JP2015063611A - Prepreg, and laminate and printed wiring board using the same - Google Patents
Prepreg, and laminate and printed wiring board using the same Download PDFInfo
- Publication number
- JP2015063611A JP2015063611A JP2013198233A JP2013198233A JP2015063611A JP 2015063611 A JP2015063611 A JP 2015063611A JP 2013198233 A JP2013198233 A JP 2013198233A JP 2013198233 A JP2013198233 A JP 2013198233A JP 2015063611 A JP2015063611 A JP 2015063611A
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- Prior art keywords
- resin
- mass
- prepreg
- parts
- compound
- 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 claims abstract description 104
- 239000011347 resin Substances 0.000 claims abstract description 104
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate group Chemical group [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims abstract description 48
- 150000001875 compounds Chemical class 0.000 claims abstract description 28
- 239000004744 fabric Substances 0.000 claims abstract description 22
- 239000011521 glass Substances 0.000 claims abstract description 19
- 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 17
- 125000001424 substituent group Chemical group 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 11
- 238000000576 coating method Methods 0.000 claims abstract description 11
- 239000007809 chemical reaction catalyst Substances 0.000 claims abstract description 7
- 125000002524 organometallic group Chemical group 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 44
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 23
- 230000008034 disappearance Effects 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 9
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 7
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- 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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
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- 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 26
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
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- 229910003475 inorganic filler Inorganic materials 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 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 8
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- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 7
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- 238000003756 stirring Methods 0.000 description 7
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 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
- 229910052500 inorganic mineral Inorganic materials 0.000 description 6
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- 239000000126 substance Substances 0.000 description 6
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- 125000003396 thiol group Chemical group [H]S* 0.000 description 6
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- 239000003480 eluent Substances 0.000 description 5
- 238000010828 elution Methods 0.000 description 5
- 239000003063 flame retardant Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000010030 laminating Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 238000005979 thermal decomposition reaction Methods 0.000 description 5
- 239000002966 varnish Substances 0.000 description 5
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 4
- 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
- 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 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 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
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 239000012796 inorganic flame retardant Substances 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
- 238000007747 plating Methods 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 4
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 4
- 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
- ALNBMSFIZFUDMD-UHFFFAOYSA-N 3,4-dimethylnaphthalene-1,2-diol Chemical compound C1=CC=C2C(O)=C(O)C(C)=C(C)C2=C1 ALNBMSFIZFUDMD-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
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- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
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- 150000004677 hydrates Chemical class 0.000 description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 3
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- OVAZZMXASSWARN-UHFFFAOYSA-N naphthalen-1-ylmethanediol Chemical compound C1=CC=C2C(C(O)O)=CC=CC2=C1 OVAZZMXASSWARN-UHFFFAOYSA-N 0.000 description 3
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 3
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- OHBQPCCCRFSCAX-UHFFFAOYSA-N 1,4-Dimethoxybenzene Chemical compound COC1=CC=C(OC)C=C1 OHBQPCCCRFSCAX-UHFFFAOYSA-N 0.000 description 2
- AUFZRCJENRSRLY-UHFFFAOYSA-N 2,3,5-trimethylhydroquinone Chemical compound CC1=CC(O)=C(C)C(C)=C1O AUFZRCJENRSRLY-UHFFFAOYSA-N 0.000 description 2
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 2
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- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 1
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- 239000006096 absorbing agent Substances 0.000 description 1
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- 239000002253 acid Substances 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000005529 alkyleneoxy 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
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- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
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- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
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- 125000006267 biphenyl group Chemical group 0.000 description 1
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- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 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
- 238000009833 condensation Methods 0.000 description 1
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- 238000007796 conventional method Methods 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
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- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
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- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
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- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 229940015043 glyoxal Drugs 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
- 238000005470 impregnation Methods 0.000 description 1
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- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 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
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
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- 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
- 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
- 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
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000004745 nonwoven fabric Substances 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
- 239000013034 phenoxy resin Substances 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
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- 229920006122 polyamide resin Polymers 0.000 description 1
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- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 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
- 239000004065 semiconductor Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910000679 solder Inorganic materials 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
- 238000006467 substitution reaction Methods 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
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- 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)
- Compositions Of Macromolecular Compounds (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Epoxy Resins (AREA)
Abstract
Description
本発明は、半導体パッケージや電子部品等に好適なプリプレグ、並びにこれを用いた積層板及びプリント配線板に関する。 The present invention relates to a prepreg suitable for a semiconductor package, an electronic component, and the like, and a laminated board and a printed wiring board using the prepreg.
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.
