２個のエポキシ基を有する化合物（ｃ）と、反応触媒として有機金属塩（ｄ）を、（ａ）と（ｂ）と（ｃ）の総和１００質量部あたりの（ａ）の使用量を１０〜５０重量部の範囲、（ｂ）の使用量を４０〜８０質量部の範囲、（ｃ）の使用量を１０〜５０質量部の範囲とし、これらを予めトルエン、キシレン、メシチレンから選ばれる溶媒中で８０〜１２０℃の反応温度でイミノカルバメート化反応、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３０〜７０ｍｏｌ％となるようにプレ反応させることにより得られる相容化樹脂を、有機繊維基材に含浸または塗工し、得られるプリプレグに関する。 The present invention relates to [1] a siloxane resin (a) having a primary amino at the terminal represented by the following general formula (I), a compound (b) having at least two cyanate groups in one molecule, and one molecule. Use of compound (c) having at least two epoxy groups therein, organometallic salt (d) as a reaction catalyst, and (a) per 100 parts by mass of sum of (a), (b) and (c) The amount is in the range of 10 to 50 parts by weight, the amount of (b) used is in the range of 40 to 80 parts by weight, the amount of (c) is in the range of 10 to 50 parts by weight, and these are preliminarily obtained from toluene, xylene and mesitylene. An iminocarbamation reaction and a triazine cyclization reaction are performed at a reaction temperature of 80 to 120 ° C. in a selected solvent so that the reaction rate (disappearance rate) of the compound (b) having a cyanate group is 30 to 70 mol%. To pre-react Ri The resulting compatibilizer resin, is impregnated or coated on the organic fiber substrate, to obtain a prepreg.
又、本発明は、［２］ 下記式（ＩＩ）で示されるトリメトキシシラン化合物により表面処理（湿式処理）された溶融シリカを、さらに含有する上記［１］に記載のプリプレグに関する。
Moreover, this invention relates to the prepreg as described in said [1] which further contains [2] the fused silica surface-treated (wet process) by the trimethoxysilane compound shown by following formula (II).
また、本発明は、［４］ 前記有機繊維基材が、シランカップリング剤、コロナ、プラズマのいずれかによって処理されてなる上記［１］から［３］のいずれかに記載のプリプレグに関する。
また、本発明は、［５］ 上記［１］から［４］のいずれかに記載のプリプレグを成形して得られる積層板に関する。
さらに、本発明は、［６］ 上記［５］に記載の積層板に配線形成して得られる配線板に関する。
The present invention also relates to [4] the prepreg according to any one of [1] to [3], wherein the organic fiber substrate is treated with any one of a silane coupling agent, corona, and plasma.
The present invention also relates to [5] a laminate obtained by molding the prepreg according to any one of [1] to [4].
Furthermore, the present invention relates to [6] a wiring board obtained by forming wiring on the laminated board according to [5].
本発明で用いる相容化樹脂を含有する樹脂組成物を有機繊維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銅張積層板は、低熱膨張率、及び高銅箔ピール強度の特性を発現しており、電子機器用のプリント配線板などに有用である。 A prepreg obtained by impregnating or coating an organic fiber base material with a resin composition containing a compatibilizing resin used in the present invention, and a copper-clad laminate produced by laminating the prepreg have a low coefficient of thermal expansion. And high copper foil peel strength, and is useful for printed wiring boards for electronic devices.
以下、本発明について詳細に説明する。
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。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。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（２．５×１０−６／Ｋ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。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。
Hereinafter, the present invention will be described in detail.
Due to the recent demand for higher density and higher reliability, the laminated plate material needs to have high copper foil adhesion, heat resistance, good low thermal expansion, and the like. For the formation of fine wiring, the copper foil adhesion is preferably 1.0 kN / m or more, more preferably 1.2 kN / m or more, as the copper foil peeling strength. 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 is low in thermal expansion, and the thermal expansion coefficient is desirably 7 ppm / ° C. or less (2.5 × 10 −6 / K or less). More preferably, it is 5 ppm / ° C. or less. Under such circumstances, the present invention described below has been made through intensive research.
本発明は、（ａ）上記一般式（Ｉ）で示される構造の末端に1級アミノ基を含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、（ｄ）反応触媒として有機金属塩を、芳香族系有機溶媒中でイミノカルバメート化反応、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３０〜７０ｍｏｌ％となるようにプレ反応させることにより得られる相容化樹脂を、有機繊維基材に塗工し、得られるプリプレグである。また、本発明で用いる相容化樹脂と（２）上記式（ＩＩ）で示される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、を必須成分とする樹脂組成物を有機繊維基材に塗工し、得られるプリプレグである。
本発明の成分（ａ）であるシロキサン樹脂は、上記一般式（Ｉ）で示される構造の1級アミノ基を含有するシロキサン樹脂であれば特に限定されない。一般式（Ｉ）中、Ｒ１は各々独立に２価の炭素数１〜５の飽和炭化水素基であり、例えば、メチレン、エチレン、プロピレン、ブチレン、ペンテンなどの２価のアルキレン基であり、側鎖を有していてもよい。Ａｒ１は各々独立に単結合、すなわち、存在しないか、又は芳香族基であり、ｍは０から１００までの整数である。
（ａ）のシロキサン樹脂は、例えば信越化学工業株式会社製、商品名ＫＦ８０１０（アミノ基当量：４５０ｇ／ｍｏｌ）、商品名Ｘ−２２−１６１Ａ（アミノ基当量：８４０ｇ／ｍｏｌ）、商品名Ｘ−２２−１６１Ｂ（アミノ基当量：１５００ｇ／ｍｏｌ）、商品名ＫＦ８０１２（アミノ基当量：２３００ｇ／ｍｏｌ）、商品名ＢＹ１６−８７１（アミノ基当量：１３０ｇ／ｍｏｌ）東レ・ダウコーニング株式会社製、等が挙げられる。これらは信越化学工業株式会社や東レ・ダウコーニング株式会社等から商業的に入手できる。
The present invention includes (a) a siloxane resin containing a primary amino group at the end of the structure represented by the above general formula (I), (b) a compound having at least two cyanate groups in one molecule; c) A compound having at least two epoxy groups in one molecule and (d) an organometallic salt as a reaction catalyst are reacted in an aromatic organic solvent with an iminocarbamate reaction and a triazine cyclization reaction, (b) This is a prepreg obtained by coating a compatibilizing resin obtained by pre-reacting the compound having a cyanate group with a reaction rate (disappearance rate) of 30 to 70 mol% on an organic fiber substrate. Moreover, an organic fiber group is used as a resin composition containing as essential components a compatibilizing resin used in the present invention and (2) fused silica surface-treated (wet-treated) with a trimethoxysilane compound represented by the above formula (II). It is a prepreg obtained by coating a material.
