JP4487448B2 - Resin material with wiring circuit, manufacturing method thereof and multilayer printed wiring board - Google Patents
Resin material with wiring circuit, manufacturing method thereof and multilayer printed wiring board Download PDFInfo
- Publication number
- JP4487448B2 JP4487448B2 JP2001190565A JP2001190565A JP4487448B2 JP 4487448 B2 JP4487448 B2 JP 4487448B2 JP 2001190565 A JP2001190565 A JP 2001190565A JP 2001190565 A JP2001190565 A JP 2001190565A JP 4487448 B2 JP4487448 B2 JP 4487448B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- wiring circuit
- silicone polymer
- layer
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920005989 resin Polymers 0.000 title claims description 246
- 239000011347 resin Substances 0.000 title claims description 246
- 239000000463 material Substances 0.000 title claims description 50
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 229920005573 silicon-containing polymer Polymers 0.000 claims description 92
- 229910052751 metal Inorganic materials 0.000 claims description 37
- 239000002184 metal Substances 0.000 claims description 37
- 239000011888 foil Substances 0.000 claims description 33
- 239000011342 resin composition Substances 0.000 claims description 30
- 239000003795 chemical substances by application Substances 0.000 claims description 26
- 239000011256 inorganic filler Substances 0.000 claims description 25
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 25
- 238000009864 tensile test Methods 0.000 claims description 4
- 238000013329 compounding Methods 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 86
- -1 chlorine and bromine Chemical class 0.000 description 83
- 229910000077 silane Inorganic materials 0.000 description 61
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 25
- 239000002966 varnish Substances 0.000 description 23
- 239000000126 substance Substances 0.000 description 22
- 125000000524 functional group Chemical group 0.000 description 21
- 239000011889 copper foil Substances 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 238000002156 mixing Methods 0.000 description 18
- 239000002904 solvent Substances 0.000 description 18
- 238000012545 processing Methods 0.000 description 16
- 238000006459 hydrosilylation reaction Methods 0.000 description 15
- 238000001035 drying Methods 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 230000001588 bifunctional effect Effects 0.000 description 13
- 229920001187 thermosetting polymer Polymers 0.000 description 13
- 238000005530 etching Methods 0.000 description 12
- 229920002545 silicone oil Polymers 0.000 description 12
- 239000000460 chlorine Substances 0.000 description 10
- 229920001971 elastomer Polymers 0.000 description 10
- 239000000806 elastomer Substances 0.000 description 10
- 150000004756 silanes Chemical class 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 230000007062 hydrolysis Effects 0.000 description 9
- 238000006460 hydrolysis reaction Methods 0.000 description 9
- 238000010030 laminating Methods 0.000 description 9
- 238000006068 polycondensation reaction Methods 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 239000003822 epoxy resin Substances 0.000 description 8
- 239000011229 interlayer Substances 0.000 description 8
- 229920000647 polyepoxide Polymers 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 125000001339 silanediyl group Chemical group [H][Si]([H])(*)* 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 125000003700 epoxy group Chemical group 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 125000000962 organic group Chemical group 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000012744 reinforcing agent Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229910000679 solder Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229910020447 SiO2/2 Inorganic materials 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 230000010354 integration Effects 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002759 woven fabric Substances 0.000 description 3
- LLPKQRMDOFYSGZ-UHFFFAOYSA-N 2,5-dimethyl-1h-imidazole Chemical compound CC1=CN=C(C)N1 LLPKQRMDOFYSGZ-UHFFFAOYSA-N 0.000 description 2
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920002367 Polyisobutene Polymers 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229910001128 Sn alloy Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000005456 alcohol based solvent Substances 0.000 description 2
- 125000005370 alkoxysilyl group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 239000004210 ether based solvent Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000005453 ketone based solvent Substances 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- ABJSOROVZZKJGI-OCYUSGCXSA-N (1r,2r,4r)-2-(4-bromophenyl)-n-[(4-chlorophenyl)-(2-fluoropyridin-4-yl)methyl]-4-morpholin-4-ylcyclohexane-1-carboxamide Chemical compound C1=NC(F)=CC(C(NC(=O)[C@H]2[C@@H](C[C@@H](CC2)N2CCOCC2)C=2C=CC(Br)=CC=2)C=2C=CC(Cl)=CC=2)=C1 ABJSOROVZZKJGI-OCYUSGCXSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- FBHPRUXJQNWTEW-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=CN1CC1=CC=CC=C1 FBHPRUXJQNWTEW-UHFFFAOYSA-N 0.000 description 1
- UGIJCMNGQCUTPI-UHFFFAOYSA-N 2-aminoethyl prop-2-enoate Chemical compound NCCOC(=O)C=C UGIJCMNGQCUTPI-UHFFFAOYSA-N 0.000 description 1
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 description 1
- QUPKCFBHJFNUEW-UHFFFAOYSA-N 2-ethyl-4,5-dihydro-1h-imidazole Chemical compound CCC1=NCCN1 QUPKCFBHJFNUEW-UHFFFAOYSA-N 0.000 description 1
- DBKWLERLIZHXIJ-UHFFFAOYSA-N 2-ethyl-5-methyl-1h-imidazole;2-phenyl-1h-imidazole Chemical compound CCC1=NC=C(C)N1.C1=CNC(C=2C=CC=CC=2)=N1 DBKWLERLIZHXIJ-UHFFFAOYSA-N 0.000 description 1
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-UHFFFAOYSA-N 0.000 description 1
- NCVGSSQICKMAIA-UHFFFAOYSA-N 2-heptadecyl-4,5-dihydro-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NCCN1 NCVGSSQICKMAIA-UHFFFAOYSA-N 0.000 description 1
- VWSLLSXLURJCDF-UHFFFAOYSA-N 2-methyl-4,5-dihydro-1h-imidazole Chemical compound CC1=NCCN1 VWSLLSXLURJCDF-UHFFFAOYSA-N 0.000 description 1
- BKCCAYLNRIRKDJ-UHFFFAOYSA-N 2-phenyl-4,5-dihydro-1h-imidazole Chemical compound N1CCN=C1C1=CC=CC=C1 BKCCAYLNRIRKDJ-UHFFFAOYSA-N 0.000 description 1
- FUOZJYASZOSONT-UHFFFAOYSA-N 2-propan-2-yl-1h-imidazole Chemical compound CC(C)C1=NC=CN1 FUOZJYASZOSONT-UHFFFAOYSA-N 0.000 description 1
- BTYIFQSAIPDZQW-UHFFFAOYSA-N 2-propan-2-yl-4,5-dihydro-1h-imidazole Chemical compound CC(C)C1=NCCN1 BTYIFQSAIPDZQW-UHFFFAOYSA-N 0.000 description 1
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 1
- FQHUDZKKDCTQET-UHFFFAOYSA-N 2-undecyl-4,5-dihydro-1h-imidazole Chemical compound CCCCCCCCCCCC1=NCCN1 FQHUDZKKDCTQET-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- CPHGOBGXZQKCKI-UHFFFAOYSA-N 4,5-diphenyl-1h-imidazole Chemical compound N1C=NC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 CPHGOBGXZQKCKI-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QYIMZXITLDTULQ-UHFFFAOYSA-N 4-(4-amino-2-methylphenyl)-3-methylaniline Chemical group CC1=CC(N)=CC=C1C1=CC=C(N)C=C1C QYIMZXITLDTULQ-UHFFFAOYSA-N 0.000 description 1
- XPAQFJJCWGSXGJ-UHFFFAOYSA-N 4-amino-n-(4-aminophenyl)benzamide Chemical compound C1=CC(N)=CC=C1NC(=O)C1=CC=C(N)C=C1 XPAQFJJCWGSXGJ-UHFFFAOYSA-N 0.000 description 1
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 1
- JJUVAPMVTXLLFR-UHFFFAOYSA-N 5-methyl-2-phenyl-4,5-dihydro-1h-imidazole Chemical compound N1C(C)CN=C1C1=CC=CC=C1 JJUVAPMVTXLLFR-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000004343 Calcium peroxide Substances 0.000 description 1