また近年、高周波対応パッケージ基板の要求が強くなってきていることから、熱膨張係数が小さく、比誘電率及び誘電正接の低い基板が求められている。
特許文献６でシロキサン樹脂とエポキシ樹脂、及びシアネート樹脂からなる熱硬化性樹脂組成物を用いたパッケージ基板が開示されているが、次世代材料にはさらに小さい熱膨張係数が要求されており、一般的な無機繊維であるＳガラスクロスの使用では上記の要求を満たすことは困難である。
In recent years, the demand for high-frequency compatible package substrates has increased, and there is a need for substrates having a low thermal expansion coefficient and a low relative dielectric constant and dielectric loss tangent.
Patent Document 6 discloses a package substrate using a thermosetting resin composition composed of a siloxane resin, an epoxy resin, and a cyanate resin, but a next-generation material is required to have a smaller thermal expansion coefficient. The use of S glass cloth, which is a typical inorganic fiber, makes it difficult to satisfy the above requirements.
本発明の目的は、低熱膨張性、低誘電率及び低誘電正接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、プリント配線板を提供するものである。 The objective of this invention is providing the prepreg which expresses low thermal expansibility, a low dielectric constant, and a low dielectric loss tangent, the laminated board using this prepreg, and a printed wiring board.
本発明者らは上記の課題を解決すべく検討を進めた結果、下記一般式（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（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）とを、（ａ）と（ｂ）と（ｃ）の総和１００質量部あたり、（ａ）の使用量が１０〜５０質量部の範囲、（ｂ）の使用量が４０〜８０質量部の範囲、（ｃ）の使用量が１０〜５０質量部の範囲として、これらを反応させることにより得られる相容化樹脂を、Ｑガラスクロスに含浸または塗工し、得られるプリプレグを用いた積層板及びプリント配線板が、低熱膨張性、低誘電特性（低誘電率、低誘電正接）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。
As a result of studying the present inventors to solve the above problems, a structure represented by the following general formula (I), a siloxane resin (a) having at least two reactive substituents in the side chain, A compound (b) having at least two cyanate groups in one molecule, a compound (c) having at least two epoxy groups in one molecule, and an organometallic salt (d) as a reaction catalyst, (a ), (B) and (c) per 100 parts by mass of total (a) in the range of 10-50 parts by mass, (b) in the range of 40-80 parts by mass, (c) As the amount used is in the range of 10 to 50 parts by mass, a compatibilized resin obtained by reacting these is impregnated or applied to Q glass cloth, and a laminate and a printed wiring board using the obtained prepreg are obtained, Low thermal expansion, low dielectric properties (low dielectric constant, low dielectric loss tangent It was found to express.
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（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）とを、（ａ）と（ｂ）と（ｃ）の総和１００質量部あたり、（ａ）の使用量が１０〜５０質量部の範囲、（ｂ）の使用量が４０〜８０質量部の範囲、（ｃ）の使用量が１０〜５０質量部の範囲として、これらを反応させることにより得られる相容化樹脂を、Ｑガラスクロスに含浸又は塗工し、得られるプリプレグに関する。 The present invention provides [1] a structure represented by the following general formula (I), a siloxane resin (a) having at least two reactive substituents in the side chain, and at least two cyanate groups in one molecule. A compound (b) having at least two epoxy groups in one molecule, an organometallic salt (d) as a reaction catalyst, and the sum of (a), (b) and (c) The range of 10-50 parts by mass of (a) used per 100 parts by mass, the range of 40-80 parts by mass of (b) used, and the range of 10-50 parts by mass of (c) used. Further, the present invention relates to a prepreg obtained by impregnating or coating a compatibilizing resin obtained by reacting these with Q glass cloth.
また、本発明は、［２］ 前記（ａ）と（ｂ）と（ｃ）とを反応させる際に、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とする上記［１］に記載のプリプレグに関する。
また、本発明は、［３］ 上記［１］又は［２］に記載のＱガラスクロスの石英含有率が９０質量％以上であるプリプレグに関する。
また、本発明は、［４］ 上記［１］〜［３］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、［５］ 上記［４］に記載の積層板の表面又は表面とその内部に導体パターンが形成されたプリント配線板に関する。
Moreover, this invention is [2] When making said (a), (b), and (c) react, these are beforehand made into the reaction temperature of 80-120 degreeC in the solvent chosen from toluene, xylene, and mesitylene. A compatibilized resin obtained by pre-reacting the iminocarbamation reaction and the triazine cyclization reaction so that the reaction rate (disappearance rate) of the compound having a cyanate group in (b) is 30 to 70 mol%. The prepreg according to [1] above.
[3] The present invention also relates to a prepreg in which the quartz content of the Q glass cloth according to [1] or [2] is 90% by mass or more.
The present invention also relates to [4] a laminate obtained by molding the prepreg according to any one of [1] to [3].
Furthermore, the present invention relates to [5] a printed wiring board in which a conductor pattern is formed on the surface or surface of the laminated board according to [4] and the inside thereof.