The siloxane resin which is the component (a) of the present invention is not particularly limited as long as it is a siloxane resin containing a primary amino group having a structure represented by the general formula (I). In general formula (I), each R 1 is independently a divalent saturated hydrocarbon group having 1 to 5 carbon atoms, for example, a divalent alkylene group such as methylene, ethylene, propylene, butylene, pentene, You may have a side chain. Ar 1 is each independently a single bond, ie, absent or an aromatic group, and m is an integer from 0 to 100.
The siloxane resin (a) is, for example, manufactured by Shin-Etsu Chemical Co., Ltd., trade name KF8010 (amino group equivalent: 450 g / mol), trade name X-22-161A (amino group equivalent: 840 g / mol), trade name X- 22-161B (amino group equivalent: 1500 g / mol), trade name KF8012 (amino group equivalent: 2300 g / mol), trade name BY16-871 (amino group equivalent: 130 g / mol) manufactured by Toray Dow Corning Co., Ltd. Can be mentioned. These are commercially available from Shin-Etsu Chemical Co., Ltd. and Toray Dow Corning Co., Ltd.
本発明で用いる成分（ｂ）である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、下記一般式（ＩＩＩ）に示すノボラック型シアネート樹脂が特に好ましい。 The compound having at least two cyanate groups in one molecule which is the component (b) used in the present invention includes, for example, a novolak type cyanate resin, a bisphenol A type cyanate resin, a bisphenol E type cyanate resin, a bisphenol F type cyanate resin, Examples thereof include tetramethylbisphenol F-type cyanate resin, and one or two or more kinds can be mixed and used. Among these, bisphenol A type cyanate resins and novolak type cyanate resins represented by the following general formula (III) are particularly preferred from the viewpoints of dielectric properties, heat resistance, flame retardancy, low thermal expansion, and low cost.
一般式（ＩＩＩ）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。これより少ないと結晶化しやすくなり取り扱いが困難となる場合がある。また、これより多いと硬化物が脆くなる場合がある。
Although the average repeating number: m of the novolak-type cyanate resin represented by the general formula (III) is not particularly limited, 0.1 to 30 is preferable. If it is less than this, it may be easy to crystallize and it may be difficult to handle. Moreover, when more than this, hardened | cured material may become weak.
本発明で用いる成分（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は、例えば、ビスフェノールＡ系、ビスフェノールＦ系、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（ＩＶ）に示すビフェニル型エポキシ樹脂が特に好ましい。 The compound having at least two epoxy groups in one molecule as component (c) used in the present invention is, for example, bisphenol A, bisphenol F, biphenyl, novolac, polyfunctional phenol, naphthalene, fat. Examples thereof include glycidyl ethers such as cyclic type and alcohol type, glycidyl amine type, and glycidyl ester type, and one kind or a mixture of two or more kinds can be used. Among these, naphthalene type epoxy resin, naphthol aralkyl type epoxy resin, dihydroxynaphthalene aralkyl type epoxy resin, naphthol aralkyl cresol and naphthol aralkyl / cresol are used in terms of high rigidity, dielectric properties, heat resistance, flame resistance, moisture resistance and low thermal expansion. Naphthalene ring-containing epoxy resins such as polymerization type epoxy resins, biphenyl type epoxy resins, biphenyl group-containing epoxy resins such as biphenyl aralkyl type epoxy resins are preferred, and naphthol aralkyl type epoxy resins from the viewpoint of solubility in aromatic organic solvents, A naphthol aralkyl / cresol copolymer type epoxy resin and a biphenyl type epoxy resin are more preferable, and a biphenyl type epoxy resin represented by the following formula (IV) is particularly preferable because it is inexpensive and has a small epoxy equivalent and may contain a small amount.
本発明の成分（ｄ）である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。アミン系やイミダゾール系の窒素原子含有反応触媒は得られる樹脂の硬化物が脆くなり、耐熱性や接着性が低下するので好ましくない。 Examples of the organic metal salt of the reaction catalyst that is component (d) of the present invention include zinc naphthenate, cobalt naphthenate, tin octylate, and cobalt octylate. An amine-based or imidazole-based nitrogen atom-containing reaction catalyst is not preferable because a cured resin obtained is brittle and heat resistance and adhesiveness are lowered.
（ａ）と（ｂ）と（ｃ）の総和１００質量部あたりの（ａ）の使用量を１０〜５０質量部の範囲とし、（ｂ）の使用量を４０〜８０質量部の範囲とし、（ｃ）の使用量を１０〜５０質量部の範囲として、これらを予めトルエン、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℃の反応温度でイミノカルバメート化反応、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３０〜７０ｍｏｌ％となるようにプレ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である必要があり、必要により少量の他の溶剤を用いてもよいが、所望の反応が進行せず、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を製造する塗工・乾燥時に残溶剤となりやすいので好ましくない。プレ反応による反応率が３０ｍｏｌ％未満であると、得られる樹脂が相容化されておらず、樹脂が分離、白濁しＢステージの塗工布が製造できない。また、反応率が７０ｍｏｌ％を超えると、得られる熱硬化性樹脂が溶剤に不溶化し、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場合がある。なお、イミノカルバメート化反応は、１級アミノ基とシアネート基の付加反応によりイミノカルバメート結合（−ＮＨ−（Ｃ＝ＮＨ）−Ｏ−）が生成される反応であり、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。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）成分が均一に分散された相容化樹脂が製造される。ここで、（ａ）の使用量が１０質量部未満であると、得られる基材の面方向の低熱膨張性が低下する場合があり、また（ａ）の使用量が５０質量部を超えると、耐熱性や耐薬品性が低下する場合がある。（ｂ）の使用量が４０質量部未満であると得られる樹脂の相容性が低下する場合があり、また（ｂ）の使用量が８０質量部を超えると、得られる基材の面方向の低熱膨張性が低下する場合がある。（ｃ）の使用量が１０質量部未満であると、耐湿耐熱性が低下する場合があり、また（ｃ）の使用量が５０質量部を超えると、銅箔接着性や誘電特性が低下する場合がある。
反応触媒の（ｄ）成分の使用量は、（ａ）と（ｂ）と（ｃ）の総和１００質量部に対して、０．０００１〜０．００４質量部が好ましい。０．０００１質量部未満であると反応に長時間を要したり、所望の反応率に達しない。また、０．００４質量部を超えると反応速度が速すぎて終点管理が難しくなる場合がある。