- 229910004726 HSiO3/2 Inorganic materials 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 1
- 229910020485 SiO4/2 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 125000004423 acyloxy 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
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229940118662 aluminum carbonate Drugs 0.000 description 1
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229940045985 antineoplastic platinum compound Drugs 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- ZJRXSAYFZMGQFP-UHFFFAOYSA-N barium peroxide Chemical compound [Ba+2].[O-][O-] ZJRXSAYFZMGQFP-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- LHJQIRIGXXHNLA-UHFFFAOYSA-N calcium peroxide Chemical compound [Ca+2].[O-][O-] LHJQIRIGXXHNLA-UHFFFAOYSA-N 0.000 description 1
- 235000019402 calcium peroxide Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012993 chemical processing Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- AQEFLFZSWDEAIP-UHFFFAOYSA-N di-tert-butyl ether Chemical compound CC(C)(C)OC(C)(C)C AQEFLFZSWDEAIP-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- XYYQWMDBQFSCPB-UHFFFAOYSA-N dimethoxymethylsilane Chemical compound COC([SiH3])OC XYYQWMDBQFSCPB-UHFFFAOYSA-N 0.000 description 1
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- DLINORNFHVEIFE-UHFFFAOYSA-N hydrogen peroxide;zinc Chemical compound [Zn].OO DLINORNFHVEIFE-UHFFFAOYSA-N 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N methyl cyanide Natural products CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- CLDVQCMGOSGNIW-UHFFFAOYSA-N nickel tin Chemical compound [Ni].[Sn] CLDVQCMGOSGNIW-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- UHCGLDSRFKGERO-UHFFFAOYSA-N strontium peroxide Chemical compound [Sr+2].[O-][O-] UHCGLDSRFKGERO-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- DIHAURBCYGTGCV-UHFFFAOYSA-N xi-4,5-Dihydro-2,4(5)-dimethyl-1H-imidazole Chemical compound CC1CN=C(C)N1 DIHAURBCYGTGCV-UHFFFAOYSA-N 0.000 description 1
- 229940105296 zinc peroxide Drugs 0.000 description 1
Images
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Production Of Multi-Layered Print Wiring Board (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、配線回路付き樹脂材料及びその製造方法と多層プリント配線板に関する。
【０００２】
【従来の技術】
電子機器に広く用いられているプリント配線板は、金属はく張積層板に配線回路加工を施して得られる。この金属はく張積層板としては、織布基材に熱硬化性樹脂組成物の樹脂ワニスを含浸乾燥して得られるプリプレグを金属はくとともに積層成形したものが広く用いられていた。すなわち、絶縁基材層が熱硬化性樹脂組成物の硬化物と織布基材とからなりこれに金属はくが接着された構造となっていた。なお、単にプリント配線板というときは、両面プリント配線板のほか多層プリント配線板を含む。また、従来汎用の多層プリント配線板は、両面プリント配線板と金属はくとをプリプレグや樹脂シートを介して加熱加圧して接着一体化し得た内層配線回路入り金属はく張多層積層板に配線回路加工を施して得られたものであった。４層金属はく張積層板は、両面プリント配線板１枚の両面に金属はくを接着一体化したものであり、６層金属はく張積層板は、両面プリント配線板２枚の間にプリプレグや樹脂シートを介し、さらに、その両面に金属はくを接着一体化したものであった。
【０００３】
近年、電子機器の小型化にともない、プリント配線板も薄型化し、さらに、配線を高密度化する必要がでてきている。材料として織布基材を用いると、薄型化には限度があることから、金属はく張多層積層板の製造において、樹脂シートを用いることが提案された。
【０００４】
【発明が解決しようとする課題】
電子機器の小型軽量化、高性能化、低コスト化が進行し、プリント配線板には高密度化、薄型化、高信頼性化、低コスト化が要求されている。高密度化のためには、微細配線が必要であり、そのためには表面の平坦性が良好でなくてはならない。表面の平坦性を良好にするためには、研磨加工が有効であるが、工程数が多くなりコストが高くなることや、均一な厚みを得ることが困難などの問題があった。また、多層化する場合も高密度化のためには、微細配線が必要であり、そのためには表面の平坦性が良好でなくてはならない。表面の平坦性を良好にするためには、内層の配線を研磨加工し、平坦化することが有効であるが、工程数が多くなりコストが高くなることや、均一な厚みに加工するのが難しいことなどの問題があった。そこで、柔軟な樹脂シートを使用し、成形時に配線を樹脂シートに潜り込ませる方法が考えられる。一般の配線板用樹脂シートに配線を潜り込ませるためには、樹脂シートが柔軟である必要がある。このため、樹脂を半硬化状態で使用することが考えられる。しかし、半硬化の状態では配線を形成するためのエッチング処理に樹脂が耐えられず，樹脂の分解が起こり、絶縁層としての役割を成さなくなる。また、樹脂を硬化させた状態で配線を潜り込ませるまで柔軟にするためには，柔軟成分としてエラストマなどを配合することも考えられるが、樹脂シートにエラストマを使用すると吸水率が高くなり、耐熱性が悪くなるなどの問題がある。
【０００５】
【課題を解決するための手段】
上記の問題を解決する手段として、半硬化の状態でもエッチング液などの薬液に対して、分解が起こらず、絶縁層としての役割を果たし、かつ成形時に配線を樹脂シートに潜り込ませることが可能で，成形後の配線の凹凸が無く、表面の平坦化が可能であり、微細配線に適した樹脂材料を本発明にて提案する。
【０００６】
本発明は、以下に記載の各事項に関する。
（１）樹脂硬化性シリコーン重合体、硬化剤及び無機充填剤を含有してなる樹脂組成物からなるＢ−Ｓｔａｇｅ状態の絶縁樹脂層上に配線回路層を有する配線回路付き樹脂材料。
（２）樹脂硬化性シリコーン重合体、硬化剤及び無機充填剤を含有してなる樹脂組成物からなるＢ−Ｓｔａｇｅ状態の絶縁樹脂シートと、その絶縁樹脂シート上に設けられた配線回路層とからなる（１）記載の配線回路付き樹脂材料。
（３）樹脂硬化性シリコーン重合体、硬化剤及び無機充填剤を含有してなる樹脂組成物からなる内層回路板上に設けられたＢ−Ｓｔａｇｅ状態の絶縁樹脂層と、さらにその絶縁樹脂層上に設けられた配線回路からなる（１）記載の配線回路付き樹脂材料。
（４）絶縁樹脂層を形成する樹脂組成物中の樹脂硬化性シリコーン重合体１００重量部に対する無機充填剤の配合量が１００重量部以上である（１）〜（３）のいずれかに記載の配線回路付き樹脂材料。
（５）絶縁樹脂層が樹脂硬化性シリコーン重合体１００重量部、硬化剤０．８〜１当量及び無機充填剤１００〜２０００重量部を含有してなる樹脂組成物からなる（４）に記載の配線回路付き樹脂材料。
（６）絶縁樹脂層が、硬化物の熱膨張係数が５０×１０-6／℃以下である樹脂組成物を使用して形成される絶縁樹脂層であることを特徴とする（１）〜（５）のいずれかに記載の配線回路付き樹脂材料。
（７）絶縁樹脂層が、硬化物の引張試験での伸びが１．０％以上である樹脂組成物を使用して形成される絶縁樹脂層であることを特徴とする（１）〜（６）のいずれかに記載の配線回路付き樹脂材料。
【０００７】
（８）（２）に記載の配線回路付き樹脂材料と内層板とを重ねて加熱加圧成形するプリント配線板の製造方法。
（９）樹脂硬化性シリコーン重合体、硬化剤及び無機充填剤を含有してなる樹脂組成物からなりＢ−Ｓｔａｇｅ状態である絶縁樹脂層と該絶縁樹脂層上に配設された金属箔とを含む積層体から不要な金属をエッチング除去して回路形成することを特徴とする配線回路付き樹脂材料の製造方法。
（１０）樹脂硬化性シリコーン重合体１００重量部に対する無機充填剤の配合量が１００重量部以上であることを特徴とする（９）に記載の配線回路付き樹脂材料の製造方法。
（１１）絶縁樹脂層が樹脂硬化性シリコーン重合体１００重量部、無機充填剤１００〜２０００重量部及び硬化剤を樹脂硬化性シリコーン重合体に対して０．８〜１当量を含有してなる樹脂組成物からなることを特徴とする（９）に記載の配線回路付き樹脂材料の製造方法。
【０００８】
【発明の実施の形態】
本発明における配線回路付き樹脂材料とは、十分な回路埋め込み性を有する状態の絶縁層上に配線回路が形成された樹脂材料であり、例えば、Ｂ−Ｓｔａｇｅ状態の熱硬化性樹脂シート上に配線回路が形成された配線回路付き樹脂シートや、内層回路板上に設けられたＢ−Ｓｔａｇｅ状態の熱硬化性樹脂からなる絶縁層の上にさらに配線回路が形成された配線板材料などが挙げられる。なお、本発明におけるＢ−Ｓｔａｇｅ状態とは、樹脂ワニス化に用いる溶剤と同じ溶剤に樹脂を浸漬し、２５℃で１時間攪拌した場合に樹脂分の５〜９５重量％が溶解せずに残る硬化状態である。樹脂分の溶解せずに残る量が９５重量％を越える硬化状態をＣ−Ｓｔａｇｅ状態、５重量％未満の硬化状態をＡ−Ｓｔａｇｅ状態とする。
【０００９】
本発明における絶縁樹脂としては、十分な回路埋め込み性を有する状態においても、配線回路加工時における金属のエッチング除去などの薬品処理に対して必要な耐薬品性を満足する樹脂を用いる。Ｂ−Ｓｔａｇｅ状態で必要な耐薬品性を満足する熱硬化性樹脂を用いることが好ましい。また、多層配線板とした場合の層間導通路などの接続信頼性を考慮すると絶縁樹脂硬化物の熱膨張係数が５０×１０-6／℃以下である樹脂を用いることが好ましく、熱膨張係数が３０×１０-6／℃以下である樹脂を用いることがさらに好ましく、熱膨張係数が１５×１０-6／℃以下である樹脂を用いることが特に好ましい。多層配線板作製時の取り扱い性や多層配線板としたときの信頼性の観点から、硬化物の引張試験での伸びが１．０％以上である樹脂を用いることが好ましく、伸びが２．０％以上である樹脂を用いることが特に好ましい。このような樹脂の例としては、樹脂硬化性シリコーン重合体とその硬化剤及び無機充填剤を含有してなる樹脂組成物が挙げられる。
【００１０】
前記樹脂硬化性シリコーン重合体は、一般式（Ｉ）
【化１】
Ｒ′m（Ｈ）kＳｉＸ4-(m+k) （Ｉ）
（式中Ｘは、加水分解、重縮合可能な基であり、例えば、塩素、臭素等のハロゲン又は−ＯＲを示し、ここで、Ｒは炭素数１〜４のアルキル基、炭素数１〜４のアルキルカルボニル基を示す。Ｒ′は、非反応性の基であり、例えば、炭素数１〜４のアルキル基、フェニル基等のアリール基を示す。ｋは１又は２、ｍは０又は１、ｍ＋ｋは１又は２を意味する）で表されるシラン化合物とヒドロシリル化反応剤とを反応させて得ることができる。一般式（Ｉ）のシラン化合物は加水分解、重縮合によってＳｉ−Ｈ基含有シリコーン重合体とされ、ヒドロシリル化反応剤をＳｉ−Ｈ基含有シリコーン重合体のＳｉ−Ｈ基との間でヒドロシリル化反応させて、樹脂硬化性官能基が導入されたシリコーン重合体が得られる。
【００１１】
一般式（Ｉ）のＳｉ−Ｈ基含有シラン化合物に一般式（ＩＩ）
【化２】
Ｒ′nＳｉＸ4-n （ＩＩ）
（式中Ｒ′及びＸは一般式（Ｉ）に同じであり、ｎは０〜２の整数を意味する。）
で表されるシラン化合物を併用することができる。
【００１２】
前記一般式（Ｉ）で表されるＳｉ−Ｈ基含有シラン化合物は、具体的には
【化３】
ＨＣＨ3Ｓｉ（ＯＣＨ3）2、ＨＣ2Ｈ5Ｓｉ（ＯＣＨ3）2、
Ｈ3ＣＨ7Ｓｉ（ＯＣＨ3）2、ＨＣ4Ｈ9Ｓｉ（ＯＣＨ3）2、
ＨＣＨ3Ｓｉ（ＯＣ2Ｈ5）2、ＨＣ2Ｈ5Ｓｉ（ＯＣ2Ｈ5）2、
ＨＣ3Ｈ7Ｓｉ（ＯＣ2Ｈ5）2、ＨＣ4Ｈ9Ｓｉ（ＯＣ2Ｈ5）2、
ＨＣＨ3Ｓｉ（ＯＣ3Ｈ7）2、ＨＣ2Ｈ5Ｓｉ（ＯＣ3Ｈ7）2、
ＨＣ3Ｈ7Ｓｉ（ＯＣ3Ｈ7）2、ＨＣ4Ｈ9Ｓｉ（ＯＣ3Ｈ7）2、
ＨＣＨ3Ｓｉ（ＯＣ4Ｈ9）2、ＨＣ2Ｈ5Ｓｉ（ＯＣ4Ｈ9）2、
ＨＣ3Ｈ7Ｓｉ（ＯＣ4Ｈ9）2、ＨＣ4Ｈ9Ｓｉ（ＯＣ4Ｈ9）2、
等のアルキルジアルコキシシラン
【００１３】
【化４】
Ｈ2Ｓｉ（ＯＣＨ3）2、Ｈ2Ｓｉ（ＯＣ2Ｈ5）2、
Ｈ2Ｓｉ（ＯＣ3Ｈ7）2、Ｈ2Ｓｉ（ＯＣ4Ｈ9）2、
等のジアルコキシシラン
【００１４】
【化５】
ＨＰｈＳｉ（ＯＣＨ3）2、ＨＰｈＳｉ（ＯＣ2Ｈ5）2、ＨＰｈＳｉ（ＯＣ3Ｈ7）2、
ＨＰｈＳｉ（ＯＣ4Ｈ9）2、
（ただし、Ｐｈはフェニル基を示す。以下同様）
等のフェニルジアルコキシシラン
【００１５】
【化６】
Ｈ2Ｓｉ（ＯＣＨ3）2、Ｈ2Ｓｉ（ＯＣ2Ｈ5）2、Ｈ2Ｓｉ（ＯＣ3Ｈ7）2、
Ｈ2Ｓｉ（ＯＣ4Ｈ9）2、
等のジアルコキシシランなどの２官能性シラン化合物（以下、シラン化合物における官能性とは、縮合反応性の官能基を有することを意味する。）
【００１６】
【化７】
ＨＳｉ（ＯＣＨ3）3、ＨＳｉ（ＯＣ2Ｈ5）3、ＨＳｉ（ＯＣ3Ｈ7）3、
ＨＳｉ（ＯＣ4Ｈ9）3、
等のトリアルコキシシランなどの３官能性シラン化合物などがある。
【００１７】
一般式（ＩＩ）で表されるシラン化合物は、具体的には、
【化８】
Ｓｉ（ＯＣＨ3）4、Ｓｉ（ＯＣ2Ｈ5）4、
Ｓｉ（ＯＣ3Ｈ7）4、Ｓｉ（ＯＣ4Ｈ9）4
等のテトラアルコキシシラン
などの４官能性シラン化合物、
【００１８】
【化９】
Ｈ3ＣＳｉ（ＯＣＨ3）3、Ｈ5Ｃ2Ｓｉ（ＯＣＨ3）3、
Ｈ7Ｃ3Ｓｉ（ＯＣＨ3）3、Ｈ9Ｃ4Ｓｉ（ＯＣＨ3）3、
Ｈ3ＣＳｉ（ＯＣ2Ｈ5）3、Ｈ5Ｃ2Ｓｉ（ＯＣ2Ｈ5）3、
Ｈ7Ｃ3Ｓｉ（ＯＣ2Ｈ5）3、Ｈ9Ｃ4Ｓｉ（ＯＣ2Ｈ5）3、
Ｈ3ＣＳｉ（ＯＣ3Ｈ7）3、Ｈ5Ｃ2Ｓｉ（ＯＣ3Ｈ7）3、
Ｈ7Ｃ3Ｓｉ（ＯＣ3Ｈ7）3、Ｈ9Ｃ4Ｓｉ（ＯＣ3Ｈ7）3、
Ｈ3ＣＳｉ（ＯＣ4Ｈ9）3、Ｈ5Ｃ2Ｓｉ（ＯＣ4Ｈ9）3、
Ｈ7Ｃ3Ｓｉ（ＯＣ4Ｈ9）3、Ｈ9Ｃ4Ｓｉ（ＯＣ4Ｈ9）3、
等のモノアルキルトリアルコキシシラン、
【００１９】
【化１０】
ＰｈＳｉ（ＯＣＨ3）3、ＰｈＳｉ（ＯＣ2Ｈ5）3、
ＰｈＳｉ（ＯＣ3Ｈ7）3、ＰｈＳｉ（ＯＣ4Ｈ9）3
（ただし、Ｐｈはフェニル基を示す。以下同様）
等のフェニルトリアルコキシシラン、
【００２０】
【化１１】
（Ｈ3ＣＣＯＯ）3ＳｉＣＨ3、（Ｈ3ＣＣＯＯ）3ＳｉＣ2Ｈ5、
（Ｈ3ＣＣＯＯ）3ＳｉＣ3Ｈ7、（Ｈ3ＣＣＯＯ）3ＳｉＣ4Ｈ9
等のモノアルキルトリアシルオキシシラン
【００２１】
【化１２】
Ｃｌ3ＳｉＣＨ3、Ｃｌ3ＳｉＣ2Ｈ5、
Ｃｌ3ＳｉＣ3Ｈ7、Ｃｌ3ＳｉＣ4Ｈ9
Ｂｒ3ＳｉＣＨ3、Ｂｒ3ＳｉＣ2Ｈ5、
Ｂｒ3ＳｉＣ3Ｈ7、Ｂｒ3ＳｉＣ4Ｈ9
等のモノアルキルトリハロゲノシランなどの３官能性シラン化合物、
【００２２】
【化１３】