本発明で用いる相容化樹脂をＱガラスクロス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、低熱膨張性、及び低誘電特性を発現するため、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 a compatibilizing resin used in the present invention on Q glass cloth, and a copper-clad laminate produced by laminating the prepreg exhibit low thermal expansion and low dielectric properties. Therefore, it 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。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２．５ｐｐｍ／℃以下（２．５×１０−６／Ｋ以下）であることが望ましく、１ｐｐｍ／℃以下であることがより望ましい。さらに、伝送特性向上の要求に対しては比誘電率及び誘電正接の低減が有効な手段となる。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。
本発明は、（ａ）上記一般式（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、（ｄ）反応触媒として有機金属塩を、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容化樹脂をＱガラスクロスに含浸又は塗工し、乾燥して得られるプリプレグである。
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. As the density increases, the base material tends to be made thinner, and it is necessary that the warp of the base material during heat treatment is small. In order to reduce warpage, it is effective that the surface direction of the substrate is low in thermal expansion, and the thermal expansion coefficient is 2.5 ppm / ° C. or less (2.5 × 10 −6 / K or less). Is desirable, and it is more desirable that it is 1 ppm / ° C. or less. Furthermore, reduction of relative permittivity and dielectric loss tangent is an effective means for the demand for improvement of transmission characteristics. Under such circumstances, the present invention described below has been made through intensive research.
The present invention comprises (a) a structure represented by the above general 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. A compound having (c) at least two epoxy groups in one molecule, (d) an organometallic salt as a reaction catalyst, and (a) the reactive substituent and cyanate in an aromatic organic solvent. It is a prepreg obtained by impregnating or coating a compatibilizing resin obtained by group addition reaction and triazine cyclization reaction on Q glass cloth and drying.
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であれば特に限定されない。
具体的には、一般式（Ｉ）の構造を有する一般式（ＩＩ）で示すように側鎖に反応性置換基を有するシロキサン樹脂である。
The siloxane resin as the component (a) of the present invention is not particularly limited as long as it is a siloxane resin having the structure represented by the general formula (I) and at least two reactive substituents in the side chain.
Specifically, it is a siloxane resin having a reactive substituent in the side chain as shown by the general formula (II) having the structure of the general formula (I).
側鎖の反応性置換基は、アルキレン基、アルキレンオキシ基などを介して間接的に側鎖の末端に位置していてもよい。
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は、例えば水酸基で置換された化合物は信越化学工業株式会社製、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式会社製、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・ダウコーニング株式会社製、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株式会社Ｘ−２２−３４３（エポキシ基当量：５２５ｇ/ｍｏｌ）、ＫＦ−１００１（エポキシ基当量：３５００）、東レ・ダウコーニング株式会社製、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株式会社、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・ダウコーニング株式会社製、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株式会社、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株式会社、商品名Ｘ−２２−３７０１Ｅ（カルボキシル基当量：４０００ｇ／ｍｏｌ）、東レ・ダウコーニング株式会社製、商品名ＢＹ１６−８８０（カルボキシル基当量：３５００ｇ／ｍｏｌ）、等が挙げられる。
The reactive substituent on the side chain may be located indirectly at the end of the side chain via an alkylene group, an alkyleneoxy group or the like.
The siloxane resin having at least two reactive substituents in the side chain is, for example, a compound substituted with a hydroxyl group, 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. The compound substituted with an amino group is manufactured by Shin-Etsu Chemical Co., Ltd., trade name KF-868 (amino group equivalent: 8800 g / mol), trade name. KF-865 (amino group equivalent: 5000 g / mol), 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 group 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, and epoxy group The compounds substituted by Shin-Etsu Chemical Co., Ltd. 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), etc., and 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), Toray Dow Corning Co., Ltd. Manufactured by the company, trade name BY16-839 (epoxy group equivalent: 3700 g / mol), and the like. The compound substituted with a mercapto group is Shin-Etsu Chemical Co., Ltd., trade name KF-2001 (mercapto group equivalent: 1900 g / mol). ), Trade name KF-2004 (mercapto group equivalent: 30000 g / mol), etc., and the compound substituted with a carboxyl group is Shin-Etsu Chemical Co., Ltd., trade name X-22-3701E (carboxyl group equivalent: 4000 g / mol). ), Manufactured by Toray Dow Corning Co., Ltd., trade name BY16-880 (carboxyl group equivalent: 3500 g / mol), and the like.
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 as 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, Tetramethylbisphenol F type cyanate resin 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 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.
（ｍは正数）
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。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。
(M is a positive number)
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. 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、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 which is the component (c) used in the present invention includes, for example, bisphenol A, bisphenol F, tetramethylbisphenol F, bisphenol S, bisphenol K, and biphenol. Glycidyl ethers, glycidyl amines, glycidyl esters, etc., such as bisphenols, tetramethylbiphenol biphenyls, novolacs, polyfunctional phenols, naphthalenes, alicyclics and alcohols. Can be used as a mixture. 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.