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 (a) used per 100 parts by mass of the sum of (a), (b) and (c) is in the range of 10 to 50 parts by mass, and the amount of (b) is in the range of 40 to 80 parts by mass. The amount of (c) used is in the range of 10 to 50 parts by mass, these are uniformly dissolved in advance in a solvent selected from toluene, xylene and mesitylene, and iminocarbamation reaction and triazine at a reaction temperature of 80 to 120 ° C. It is necessary to carry out the pre-reaction so that the reaction rate (disappearance rate) of the compound having a cyanate group (b) is 30 to 70 mol% by cyclization reaction. Here, the reaction solvent must be an aromatic solvent selected from toluene, xylene, and mesitylene, and a small amount of other solvent may be used if necessary, but the desired reaction does not proceed, heat resistance, etc. Decreases. Also, benzene is highly toxic, and an aromatic solvent having a molecular weight larger than that of mesitylene is not preferable because it easily becomes a residual solvent during coating and drying for producing a prepreg. If the reaction rate due to the pre-reaction is less than 30 mol%, the resulting resin is not compatibilized, the resin is separated and clouded, and a B-stage coated fabric cannot be produced. On the other hand, if the reaction rate exceeds 70 mol%, the resulting thermosetting resin becomes insoluble in the solvent, making it impossible to produce an A-stage varnish (thermosetting resin composition), or the gel time of the prepreg becomes too short. In this case, the moldability may deteriorate. The iminocarbamate reaction is a reaction in which an iminocarbamate bond (—NH— (C═NH) —O—) is generated by the addition reaction of a primary amino group and a cyanate group, and the triazine cyclization reaction is a cyanate This is a reaction in which a group is trimerized to form a triazine ring. 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. A compatibilized resin in which the components (a), (b) and (c) are uniformly dispersed is produced by uniformly dispersing in the structure. Here, when the usage amount of (a) is less than 10 parts by mass, the low thermal expansion property in the surface direction of the obtained base material may be reduced, and when the usage amount of (a) exceeds 50 parts by mass. , Heat resistance and chemical resistance may decrease. When the amount of (b) used is less than 40 parts by mass, the compatibility of the resulting resin may be reduced, and when the amount of (b) used exceeds 80 parts by mass, the surface direction of the obtained base material In some cases, the low thermal expansibility of the resin may decrease. When the amount of (c) used is less than 10 parts by mass, the moisture and heat resistance may be reduced. When the amount of (c) used exceeds 50 parts by mass, the copper foil adhesiveness and dielectric properties are reduced. There is a case.
The amount of component (d) used in the reaction catalyst is preferably 0.0001 to 0.004 parts by mass with respect to 100 parts by mass as the sum of (a), (b) and (c). If it is less than 0.0001 parts by mass, the reaction takes a long time or does not reach the desired reaction rate. On the other hand, if the amount exceeds 0.004 parts by mass, the reaction rate may be too high to make end point management 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.
本発明で用いる相容化樹脂（１）成分に、成分（２）である上記式（ＩＩ）で示されるトリメトキシシラン化合物により表面処理（湿式処理）された溶融シリカは、溶融シリカを上記式（ＩＩ）で示されるトリメトキシシラン化合物を使用し、表面処理（湿式処理）することにより得られる。成分（２）の製造法の例としては、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系有機溶剤やエチレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテル等のアルコール系有機溶剤に、溶融シリカを添加して混合した後、上記式（ＩＩ）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、成分（２）は、株式会社アドマテックス等から商業的にも入手でき、例えば、株式会社アドマテックス製の商品名ＳＣ−２０５０ＫＮＫや、ＳＣ−２０５０ＨＮＫ等がある。該成分（２）の使用量は、固形分換算の該成分（１）１００質量部に対し、１０〜３００質量部とすることが好ましく、１００〜２５０質量部とすることがより好ましく、１５０〜２５０質量部とすることが特に好ましい。１０質量部未満であると、基材の剛性や、耐湿耐熱性、難燃性が不足したり、また、３００質量部を超えると成形性や耐めっき液性等の耐薬品性が低下する場合がある。 The fused silica obtained by subjecting the compatibilizing resin (1) component used in the present invention to surface treatment (wet treatment) with the trimethoxysilane compound represented by the formula (II) as the component (2) It is obtained by surface treatment (wet treatment) using the trimethoxysilane compound represented by (II). Examples of the production method of component (2) include adding fused silica to a ketone organic solvent such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, and an alcohol organic solvent such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether. Then, the trimethoxysilane compound represented by the above formula (II) is added and reacted (surface treatment) with stirring at 60 to 120 ° C. for about 0.5 to 5 hours. Component (2) can also be obtained commercially from Admatechs Co., Ltd., for example, trade names SC-2050KNK and SC-2050HNK manufactured by Admatechs Co., Ltd. The amount of the component (2) used is preferably 10 to 300 parts by mass, more preferably 100 to 250 parts by mass, with respect to 100 parts by mass of the component (1) in terms of solid content. It is especially preferable to set it as 250 mass parts. When the amount is less than 10 parts by mass, the rigidity of the base material, moisture heat resistance, and flame resistance are insufficient, and when it exceeds 300 parts by mass, chemical resistance such as formability and plating solution resistance decreases. There is.
本発明で用いる相容化樹脂の成分（１）には、他の無機充填剤（成分（３））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）が好ましい。これらの無機充填剤（成分（３））の使用量は、固形分換算の該成分（１）１００質量部に対し、１０〜２００質量部とすることが好ましく、１０〜１５０質量部とすることがより好ましく、５０〜１５０質量部とすることが特に好ましい。１０質量部未満であると難燃性が不足したり、２００質量部を超えると耐めっき液性等の耐薬品性や成形性が低下する場合がある。 For the component (1) of the compatibilizing resin used in the present invention, other inorganic fillers (component (3)) may be used. For example, crushed silica, mica, talc, short glass fiber or fine powder and Examples include hollow glass, calcium carbonate, quartz powder, and metal hydrates. Among these, metals such as aluminum hydroxide and magnesium hydroxide are preferred because of their low thermal expansion, high elasticity, heat resistance, and flame resistance. Hydrates are preferred, and among metal hydrates, metal hydrates having a thermal decomposition temperature of 300 ° C. or higher from the viewpoint of achieving both high heat resistance and flame retardancy, such as boehmite type aluminum hydroxide (AlOOH), Alternatively, gibbsite-type aluminum hydroxide (Al (OH) 3) is preferably a compound in which the thermal decomposition temperature is adjusted to 300 ° C. or higher by heat treatment, magnesium hydroxide, etc., particularly inexpensive and 350 ° C. or lower. A thermal decomposition temperature higher, boehmite-type aluminum hydroxide having a high chemical resistance (AlOOH) are preferred. The amount of these inorganic fillers (component (3)) used is preferably 10 to 200 parts by weight, and preferably 10 to 150 parts by weight, per 100 parts by weight of the component (1) in terms of solid content. Is more preferable, and 50 to 150 parts by mass is particularly preferable. If it is less than 10 parts by mass, the flame retardancy may be insufficient, and if it exceeds 200 parts by mass, chemical resistance such as plating solution resistance and moldability may be deteriorated.