（Ｈ3Ｃ）2Ｓｉ（ＯＣＨ3）2、（Ｈ5Ｃ2）2Ｓｉ（ＯＣＨ３）2、
（Ｈ7Ｃ3）2Ｓｉ（ＯＣＨ3）2、（Ｈ9Ｃ4）2Ｓｉ（ＯＣＨ3）2、
（Ｈ３Ｃ）2Ｓｉ（ＯＣ2Ｈ5）2、（Ｈ5Ｃ2）2Ｓｉ（ＯＣ2Ｈ5）2、
（Ｈ7Ｃ3）2Ｓｉ（ＯＣ2Ｈ5）2、（Ｈ9Ｃ4）2Ｓｉ（ＯＣ2Ｈ5）2、
（Ｈ3Ｃ）2Ｓｉ（ＯＣ3Ｈ7）2、（Ｈ5Ｃ2）2Ｓｉ（ＯＣ3Ｈ7）2、
（Ｈ7Ｃ3）2Ｓｉ（ＯＣ3Ｈ7）2、（Ｈ9Ｃ4）2Ｓｉ（ＯＣ3Ｈ7）2、
（Ｈ3Ｃ）2Ｓｉ（ＯＣ4Ｈ9）2、（Ｈ5Ｃ2）2Ｓｉ（ＯＣ4Ｈ9）2、
（Ｈ7Ｃ3）2Ｓｉ（ＯＣ4Ｈ9）2、（Ｈ9Ｃ4）2Ｓｉ（ＯＣ4Ｈ9）2
等のジアルキルジアルコキシシラン、
【００２３】
【化１４】
Ｐｈ2Ｓｉ（ＯＣＨ3）2、Ｐｈ2Ｓｉ（ＯＣ2Ｈ5）2
等のジフェニルジアルコキシシラン、
【００２４】
【化１５】
（Ｈ3ＣＣＯＯ）2Ｓｉ（ＣＨ3）2、（Ｈ3ＣＣＯＯ）2Ｓｉ（Ｃ2Ｈ5）2、
（Ｈ3ＣＣＯＯ）2Ｓｉ（Ｃ3Ｈ7）2、（Ｈ3ＣＣＯＯ）2Ｓｉ（Ｃ4Ｈ9）2
等のジアルキルジアシルオキシシラン、
【００２５】
【化１６】
Ｃｌ2Ｓｉ（ＣＨ3）2、Ｃｌ2Ｓｉ（Ｃ2Ｈ5）2、
Ｃｌ2Ｓｉ（Ｃ3Ｈ7）3、Ｃｌ2Ｓｉ（Ｃ4Ｈ9）2、
Ｂｒ2Ｓｉ（ＣＨ3）2、Ｂｒ2Ｓｉ（Ｃ2Ｈ5）2、
Ｂｒ2Ｓｉ（Ｃ3Ｈ7）2、Ｂｒ2Ｓｉ（Ｃ4Ｈ9）2
等のアルキルジハロゲノシランなどの２官能性シラン化合物がある。
【００２６】
本発明に用いられる前記一般式（Ｉ）で表されるＳｉ−Ｈ基含有シラン化合物は必須成分として使用され、前記一般式（ＩＩ）で表されるシラン化合物は任意成分とされる。前記一般式（Ｉ）又は前記一般式（ＩＩ）のシラン化合物中に含まれる加水分解・重縮合可能な基としては、反応性などを考慮すると、アルコキシ基が好ましく、前記一般式（Ｉ）で表されるＳｉ−Ｈ基含有シラン化合物としてはトリアルコキシシラン又はモノアルキルジアルコキシシランが特に好ましく、前記一般式（ＩＩ）で表されるシラン化合物としてはテトラアルコキシシラン、モノアルキルトリアルコキシシラン又はジアルキルジアルコキシシランが特に好ましい。また、重合度の大きいシリコーン重合体を製造する場合には一般式（Ｉ）で表されるシラン化合物として、３官能性シラン化合物を含むことが好ましく、一般式（ＩＩ）で表されるシラン化合物を用いる場合には４官能又は３官能の一般式（ＩＩ）で表されるシラン化合物を含むことが好ましい。
【００２７】
本発明のシリコーン重合体の製造方法はシラン化合物の総量に対して、Ｓｉ−Ｈ基含有シラン化合物３５モル％以上配合するものであり、シラン化合物の総量に対して、一般式（Ｉ）で表されるＳｉ−Ｈ基含有シラン化合物３５〜１００モル％（より好ましくは３５〜８５モル％）及び一般式（ＩＩ）で表されるシラン化合物０〜６５モル％（１５〜６５モル％）の割合で使用されることが好ましい。
【００２８】
本発明のシリコーン重合体は三次元架橋しているものであることが好ましい。このため、全シラン化合物のうち３〜１００モル％が３官能以上のシラン化合物であることが好ましく、全シラン化合物のうち３〜７５モル％が３官能以上のシラン化合物であることが特に好ましい。また、シラン化合物のうち１５〜１００モル％が４官能性シラン化合物又は３官能性シラン化合物であることが好ましく、２０〜８５モル％が４官能性シラン化合物又は３官能性シラン化合物であることがより好ましい。すなわち、一般式（ＩＩ）で表されるシラン化合物のうち２官能性シラン化合物は、０〜８５モル％であることが好ましく、より好ましくは０〜８０モル％の割合で使用される。特に好ましくは、一般式（ＩＩ）で表されるシラン化合物のうち４官能性シラン化合物が１５〜１００モル％、より好ましくは２０〜１００モル％、３官能性シラン化合物が０〜８５モル％、より好ましくは０〜８０モル％及び２官能性シラン化合物が０〜８５モル％、より好ましくは０〜８０モル％の割合で使用される。
【００２９】
２官能性シラン化合物が８５モル％を越えると、シリコーン重合体の鎖が長くなり、メチル基等の疎水性基の配向等により無機材料表面に横向きとなる可能性が高く、リジットな層を形成しやすいため、低応力化が難しくなる。
【００３０】
本発明におけるシリコーン重合体は、前記した一般式（Ｉ）で表されるＳｉ−Ｈ基含有シラン化合物と一般式（ＩＩ）で表されるシラン化合物を加水分解・重縮合させ、さらにヒドロシリル化反応して製造されるが、このとき、加水分解・重縮合触媒としては、塩酸、硫酸、リン酸、硝酸、フッ酸等の無機酸、シュウ酸、マレイン酸、スルホン酸、ギ酸等の有機酸を使用することが好ましく、アンモニア、トリメチルアンモニウムなどの塩基性触媒を用いることもできる。これら加水分解・重縮合触媒は、一般式（Ｉ）で表されるＳｉ−Ｈ基含有シラン化合物と一般式（ＩＩ）で表されるシラン化合物の量に応じて適当量用いられるが、好適には一般式（Ｉ）で表されるＳｉ−Ｈ基含有シラン化合物と一般式（ＩＩ）で表されるシラン化合物の合計１モルに対し０．００１〜１０モルの範囲で用いられる。ヒドロシリル化触媒としては、白金、パラジウム、ロジウム系の遷移金属化合物を用いることができ、特に塩化白金酸等の白金化合物を使用することが好ましく、過酸化亜鉛、過酸化カルシウム、過酸化水素、過酸化ジ−ｔｅｒｔ−ブチル、過酸化ストロンチウム、過酸化ナトリウム、過酸化鉛、過酸化バリウム等の過酸化物、また、３級アミン、ホスフィンを用いることもできる。これらヒドロシリル化触媒は、一般式（Ｉ）で表されるＳｉ−Ｈ基含有シラン化合物のＳｉ−Ｈ基１モルに対し、好ましくは０．００００００１〜０．０００１モルの範囲で用いられる。
【００３１】
本発明のヒドロシリル化反応剤は、ビニル基等のヒドロシリル化反応のための二重結合と、エポキシ基やアミノ基等の樹脂硬化性官能基を有しているものである。樹脂硬化性官能基とは有機化合物又は無機化合物と反応又は相互作用する官能基のことである。ここで、この官能基としては、硬化剤又は架橋剤と反応する反応性有機基、自硬化反応する反応性有機基、無機充填剤の表面に存在する官能基と反応又は相互作用しする有機基、水酸基と反応する基等がある。具体例としては、エポキシ基を有するヒドロシリル化反応剤としてアリルグリシジルエーテル等を用いることができ、また、アミノ基を有するヒドロシリル化反応剤としてアリルアミン、塩酸アリルアミン、アミノエチルアクリレート等のアミノアルキルアクリレート、アミノエチルメタクリレート等のアミノアルキルメタクリレートなどを用いることができる。これらヒドロシリル化反応剤は、一般式（Ｉ）で表されるＳｉ−Ｈ基含有シラン化合物のＳｉ−Ｈ基に対し、０．１〜２当量の範囲とすることが好ましく、さらに０．５〜１．５当量が好ましく、特に０．９〜１．１当量とすることが好ましい。
【００３２】
また、上記の加水分解・重縮合、ヒドロシリル化反応は、メタノール、エタノールなどのアルコール系溶剤、エチレングリコールモノメチルエーテルなどのエーテル系溶剤、アセトン、メチルエチルケトン、メチルイソブチルケトンなどのケトン系溶剤、Ｎ，Ｎ−ジメチルホルムアミドなどのアミド系溶剤、トルエン、キシレンなどの芳香族炭化水素系溶剤、酢酸エチルなどのエステル系溶剤、ブチロニトリルなどのニトリル系溶剤等の溶剤中で行うことが好ましい。これら溶剤は単独で用いてもよく、数種類を併用した混合溶剤を用いることもできる。また、前記加水分解・重縮合は特に水を添加しなくても大気雰囲気下で進行するが、水を添加してもよい。水の量は適宜決められるが、多すぎる場合には塗布液の保存安定性が低下するなどの問題があるので、水の量は、前記シラン化合物の総量１モルに対して０〜５モルの範囲とすることが好ましく、特に、０．５〜４モルが好ましい。
【００３３】
シリコーン重合体の製造は、上記の条件、配合を調整してゲル化しないように行われる。シリコーン重合体は、上記の反応溶媒と同じ溶媒に溶解して使用することが作業性の点で好ましい。このためには、上記の反応生成溶液をそのまま使用してもよく、反応生成溶液からシリコーン重合体を分離し、改めて上記溶媒に溶解してもよい。
【００３４】
本発明におけるシリコーン重合体は、三次元架橋しているが完全硬化又はゲル化していないものであり、本発明おけるシリコーン重合体の重合は、例えば、反応溶媒に溶解する程度に制御される。このために、樹脂硬化性シリコーン重合体の製造、保管及び使用に際し、温度は、常温以上２００℃以下であることが好ましく、１５０℃以下であることがより好ましい。
【００３５】
本発明におけるシリコーン重合体の製造にあたっては、Ｓｉ−Ｈ基含有シリコーン重合体を中間生成物として作製することができる。このＳｉ−Ｈ基含有シリコーン重合体のＳｉ−Ｈ基はＳｉ−Ｈ基含有２官能性シロキサン単位（ＨＲ′ＳｉＯ2/2）又は（Ｈ2ＳｉＯ2/2）（式中、Ｒ′は前記の通りであり、シリコーン重合体中のＲ′基は互いに同一であってもよいし、異なってもよい。以下同様）又はＳｉ−Ｈ基含有３官能性シロキサン単位（ＨＳｉＯ3/2）によって導入されている。
【００３６】
本発明のシリコーン重合体は、重合度が３以上のものであればよく、重合度が７０００以下であることが好ましい。溶液としての使用する際の効率を考慮すると重合度が２０００以下であることが好ましく、重合度を３〜５００の範囲とすることが特に好ましい。このシリコーン重合体の側鎖及び末端には、Ｓｉ−Ｈ基に対するヒドロシリル化反応によって導入された樹脂硬化性官能基が存在する。ここで、シリコーン重合体の重合度は、その重合体の分子量（低重合度の場合）又はゲルパーミエーションクロマトグラフィーにより標準ポリスチレン若しくはポリエチレングリコールの検量線を利用して測定した数平均分子量から算出したものである。
【００３７】
なお、シリコーン重合体を作製する際には、前記の様にシリコーン重合体を製造してからヒドロシリル化反応剤を添加してヒドロシリル化反応を行ってもよく、また、ヒドロシリル化反応剤を前記シラン化合物と同時に配合し、シラン化合物の加水分解・重縮合と同時に又はその途中でヒドロシリル化反応を行ってもよい。
【００３８】
上記の樹脂硬化性官能基を有するシリコーン重合体（本発明において、樹脂硬化性シリコーン重合体と記載する。）を含有してなる熱硬化性樹脂組成物には、無機充填剤を多量に配合することができる。無機充填剤としては、その種類は特に制約はなく、例えば、炭酸カルシウム、アルミナ、酸化チタン、マイカ、炭酸アルミニウム、水酸化アルミニウム、ケイ酸マグネシウム、ケイ酸アルミニウム、シリカ、ガラス短繊維、ホウ酸アルミニウムウィスカや炭化ケイ素ウィスカ等の各種ウィスカ等が用いられる。また、これらを数種類併用しても良い。無機充填剤の形状、粒径については特に制限はなく、通常用いられている粒径０．００１〜５０μｍのものを本発明においても用いることができ、好ましくは０．０１〜１０μｍのものが好適に用いられる。これら無機充填剤の配合量は、樹脂硬化性シリコーン重合体１００重量部に対して１００〜２０００重量部が好ましく、３００〜１５００重量部が特に好ましい。無機充填剤の配合量が少なすぎると熱膨張係数が大きくなる傾向があり、無機充填剤が多すぎるとフィルム化が困難になる傾向がある。
【００３９】
本発明おけるシリコーン重合体を含有する熱硬化性樹脂組成物の硬化剤は、シリコーン重合体の樹脂硬化性官能基と反応（硬化）する化合物であればよく、特に制限はない。例えば樹脂硬化性官能基がエポキシ基の場合には、アミン系硬化剤やフェノール系硬化剤などの一般にエポキシ樹脂用硬化剤として用いられるものを利用することができる。エポキシ樹脂用硬化剤としては多官能フェノール化合物が好ましい。多官能フェノール化合物としては、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、レゾルシン、カテコール等の多価フェノールがあり、また、これらの多価フェノール、フェノール、クレゾール等の一価のフェノール化合物とホルムアルデヒドを反応させて得られるノボラック樹脂などがある。多官能フェノール化合物は臭素等のハロゲンで置換されていてもよい。硬化剤の使用量は、シリコーン重合体の樹脂硬化性官能基１当量に対して、０．２〜１．５当量使用することが好ましく、０．５〜１．２当量使用することが特に好ましい。硬化物と金属との接着性を向上させるためにはエポキシ樹脂用硬化剤にアミン化合物を含むことが好ましく、また、硬化剤が過剰に含まれていることが好ましい。このアミン化合物は接着性補強剤として作用するものであり、具体例については後に記載する。耐熱性などの他の特性と接着性とのバランスを考慮すると、アミン化合物を含む硬化剤をシリコーン重合体の樹脂硬化性官能基１当量に対して１．０〜１．５当量用いることが好ましく、樹脂硬化性官能基１当量に対して１．０〜１．２当量用いることが特に好ましい。
【００４０】
また、硬化剤とともに硬化促進剤を加えてもよい。例えば樹脂硬化性官能基がエポキシ基の場合には、イミダゾール化合物などが一般に使用されており、本発明においてもこれを用いることができる。硬化促進剤として用いられるイミダゾール化合物の具体例としてはイミダゾール、２−エチルイミダゾール、２−エチル−４−メチルイミダゾール２−フェニルイミダゾール、２−ウンデシルイミダゾール、１−ベンジル−２−メチルイミダゾール、２−ヘプタデシルイミダゾール、４，５−ジフェニルイミダゾール、２−メチルイミダゾリン、２−フェニルイミダゾリン、２−ウンデシルイミダゾリン、２−ヘプタデシルイミダゾリン、２−イソプロピルイミダゾール、２，４−ジメチルイミダゾール、２−フェニル−４−メチルイミダゾール、２−エチルイミダゾリン、２−イソプロピルイミダゾリン、２，４−ジメチルイミダゾリン、２−フェニル−４−メチルイミダゾリン等が挙げられる。硬化促進剤の十分な効果を得るためには、シリコーン重合体１００重量部に対して０．０１重量部以上使用することが好ましく、熱膨張率や伸び等の観点から１０重量部以下が好ましい。
【００４１】
本発明おけるシリコーン重合体を含有する熱硬化性樹脂組成物には必要に応じて両末端シリル基変性エラストマを加えることができる。熱硬化性樹脂組成物に両末端シリル基変性エラストマを加えることで樹脂硬化物の破断応力が大きくなり、取り扱い性が向上する。本発明における両末端シリル基変性エラストマとは、重量平均分子量が３０００〜１０万程度の長鎖状エラストマであり、主鎖の両末端にアルコキシシリル基を有する。エラストマの主鎖については特に制限はなく、ポリイソブチレンやポリプロピレンなどのポリオレフィン、ポリプロピレンオキシドなどのポリエーテル、ブタジエンゴム又はアクリルゴム等の主鎖骨格を有するエラストマが利用できる。アルコキシシリル基はＳｉ元素に１〜３個のアルコキシ基が結合したものでよく、Ｓｉ元素に結合したアルコキシ基の炭素数は１〜４であることが好ましい。両末端シリル基変性エラストマとしては、例えばＳＡＴ２００（両末端シリル基変性ポリエーテル、鐘淵化学工業株式会社製商品名）、ＥＰ１０３Ｓ、ＥＰ３０３Ｓ（両末端シリル基変性ポリイソブチレン、鐘淵化学工業株式会社製商品名）等を用いることができる。両末端シリル基変性エラストマの配合量は、シリコーン重合体１００重量部に対して０．１〜３０重量部であることが好ましい。０．１重量部未満では配合することによる効果が現れにくく、３０重量部を越えると熱膨張率が大きくなる傾向がある。
【００４２】
本発明における熱硬化性樹脂組成物においては、本発明の樹脂硬化性シリコーン重合体にエポキシ基を持つシリコーンオイル（本発明において、エポキシ変性シリコーンオイルと記載する）を併用することもできる。樹脂硬化性シリコーン重合体とエポキシ変性シリコーンオイルの配合割合は、これらの合計１００重量部に対して樹脂硬化性シリコーン重合体が０．１重量部以上含まれていることが好ましく、熱膨張率、伸び、破断応力の観点から、樹脂硬化性シリコーン重合体が５重量部以上含まれていることがより好ましく、２０重量部以上含まれていることが特に好ましい。また、伸び、破断応力の観点から、樹脂硬化性シリコーン重合体とエポキシ変性シリコーンオイルの配合の合計１００重量部に対してエポキシ変性シリコーンオイルが５重量部以上含まれていることが好ましく、４０重量部以上が特に好ましい。樹脂硬化性シリコーン重合体が０．１重量部未満の場合は無機充填剤の分散性が低下する傾向がある。樹脂硬化性シリコーン重合体とエポキシ変性シリコーンオイルの配合比は熱膨張係数と伸びの値から、目的に応じて決めることができる。すなわち、樹脂硬化性シリコーン重合体の配合比が大きいほど熱膨張係数が小さくなり、エポキシ変性シリコーンオイルの配合比を増やすことで伸びの値を大きくすることができる。ここで、エポキシ変性シリコーンオイルとは側鎖にエポキシ基を含む官能基を有する鎖状ポリシロキサン化合物であり、２５℃における粘度が１０−２〜１０３Ｐａ・ｓの範囲にあるものである。なお、本発明における粘度は東京計器（株）製ＥＭＤ型粘度計を用いて、２５℃で測定した。エポキシ変性シリコーンオイルのエポキシ当量は１５０〜５０００であることが好ましく、３００〜１０００であることが特に好ましい。
【００４３】