本発明で用いる成分（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 metal salt of the reaction catalyst as the component (d) used in the present invention include zinc naphthenate, manganese naphthenate, cobalt naphthenate, tin octylate, and cobalt octylate.
（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、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（ａ）の反応性置換基を有するシロキサン樹脂と、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際の含浸または塗工後の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。
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質量部未満であると、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質量部を超えると得られる樹脂の相容性が良好となり、また（ｂ）の使用量が８０質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質量部を超えると、耐湿耐熱性が低下せず良好であり、また（ｃ）の使用量が５０質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。
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, and these are uniformly dissolved in a solvent selected beforehand from toluene, xylene, and mesitylene, and the reactive substitution of (a) is performed at a reaction temperature of 80 to 120 ° C. It is necessary to carry out a pre-reaction so that the reaction rate (disappearance rate) of the compound having a cyanate group in (b) is 30 to 70 mol% by causing a siloxane resin having a group to undergo a cyanate group addition reaction and a triazine cyclization reaction. There is. 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 tends to become a residual solvent during impregnation or drying after coating. If the reaction rate by 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. 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 prepreg gel time becomes too short. In this case, the moldability may deteriorate. 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.
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 amount of use of (a) exceeds 10 parts by mass, 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 mass, heat resistance is obtained. And chemical resistance does not decrease. When the use amount of (b) exceeds 40 parts by mass, the compatibility of the obtained resin is good, and when the use amount of (b) is less than 80 parts by mass, low heat in the surface direction of the obtained substrate is obtained. Good expandability. When the amount of (c) used exceeds 10 parts by mass, the moisture and heat resistance is good without decreasing, and when the amount of (c) used is less than 50 parts by mass, 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 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エポキシ樹脂を更に添加することができる。フェノール樹脂は、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−ｔｅｒｔ−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、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。
上記において例示されたフェノール類としては、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−ナフトール等の一分子中に１個しかフェノール性水酸基を持たないフェノール化合物、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−ｔｅｒｔ−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が挙げられる。
また、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、ジヒドロキシナフタレン、ジヒドロキシメチルナフタレン、ジヒドロキシジメチルナフタレン、トリヒドロキシナフタレン等が挙げられる。
更に、アルデヒド類としては、ホルムアルデヒド、アセトアルデヒド、プロピルアルデヒド、ブチルアルデヒド、バレルアルデヒド、カプロンアルデヒド、ベンズアルデヒド、クロルベンズアルデヒド、ブロムベンズアルデヒド、グリオキザール、マロンアルデヒド、スクシンアルデヒド、グルタルアルデヒド、アジピンアルデヒド、ピメリンアルデヒド、セバシンアルデヒド、アクロレイン、クロトンアルデヒド、サリチルアルデヒド、フタルアルデヒド、ヒドロキシベンズアルデヒド等が挙げられる。
A phenol resin or an epoxy resin can be further added to the compatibilizing resin used in the present invention for the purpose of reducing the residual cyanate group after thermosetting. Examples of the phenol resin 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-tert-butylhydroquinone, resorcinol, methylresorcinol, catechol, methylcatechol , Dihydroxynaphthalene, dihydroxymethylnaphthalene, dihydroxydimethylnaphthalene, bisphenolfluorene, biscresolfluorene and other bifunctional compounds, phenols, or condensates of naphthols with aldehydes, condensation of phenols or naphthols with xylylene glycol Products, phenols or naphthols and bismethoxymethylbiphenyl Condensates, condensates of phenols with isopropenyl acetophenone, reaction products of phenols and dicyclopentadiene. These can be obtained by known methods.
The phenols exemplified above have only one phenolic hydroxyl group in one molecule such as phenol, cresol, xylenol, butylphenol, amylphenol, nonylphenol, p-cumylphenol, 1-naphthol and 2-naphthol. No phenolic compounds, bisphenol A, tetramethylbisphenol F, bisphenol F, bisphenol S, bisphenol K, biphenol, tetramethylbiphenol, hydroquinone, methylhydroquinone, dimethylhydroquinone, trimethylhydroquinone, di-tert-butylhydroquinone, resorcinol, methylresorcinol, Catechol, methylcatechol, dihydroxynaphthalene, dihydroxymethylnaphthalene, dihydroxydimethylnaphthalene Array type, bisphenol fluorene and a bis-cresol fluorene.
Similarly, examples of naphthols include 1-naphthol, 2-naphthol, dihydroxynaphthalene, dihydroxymethylnaphthalene, dihydroxydimethylnaphthalene, and trihydroxynaphthalene.