本発明で用いる樹脂組成物には、耐熱性や難燃性、銅箔接着性等の向上化のため硬化促進剤を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。 In the resin composition used in the present invention, it is desirable to use a curing accelerator for improving heat resistance, flame retardancy, copper foil adhesion, etc. Examples of the curing accelerator include zinc naphthenate and naphthenic acid. Examples thereof include organometallic salts such as cobalt, 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.
本発明で用いる樹脂組成物には、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容化樹脂１００質量部に対し、５〜２０質量部とすることが好ましい。５質量部未満であると難燃性やドリル加工性の向上効果が上がらなかったり、また２０質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。 The resin composition used in the present invention can optionally be used in combination with other flame retardants, but halogen-containing flame retardants containing bromine and chlorine, metal hydroxides having a thermal decomposition temperature of less than 300 ° C., etc. It does not meet the purpose of the 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 used is preferably 5 to 20 parts by mass with respect to 100 parts by mass of the compatibilizing resin of the present invention. If the amount is less than 5 parts by mass, the effect of improving flame retardancy and drilling workability will not be improved, and if it exceeds 20 parts by mass, the gel time of the varnish will be too short, and the moldability will be reduced when forming a laminate by pressing. There is a case.
本発明で用いる樹脂組成物には、任意に公知の熱可塑性樹脂、エラストマー、難燃剤、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。
In the resin composition used in the present invention, a known thermoplastic resin, elastomer, flame retardant, organic filler and the like can be used in combination.
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.
本発明において、任意に該樹脂組成物に対して、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 present invention, an ultraviolet absorber, an antioxidant, a photopolymerization initiator, a fluorescent whitening agent, an adhesion improver, and the like can be arbitrarily added to the resin composition, and the resin composition is 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。
本発明のプリプレグは、上述の樹脂組成物が有機繊維基材に含浸又は塗工されてなる。本発明のプリプレグは、樹脂組成物を、有機繊維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。有機繊維基材としては、アラミド樹脂、ＰＬＣ樹脂、ＰＢＯ樹脂、ポリエステル樹脂、芳香族ポリエステル樹脂、ポリイミド樹脂、超高分子ポリエチレン及びテトラフルオロエチレン樹脂を含む有機繊維基材、並びにそれらの混合物等が挙げられる。
これらの有機繊維基材は、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、コロナ、プラズマ等で表面処理したものは耐熱性や耐湿性、加工性の面から好適である。該基材に対する樹脂組成物の付着量が、乾燥後のプリプレグの樹脂含有率で、２０〜９０質量％となるように、基材に含浸又は塗工した後、通常、１００〜２００℃の温度で１〜３０分加熱乾燥し、半硬化（Ｂステージ化）させる。
以上の工程により、本発明のプリプレグを得ることができる。
The prepreg of the present invention is obtained by impregnating or coating a base material with the above-described resin composition. Hereinafter, the prepreg of the present invention will be described in detail.
The prepreg of the present invention is obtained by impregnating or coating the above-mentioned resin composition on an organic fiber base material. The prepreg of the present invention can be produced by impregnating or coating a resin composition on an organic fiber substrate and semi-curing (B-stage) by heating or the like. Examples of the organic fiber base material include an aramid resin, a PLC resin, a PBO resin, a polyester resin, an aromatic polyester resin, a polyimide resin, an organic fiber base material including ultrahigh molecular weight polyethylene and tetrafluoroethylene resin, and a mixture thereof. It is done.
These organic fiber base materials have 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 are necessary. Thus, it is possible to combine a single material or two or more materials and shapes. The thickness of the substrate is not particularly limited, and for example, about 0.03 to 0.5 mm can be used, and the surface treated with a silane coupling agent, corona, plasma, etc. has heat resistance and moisture resistance, It is suitable from the viewpoint of workability. After impregnating or coating the base material so that the amount of the resin composition attached to the base material is 20 to 90% by mass in terms of the resin content of the prepreg after drying, the temperature is usually 100 to 200 ° C. And dried for 1 to 30 minutes and semi-cured (B-stage).
Through the above steps, the prepreg of the present invention can be obtained.
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（０．２〜９．８ＭＰａ）、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。
これ等の積層板を常法によりエッチングしたり、めっきをすることにより配線板とすることができる。
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 multi-stage press, a multi-stage vacuum press, continuous molding, an autoclave molding machine, etc. are used, and It can be molded in a range of ˜100 kg / cm 2 (0.2 to 9.8 MPa) and 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.
These laminated boards can be made into a wiring board by etching or plating them by a conventional method.
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。
製造例１：相容化樹脂（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、１分子中に少なくとも２個のシアネート基を有する化合物（ｂ）としてビスフェノールＡ型シアネート樹脂（ロンザジャパン株式会社製；商品名Ｐｒｉｍａｓｅｔ ＢＡＤＣｙ）：６００．０ｇと、一般式（Ｉ）で示される末端に１級アミノを有するシロキサン樹脂（ａ）として下記式（Ｖ）に示すシロキサン樹脂（信越化学工業株式会社製；商品名ＫＦ−８０１０、アミノ基当量；４５０）：２００．０g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）としてビフェニル型エポキシ樹脂（ジャパンエポキシレジン株式会社製；商品名ＹＸ−４０００、エポキシ当量；１８６）：２００．０ｇと、溶媒としてトルエン：１０００．０ｇを投入した。次いで、攪拌しながら１２０℃に昇温し、樹脂固形分が溶解し均一な溶液になっていることを確認した後、ナフテン酸亜鉛の８質量％ミネラルスピリット溶液を０．０１ｇ添加し、約１１０℃で４時間反応を行った。その後、室温（２５℃）に冷却し相容化樹脂（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６８％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樹脂の生成物のピークが確認された。さらに、少量取り出した反応溶液を、メタノールとベンゼンの混合溶媒（混合質量比１：１）に滴下して再沈殿させることにより、精製された固形分を取り出し、ＦＴ−ＩＲ測定を行ったところ、イミノカルバメート基に起因する１７００ｃｍ−１付近のピーク、また、トリアジン環に起因する１５６０ｃｍ−１付近、及び１３８０ｃｍ−１付近の強いピークが確認でき、相容化樹脂（１−１）が製造されていることを確認した。
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.