前記のエポキシ変性シリコーンオイルを含む熱硬化性樹脂組成物において、本発明の樹脂硬化性シリコーン重合体の一部又は全部に換えて樹脂硬化性官能基を含まないシリコーン重合体（本発明において、非樹脂硬化性シリコーン重合体と記載する。）を使用することもできる。非樹脂硬化性シリコーン重合体を用いる場合には、非樹脂硬化性シリコーン重合体の配合量は、エポキシ変性シリコーンオイルとシリコーン重合体の合計１００重量部に対して３０重量部以下であることが好ましい。非樹脂硬化性シリコーン重合体が３０重量部を越える場合は樹脂硬化物の伸びの値が低下する傾向がある。
【００４４】
ここで、非樹脂硬化性シリコーン重合体とは、２官能性シロキサン単位（Ｒ2ＳｉＯ2/2）、３官能性シロキサン単位（ＲＳｉＯ3/2）（式中、Ｒは有機基であり、シリコーン重合体中のＲ基は互いに同一であってもよいし、異なっていてもよい。）及び４官能性シロキサン単位（ＳｉＯ4/2）から選ばれる少なくとも１種類のシロキサン単位を含有し、末端に水酸基と反応する官能基を１個以上有するものである。重合度は２〜７０００が好ましく、さらに好ましい重合度は２〜１００、特に好ましい重合度は２〜７０である。前記Ｒとしては、炭素数１〜４のアルキル基、フェニル基等の芳香族基などがある。水酸基と反応する官能基としては、シラノール基、炭素数１〜４のアルコキシル基、炭素数１〜４のアシルオキシ基、塩素等の臭素以外のハロゲン等がある。
【００４５】
このような非樹脂硬化性シリコーン重合体は、前記一般式（ＩＩ）で表されるシラン化合物を加水分解、重縮合させて得ることができる。非樹脂硬化性シリコーン重合体の合成に用いられる前記一般式（ＩＩ）で表されるシラン化合物としては、４官能性シラン化合物又は３官能性シラン化合物が必須成分として用いられ、２官能性シラン化合物は必要に応じて適宜使用される。特に、４官能性シラン化合物としてはテトラアルコキシシランが好ましく、３官能性シラン化合物としてはモノアルキルトリアルコキシシランが好ましく、２官能性シラン化合物としてはジアルキルジアルコキシシランが好ましい。シラン化合物の使用割合は、好ましくは、４官能性シラン化合物又は３官能性シラン化合物１５〜１００モル％及び２官能性シラン化合物を０〜８５モル％が好ましく、４官能性シラン化合物または３官能性シラン化合物の１種以上を２０〜１００モル％及び２官能性シラン化合物を０〜８０モル％がより好ましい。また、特に、４官能性シラン化合物を１５〜１００モル％、３官能性シラン化合物０〜８５モル％及び２官能性シラン化合物０〜８５モル％の割合で使用することが好ましく、４官能性シラン化合物を２０〜１００モル％、３官能性シラン化合物を０〜８０モル％と、２官能性シラン化合物を０〜８０モル％の割合で使用することがより好ましい。加水分解・重縮合反応の触媒及び溶剤は樹脂硬化性シリコーン重合体を製造する際の加水分解・重縮合反応と同様のものを適用することができる。非樹脂硬化性シリコーン重合体の製造は条件、配合を調整してゲル化しないように行われる。非樹脂硬化性シリコーン重合体は、３次元架橋しているが完全硬化又はゲル化していないものであり、３次元架橋は、例えば、反応溶媒に溶解する程度に制御される。このために、非樹脂硬化性シリコーン重合体の製造、保管及び使用に際し、温度は、常温以上２００℃以下であることが好ましく、１５０℃以下であることがより好ましい。
【００４６】
樹脂硬化性シリコーン重合体又は非樹脂硬化性シリコーン重合体と、エポキシ変性シリコーンオイルとを併用する場合において、シリコーン重合体成分として非樹脂硬化性シリコーン重合体のみを用いた場合と比較し、樹脂硬化性シリコーン重合体を含む場合は熱膨張率、伸び、破断応力の観点から好ましく、シリコーン重合体成分として樹脂硬化性シリコーン重合体のみを用いることが特に好ましい。
【００４７】
本発明の熱硬化性樹脂組成物には、金属箔との接着性を高め、樹脂硬化物と金属箔との引き剥がし強度を高めるために、必要に応じて接着性補強剤を加えることができる。接着性補強剤としてはアミノ基や水酸基などの反応性官能基を複数持つ化合物を用いることができ、これらはエポキシ樹脂硬化剤としても作用する。反応性官能基を複数持つアミン化合物としては、例えば、ｍ−フェニレンジアミン、４，４'−ジアミノベンズアニリド、４，４'−ジアミノ−２，２'−ジメチルビフェニル等の分子内に複数のアミノ基を持つ化合物やジシアンジアミドなどの、分子内に複数の活性Ｎ−Ｈ基を有する化合物、３−アミノ−１−プロパノール、４−アミノフェノール等の分子内にアミノ基と水酸基を併せ持つ化合物などを用いることができる。接着性補強剤の配合量は前記シリコーン重合体１００重量部に対して０．０１〜９重量部であることが好ましく、０．１〜６重量部であることが特に好ましい。０．０１重量部未満の場合は配合による効果が現れにくい傾向があり、また、９重量部を越える場合は、硬化物の耐熱性が低下する傾向がある。
【００４８】
前記樹脂組成物は、溶剤に溶解ないし分散させて樹脂ワニスとすることができる。樹脂ワニスの濃度は、作業性等を考慮して適宜決定される。また、シリコーン重合体の合成に続いて、樹脂組成物の調整を行う場合、シリコーン重合体の合成に用いた溶剤と同じものを使用することが好ましい。溶剤としては、メタノール、エタノールなどのアルコール系溶剤、エチレングリコールモノメチルエーテルなどのエーテル系溶剤、アセトン、メチルエチルケトン、メチルイソブチルケトンなどのケトン系溶剤、Ｎ，Ｎ−ジメチルホルムアミドなどのアミド系溶剤、トルエン、キシレンなどの芳香族炭化水素系溶剤、酢酸エチルなどのエステル系溶剤、ブチロニトリルなどのニトリル系溶剤等が好ましく使用される。また、これら溶剤の数種類を併用した混合溶剤を用いることもできる。
【００４９】
（樹脂付金属箔）
樹脂ワニスを、金属箔に塗布し、乾燥炉内で８０〜２００℃の範囲で乾燥させることにより樹脂付き金属箔を製造することができる。乾燥時間は、室温での樹脂の流動性がなくなる程度でよく、高温で乾燥させた場合は樹脂が完全硬化しない程度であればよい。金属箔は、特に制限はなく、一般に配線板分野で配線回路導体として使用されている金属箔を使用することができ、電気的特性やコスト面を考慮すると銅箔を用いることが好ましい。特に好ましくは、少なくとも片面に粗化面を有する電解銅箔、圧延銅箔又はキャリアフィルム付き極薄銅箔を使用することができる。金属箔は通常用いられている厚さ５〜２００μｍのものを使用することができる。また、ニッケル、ニッケル−リン、ニッケル−スズ合金、ニッケル−鉄合金、鉛、鉛−スズ合金等を中間層とし、この両面に銅層を設けた３層構造の複合箔や、あるいはアルミニウムと銅箔を複合した複合箔等の複合箔を用いることもできる。
【００５０】
樹脂付き金属箔の絶縁樹脂層の厚みは、銅箔の厚み以上であることが好ましく、また、配線回路加工後に内層配線回路板に積層する場合は、その内層配線回路の導体厚みと、樹脂付き金属箔の銅箔厚みの和よりも大きいことが好ましい。また、厚すぎると重量が必要以上に増え、加えてコスト高になりやすい。厚さは好ましくは６〜２００μｍとされるが、これより厚くてもよい。厚い絶縁樹脂層を作製するために、数回に分けて塗工と乾燥を繰り返すこともできる。なお、内層配線回路板とは、最外層に回路形成された配線板であり、例えば、紙・繊維等の基材を樹脂に含浸硬化させた基板の片面又は両面に回路形成された配線板や、複数の配線板をプリプレグを介して積層した多層配線板、ビルドアップ工法で多層化された多層配線板などが挙げられる。
【００５１】
（配線回路付き樹脂シート）
樹脂付き金属箔の絶縁樹脂層が十分な回路埋め込み性を有する状態で配線回路加工を施すことで、配線回路付き樹脂シートが作製される。絶縁樹脂層が十分な回路埋め込み性を有する状態としては、熱硬化性樹脂におけるＢ−Ｓｔａｇｅ状態が挙げられる。絶縁樹脂層をＢ−Ｓｔａｇｅ状態に調整する方法としては、金属箔に樹脂ワニスを塗布・乾燥する際に乾燥温度、乾燥時間を調整する方法、樹脂付き金属箔に配線回路加工を施す際に、加熱することによってＢ−Ｓｔａｇｅ状態に調整する方法が挙げられる。Ｂ−Ｓｔａｇｅ状態に調整するためのＢ−Ｓｔａｇｅ化の条件は温度８０〜２００℃、時間１〜１２０分の範囲とすることが好ましい。
【００５２】
樹脂付き金属箔に配線回路加工を施すことによって、本発明の配線回路付き樹脂材料を作製することができる。配線回路加工は、サブトラクティブ法など一般的に知られる方法を適用することができる。例えば、樹脂付き金属箔の表面にレジストパターンを形成し、エッチングによって不要部分の銅箔を除去して、レジストパターンを剥離することによって、配線回路が形成される。また、樹脂付き金属箔にあらかじめレーザーやドリルなどで孔部を形成してもよく、配線回路加工後に孔部を形成しても良い。さらに、孔部に導電ペーストを充填してもよく、また、めっき等によって孔部を金属で充たしても良い。
【００５３】
配線回路付き樹脂シートと内層配線回路板とを積層成形し、層間導通をとることによって、多層配線板を作製することができる。積層成形や層間導通は、常法に従い行うことができる。積層成形の条件は、１３０〜２００℃の温度範囲で、好ましくは１５０〜１８０℃の範囲で、また、０．５〜２０ＭＰａの圧力で、好ましくは２〜８ＭＰａの圧力で加熱加圧して行われ、プレス機の能力、目的の厚さ等により適宜選択される。加熱加圧の処理時間は、温度や圧力など他の条件に合わせて適時決められるが、一般には３０分〜２時間程度とされる。層間導通は、導電ペーストやめっきなどによる一般的な方法でとることができる。例えば、配線回路付き樹脂材料と内層配線回路板を積層成形した後、レーザーやドリルなどで孔部を設けて層間導通路を設け、配線回路上にレジストパターンを形成し、メッキによって内層配線回路との導通をとり、レジストパターンを剥離することにより層間導通がなされた多層配線板とすることができる。
【００５４】
以上のようにして作製された多層配線板にさらに前記樹脂付金属箔や前記回路付き樹脂シートを積層し、一体化、層間導通形成を繰り返してビルドアップすることができる。本発明の配線回路付き樹脂材料を用いて作製したビルドアップ層は、積層成型した際に配線回路層が樹脂中に埋没することにより、薄型化が可能である。また、複数の配線回路付き樹脂材料を用いて一括積層しても良い。
【００５５】
（内層回路入り配線回路付き樹脂材料）
内層回路板上に前記樹脂ワニスからなるＢ−Ｓｔａｇｅ状態の樹脂層が積層され、さらに金属箔が積層されてなる積層板に配線回路加工を施すことで、配線回路付き樹脂材料を作製することができる。この配線回路付き樹脂材料の作製に用いる積層板を作製する方法としては、前記樹脂付き金属箔を内層回路板に積層・一体化する方法や、前記樹脂ワニスを内層回路板に塗布し乾燥したのち金属箔を積層・一体化する方法、内層回路板に前記樹脂ワニスをキャリアフィルムに塗布し乾燥してなる樹脂シート及び金属箔を積層・一体化する方法等があげられる。Ｂ−Ｓｔａｇｅ状態に調整する方法としては、積層・一体化の際に同時にＢ−Ｓｔａｇｅ状態に調整することが好ましい。また、一体化した後さらに加熱することにより調整することもできる。積層・一体化により適切なＢ−Ｓｔａｇｅ状態に調整するためのＢ−Ｓｔａｇｅ化の条件は温度８０〜２００℃、時間１〜１２０分、圧力０．１〜８ＭＰａの範囲とすることが好ましい。
【００５６】
この配線回路付き樹脂材料に、前記樹脂付金属箔、前記配線回路付き樹脂シートなどのビルドアップ材を積層し、一体化して、層間導通を形成することにより多層配線板を製造することができる。また、これを繰り返してビルドアップすることによって、さらに多層化することができる。本発明の配線回路付き樹脂材料を用いて作製したビルドアップ層は、積層成型した際に配線回路層が樹脂中に埋没することにより、薄型化が可能である。
【００５７】
【実施例】
（参考例）
撹拌装置、コンデンサ及び温度計を備えたガラスフラスコに、テトラメトキシシラン（東京化成工業株式会社製）を２０ｇ、ジメトキシジメチルシラン（東京化成工業株式会社製）を６０ｇ、ジメトキシメチルシラン（東京化成工業株式会社製）を６７ｇ、合成溶剤としてメタノール（東京化成工業株式会社製）を３７ｇ配合した溶液に、合成触媒としてマレイン酸を１.５ｇ、蒸留水を５０ｇ配合して８０℃で２時間攪拌した後、アリルグリシジルエーテル（東京化成工業株式会社製）を７２ｇと塩化白金酸塩（２重量％イソプロピルアルコール溶液）を０.２ｇ添加し、更に４時間撹拌してエポキシ変性のシリコーン重合体、を合成した。得られたシリコーン重合体のシロキサン単位の重合度は６５であった（ＧＰＣによって標準ポリスチレンの検量線を利用して測定した数平均分子量から換算、以下同じ）。
【００５８】
（実施例１）
撹拌装置、コンデンサ及び温度計を備えたガラスフラスコに、前記参考例と同様な方法で合成したシリコーン重合体の固形分１００重量部に対してシリカ粉末（製品名：ＳＯ−２５Ｒ，平均粒径：０．５μｍ，株式会社アドマテックス製）４５０重量部と希釈溶剤としてメタノールを２０２重量部配合し、８０℃で１時間攪拌した後、室温まで冷却し、シリコーン重合体の固形分１００重量部に対してテトラブロモビスフェノールＡを７８重量部と２−エチル−４−メチルイミダゾール３重量部を配合し、室温で１時間撹拌して樹脂ワニスを調製した。この樹脂ワニスの硬化物の熱膨張係数は２２×１０−６／℃であり、伸びは３．１％であった。
【００５９】
なお、本発明において、樹脂硬化物の熱膨張係数及び伸びの測定には、樹脂ワニスを、厚さ５０μｍのポリエチレンテレフタレートフィルムをキャリヤーフィルムとして用い、加熱乾燥後の厚さが5０μｍとなるようにナイフコータにより塗工し、１７０℃・２時間の条件で加熱・硬化させ、キャリヤーフィルムを取り外して、作製された樹脂シートを試料として用いた。熱膨張率は、熱機械分析（ＴＭＡ：ＭＡＣ ＳＣＩＥＮＣＥ社製ＴＭＡ）により引張モードで測定した。伸びは、幅１０ｍｍ×長さ８０ｍｍ、厚み５０〜１００μｍのフィルムを試料として用いて、引張試験機（島津製作所オートグラフＡＧ−１００Ｃ）により、測定条件をチャック間距離：６０ｍｍ、引張速度：５ｍｍ／ｍｉｎとして、引張試験で測定した。
【００６０】
この樹脂ワニスを、厚さ５０μｍのポリエチレンテレフタレートフィルムをキャリヤーフィルムとして用い、加熱乾燥後の厚さが5０μｍとなるようにナイフコータにより塗工し、温度１3０℃で１０分間加熱乾燥し、加熱乾燥後にキャリヤーフィルムを剥がして樹脂シートを作製した。
【００６１】
また、この樹脂ワニスを、厚さ１８μｍの片面粗化銅はくを用い、加熱乾燥後の樹脂シートの厚さが５０μｍとなるようにナイフコータにより粗化面側に塗工し、温度１3０℃で１０分間加熱乾燥し、銅箔付樹脂シートを作製した。
【００６２】
前記樹脂ワニスを、厚さ１８μｍの片面粗化銅はくを用い、加熱乾燥後の樹脂シートの厚さが５０μｍとなるようにナイフコータにより粗化面側に塗工し、温度１3０℃で６０分間加熱乾燥し、エッチング液（水1ｋｇに対し，過硫酸アンモニウム（三菱ガス化学製）２００ｇを溶解。）を用いて配線回路加工を施して、配線回路付き樹脂材料（配線回路付き樹脂シート）（図１）とした。
【００６３】
厚さ０．８ｍｍのガラス布基材エポキシ樹脂両面銅張積層板（日立化成工業株式会社製、ＭＣＬ−Ｅ−６７（商品名）を使用）に配線回路加工を施し、その上下に前記で作製した銅箔付樹脂シートを重ね、１３０℃、３ＭＰａで６０分間加熱加圧して最外絶縁層がＢ−Ｓｔａｇｅ状態である銅張４層積層板Ａ１を作製した。銅張４層積層板Ａ１にエッチングにより配線回路加工を施し回路付き絶縁樹脂材料（図２）とした。この回路付き絶縁樹脂材料の両面に先に作製した銅箔付樹脂シートを重ね、温度１７５℃、圧力３ＭＰａで６０分間加熱加圧して銅張６層積層板Ｂ１（図３）を作製した。
【００６４】
厚さ０．８ｍｍのガラス布基材エポキシ樹脂両面銅張積層板（日立化成工業株式会社製、ＭＣＬ−Ｅ−６７（商品名）を使用）に配線回路加工を施し、その上下に前記で作製した銅箔付樹脂シートを重ね、１７５℃、３ＭＰａで６０分間加熱加圧して、最外絶縁層がＣ−Ｓｔａｇｅ状態である銅張４層積層板Ｃ１を作製した。銅張積層板Ｃ１にエッチングにより配線回路加工を施し、その両面に先に作製した銅箔付樹脂シートを重ね、温度１７５℃、圧力３ＭＰａで６０分間加熱加圧して銅張６層積層板Ｄ１を作製した。
【００６５】
厚さ０．８ｍｍのガラス布基材エポキシ樹脂両面銅張積層板（日立化成工業株式会社製、ＭＣＬ−Ｅ−６７（商品名）を使用）に配線回路加工を施し、その上下に前記で作製した配線回路付き樹脂シートを重ね、更にその上下に前記で作製した銅箔付樹脂シートを重ねて温度１７５℃、圧力３ＭＰａで６０分間加熱加圧して銅張６層積層板E１を作製した。
【００６６】
（実施例２）
シリコーン重合体の固形分１００重量部に対して、シリカ粉末（商品名：ＳＯ−２５Ｒ，平均粒径：０．５μｍ，株式会社アドマテックス製）の配合量を９００重量部、メタノールの配合量を２５０重量部に変えた以外は実施例１と同様にして樹脂ワニスを調製した。この樹脂ワニスの硬化物の熱膨張係数は１５×１０−６／℃であり、伸びは２．２％であった。
この樹脂ワニスを用いて、実施例１と同様の方法で樹脂シート、銅箔付樹脂シート、配線回路付き樹脂シート、銅張４層積層板Ａ２、銅張６層積層板Ｂ２、銅張４層積層板Ｃ２、銅張６層積層板Ｄ２および銅張６層積層板Ｅ２を作製した。
【００６７】
（実施例３）