Furthermore, as aldehydes, formaldehyde, acetaldehyde, propyl aldehyde, butyraldehyde, valeraldehyde, capronaldehyde, benzaldehyde, chlorbenzaldehyde, bromobenzaldehyde, glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde, adipine aldehyde, pimelin aldehyde, Examples include sebacic aldehyde, acrolein, crotonaldehyde, salicylaldehyde, phthalaldehyde, and hydroxybenzaldehyde.
本発明で用いる相容化樹脂には、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よく、ビニルトリエトキシシラン、３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルメチルジエトキシシラン、３−メタクリロキシプロピルメチルジエトキシシラン、３−メタクリロキシプロピルトリメトキシシラン、３−グリシドキシプロピルメチルジメトキシシラン、３−メタクリロキシプロピルトリエトキシシラン、Ｎ−２−（アミノエチル）−３−アミノプロピルメチルジメトキシシラン、Ｎ−２−（アミノエチル）−３−アミノプロピルトリメトキシシラン、Ｎ−２−（アミノエチル）−３−アミノプロピルトリエトキシシラン、３−アミノプロピルトリメトキシシラン、３−アミノプロピルトリエトキシシラン、Ｎ−フェニル−３−アミノプロピルトリメトキシシランなどが上げられる。この中でも特に、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特に好ましい。 In the compatibilizing resin used in the present invention, it is desirable to use an inorganic filler for the purpose of improving low thermal expansion, heat resistance, flame retardancy, etc., and it is particularly preferable to use fused silica. It is more preferable to use fused silica whose surface is treated with a silane compound. The silane compound having a functional group may be any silane compound having a functional group and an alkoxyl group, such as vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropylmethyl. Diethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane , 3-aminopropyl Triethoxysilane, etc. N- phenyl-3-aminopropyltrimethoxysilane, and the like. Among these, N-phenyl-3-aminopropyltrimethoxysilane represented by the following formula (IV) is particularly preferable.
無機充填材への表面処理方法の例としては、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系有機溶剤やエチレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテル等のアルコール系有機溶剤に、溶融シリカを添加して混合した後、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、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。これら溶融シリカの使用量は、固形分換算の該樹脂組成物１００質量部に対し、１０〜３００質量部とすることが好ましく、１００〜２５０質量部とすることがより好ましく、１５０〜２５０質量部とすることが特に好ましい。１０質量部以上であると、基材の剛性や、耐湿耐熱性、難燃性が十分であり、また、３００質量部以下であると成形性や耐めっき液性等の耐薬品性が向上する。 Examples of surface treatment methods for inorganic fillers include adding fused silica to ketone organic solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, and alcohol organic solvents such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether. After mixing, for example, the trimethoxysilane compound represented by the above structural formula (IV) is added and reacted (surface treatment) with stirring at 60 to 120 ° C. for about 0.5 to 5 hours. Also, commercially available from Admatechs Co., Ltd., for example, trade names SC-2050KNK and SC-2050HNK manufactured by Admatechs Co., Ltd. are available. The amount of these fused silica used is preferably 10 to 300 parts by weight, more preferably 100 to 250 parts by weight, and more preferably 150 to 250 parts by weight with respect to 100 parts by weight of the resin composition in terms of solid content. It is particularly preferable that If it is 10 parts by mass or more, the rigidity, heat resistance, and flame resistance of the substrate are sufficient, and if it is 300 parts by mass or less, chemical resistance such as moldability and plating solution resistance is improved. .
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、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。これら溶融シリカの使用量は、固形分換算の該樹脂組成物１００質量部に対し、１０〜３００質量部とすることが好ましく、１００〜２５０質量部とすることがより好ましく、１５０〜２５０質量部とすることが特に好ましい。１０質量部以上であると、基材の剛性や、耐湿耐熱性、難燃性が十分であり、また、３００質量部以下であると成形性や耐めっき液性等の耐薬品性が向上する。 Examples of surface treatment methods for inorganic fillers include adding fused silica to ketone organic solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, and alcohol organic solvents such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether. After mixing, for example, the trimethoxysilane compound represented by the above structural formula (IV) is added and reacted (surface treatment) with stirring at 60 to 120 ° C. for about 0.5 to 5 hours. Also, commercially available from Admatechs Co., Ltd., for example, trade names SC-2050KNK and SC-2050HNK manufactured by Admatechs Co., Ltd. are available. The amount of these fused silica used is preferably 10 to 300 parts by weight, more preferably 100 to 250 parts by weight, and more preferably 150 to 250 parts by weight with respect to 100 parts by weight of the resin composition in terms of solid content. It is particularly preferable that If it is 10 parts by mass or more, the rigidity, heat resistance, and flame resistance of the substrate are sufficient, and if it is 300 parts by mass or less, chemical resistance such as moldability and plating solution resistance is improved. .