Production Example 1: Production of compatibilizing resin (1-1) At least two cyanate groups in one molecule were added to a reaction vessel having a volume of 3 liters which can be heated and cooled with a thermometer, a stirrer and a reflux condenser. Bisphenol A type cyanate resin (manufactured by Lonza Japan Co., Ltd .; trade name Primaset BADCy): 600.0 g and a siloxane resin having a primary amino group represented by the general formula (I) (a) As a siloxane resin represented by the following formula (V) (manufactured by Shin-Etsu Chemical Co., Ltd .; trade name KF-8010, amino group equivalent; 450): 200.0 g and a compound having at least two epoxy groups in one molecule ( c) Biphenyl type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd .; trade name YX-4000, epoxy equivalent; 186): 200.0 g Toluene as the solvent: 1000.0 g was charged. Next, the temperature was raised to 120 ° C. with stirring, and after confirming that the resin solids had dissolved and became a uniform solution, 0.01 g of an 8% by mass mineral spirit solution of zinc naphthenate was added, and about 110 The reaction was carried out at 4 ° C. for 4 hours. Then, it cooled to room temperature (25 degreeC) and the solution of the compatibilizing resin (1-1) was obtained. A small amount of this reaction solution was taken out and subjected to GPC measurement (polystyrene conversion, eluent: tetrahydrofuran). As a result, the peak area of the bisphenol A type cyanate resin, which is a synthetic raw material and the elution time appears around 12.4 minutes, is the start of the reaction. Compared to the peak area of the bisphenol A type cyanate resin at the time, the disappearance rate of the peak area was 68%. Moreover, the peak of the product of the thermosetting resin which appears at about 10.9 minutes vicinity and 8.0-10.0 vicinity was confirmed. Furthermore, when the reaction solution taken out in a small amount was dropped into a mixed solvent of methanol and benzene (mixing mass ratio 1: 1) and reprecipitated, the purified solid content was taken out and subjected to FT-IR measurement. A peak around 1700 cm −1 due to the iminocarbamate group, a strong peak near 1560 cm −1 due to the triazine ring, and a strong peak near 1380 cm −1 can be confirmed, and the compatibilizing resin (1-1) was produced. I confirmed.
製造例２：相容化樹脂（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（ロンザジャパン株式会社製；商品名Ｐｒｉｍａｓｅｔ ＰＴ−１５，重量平均分子量５００〜１,０００）：８００．０ｇと、下記式（ＶＩ）に示すシロキサン樹脂（信越化学工業株式会社製；商品名Ｘ−２２−１６１Ａ、アミノ基当量；８４０）：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（ＤＩＣ株式会社製；商品名ＮＣ−７０００Ｌ、エポキシ当量；２３０）：１００．０ｇと、トルエン：１０００．０ｇを投入した。次いで、攪拌しながら１２０℃に昇温し、樹脂固形分が溶解し均一な溶液になっていることを確認した後、ナフテン酸亜鉛の８質量％ミネラルスピリット溶液を０．０１ｇ添加し、約１１０℃で４時間反応を行った。その後、室温に冷却し相容化樹脂（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樹脂の生成物のピークが確認された。さらに、少量取り出した反応溶液を、メタノールとベンゼンの混合溶媒（混合質量比１：１）に滴下して再沈殿させることにより、精製された固形分を取り出し、ＦＴ−ＩＲ測定を行ったところ、イミノカルバメート基に起因する１７００ｃｍ−１付近のピーク、また、トリアジン環に起因する１５６０ｃｍ−１付近、及び１３８０ｃｍ−１付近の強いピークが確認でき、相容化樹脂（１−２）が製造されていることを確認した。
Production Example 2: Production of compatibilizing resin (1-2) A novolak cyanate resin (manufactured by Lonza Japan Co., Ltd.) was placed in a 3 liter reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser. Trade name: Primaset PT-15, weight average molecular weight: 500 to 1,000): 800.0 g and a siloxane resin represented by the following formula (VI) (manufactured by Shin-Etsu Chemical Co., Ltd .; trade name: X-22-161A, amino group) Equivalent; 840): 100.0 g and naphthol aralkyl-cresol copolymerized epoxy resin (manufactured by DIC Corporation; trade name NC-7000L, epoxy equivalent; 230): 100.0 g and toluene: 1000.0 g . Next, the temperature was raised to 120 ° C. with stirring, and after confirming that the resin solids had dissolved and became a uniform solution, 0.01 g of an 8% by mass mineral spirit solution of zinc naphthenate was added, and about 110 The reaction was carried out at 4 ° C. for 4 hours. Then, it cooled to room temperature and obtained the solution of compatibilizing 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 at about 10.9 minutes vicinity and 8.0-10.0 vicinity was confirmed. Furthermore, when the reaction solution taken out in a small amount was dropped into a mixed solvent of methanol and benzene (mixing mass ratio 1: 1) and reprecipitated, the purified solid content was taken out and subjected to FT-IR measurement. A peak near 1700 cm −1 due to the iminocarbamate group, a strong peak near 1560 cm −1 due to the triazine ring, and a strong peak near 1380 cm −1 can be confirmed, and the compatibilizing resin (1-2) is produced. I confirmed.