シリコーン重合体の固形分１００重量部に対して、シリカ粉末（商品名：ＳＯ−２５Ｒ，平均粒径：０．５μｍ，株式会社アドマテックス製）の配合量を１３００重量部、メタノールの配合量を４９０重量部に変えた以外は実施例１と同様にして樹脂ワニスを調製した。この樹脂ワニスの硬化物の熱膨張係数は１０×１０−６／℃であり、伸びは１．２％であった。
この樹脂ワニスを用いて、実施例１と同様の方法で樹脂シート、銅箔付樹脂シート、配線回路付き樹脂シート、銅張４層積層板Ａ３、銅張６層積層板Ｂ３、銅張４層積層板Ｃ３、銅張６層積層板Ｄ３および銅張６層積層板Ｅ３を作製した。
【００６８】
（比較例）
ビスフェノールＡノボラック型エポキシ樹脂（エポキシ当量２１０、大日本インキ化学工業株式会社製、エピクロンＮ８６５（商品名）を使用）１００部，ビスフェノールＡノボラック樹脂（水酸基当量１１８、大日本インキ化学工業株式会社製、プライオーフェンＶＨ−４１７０（商品名）を使用）６０部及びジシアンジアミド２部をメチルエチルケトン１２０部に溶解し，室温で１時間撹拌して樹脂ワニスを調製した。
この樹脂ワニスを用いて、実施例１と同様の方法で樹脂シート、銅箔付樹脂シート、銅張４層積層板Ａ４、銅張６層積層板Ｂ４、銅張４層積層板Ｃ４および銅張６層積層板D４を作製した。なお、配線回路付き樹脂シート及び銅張６層積層板Ｅ４については、エッチング時に配線回路付き樹脂シートの形状が保てず、作製が不可能であった。
【００６９】
実施例１〜４及び比較例の樹脂シート１０ｇをエッチング液（水1ｋｇに対し，過硫酸アンモニウム（三菱ガス化学製）２００ｇを溶解。）で室温にて1時間処理した後の重量減少と樹脂シート形状を表１に示す。
銅張６層積層板Ｂ１〜Ｂ４、銅張６層積層板Ｄ１〜Ｄ４、銅張６層積層板Ｅ１〜Ｅ３の表面粗さを、触針式表面粗さ計にて測定した。測定箇所は直下に内層配線回路が存在する部分から存在しない部分にかけて長さ２５ｍｍの一直線上とし，直下に内層配線回路が存在する部分から存在しない部分の段差の１０点平均粗さを測定した。結果を表１に示す。
また，銅張６層積層板Ｂ１〜Ｂ４、銅張６層積層板Ｄ１〜Ｄ４、銅張６層積層板Ｅ１〜Ｅ３の260℃で30秒間半田槽にフロートし、半田耐熱性を評価した。結果を表１に示す。
【００７０】
【表１】
表１に示すように、本発明の樹脂シートは低温で硬化させてもエッチング液に溶解しないため，銅張６層積層板Ｂや銅張６層積層板Ｅの状態でも半田耐熱性を有し、また、回路埋め込み性に優れ、半田耐熱性に優れることが分かる。
【００７２】
【発明の効果】
本発明によって、完全に硬化していない状態でもエッチング液などの薬液に対して分解が起こらない樹脂を用いることで、絶縁層としての役割を果たし、成形時に配線を樹脂シートに潜り込ませることが可能で、成形後に内層配線回路による凸の影響が小さいことから表面の平坦化が可能であり、微細配線に適した樹脂材料を提供することができる。
【図面の簡単な説明】
【図１】本発明の配線回路付き樹脂材料の一例を示す断面図である。
【図２】本発明の配線回路付き樹脂材料の一例を示す断面図である。
【図３】本発明の配線回路付き樹脂材料を使用して作製される銅張６層積層板を示す断面図である。
【符号の説明】
１，１'，１''．樹脂層（銅箔付樹脂シート由来）
２，２'．配線導体（銅箔付樹脂シート由来）
３．内層回路板の絶縁層
４．内層回路板の回路配線
５．銅層（銅箔付樹脂シート由来）[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a resin material with a wiring circuit, a manufacturing method thereof, and a multilayer printed wiring board.
[0002]
[Prior art]
A printed wiring board widely used in electronic devices is obtained by performing wiring circuit processing on a metal-laminated laminate. As this metal-laminated laminate, a prepreg obtained by impregnating and drying a resin varnish of a thermosetting resin composition on a woven fabric base material and laminate-molded with a metal foil has been widely used. That is, the insulating base material layer was composed of a cured product of a thermosetting resin composition and a woven fabric base material, and metal foil was adhered thereto. The simple printed wiring board includes a multilayer printed wiring board in addition to a double-sided printed wiring board. In addition, the conventional general-purpose multilayer printed wiring board is wired to the metal multilayer multilayer board with the inner layer wiring circuit that can be bonded and integrated by heating and pressing the double-sided printed wiring board and the metal foil through a prepreg or resin sheet. It was obtained by applying circuit processing. A four-layer metal laminate is obtained by bonding and integrating metal foil on both sides of a double-sided printed wiring board. A six-layer metal laminate is placed between two double-sided printed wiring boards. Metal foil was bonded and integrated on both sides through a prepreg and a resin sheet.
[0003]
In recent years, with the miniaturization of electronic devices, printed wiring boards have become thinner and the wiring needs to be denser. When a woven fabric substrate is used as a material, there is a limit to reducing the thickness, and therefore it has been proposed to use a resin sheet in the production of a metal-laminated multilayer laminate.
[0004]
[Problems to be solved by the invention]
As electronic devices become smaller, lighter, higher in performance, and lower in cost, printed wiring boards are required to have higher density, thinner thickness, higher reliability, and lower cost. In order to increase the density, fine wiring is necessary. For this purpose, the surface flatness must be good. In order to improve the flatness of the surface, polishing is effective, but there are problems such as an increase in the number of steps and cost, and difficulty in obtaining a uniform thickness. Even in the case of multi-layering, fine wiring is necessary for high density, and for that purpose the surface flatness must be good. In order to improve the surface flatness, it is effective to polish and planarize the inner layer wiring. However, the number of steps is increased and the cost is increased. There were problems such as difficult things. Therefore, a method is considered in which a flexible resin sheet is used and the wiring is embedded in the resin sheet during molding. In order for the wiring to sink into a general resin sheet for wiring boards, the resin sheet needs to be flexible. For this reason, it is conceivable to use the resin in a semi-cured state. However, in the semi-cured state, the resin cannot withstand the etching process for forming the wiring, the resin is decomposed, and does not serve as an insulating layer. In addition, in order to make it flexible until the wiring is embedded in a state where the resin is cured, it may be possible to add an elastomer as a flexible component. However, if an elastomer is used for the resin sheet, the water absorption rate is increased and the heat resistance is increased. There are problems such as getting worse.
[0005]
[Means for Solving the Problems]
As a means to solve the above problems, chemical solution such as etching solution does not decompose even in a semi-cured state, it serves as an insulating layer, and it is possible to let the wiring enter the resin sheet at the time of molding Therefore, the present invention proposes a resin material suitable for fine wiring, in which there is no unevenness of the wiring after molding and the surface can be flattened.
[0006]
The present invention relates to each item described below.
(1)A resin composition comprising a resin curable silicone polymer, a curing agent and an inorganic filler.A resin material with a wiring circuit having a wiring circuit layer on an insulating resin layer in a B-Stage state.
(2)A resin composition comprising a resin curable silicone polymer, a curing agent and an inorganic filler.The resin material with a wiring circuit according to (1), comprising an insulating resin sheet in a B-Stage state and a wiring circuit layer provided on the insulating resin sheet.
(3)A resin composition comprising a resin curable silicone polymer, a curing agent and an inorganic filler.The resin material with a wiring circuit according to (1), comprising an insulating resin layer in a B-Stage state provided on an inner layer circuit board and a wiring circuit provided on the insulating resin layer.
(4)The blending amount of the inorganic filler with respect to 100 parts by weight of the resin curable silicone polymer in the resin composition forming the insulating resin layer is 100 parts by weight or more (1) to(3)A resin material with a wiring circuit according to any one of the above.
(5)With a wiring circuit according to (4), wherein the insulating resin layer comprises a resin composition containing 100 parts by weight of a resin curable silicone polymer, 0.8 to 1 equivalent of a curing agent and 100 to 2000 parts by weight of an inorganic filler. Resin material.
(6)The insulating resin layer has a thermal expansion coefficient of 50 × 10-6It is an insulating resin layer formed using a resin composition having a temperature of / ° C. or less (1) to(5)A resin material with a wiring circuit according to any one of the above.
(7)The insulating resin layer is an insulating resin layer formed using a resin composition having an elongation in a tensile test of a cured product of 1.0% or more (1) to(6)A resin material with a wiring circuit according to any one of the above.