本発明で用いる相容化樹脂には、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の使用量は、固形分換算の該樹脂組成物１００質量部に対し、１０〜２００質量部とすることが好ましく、１０〜１５０質量部とすることがより好ましく、５０〜１５０質量部とすることが特に好ましい。１０質量部を超えると難燃性が十分となり、２００質量部未満であると耐めっき液性等の耐薬品性や成形性が低下せず、良好となる。 For the compatibilizing resin used in the present invention, other inorganic fillers may be used. For example, crushed silica, mica, talc, short glass fiber or fine powder and hollow glass, calcium carbonate, quartz powder, metallic water 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 further metal hydrates. Among them, metal hydrates having a thermal decomposition temperature of 300 ° C. or higher, for example, boehmite type aluminum hydroxide (AlOOH), or gibbsite type aluminum hydroxide (Al (OH)), since both high heat resistance and flame retardancy are compatible. More preferred is a compound in which the thermal decomposition temperature of 3) is adjusted to 300 ° C. or higher by heat treatment, magnesium hydroxide, etc., particularly inexpensive, high thermal decomposition temperature of 350 ° C. or higher, and high Boehmite type aluminum hydroxide having a chemical resistance (AlOOH) are preferred. The amount of these inorganic fillers used is preferably 10 to 200 parts by weight, more preferably 10 to 150 parts by weight, and more preferably 50 to 150 parts per 100 parts by weight of the resin composition in terms of solid content. It is particularly preferable to use parts by mass. If it exceeds 10 parts by mass, the flame retardancy will be sufficient, and if it is less than 200 parts by mass, chemical resistance such as plating solution resistance and moldability will not be deteriorated, and it will be good.
本発明で用いる相容化樹脂には、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。 For the compatibilizing resin 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, naphthenic acid. Examples include organic metal salts such as cobalt acid, 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.
本発明で用いる相容化樹脂には、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 compatibilizing resin 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 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 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.
本発明によれば、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。
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。
According to the present invention, known thermoplastic resins, elastomers, flame retardants, organic fillers 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.
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、前記した本発明で用いる相容化樹脂組成物を、Ｑガラスクロス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、上述の相容化樹脂組成物がＱガラスクロスに含浸又は塗布されてなる。本発明のプリプレグは、本発明で用いる相容化樹脂組成物を、Ｑガラスクロスに含浸又は塗工し、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。
このＱガラスクロスの形状としては、例えば、織布、不織布、ロービング、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、目的とする成型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。Ｑガラスクロスとは、二酸化珪素の含有率が９０質量％以上を占めるガラス繊維のことをいう（例えば、ＩＰＣ規格２１１６タイプクロスやＩＰＣ規格１０３５タイプクロス）。Ｑガラスクロスの厚さは、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 the compatibilizing resin composition used in the present invention on Q glass cloth. Hereinafter, the prepreg of the present invention will be described in detail.
The prepreg of the present invention is formed by impregnating or coating the above-mentioned compatibilizing resin composition on Q glass cloth. The prepreg of the present invention can be produced by impregnating or coating the compatibilizing resin composition used in the present invention into a Q glass cloth and semi-curing (B-stage) by heating or the like. .
As the shape of the Q glass cloth, for example, it has a shape such as a woven fabric, a non-woven fabric, a roving, a chopped strand mat, and a surfacing mat, but the material and shape are selected depending on the intended use and performance of the molded product, If necessary, one or two or more materials and shapes can be combined. Q glass cloth means a glass fiber in which the content of silicon dioxide occupies 90% by mass or more (for example, IPC standard 2116 type cloth or IPC standard 1035 type cloth). The thickness of the Q glass cloth is not particularly limited. For example, a thickness of 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 opened. A thing is suitable from the surface of heat resistance, moisture resistance, and workability. After impregnating or coating the base material so that the amount of the resin composition attached to the base material is 20 to 90% by mass in terms of the resin content of the prepreg after drying, the temperature is usually 100 to 200 ° C. And dried for 1 to 30 minutes and semi-cured (B-stage).
Through the above steps, the prepreg of the present invention can be obtained.
本発明の積層板は、前述の本発明のプリプレグを用いて、所定の枚数を積層成形して、製造することができる。本発明のプリプレグを、例えば、１〜２０枚重ね、その片面又は両面に銅及びアルミニウム等の金属箔を配置した構成で積層成形することにより製造することができる。金属箔は、電気絶縁材料用途で用いるものであれば特に制限されない。また、成形条件は、例えば、電気絶縁材料用積層板及び多層板の手法が適用でき、例えば多段プレス、多段真空プレス、連続成形、オートクレーブ成形機等を使用し、温度１００〜２５０℃、圧力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。
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プリント配線板とすることができる。
The laminate of the present invention can be produced by laminating a predetermined number of sheets using the prepreg of the present invention described above. The prepreg of the present invention can be produced, for example, by laminating 1 to 20 sheets and laminating and forming a metal foil such as copper and aluminum on one or both sides thereof. The metal foil is not particularly limited as long as it is used for electrical insulating material applications. 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 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.