製造例３：相容化樹脂（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（ロンザジャパン株式会社製；商品名Ｐｒｉｍａｓｅｔ ＤＴ−４０００，重量平均分子量５００〜１，０００）：４００．０ｇと、下記式（ＶＩＩ）に示すシロキサン樹脂（信越化学工業株式会社製；商品名ＫＦ−８０１２、アミノ基当量；２,３００）：１００．０gと、ビフェニルアラルキル型エポキシ樹脂（日本化薬株式会社製；商品名ＮＣ−３０００Ｈ、エポキシ当量；２８０）：５００．０ｇと、メシチレン：１０００．０ｇを投入した。次いで、攪拌しながら１２０℃に昇温し、樹脂固形分が溶解し均一な溶液になっていることを確認した後、ナフテン酸亜鉛の８質量％ミネラルスピリット溶液を０．３０ｇ添加し、約１１０℃で４時間反応を行った。その後、室温に冷却し、相容化樹脂（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樹脂の生成物のピークが確認された。さらに、少量取り出した反応溶液を、メタノールとベンゼンの混合溶媒（混合質量比１：１）に滴下して再沈殿させることにより、精製された固形分を取り出し、ＦＴ−ＩＲ測定を行ったところ、イミノカルバメート基に起因する１７００ｃｍ−１付近のピーク、また、トリアジン環に起因する１５６０ｃｍ−１付近、及び１３８０ｃｍ−１付近の強いピークが確認でき、相容化樹脂（１−３）が製造されていることを確認した。
Production Example 3: Production of compatibilizing resin (1-3) Dicyclopentadiene-type cyanate resin (Lonza Japan Co., Ltd.) was added to a 3 liter reaction vessel with a thermometer, a stirrer, a reflux condenser and a heatable and coolable volume. Product name: Primaset DT-4000, weight average molecular weight 500 to 1,000): 400.0 g and a siloxane resin represented by the following formula (VII) (manufactured by Shin-Etsu Chemical Co., Ltd .; product name KF-8012, amino group) Equivalent; 2,300): 100.0 g and biphenyl aralkyl 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% by mass mineral spirit solution of zinc naphthenate was added, and about 110 The reaction was carried out at 4 ° C. for 4 hours. Then, it cooled to room temperature and obtained the solution of compatibilizing 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 at about 10.9 minutes vicinity and 8.0-10.0 vicinity was confirmed. Furthermore, when the reaction solution taken out in a small amount was dropped into a mixed solvent of methanol and benzene (mixing mass ratio 1: 1) and reprecipitated, the purified solid content was taken out and subjected to FT-IR measurement. imino carbamate due to group 1700 cm -1 vicinity of the peak, also around 1560 cm -1 due to the triazine ring, and 1380cm vicinity of can strong peak is confirmed -1, compatibilizing resin (1-3) is prepared I confirmed.
製造例４：相容化樹脂（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（ロンザジャパン株式会社製；商品名Ｐｒｉｍａｓｅｔ ＢＡＤＣｙ）：４００．０ｇと、下記式（ＶＩＩＩ）に示すシロキサン樹脂（東レ・ダウコーニング株式会社製；商品名ＢＹ１６−８７１、アミノ基当量；１３０）：５００．０gと、ナフタレン型エポキシ樹脂（ＤＩＣ株式会社製；商品名エピクロンＨＰ−４０３２、エポキシ当量；１５０）：１００．０ｇと、トルエン：１０００．０ｇを投入した。次いで、攪拌しながら１２０℃に昇温し、樹脂固形分が溶解し均一な溶液になっていることを確認した後、ナフテン酸亜鉛の８質量％ミネラルスピリット溶液を０．０１ｇ添加し、約１１０℃で４時間反応を行った。その後、室温に冷却し相容化樹脂（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樹脂の生成物のピークが確認された。さらに、少量取り出した反応溶液を、メタノールとベンゼンの混合溶媒（混合質量比１：１）に滴下して再沈殿させることにより、精製された固形分を取り出し、ＦＴ−ＩＲ測定を行ったところ、イミノカルバメート基に起因する１７００ｃｍ−１付近のピーク、また、トリアジン環に起因する１５６０ｃｍ−１付近、及び１３８０ｃｍ−１付近の強いピークが確認でき、相容化樹脂（１−４）が製造されていることを確認した。
Production Example 4: Production of Compatibilized Resin (1-4) A bisphenol A type cyanate resin (Lonza Japan Co., Ltd.) 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. Product name: Primaset BADCy): 400.0 g and siloxane resin represented by the following formula (VIII) (manufactured by Toray Dow Corning Co., Ltd .; product name BY16-871, amino group equivalent: 130): 500.0 g, naphthalene Type epoxy resin (manufactured by DIC Corporation; trade name: Epicron HP-4032, epoxy equivalent: 150): 100.0 g and toluene: 1000.0 g were charged. Next, the temperature was raised to 120 ° C. with stirring, and after confirming that the resin solids had dissolved and became a uniform solution, 0.01 g of an 8% by mass mineral spirit solution of zinc naphthenate was added, and about 110 The reaction was carried out at 4 ° C. for 4 hours. Then, it cooled to room temperature and obtained the solution of compatibilizing 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 at about 10.9 minutes vicinity and 8.0-10.0 vicinity was confirmed. Furthermore, when the reaction solution taken out in a small amount was dropped into a mixed solvent of methanol and benzene (mixing mass ratio 1: 1) and reprecipitated, the purified solid content was taken out and subjected to FT-IR measurement. imino carbamate due to group 1700 cm -1 vicinity of the peak, also around 1560 cm -1 due to the triazine ring, and 1380cm vicinity of can strong peak is confirmed -1, compatibilizing resin (1-4) is prepared I confirmed.