[0007]
(8)A method for producing a printed wiring board, wherein the resin material with a wiring circuit according to (2) and an inner layer board are overlaid and heated and pressed.
(9) A resin composition comprising a resin curable silicone polymer, a curing agent and an inorganic filler.A resin material with a wiring circuit, characterized in that a circuit is formed by etching away unnecessary metal from a laminate including an insulating resin layer in a B-stage state and a metal foil disposed on the insulating resin layer. Production method.
(10)The blending amount of the inorganic filler with respect to 100 parts by weight of the resin curable silicone polymer is 100 parts by weight or more.(9)The manufacturing method of the resin material with a wiring circuit of description.
(11)From the resin composition in which the insulating resin layer contains 100 parts by weight of the resin curable silicone polymer, 100 to 2000 parts by weight of the inorganic filler, and 0.8 to 1 equivalent of the curing agent with respect to the resin curable silicone polymer. It is characterized by(9)The manufacturing method of the resin material with a wiring circuit of description.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
The resin material with a wiring circuit in the present invention is a resin material in which a wiring circuit is formed on an insulating layer having a sufficient circuit embedding property. For example, a wiring is formed on a thermosetting resin sheet in a B-Stage state. Examples thereof include a resin sheet with a wiring circuit in which a circuit is formed, and a wiring board material in which a wiring circuit is further formed on an insulating layer made of a thermosetting resin in a B-Stage state provided on an inner layer circuit board. . The B-Stage state in the present invention means that when the resin is immersed in the same solvent used for resin varnishing and stirred at 25 ° C. for 1 hour, 5 to 95% by weight of the resin component remains undissolved. It is in a cured state. The cured state in which the amount of the resin component remaining without being dissolved exceeds 95% by weight is defined as C-Stage state, and the cured state of less than 5% by weight is defined as A-Stage state.
[0009]
As the insulating resin in the present invention, a resin satisfying chemical resistance necessary for chemical processing such as etching removal of metal during wiring circuit processing is used even in a state where sufficient circuit embedding property is provided. It is preferable to use a thermosetting resin that satisfies the chemical resistance required in the B-Stage state. Further, considering the connection reliability such as the interlayer conduction path in the case of the multilayer wiring board, the thermal expansion coefficient of the cured insulating resin is 50 × 10.-6It is preferable to use a resin having a thermal expansion coefficient of 30 × 10-6It is more preferable to use a resin having a thermal expansion coefficient of 15 × 10-6It is particularly preferable to use a resin having a temperature of / ° C. or lower. From the viewpoint of handling at the time of producing the multilayer wiring board and reliability when the multilayer wiring board is obtained, it is preferable to use a resin having an elongation of 1.0% or more in the tensile test of the cured product, and an elongation of 2.0%. It is particularly preferable to use a resin that is at least%. An example of such a resin is a resin composition containing a resin curable silicone polymer, its curing agent, and an inorganic filler.
[0010]
The resin curable silicone polymer has the general formula (I)
[Chemical 1]
R 'm(H)kSiX4- (m + k) (I)
(In the formula, X is a group capable of hydrolysis and polycondensation, and represents, for example, halogen such as chlorine and bromine, or -OR, wherein R is an alkyl group having 1 to 4 carbon atoms and 1 to 4 carbon atoms. R ′ is a non-reactive group, for example, an alkyl group having 1 to 4 carbon atoms, an aryl group such as a phenyl group, k is 1 or 2, m is 0 or 1 , M + k means 1 or 2) and can be obtained by reacting a hydrosilylation reagent. The silane compound of the general formula (I) is converted into a Si-H group-containing silicone polymer by hydrolysis and polycondensation, and the hydrosilylation reagent is hydrosilylated with the Si-H group of the Si-H group-containing silicone polymer. By reacting, a silicone polymer having a resin curable functional group introduced therein is obtained.
[0011]
The Si—H group-containing silane compound of the general formula (I) is added to the general formula (II)
[Chemical 2]
R 'nSiX4-n (II)
(In the formula, R ′ and X are the same as those in formula (I), and n means an integer of 0 to 2).
The silane compound represented by these can be used together.
[0012]
Specifically, the Si—H group-containing silane compound represented by the general formula (I)
[Chemical Formula 3]
HCHThreeSi (OCHThree)2, HC2HFiveSi (OCHThree)2,
HThreeCH7Si (OCHThree)2, HCFourH9Si (OCHThree)2,
HCHThreeSi (OC2HFive)2, HC2HFiveSi (OC2HFive)2,
HCThreeH7Si (OC2HFive)2, HCFourH9Si (OC2HFive)2,
HCHThreeSi (OCThreeH7)2, HC2HFiveSi (OCThreeH7)2,
HCThreeH7Si (OCThreeH7)2, HCFourH9Si (OCThreeH7)2,
HCHThreeSi (OCFourH9)2, HC2HFiveSi (OCFourH9)2,
HCThreeH7Si (OCFourH9)2, HCFourH9Si (OCFourH9)2,
Alkyl dialkoxysilane
[0013]
[Formula 4]
H2Si (OCHThree)2, H2Si (OC2HFive)2,
H2Si (OCThreeH7)2, H2Si (OCFourH9)2,
Dialkoxysilane etc.
[0014]
[Chemical formula 5]
HPhSi (OCHThree)2, HPhSi (OC2HFive)2, HPhSi (OCThreeH7)2,
HPhSi (OCFourH9)2,
(However, Ph represents a phenyl group. The same applies hereinafter.)
Phenyldialkoxysilane such as
[0015]
[Chemical 6]
H2Si (OCHThree)2, H2Si (OC2HFive)2, H2Si (OCThreeH7)2,
H2Si (OCFourH9)2,
A bifunctional silane compound such as dialkoxysilane (hereinafter, the functionality in the silane compound means that it has a condensation-reactive functional group)
[0016]
[Chemical 7]
HSi (OCHThree)Three, HSi (OC2HFive)Three, HSi (OCThreeH7)Three,
HSi (OCFourH9)Three,
And trifunctional silane compounds such as trialkoxysilane.
[0017]
Specifically, the silane compound represented by the general formula (II) is:
[Chemical 8]
Si (OCHThree)Four, Si (OC2HFive)Four,
Si (OCThreeH7)Four, Si (OCFourH9)Four
Tetraalkoxysilane such as
Tetrafunctional silane compounds such as
[0018]
[Chemical 9]
HThreeCSi (OCHThree)Three, HFiveC2Si (OCHThree)Three,
H7CThreeSi (OCHThree)Three, H9CFourSi (OCHThree)Three,
HThreeCSi (OC2HFive)Three, HFiveC2Si (OC2HFive)Three,
H7CThreeSi (OC2HFive)Three, H9CFourSi (OC2HFive)Three,
HThreeCSi (OCThreeH7)Three, HFiveC2Si (OCThreeH7)Three,
H7CThreeSi (OCThreeH7)Three, H9CFourSi (OCThreeH7)Three,
HThreeCSi (OCFourH9)Three, HFiveC2Si (OCFourH9)Three,
H7CThreeSi (OCFourH9)Three, H9CFourSi (OCFourH9)Three,
Monoalkyltrialkoxysilane such as
[0019]
[Chemical Formula 10]
PhSi (OCHThree)Three, PhSi (OC2HFive)Three,
PhSi (OCThreeH7)Three, PhSi (OCFourH9)Three
(However, Ph represents a phenyl group. The same applies hereinafter.)
Phenyltrialkoxysilane, etc.
[0020]
Embedded image
(HThreeCCOO)ThreeSiCHThree, (HThreeCCOO)ThreeSiC2HFive,
(HThreeCCOO)ThreeSiCThreeH7, (HThreeCCOO)ThreeSiCFourH9
Monoalkyl triacyloxysilane such as
[0021]
Embedded image
ClThreeSiCHThree, ClThreeSiC2HFive,
ClThreeSiCThreeH7, ClThreeSiCFourH9
BrThreeSiCHThree, BrThreeSiC2HFive,
BrThreeSiCThreeH7, BrThreeSiCFourH9
Trifunctional silane compounds such as monoalkyltrihalogenosilanes, etc.
[0022]
Embedded image
(HThreeC)2Si (OCHThree)2, (HFiveC2)2Si (OCH3)2,
(H7CThree)2Si (OCHThree)2, (H9CFour)2Si (OCHThree)2,
(H3C)2Si (OC2HFive)2, (HFiveC2)2Si (OC2HFive)2,
(H7CThree)2Si (OC2HFive)2, (H9CFour)2Si (OC2HFive)2,
(HThreeC)2Si (OCThreeH7)2, (HFiveC2)2Si (OCThreeH7)2,
(H7CThree)2Si (OCThreeH7)2, (H9CFour)2Si (OCThreeH7)2,
(HThreeC)2Si (OCFourH9)2, (HFiveC2)2Si (OCFourH9)2,
(H7CThree)2Si (OCFourH9)2, (H9CFour)2Si (OCFourH9)2
Dialkyl dialkoxysilanes such as
[0023]
Embedded image
Ph2Si (OCHThree)2, Ph2Si (OC2HFive)2
Diphenyl dialkoxysilane, etc.
[0024]
Embedded image
(HThreeCCOO)2Si (CHThree)2, (HThreeCCOO)2Si (C2HFive)2,
(HThreeCCOO)2Si (CThreeH7)2, (HThreeCCOO)2Si (CFourH9)2
Dialkyldiacyloxysilane, etc.
[0025]
Embedded image
Cl2Si (CHThree)2, Cl2Si (C2HFive)2,
Cl2Si (CThreeH7)Three, Cl2Si (CFourH9)2,
Br2Si (CHThree)2, Br2Si (C2HFive)2,
Br2Si (CThreeH7)2, Br2Si (CFourH9)2
There are bifunctional silane compounds such as alkyl dihalogenosilanes.
[0026]
The Si—H group-containing silane compound represented by the general formula (I) used in the present invention is used as an essential component, and the silane compound represented by the general formula (II) is an optional component. As the hydrolyzable / polycondensable group contained in the silane compound of the general formula (I) or the general formula (II), an alkoxy group is preferable in consideration of reactivity and the like. As the Si—H group-containing silane compound represented, trialkoxysilane or monoalkyldialkoxysilane is particularly preferred. As the silane compound represented by the general formula (II), tetraalkoxysilane, monoalkyltrialkoxysilane or dialkyl is used. Dialkoxysilane is particularly preferred. In the case of producing a silicone polymer having a high degree of polymerization, the silane compound represented by the general formula (I) preferably contains a trifunctional silane compound, and the silane compound represented by the general formula (II) In the case of using, it is preferable to contain a tetrafunctional or trifunctional silane compound represented by the general formula (II).
[0027]
The method for producing a silicone polymer of the present invention comprises blending 35 mol% or more of a Si—H group-containing silane compound with respect to the total amount of the silane compound, and represented by the general formula (I) with respect to the total amount of the silane compound. Of Si—H group-containing silane compound 35 to 100 mol% (more preferably 35 to 85 mol%) and 0 to 65 mol% (15 to 65 mol%) of the silane compound represented by the general formula (II) Are preferably used.
[0028]
The silicone polymer of the present invention is preferably one that is three-dimensionally crosslinked. For this reason, it is preferable that 3-100 mol% is a trifunctional or more silane compound among all the silane compounds, and it is especially preferable that 3-75 mol% is a trifunctional or more silane compound among all silane compounds. Moreover, it is preferable that 15-100 mol% is a tetrafunctional silane compound or a trifunctional silane compound among silane compounds, and 20-85 mol% is a tetrafunctional silane compound or a trifunctional silane compound. More preferred. That is, it is preferable that a bifunctional silane compound is 0-85 mol% among the silane compounds represented by general formula (II), More preferably, it is used in the ratio of 0-80 mol%. Particularly preferably, among the silane compounds represented by the general formula (II), the tetrafunctional silane compound is 15 to 100 mol%, more preferably 20 to 100 mol%, the trifunctional silane compound is 0 to 85 mol%, More preferably, 0 to 80 mol% and the bifunctional silane compound are used in a proportion of 0 to 85 mol%, more preferably 0 to 80 mol%.
[0029]
If the bifunctional silane compound exceeds 85 mol%, the silicone polymer chain becomes longer, and it is highly possible that it will be on the surface of the inorganic material due to the orientation of hydrophobic groups such as methyl groups, forming a rigid layer. This makes it difficult to reduce the stress.
[0030]
The silicone polymer in the present invention is obtained by hydrolyzing and polycondensing the Si—H group-containing silane compound represented by the general formula (I) and the silane compound represented by the general formula (II), and further hydrosilylation reaction. At this time, as the hydrolysis / polycondensation catalyst, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, and hydrofluoric acid, and organic acids such as oxalic acid, maleic acid, sulfonic acid, and formic acid are used. It is preferable to use a basic catalyst such as ammonia or trimethylammonium. These hydrolysis / polycondensation catalysts are used in an appropriate amount depending on the amount of the Si-H group-containing silane compound represented by the general formula (I) and the silane compound represented by the general formula (II). Is used in the range of 0.001 to 10 mol with respect to 1 mol in total of the Si—H group-containing silane compound represented by the general formula (I) and the silane compound represented by the general formula (II). As the hydrosilylation catalyst, platinum, palladium, and rhodium-based transition metal compounds can be used. In particular, platinum compounds such as chloroplatinic acid are preferably used, and zinc peroxide, calcium peroxide, hydrogen peroxide, hydrogen peroxide, Peroxides such as di-tert-butyl oxide, strontium peroxide, sodium peroxide, lead peroxide, and barium peroxide, tertiary amines, and phosphines can also be used. These hydrosilylation catalysts are preferably used in a range of 0.0000001 to 0.0001 mol with respect to 1 mol of Si-H groups of the Si-H group-containing silane compound represented by the general formula (I).
[0031]
The hydrosilylation reagent of the present invention has a double bond for a hydrosilylation reaction such as a vinyl group and a resin curable functional group such as an epoxy group or an amino group. The resin curable functional group is a functional group that reacts or interacts with an organic compound or an inorganic compound. Here, as this functional group, a reactive organic group that reacts with a curing agent or a crosslinking agent, a reactive organic group that undergoes a self-curing reaction, an organic group that reacts or interacts with a functional group present on the surface of an inorganic filler. And groups that react with hydroxyl groups. As specific examples, allyl glycidyl ether or the like can be used as a hydrosilylation reagent having an epoxy group, and aminoalkyl acrylates such as allylamine, allylamine hydrochloride, aminoethyl acrylate, and the like as hydrosilylation reagents having an amino group. An aminoalkyl methacrylate such as ethyl methacrylate can be used. These hydrosilylation reagents are preferably in the range of 0.1 to 2 equivalents relative to the Si—H group of the Si—H group-containing silane compound represented by the general formula (I), and more preferably 0.5 to 1.5 equivalents are preferable, and 0.9 to 1.1 equivalents are particularly preferable.