These laminated boards can be made into a printed 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（ａ）としてアルコール変性シロキサン樹脂（信越化学工業株式会社製；商品名Ｘ−２２−４０３９、水酸基当量；９５０）：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６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樹脂の生成物のピークが確認された。
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. As a compound (b) having bisphenol A type cyanate resin (manufactured by Lonza Japan Co., Ltd .; trade name Primaset BADCy): 600.0 g, a structure represented by the general formula (I), and at least two reactivity in the side chain Alcohol-modified siloxane resin (manufactured by Shin-Etsu Chemical Co., Ltd .; trade name X-22-4039, hydroxyl group equivalent; 950): 200.0 g and at least two epoxies per molecule as the siloxane resin (a) having a substituent Biphenyl type epoxy resin (made by Japan Epoxy Resin Co., Ltd .; trade name YX-4000, epoxy equivalent) as the compound (c) having a group 186): and 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 6 ° C. for 6 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 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 at about 10.9 minutes vicinity and 8.0-10.0 vicinity was 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、アミン変性シロキサン樹脂（信越化学工業株式会社製；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。
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, amine-modified siloxane resin (manufactured by Shin-Etsu Chemical Co., Ltd .; trade name KF-864, amino group equivalent; 3,800): 100.0 g, naphthol aralkyl-cresol copolymer 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. 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.
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、カルボキシル変性シロキサン樹脂（信越化学工業株式会社製；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３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。
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 500-1,000): 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, and 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. 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 3 ° C. for 3 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.
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、エポキシ変性シロキサン樹脂（信越化学工業株式会社製；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（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。
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, epoxy-modified siloxane resin (manufactured by Shin-Etsu Chemical Co., Ltd .; product name KF-1001, epoxy group equivalent: 3,500): 500.0 g, naphthalene type epoxy resin ( Made 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.
製造例５：相容化樹脂（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（ロンザジャパン株式会社製；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（信越化学工業株式会社製；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６時間反応を行った。その後、室温に冷却し相容化樹脂（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樹脂の生成物のピークが確認された。
Production Example 5: Production of compatibilizing resin (1-5) A novolak-type cyanate resin (manufactured by Lonza Japan Co., Ltd.) was added to a reaction vessel having a volume of 3 liters that can be heated and cooled with a thermometer, a stirrer, and a reflux condenser. Trade name Primaset PT-15, weight average molecular weight 500 to 1,000): 600.0 g, thiol-modified siloxane resin (manufactured by Shin-Etsu Chemical Co., Ltd .; trade name KF-2001, thiol group equivalent; 1,900): 200.0 g, biphenyl type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd .; trade name YX-4000, epoxy equivalent; 186): 200.0 g and toluene: 1000.0 g were 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 6 ° C. for 6 hours. Then, it cooled to room temperature and obtained the solution of compatibilizing 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 at about 10.9 minutes vicinity and 8.0-10.0 vicinity was confirmed.
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（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 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 Co., Ltd .; trade name SO-25R): 700.0 g and propylene glycol monomethyl ether: 1000.0 g were mixed and stirred with N-phenyl-3-aminopropyltrimethoxysilane (Shin-Etsu) Chemical Industry 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.
（実施例１〜６、比較例１〜６）
製造例１〜４により得られた成分（１）の相容化樹脂、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Ｑガラスクロスに含浸し、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、線熱膨張係数と比誘電率及び誘電正接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 1-6)
Component (1) compatibilizing resin obtained in Production Examples 1 to 4, and Production Example 5 or commercially available component (2), and optionally component (3), curing accelerator, and dilution Using methyl ethyl ketone as a solvent, the mixture was mixed at the blending ratio (parts by mass) shown in Tables 1 and 2 to obtain a uniform varnish having a resin content of 60% by mass. Next, the varnish was impregnated into a 0.2 mm thick Q glass cloth and dried by heating at 160 ° C. for 10 minutes to obtain a prepreg having a resin content of 55 mass%. 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, the linear thermal expansion coefficient, relative dielectric constant, and dielectric loss tangent were measured and evaluated by the following methods. Tables 3 and 4 show the measurement and evaluation results.
（１）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。
（２）比誘電率及び誘電正接の測定
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１００ｍｍ×２ｍｍの評価基板を作製し、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。
(1) Measurement of linear thermal expansion coefficient A 5-mm square evaluation board | substrate which removed the copper foil was produced by immersing a copper clad laminated board in copper etching liquid, and it evaluated using a TMA test device (the DuPont make, TMA2940). The linear thermal expansion coefficient of 30 to 100 ° C. in the surface direction of the substrate was measured.