製造例５：式（ＩＩ）で示される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（株式会社アドマテックス製；商品名ＳＯ−２５Ｒ）：７００．０ｇと、プロピレングリコールモノメチルエーテル：１０００．０ｇを配合し、攪拌しながらＮ−フェニル−３−アミノプロピルトリメトキシシラン（信越化学工業株式会社製；商品名ＫＢＭ−５７３）：７．０ｇを添加した。次いで８０℃に昇温し、８０℃で１時間反応を行い溶融シリカの表面処理（湿式処理）を行った後、室温に冷却し、Ｎ−フェニル−３−アミノプロピルトリメトキシシランにより表面処理（湿式処理）された溶融シリカ（２−１）の溶液を得た。
Production Example 5: Production of fused silica (2-1) surface-treated (wet treatment) with a trimethoxysilane compound represented by the formula (II) Heatable and coolable with thermometer, stirrer and reflux condenser Fused silica (manufactured by Admatechs Co., Ltd .; trade name SO-25R): 700.0 g and propylene glycol monomethyl ether: 1000.0 g were blended in a reaction vessel having a volume of 3 liters 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 solution 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（ロンザジャパン株式会社製；商品名Ｐｒｉｍａｓｅｔ ＢＡＤＣｙ）：６００．０ｇと、上記式（ＶＩ）に示すシロキサン樹脂（信越化学工業株式会社製；商品名Ｘ−２２−１６１Ａ、アミノ基当量；８４０）：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株式会社製；商品名ＹＸ−４０００、エポキシ当量；１８６）：２００．０ｇと、トルエン：１０００．０ｇを投入した。次いで、攪拌しながら１２０℃に昇温し、樹脂固形分が溶解し均一な溶液になっていることを確認した後、ナフテン酸亜鉛の８質量％ミネラルスピリット溶液を０．０１ｇ添加し、約１１０℃で１時間反応を行った。その後、室温に冷却し（比較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１８％であった。また、この溶液は翌日結晶化により沈殿物が生じた。
Comparative Production Example 1: Production of (Comparative 1) A bisphenol A type cyanate resin (manufactured by Lonza Japan Co., Ltd.) was added to a reaction vessel having a volume of 3 liters which can be heated and cooled with a thermometer, a stirrer and a reflux condenser. Primeset BADCy): 600.0 g and a siloxane resin represented by the above formula (VI) (manufactured by Shin-Etsu Chemical Co., Ltd .; trade name X-22-161A, amino group equivalent; 840): 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. with stirring, and after confirming that the resin solids had dissolved and became a uniform solution, 0.01 g of an 8% by mass mineral spirit solution of zinc naphthenate was added, and about 110 The reaction was carried out at 1 ° C. for 1 hour. Then, it cooled to room temperature and obtained the solution of (Comparative 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 18%. 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（ロンザジャパン株式会社製；商品名Ｐｒｉｍａｓｅｔ ＢＡＤＣｙ）：６００．０ｇと、上記式（ＶＩ）に示すシロキサン樹脂（信越化学工業株式会社製；商品名Ｘ−２２−１６１Ａ、アミノ基当量；８４０）：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株式会社製；商品名ＹＸ−４０００、エポキシ当量；１８６）：２００．０ｇと、トルエン：１０００．０ｇを投入した。次いで、攪拌しながら１２０℃に昇温し、樹脂固形分が溶解し均一な溶液になっていることを確認した後、ナフテン酸亜鉛の８質量％ミネラルスピリット溶液を０．０１ｇ添加し、約１２０℃で６時間反応を行った。その後、室温に冷却し（比較２）の溶液を得た。この反応溶液を少量取り出し、ＧＰＣ測定（ポリスチレン換算、溶離液：テトラヒドロフラン）を行ったところ、溶出時間が約１２．４分付近に出現する合成原料のビスフェノールＡ型シアネート樹脂のピーク面積が、反応開始時のビスフェノールＡ型シアネート樹脂のピーク面積と比較し、ピーク面積の消失率が７６％であった。
Comparative Production Example 2: Production of (Comparative 2) A bisphenol A type cyanate resin (manufactured by Lonza Japan, Inc. Primeset BADCy): 600.0 g and a siloxane resin represented by the above formula (VI) (manufactured by Shin-Etsu Chemical Co., Ltd .; trade name X-22-161A, amino group equivalent; 840): 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% by mass mineral spirit solution of zinc naphthenate was added, and about 120 The reaction was carried out at 6 ° C. for 6 hours. Then, it cooled to room temperature and obtained the solution of (comparative 2). A small amount of this reaction solution was taken out and subjected to GPC measurement (polystyrene conversion, eluent: tetrahydrofuran). As a result, the peak area of the bisphenol A type cyanate resin, which is a synthetic raw material and the elution time appears around 12.4 minutes, is the start of the reaction. Compared with the peak area of the bisphenol A type cyanate resin at the time, the disappearance rate of the peak area was 76%.
比較製造例３：（比較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（ロンザジャパン株式会社製；商品名Ｐｒｉｍａｓｅｔ ＢＡＤＣｙ）：６００．０ｇと、上記式（ＶＩ）に示すシロキサン樹脂（信越化学工業株式会社製；商品名Ｘ−２２−１６１Ａ、アミノ基当量；８４０）：２００．０gと、トルエン：８００．０ｇを投入した。次いで、攪拌しながら１２０℃に昇温し、樹脂固形分が溶解し均一な溶液になっていることを確認した後、ナフテン酸亜鉛の８質量％ミネラルスピリット溶液を０．０１ｇ添加し、約１１０℃で４時間反応を行った。その後、室温に冷却し（比較３）の溶液を得た。この反応溶液を少量取り出し、ＧＰＣ測定（ポリスチレン換算、溶離液：テトラヒドロフラン）を行ったところ、溶出時間が約１２．４分付近に出現する合成原料のビスフェノールＡ型シアネート樹脂のピーク面積が、反応開始時のビスフェノールＡ型シアネート樹脂のピーク面積と比較し、ピーク面積の消失率が５３％であった。
Comparative Production Example 3: Production of (Comparative 3) A bisphenol A type cyanate resin (manufactured by Lonza Japan Co., Ltd.) was added to a 2 liter heatable and coolable reaction vessel equipped with a thermometer, a stirrer and a reflux condenser. (Primaset BADCy): 600.0 g, a siloxane resin represented by the above formula (VI) (manufactured by Shin-Etsu Chemical Co., Ltd .; trade name X-22-161A, amino group equivalent; 840): 200.0 g, toluene: 800. 0 g was charged. Next, the temperature was raised to 120 ° C. with stirring, and after confirming that the resin solids had dissolved and became a uniform solution, 0.01 g of an 8% by mass mineral spirit solution of zinc naphthenate was added, and about 110 The reaction was carried out at 4 ° C. for 4 hours. Then, it cooled to room temperature and obtained the solution of (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%.
（実施例１〜６、比較例１〜５）
製造例１〜４により得られた成分（１）の相容化樹脂、及び比較製造例１〜３で得られた樹脂、及び、製造例５又は商業的に入手した成分（２）、また、必要により成分（３）、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（質量部）で混合して樹脂分６０質量％の均一なワニスを得た。次に、上記ワニスを厚さ０．２ｍｍの有機繊維基材に含浸塗工し、１６０℃で１０分加熱乾燥して樹脂含有量５５質量％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１８５℃で９０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、吸湿性（吸水率）、難燃性、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に測定・評価結果を示した。
(Examples 1-6, Comparative Examples 1-5)
Component (1) compatibilizing resin obtained in Production Examples 1 to 4, and resin obtained in Comparative Production Examples 1 to 3, and Production Example 5 or commercially available component (2), If necessary, use methyl ethyl ketone as a component (3), a curing accelerator, and a diluent solvent, and mix at a blending ratio (parts by mass) shown in Tables 1 and 2 to obtain a uniform varnish having a resin content of 60% by mass. It was. Next, the organic varnish having a thickness of 0.2 mm was impregnated with the varnish and dried by heating at 160 ° C. for 10 minutes to obtain a prepreg having a resin content of 55% by mass. Next, four prepregs 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 185 ° C. for 90 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, moisture absorption (water absorption), flame retardancy, relative dielectric constant (1 GHz ) And dielectric loss tangent (1 GHz) were measured and evaluated by the following method. Tables 3 and 4 show the measurement and 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（ピール強度）を測定した。
（２）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。
(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 adhesion (peel strength) of the foil was measured.