[0032]
The hydrolysis / polycondensation and hydrosilylation reactions described above can be carried out using alcohol solvents such as methanol and ethanol, ether solvents such as ethylene glycol monomethyl ether, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, N, N -It is preferably carried out in a solvent such as an amide solvent such as dimethylformamide, an aromatic hydrocarbon solvent such as toluene or xylene, an ester solvent such as ethyl acetate, or a nitrile solvent such as butyronitrile. These solvents may be used alone, or a mixed solvent in which several types are used in combination. In addition, the hydrolysis / polycondensation proceeds in an air atmosphere without adding water, but water may be added. The amount of water is appropriately determined, but if it is too large, there is a problem such as a decrease in storage stability of the coating solution. Therefore, the amount of water is 0 to 5 mol relative to 1 mol of the total amount of the silane compound. It is preferable to set it as a range, and 0.5-4 mol is especially preferable.
[0033]
The production of the silicone polymer is carried out so as not to gel by adjusting the above-mentioned conditions and blending. It is preferable from the viewpoint of workability that the silicone polymer is used by dissolving in the same solvent as the above reaction solvent. For this purpose, the reaction product solution may be used as it is, or the silicone polymer may be separated from the reaction product solution and dissolved in the solvent again.
[0034]
The silicone polymer in the present invention is three-dimensionally crosslinked but not completely cured or gelled, and the polymerization of the silicone polymer in the present invention is controlled to such an extent that it is dissolved in a reaction solvent, for example. For this reason, when manufacturing, storing, and using the resin curable silicone polymer, the temperature is preferably normal temperature or higher and 200 ° C. or lower, and more preferably 150 ° C. or lower.
[0035]
In the production of the silicone polymer in the present invention, the Si—H group-containing silicone polymer can be produced as an intermediate product. The Si—H group of this Si—H group-containing silicone polymer is a Si—H group-containing bifunctional siloxane unit (HR′SiO2/2) Or (H2SiO2/2(Wherein, R ′ is as defined above, and the R ′ groups in the silicone polymer may be the same or different from each other, the same shall apply hereinafter) or a Si—H group-containing trifunctional siloxane Unit (HSiO3/2).
[0036]
The silicone polymer of the present invention has only to have a polymerization degree of 3 or more, and preferably has a polymerization degree of 7000 or less. Considering the efficiency when used as a solution, the degree of polymerization is preferably 2000 or less, and particularly preferably in the range of 3 to 500. Resin curable functional groups introduced by a hydrosilylation reaction on Si—H groups are present at the side chain and terminal of the silicone polymer. Here, the degree of polymerization of the silicone polymer was calculated from the molecular weight of the polymer (in the case of a low degree of polymerization) or the number average molecular weight measured by gel permeation chromatography using a standard polystyrene or polyethylene glycol calibration curve. Is.
[0037]
In preparing the silicone polymer, the hydrosilylation reaction may be performed by adding the hydrosilylation reaction agent after the production of the silicone polymer as described above. You may mix | blend with a compound and may perform hydrosilylation reaction simultaneously with the hydrolysis and polycondensation of a silane compound or in the middle.
[0038]
A large amount of an inorganic filler is blended in the thermosetting resin composition containing the above-described silicone polymer having a resin-curable functional group (in the present invention, described as a resin-curable silicone polymer). be able to. There are no particular restrictions on the type of inorganic filler, such as calcium carbonate, alumina, titanium oxide, mica, aluminum carbonate, aluminum hydroxide, magnesium silicate, aluminum silicate, silica, short glass fiber, and aluminum borate. Various whiskers such as whisker and silicon carbide whisker are used. These may be used in combination. The shape and particle size of the inorganic filler are not particularly limited, and those having a particle size of 0.001 to 50 μm that are usually used can be used in the present invention, and those having a particle size of 0.01 to 10 μm are preferable. Used for. The blending amount of these inorganic fillers is preferably 100 to 2000 parts by weight, particularly preferably 300 to 1500 parts by weight with respect to 100 parts by weight of the resin curable silicone polymer. If the blending amount of the inorganic filler is too small, the thermal expansion coefficient tends to increase, and if the inorganic filler is too large, film formation tends to be difficult.
[0039]
The curing agent of the thermosetting resin composition containing the silicone polymer in the present invention is not particularly limited as long as it is a compound that reacts (cures) with the resin curable functional group of the silicone polymer. For example, when the resin curable functional group is an epoxy group, those generally used as a curing agent for an epoxy resin such as an amine curing agent and a phenol curing agent can be used. A polyfunctional phenol compound is preferable as the curing agent for the epoxy resin. Polyfunctional phenolic compounds include polyphenols such as bisphenol A, bisphenol F, bisphenol S, resorcin, and catechol. In addition, these polyhydric phenols, phenols, cresols, and other monovalent phenolic compounds are reacted with formaldehyde. There are novolak resins obtained. The polyfunctional phenol compound may be substituted with a halogen such as bromine. The amount of the curing agent used is preferably 0.2 to 1.5 equivalents, particularly preferably 0.5 to 1.2 equivalents, relative to 1 equivalent of the resin curable functional group of the silicone polymer. . In order to improve the adhesiveness between the cured product and the metal, the epoxy resin curing agent preferably contains an amine compound, and it is preferred that the curing agent is contained excessively. This amine compound acts as an adhesive reinforcing agent, and specific examples will be described later. In consideration of the balance between other properties such as heat resistance and adhesiveness, it is preferable to use 1.0 to 1.5 equivalents of a curing agent containing an amine compound with respect to 1 equivalent of the resin curable functional group of the silicone polymer. It is particularly preferable to use 1.0 to 1.2 equivalents per equivalent of the resin curable functional group.
[0040]
Moreover, you may add a hardening accelerator with a hardening | curing agent. For example, when the resin curable functional group is an epoxy group, an imidazole compound or the like is generally used, and this can also be used in the present invention. Specific examples of the imidazole compound used as a curing accelerator include imidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2- Heptadecylimidazole, 4,5-diphenylimidazole, 2-methylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2-heptadecylimidazoline, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-phenyl-4 -Methylimidazole, 2-ethylimidazoline, 2-isopropylimidazoline, 2,4-dimethylimidazoline, 2-phenyl-4-methylimidazoline and the like. In order to obtain a sufficient effect of the curing accelerator, it is preferably used in an amount of 0.01 parts by weight or more with respect to 100 parts by weight of the silicone polymer, and preferably 10 parts by weight or less from the viewpoint of thermal expansion coefficient and elongation.
[0041]
If necessary, both terminal silyl group-modified elastomers can be added to the thermosetting resin composition containing the silicone polymer in the present invention. By adding a both-end silyl group-modified elastomer to the thermosetting resin composition, the breaking stress of the resin cured product is increased, and the handleability is improved. The both-end silyl group-modified elastomer in the present invention is a long-chain elastomer having a weight average molecular weight of about 3000 to 100,000, and has alkoxysilyl groups at both ends of the main chain. The main chain of the elastomer is not particularly limited, and an elastomer having a main chain skeleton such as a polyolefin such as polyisobutylene or polypropylene, a polyether such as polypropylene oxide, butadiene rubber or acrylic rubber can be used. The alkoxysilyl group may be one in which 1 to 3 alkoxy groups are bonded to the Si element, and the alkoxy group bonded to the Si element preferably has 1 to 4 carbon atoms. Examples of the both-end silyl group-modified elastomer include SAT200 (both end silyl group-modified polyether, trade name manufactured by Kaneka Chemical Co., Ltd.), EP103S, EP303S (both end silyl group-modified polyisobutylene, Kaneka Chemical Industry Co., Ltd.). Product name) and the like can be used. It is preferable that the compounding quantity of a both terminal silyl group modified elastomer is 0.1-30 weight part with respect to 100 weight part of silicone polymers. If the amount is less than 0.1 part by weight, the effect of blending hardly appears, and if it exceeds 30 parts by weight, the coefficient of thermal expansion tends to increase.
[0042]
In the thermosetting resin composition of the present invention, a silicone oil having an epoxy group (in the present invention, described as an epoxy-modified silicone oil) can be used in combination with the resin-curable silicone polymer of the present invention. The blending ratio of the resin curable silicone polymer and the epoxy-modified silicone oil is preferably such that the resin curable silicone polymer is contained in an amount of 0.1 part by weight or more with respect to the total of 100 parts by weight, the coefficient of thermal expansion, From the viewpoint of elongation and breaking stress, the resin curable silicone polymer is more preferably contained in an amount of 5 parts by weight or more, and particularly preferably 20 parts by weight or more. Further, from the viewpoint of elongation and breaking stress, it is preferable that 5 parts by weight or more of the epoxy-modified silicone oil is contained with respect to 100 parts by weight in total of the blend of the resin curable silicone polymer and the epoxy-modified silicone oil. Part or more is particularly preferable. When the resin curable silicone polymer is less than 0.1 parts by weight, the dispersibility of the inorganic filler tends to decrease. The blending ratio of the resin curable silicone polymer and the epoxy-modified silicone oil can be determined according to the purpose from the thermal expansion coefficient and the elongation value. That is, the larger the blending ratio of the resin curable silicone polymer, the smaller the thermal expansion coefficient, and the elongation value can be increased by increasing the blending ratio of the epoxy-modified silicone oil. Here, the epoxy-modified silicone oil is a chain polysiloxane compound having a functional group containing an epoxy group in the side chain, and the viscosity at 25 ° C. is 10-2-103It is in the range of Pa · s. The viscosity in the present invention was measured at 25 ° C. using an EMD viscometer manufactured by Tokyo Keiki Co., Ltd. The epoxy equivalent of the epoxy-modified silicone oil is preferably 150 to 5000, and particularly preferably 300 to 1000.
[0043]
In the thermosetting resin composition containing the epoxy-modified silicone oil described above, a silicone polymer containing no resin-curable functional group in place of part or all of the resin-curable silicone polymer of the present invention (in the present invention, non- (It is described as a resin curable silicone polymer.)). When a non-resin curable silicone polymer is used, the blending amount of the non-resin curable silicone polymer is preferably 30 parts by weight or less with respect to 100 parts by weight of the total of the epoxy-modified silicone oil and the silicone polymer. . When the non-resin curable silicone polymer exceeds 30 parts by weight, the elongation value of the cured resin tends to decrease.
[0044]
Here, the non-resin curable silicone polymer is a bifunctional siloxane unit (R2SiO2/2) Trifunctional siloxane units (RSiO3/2(Wherein R is an organic group and the R groups in the silicone polymer may be the same or different from each other) and tetrafunctional siloxane units (SiO4/2And at least one functional group that reacts with a hydroxyl group at the terminal. The polymerization degree is preferably 2 to 7000, more preferably 2 to 100, and particularly preferably 2 to 70. Examples of R include an aromatic group such as an alkyl group having 1 to 4 carbon atoms and a phenyl group. Examples of the functional group that reacts with a hydroxyl group include a silanol group, an alkoxyl group having 1 to 4 carbon atoms, an acyloxy group having 1 to 4 carbon atoms, and a halogen other than bromine such as chlorine.
[0045]
Such a non-resin curable silicone polymer can be obtained by hydrolyzing and polycondensing the silane compound represented by the general formula (II). As the silane compound represented by the general formula (II) used for the synthesis of the non-resin curable silicone polymer, a tetrafunctional silane compound or a trifunctional silane compound is used as an essential component, and a bifunctional silane compound. Is used as needed. In particular, the tetrafunctional silane compound is preferably a tetraalkoxysilane, the trifunctional silane compound is preferably a monoalkyltrialkoxysilane, and the bifunctional silane compound is preferably a dialkyldialkoxysilane. The use ratio of the silane compound is preferably 15 to 100 mol% of the tetrafunctional silane compound or trifunctional silane compound and 0 to 85 mol% of the bifunctional silane compound, preferably tetrafunctional silane compound or trifunctional. 20-100 mol% of 1 or more types of a silane compound and 0-80 mol% of bifunctional silane compounds are more preferable. In particular, the tetrafunctional silane compound is preferably used at a ratio of 15 to 100 mol%, the trifunctional silane compound 0 to 85 mol%, and the bifunctional silane compound 0 to 85 mol%. More preferably, the compound is used in a proportion of 20 to 100 mol%, the trifunctional silane compound is 0 to 80 mol%, and the bifunctional silane compound is used in a proportion of 0 to 80 mol%. As the catalyst and solvent for the hydrolysis / polycondensation reaction, those similar to the hydrolysis / polycondensation reaction in the production of the resin curable silicone polymer can be applied. The production of the non-resin curable silicone polymer is carried out so as not to gel by adjusting the conditions and blending. The non-resin curable silicone polymer is three-dimensionally crosslinked but not completely cured or gelled, and the three-dimensional crosslinking is controlled to such an extent that it is dissolved in a reaction solvent, for example. For this reason, when manufacturing, storing, and using a non-resin curable silicone polymer, the temperature is preferably normal temperature or higher and 200 ° C. or lower, and more preferably 150 ° C. or lower.
[0046]
In the case of using a resin curable silicone polymer or a non-resin curable silicone polymer in combination with an epoxy-modified silicone oil, compared with the case where only the non-resin curable silicone polymer is used as the silicone polymer component, the resin curing In the case of containing a curable silicone polymer, it is preferable from the viewpoint of thermal expansion coefficient, elongation, and breaking stress, and it is particularly preferable to use only a resin curable silicone polymer as a silicone polymer component.
[0047]
An adhesive reinforcing agent can be added to the thermosetting resin composition of the present invention as necessary in order to increase the adhesion to the metal foil and increase the peel strength between the cured resin and the metal foil. . As the adhesive reinforcing agent, a compound having a plurality of reactive functional groups such as an amino group and a hydroxyl group can be used, and these also act as an epoxy resin curing agent. Examples of the amine compound having a plurality of reactive functional groups include m-phenylenediamine, 4,4′-diaminobenzanilide, and 4,4′-diamino-2,2′-dimethylbiphenyl. A compound having a plurality of active NH groups in the molecule, such as a compound having a group or dicyandiamide, or a compound having both an amino group and a hydroxyl group in the molecule, such as 3-amino-1-propanol and 4-aminophenol. be able to. The compounding amount of the adhesive reinforcing agent is preferably 0.01 to 9 parts by weight, particularly preferably 0.1 to 6 parts by weight with respect to 100 parts by weight of the silicone polymer. When the amount is less than 0.01 part by weight, the effect of the blending tends to hardly appear. When the amount exceeds 9 parts by weight, the heat resistance of the cured product tends to decrease.
[0048]
The resin composition can be dissolved or dispersed in a solvent to form a resin varnish. The concentration of the resin varnish is appropriately determined in consideration of workability and the like. Moreover, when adjusting a resin composition following the synthesis | combination of a silicone polymer, it is preferable to use the same thing as the solvent used for the synthesis | combination of a silicone polymer. Solvents include alcohol solvents such as methanol and ethanol, ether solvents such as ethylene glycol monomethyl ether, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, amide solvents such as N, N-dimethylformamide, toluene, Aromatic hydrocarbon solvents such as xylene, ester solvents such as ethyl acetate, and nitrile solvents such as butyronitrile are preferably used. Moreover, the mixed solvent which used several types of these solvents together can also be used.