(2) Measurement of relative dielectric constant and dielectric loss tangent A 100 mm × 2 mm evaluation board from which a copper foil was removed by immersing a copper clad laminate in a copper etching solution was prepared, 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.
表中の数字は、固形分の質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１．０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１．０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−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：ナフテン酸亜鉛の８質量％ミネラルスピリット溶液
*６：信越石英株式会社製：＃２１１６スタイルＱガラスクロス（８５μｍ）（ＳＱＦ−２１１６ＡＣ）
*７：日東紡績株式会社製：＃２１１６スタイルＳガラスクロス（９０μｍ）（ＧＡＴ−７０１０）
The numbers in the table are indicated by mass parts of solid content. Each order is
* 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% by mass of N-phenyl-3-aminopropyltrimethoxysilane based on the fused silica (manufactured by Admatech Co., Ltd .; trade name SC-2050HNK, diluent solvent: cyclohexanone)
* 3: Boehmite type aluminum hydroxide (manufactured by Kawai Lime Industry Co., Ltd .; trade name BMT-3L, thermal decomposition temperature: 400 ° C.)
* 4: Inorganic flame retardant aid with zinc molybdate supported on talc (manufactured by Sherwin Williams; trade name Chemguard 1100)
* 5: 8% by mass mineral spirit solution of zinc naphthenate
* 6: Shin-Etsu Quartz Co., Ltd .: # 2116 Style Q Glass Cloth (85 μm) (SQF-2116AC)
* 7: Nitto Boseki Co., Ltd .: # 2116 style S glass cloth (90 μm) (GAT-7010)
実施例で示していないが、ピーク面積の消失率が１８％の樹脂を用いたものは、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％の樹脂を用いたものは、成形性が不良であり積層板を作製できなかった。シロキサン樹脂（ａ）と、シアネート基を有する化合物（ｂ）のみをプレ反応させエポキシ樹脂を配合したものは、樹脂が分離し、プリプレグ及び積層板を作製できなかった。
表から明らかなように、本発明の実施例は、低熱膨張性、比誘電率及び誘電正接に優れている。一方、比較例は、低熱膨張性、比誘電率及び誘電正接のいずれにおいても特性に劣っている。
本発明で用いる相容化樹脂組成物をＱガラスクロス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、良好な低熱膨張率、及び低誘電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。
Although not shown in the examples, those using a resin with a peak area disappearance rate of 18% were unable to produce a varnish due to the deposition of a thermosetting resin. A resin using a resin with a peak area disappearance rate of 76% had poor moldability and could not produce a laminate. When the siloxane resin (a) and the compound (b) having a cyanate group were pre-reacted and the epoxy resin was blended, the resin was separated and a prepreg and a laminate could not be produced.
As is apparent from the table, the examples of the present invention are excellent in low thermal expansion, relative permittivity, and dielectric loss tangent. On the other hand, the comparative example is inferior in characteristics in all of low thermal expansion, specific permittivity, and dielectric loss tangent.
A prepreg obtained by impregnating or coating a compatibilizing resin composition used in the present invention on Q glass cloth, and a copper clad laminate produced by laminating the prepreg have a good low thermal expansion coefficient and low It exhibits dielectric properties and is useful for printed wiring boards for electronic equipment.
Claims (5)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109810468A (en) * | 2019-01-25 | 2019-05-28 | 常熟生益科技有限公司 | A kind of compositions of thermosetting resin and prepreg and laminate using its preparation |
| CN109867912A (en) * | 2019-01-25 | 2019-06-11 | 苏州生益科技有限公司 | A kind of compositions of thermosetting resin and prepreg and laminate using its preparation |
| JP2021091814A (en) * | 2019-12-11 | 2021-06-17 | 味の素株式会社 | Resin composition |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109810468A (en) * | 2019-01-25 | 2019-05-28 | 常熟生益科技有限公司 | A kind of compositions of thermosetting resin and prepreg and laminate using its preparation |
| CN109867912A (en) * | 2019-01-25 | 2019-06-11 | 苏州生益科技有限公司 | A kind of compositions of thermosetting resin and prepreg and laminate using its preparation |
| CN109810468B (en) * | 2019-01-25 | 2021-12-28 | 常熟生益科技有限公司 | Thermosetting resin composition, and prepreg and laminated board prepared from thermosetting resin composition |
| JP2021091814A (en) * | 2019-12-11 | 2021-06-17 | 味の素株式会社 | Resin composition |
| JP7298466B2 (en) | 2019-12-11 | 2023-06-27 | 味の素株式会社 | resin composition |
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