(2) Measurement of linear thermal expansion coefficient 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 evaluated 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.
*１：溶融シリカに対し１．０質量%のＮ−フェニル−３−アミノプロピルトリメトキシシランにより表面処理された溶融シリカ（株式会社アドマテック製；商品名ＳＣ−２０５０ＫＮＫ，希釈溶剤；メチルイソブチルケトン）
*2：溶融シリカに対し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（株式会社アドマテック製；商品名ＳＣ−２０５０ＨＮＫ，希釈溶剤；シクロヘキサノン）
*3：ベーマイト型水酸化アルミニウム（河合石灰工業株式会社製；商品名ＢＭＴ−３Ｌ，熱分解温度：４００℃）
*4：モリブデン酸亜鉛をタルクに担持した無機難燃助剤（シャーウィン・ウィリアムス社製；商品名 ケムガード１１００）
*5：アラミド繊維（帝人株式会社）
*6：芳香族ポリエステル繊維（ＬＣＰ繊維、ＫＢセーレン株式会社）
*7：ＢＰＯ繊維（ポリパラフェニレンベンズオキサゾール繊維、東洋紡株式会社）
*8：ナフテン酸亜鉛の８質量％ミネラルスピリット溶液
*9：ビフェニル型エポキシ樹脂（ジャパンエポキシレジン株式会社製；商品名ＹＸ−４０００、エポキシ当量；１８６）
*10：溶融シリカ（株式会社アドマテック製；商品名ＳＯ−２５Ｒ）
*11：溶融シリカに対し１．０質量％のγ−グリシドキシプロピルトリメトキシシランにより表面処理された溶融シリカ（株式会社アドマテック製；商品名ＳＣ１０３０−ＭＪＡ，希釈溶剤；メチルエチルケトン）を意味する。
* 1: Fused silica surface-treated with 1.0% by mass of N-phenyl-3-aminopropyltrimethoxysilane with respect to fused silica (manufactured by Admatech Co., Ltd .; trade name SC-2050KNK, diluent solvent: methyl isobutyl ketone)
* 2: Fused silica surface-treated with 1.0 wt% N-phenyl-3-aminopropyltrimethoxysilane with respect to fused silica (manufactured by Admatech Co., Ltd .; trade name SC-2050HNK, diluent solvent: cyclohexanone)
* 3: Boehmite type aluminum hydroxide (manufactured by Kawai Lime Industry Co., Ltd .; trade name BMT-3L, thermal decomposition temperature: 400 ° C.)
* 4: Inorganic flame retardant aid with zinc molybdate supported on talc (manufactured by Sherwin Williams; trade name Chemguard 1100)
* 5: Aramid fiber (Teijin Limited)
* 6: Aromatic polyester fiber (LCP fiber, KB Seiren Co., Ltd.)
* 7: BPO fiber (polyparaphenylene benzoxazole fiber, Toyobo Co., Ltd.)
* 8: 8% by weight mineral spirit solution of zinc naphthenate
* 9: Biphenyl type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd .; trade name YX-4000, epoxy equivalent: 186)
* 10: Fused silica (manufactured by Admatech Co., Ltd .; trade name SO-25R)
* 11: Means fused silica (manufactured by Admatech Co., Ltd .; trade name SC1030-MJA, diluent solvent: methyl ethyl ketone) surface-treated with 1.0% by mass of γ-glycidoxypropyltrimethoxysilane based on fused silica.
ピーク面積の消失率が１８％の比較１の樹脂を用いた比較例１は、熱硬化性樹脂が析出しワニスを製造できなかった。ピーク面積の消失率が７６％の比較２の樹脂を用いた比較例２は、成形性が不良であり積層板を作製できなかった（溶融シリカとの組み合わせで比較例４、５ではかろうじて作製可）。シロキサン樹脂（ａ）と、シアネート基を有する化合物（ｂ）のみのをプレ反応させた比較例３は、樹脂が分離し、プリプレグ及び積層板を作製できなかった。 In Comparative Example 1 using the resin of Comparative 1 having a peak area disappearance rate of 18%, the thermosetting resin was precipitated and the varnish could not be produced. Comparative Example 2 using the resin of Comparative 2 having a peak area disappearance ratio of 76% was poor in moldability and could not produce a laminate (comparable to Comparative Examples 4 and 5 in combination with fused silica). ). In Comparative Example 3 in which only the siloxane resin (a) and only the compound (b) having a cyanate group were pre-reacted, the resin was separated, and a prepreg and a laminate could not be produced.
表から明らかなように、シロキサン樹脂（ａ）とシアネート基を有する化合物（ｂ）とエポキシ基を有する化合物（ｃ）をプレ反応させて、（ｂ）のシアネート基を有する化合物の反応率（消失率）を３０〜７０ｍｏｌ％となるようにして得られる相容化樹脂と有機繊維基材を用いた本発明の実施例は、銅箔ピール強度、低熱膨張性に優れている。一方、比較例は、銅箔ピール強度、熱膨張性のいずれにおいても特性に劣っている。 As is apparent from the table, the reaction rate (disappearance) of the compound (c) having a cyanate group is pre-reacted with the siloxane resin (a), the compound (b) having a cyanate group, and the compound (c) having an epoxy group. The embodiment of the present invention using the compatibilizing resin and the organic fiber base material obtained so that the ratio is 30 to 70 mol% is excellent in copper foil peel strength and low thermal expansion. On the other hand, the comparative example is inferior in characteristics in both copper foil peel strength and thermal expansibility.
本発明の相容化樹脂を有機繊維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銅張積層板は、低熱膨張率、高銅箔ピール強度の特性を発現しており、電子機器用のプリント配線板などに有用である。 A prepreg obtained by impregnating or coating the compatibilizing resin of the present invention on an organic fiber base material, and a copper-clad laminate produced by laminating the prepreg have a low thermal expansion coefficient and a high copper foil peel strength. It exhibits its characteristics and is useful for printed wiring boards for electronic devices.
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