[0049]
(Metal foil with resin)
A resin-coated metal foil can be produced by applying a resin varnish to a metal foil and drying the resin varnish within a range of 80 to 200 ° C. in a drying furnace. The drying time may be such that the fluidity of the resin at room temperature is lost, and may be such that the resin is not completely cured when dried at a high temperature. The metal foil is not particularly limited, and a metal foil generally used as a wiring circuit conductor in the wiring board field can be used. In consideration of electrical characteristics and cost, it is preferable to use a copper foil. Particularly preferably, an electrolytic copper foil having a roughened surface on at least one surface, a rolled copper foil, or an ultrathin copper foil with a carrier film can be used. The metal foil having a thickness of 5 to 200 μm that is usually used can be used. Also, a composite foil with a three-layer structure in which nickel, nickel-phosphorus, nickel-tin alloy, nickel-iron alloy, lead, lead-tin alloy, etc. are used as an intermediate layer and copper layers are provided on both sides, or aluminum and copper A composite foil such as a composite foil obtained by combining foils can also be used.
[0050]
The thickness of the insulating resin layer of the metal foil with resin is preferably equal to or greater than the thickness of the copper foil. Also, when laminated on the inner wiring circuit board after processing the wiring circuit, the conductor thickness of the inner wiring circuit and the resin It is preferable that it is larger than the sum of the copper foil thickness of metal foil. On the other hand, if it is too thick, the weight increases more than necessary, and the cost tends to increase. The thickness is preferably 6 to 200 μm, but may be thicker. In order to produce a thick insulating resin layer, coating and drying can be repeated several times. The inner layer circuit board is a circuit board formed on the outermost layer, for example, a circuit board formed on one or both sides of a substrate obtained by impregnating and curing a base material such as paper or fiber in a resin, A multilayer wiring board obtained by laminating a plurality of wiring boards via a prepreg, a multilayer wiring board multilayered by a build-up method, and the like can be mentioned.
[0051]
(Resin sheet with wiring circuit)
By performing wiring circuit processing in a state where the insulating resin layer of the metal foil with resin has sufficient circuit embedding properties, a resin sheet with wiring circuit is produced. As a state in which the insulating resin layer has a sufficient circuit embedding property, there is a B-Stage state in a thermosetting resin. As a method of adjusting the insulating resin layer to the B-Stage state, when applying and drying the resin varnish on the metal foil, a method of adjusting the drying temperature and drying time, when performing wiring circuit processing on the resin-coated metal foil, The method of adjusting to a B-Stage state by heating is mentioned. It is preferable that the B-Stage condition for adjusting to the B-Stage state is a temperature of 80 to 200 ° C. and a time of 1 to 120 minutes.
[0052]
By subjecting the metal foil with resin to wiring circuit processing, the resin material with wiring circuit of the present invention can be produced. For wiring circuit processing, a generally known method such as a subtractive method can be applied. For example, a wiring pattern is formed by forming a resist pattern on the surface of the metal foil with resin, removing unnecessary copper foil by etching, and peeling the resist pattern. Moreover, a hole may be formed in the metal foil with resin with a laser or a drill in advance, or the hole may be formed after processing the wiring circuit. Furthermore, the hole may be filled with a conductive paste, or the hole may be filled with metal by plating or the like.
[0053]
A multilayer wiring board can be produced by laminating a resin sheet with a wiring circuit and an inner wiring circuit board to obtain interlayer conduction. Lamination molding and interlayer conduction can be performed according to conventional methods. The conditions for the lamination molding are carried out by heating and pressurizing at a temperature range of 130 to 200 ° C, preferably at a range of 150 to 180 ° C, at a pressure of 0.5 to 20 MPa, preferably at a pressure of 2 to 8 MPa. Depending on the capacity of the press, the desired thickness, etc. The heat and pressure treatment time is determined in a timely manner according to other conditions such as temperature and pressure, but is generally about 30 minutes to 2 hours. Interlayer conduction can be achieved by a general method such as conductive paste or plating. For example, after laminating a resin material with a wiring circuit and an inner layer wiring circuit board, a hole is provided with a laser or a drill to provide an interlayer conduction path, a resist pattern is formed on the wiring circuit, and an inner layer wiring circuit is formed by plating. A multilayer wiring board having interlayer conduction can be obtained by removing the resist pattern and removing the resist pattern.
[0054]
The metal foil with resin and the resin sheet with circuit can be further laminated on the multilayer wiring board produced as described above, and integration and interlayer conduction formation can be repeated to build up. The build-up layer produced using the resin material with a wiring circuit of the present invention can be thinned by burying the wiring circuit layer in the resin when laminated. Moreover, you may laminate | stack collectively using the resin material with a some wiring circuit.
[0055]
(Resin material with wiring circuit with inner layer circuit)
A resin material with a wiring circuit can be produced by laminating a resin layer in a B-Stage state made of the resin varnish on an inner circuit board and further performing wiring circuit processing on the laminated board obtained by laminating metal foil. it can. As a method of producing a laminated board used for producing this resin material with wiring circuit, a method of laminating and integrating the resin-coated metal foil on an inner circuit board, or applying and drying the resin varnish on an inner circuit board Examples include a method of laminating and integrating a metal foil, a method of laminating and integrating a resin sheet and a metal foil obtained by applying the resin varnish to a carrier film and drying on an inner circuit board. As a method for adjusting to the B-Stage state, it is preferable to adjust to the B-Stage state at the same time of stacking and integration. Moreover, it can also adjust by heating after integrating. B-Stage conversion conditions for adjusting to an appropriate B-Stage state by stacking and integration are preferably a temperature of 80 to 200 ° C., a time of 1 to 120 minutes, and a pressure of 0.1 to 8 MPa.
[0056]
A multilayer wiring board can be manufactured by laminating a build-up material such as the resin-coated metal foil and the resin sheet with a wiring circuit on the resin material with a wiring circuit and integrating them to form interlayer conduction. Further, it is possible to further increase the number of layers by repeating this build-up. The build-up layer produced using the resin material with a wiring circuit of the present invention can be thinned by burying the wiring circuit layer in the resin when laminated.
[0057]
【Example】
(Reference example)
In a glass flask equipped with a stirrer, a condenser and a thermometer, 20 g of tetramethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.), 60 g of dimethoxydimethylsilane (manufactured by Tokyo Chemical Industry Co., Ltd.), dimethoxymethylsilane (Tokyo Chemical Industry Co., Ltd.) (Compared with 67 g) and 37 g of methanol (manufactured by Tokyo Chemical Industry Co., Ltd.) as a synthesis solvent, 1.5 g of maleic acid and 50 g of distilled water as a synthesis catalyst were mixed and stirred at 80 ° C. for 2 hours. Then, 72 g of allyl glycidyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.2 g of chloroplatinate (2 wt% isopropyl alcohol solution) were added, and the mixture was further stirred for 4 hours to synthesize an epoxy-modified silicone polymer. . The degree of polymerization of the siloxane units of the obtained silicone polymer was 65 (converted from the number average molecular weight measured by GPC using a standard polystyrene calibration curve, the same applies hereinafter).
[0058]
Example 1
In a glass flask equipped with a stirrer, a condenser and a thermometer, silica powder (product name: SO-25R, average particle size: 100 parts by weight of the solid content of the silicone polymer synthesized by the same method as in the above Reference Example). 0.5 μm, manufactured by Admatechs Co., Ltd.) 450 parts by weight and 202 parts by weight of methanol as a diluent solvent, stirred at 80 ° C. for 1 hour, cooled to room temperature, and 100 parts by weight of the solid content of the silicone polymer Then, 78 parts by weight of tetrabromobisphenol A and 3 parts by weight of 2-ethyl-4-methylimidazole were blended and stirred at room temperature for 1 hour to prepare a resin varnish. The thermal expansion coefficient of the cured resin varnish is 22 × 10.-6The elongation was 3.1%.
[0059]
In the present invention, the thermal expansion coefficient and elongation of the cured resin are measured using a resin varnish, a polyethylene terephthalate film having a thickness of 50 μm as a carrier film, and a knife coater so that the thickness after heating and drying is 50 μm. Then, it was heated and cured under conditions of 170 ° C. for 2 hours, the carrier film was removed, and the produced resin sheet was used as a sample. The coefficient of thermal expansion was measured in a tensile mode by thermomechanical analysis (TMA: TMA manufactured by MAC SCIENCE). Elongation is measured using a tensile tester (Shimadzu Autograph AG-100C) using a film having a width of 10 mm × length of 80 mm and a thickness of 50 to 100 μm as a sample. As min, it was measured by a tensile test.
[0060]
This resin varnish was coated with a knife coater using a polyethylene terephthalate film having a thickness of 50 μm as a carrier film so that the thickness after heating and drying was 50 μm, and was dried by heating at a temperature of 30 ° C. for 10 minutes. The film was peeled off to produce a resin sheet.
[0061]
Also, this resin varnish was coated on the roughened surface side with a knife coater so that the thickness of the resin sheet after heating and drying was 50 μm using a single-side roughened copper foil having a thickness of 18 μm, and the temperature was 1300 ° C. The resin sheet with copper foil was produced by heating and drying for 10 minutes.
[0062]
The resin varnish was coated on the roughened surface side with a knife coater so that the thickness of the heat-dried resin sheet was 50 μm using a 18 μm thick single-side roughed copper foil, and the temperature was 1300 ° C. for 60 minutes. Heat-dried and subjected to wiring circuit processing using an etching solution (dissolving 200 g of ammonium persulfate (Mitsubishi Gas Chemical Co., Ltd. in 1 kg of water)), and a resin material with a wiring circuit (resin sheet with a wiring circuit) (FIG. 1 ).
[0063]
A 0.8-mm-thick glass cloth base epoxy resin double-sided copper-clad laminate (manufactured by Hitachi Chemical Co., Ltd., using MCL-E-67 (trade name)) is subjected to wiring circuit processing, and the above and below are prepared as described above. The copper foil-coated resin sheets were stacked and heated and pressed at 130 ° C. and 3 MPa for 60 minutes to prepare a copper-clad four-layer laminate A1 in which the outermost insulating layer was in the B-Stage state. The copper-clad four-layer laminate A1 was subjected to wiring circuit processing by etching to obtain an insulating resin material with circuit (FIG. 2). The copper foil-attached resin sheets prepared previously were placed on both sides of this insulating resin material with circuit, and heated and pressed at a temperature of 175 ° C. and a pressure of 3 MPa for 60 minutes to prepare a copper-clad 6-layer laminate B1 (FIG. 3).
[0064]
A 0.8-mm-thick glass cloth base epoxy resin double-sided copper-clad laminate (manufactured by Hitachi Chemical Co., Ltd., using MCL-E-67 (trade name)) is subjected to wiring circuit processing, and the above and below are prepared as described above. The obtained copper foil-attached resin sheets were stacked and heated and pressurized at 175 ° C. and 3 MPa for 60 minutes to prepare a copper-clad four-layer laminate C1 in which the outermost insulating layer was in the C-Stage state. The copper-clad laminate C1 is subjected to wiring circuit processing by etching, and the previously prepared resin sheet with copper foil is laminated on both sides, and heated and pressed at a temperature of 175 ° C. and a pressure of 3 MPa for 60 minutes to form a copper-clad laminate 6 Produced.
[0065]
A 0.8-mm-thick glass cloth base epoxy resin double-sided copper-clad laminate (manufactured by Hitachi Chemical Co., Ltd., using MCL-E-67 (trade name)) is subjected to wiring circuit processing, and the above and below are prepared as described above. The above-mentioned resin sheets with wiring circuits were stacked, and the above-prepared resin sheets with copper foil were stacked on top and bottom, and heated and pressed at a temperature of 175 ° C. and a pressure of 3 MPa for 60 minutes to prepare a copper-clad 6-layer laminate E1.
[0066]
(Example 2)
The blending amount of silica powder (trade name: SO-25R, average particle size: 0.5 μm, manufactured by Admatex Co., Ltd.) is 900 parts by weight and the blending amount of methanol is 100 parts by weight of the solid content of the silicone polymer. A resin varnish was prepared in the same manner as in Example 1 except that the amount was changed to 250 parts by weight. The thermal expansion coefficient of the cured resin varnish is 15 × 10-6/ ° C., and the elongation was 2.2%.
Using this resin varnish, a resin sheet, a resin sheet with copper foil, a resin sheet with a wiring circuit, a copper-clad four-layer laminate A2, a copper-clad six-layer laminate B2, and a copper-clad four-layer in the same manner as in Example 1. A laminate C2, a copper-clad 6-layer laminate D2, and a copper-clad 6-layer laminate E2 were produced.
[0067]
(Example 3)
The blending amount of silica powder (trade name: SO-25R, average particle size: 0.5 μm, manufactured by Admatechs) is 1300 parts by weight and the blending amount of methanol is 100 parts by weight of the solid content of the silicone polymer. A resin varnish was prepared in the same manner as in Example 1 except that the amount was changed to 490 parts by weight. The thermal expansion coefficient of the cured resin varnish is 10 × 10-6/ ° C., and the elongation was 1.2%.
Using this resin varnish, a resin sheet, a resin sheet with copper foil, a resin sheet with a wiring circuit, a copper-clad four-layer laminate A3, a copper-clad six-layer laminate B3, and a copper-clad four-layer in the same manner as in Example 1. A laminate C3, a copper-clad 6-layer laminate D3, and a copper-clad 6-layer laminate E3 were produced.
[0068]
(Comparative example)
100 parts of bisphenol A novolac type epoxy resin (epoxy equivalent 210, manufactured by Dainippon Ink & Chemicals, Inc., using Epicron N865 (trade name)), bisphenol A novolak resin (hydroxyl equivalent 118, manufactured by Dainippon Ink & Chemicals, Inc.) 60 parts of PRIOFEN VH-4170 (trade name) and 2 parts of dicyandiamide were dissolved in 120 parts of methyl ethyl ketone and stirred at room temperature for 1 hour to prepare a resin varnish.
Using this resin varnish, a resin sheet, a resin sheet with copper foil, a copper-clad four-layer laminate A4, a copper-clad six-layer laminate B4, a copper-clad four-layer laminate C4 and a copper-clad in the same manner as in Example 1 A six-layer laminate D4 was produced. In addition, about the resin sheet with a wiring circuit and the copper clad 6 layer laminated board E4, the shape of the resin sheet with a wiring circuit could not be maintained at the time of an etching, and production was impossible.
[0069]
Weight loss and resin sheet shape after 10 g of resin sheets of Examples 1 to 4 and Comparative Example were treated with an etching solution (200 g of ammonium persulfate (Mitsubishi Gas Chemical) dissolved in 1 kg of water) at room temperature for 1 hour. Is shown in Table 1.
The surface roughness of the copper-clad 6-layer laminates B1 to B4, the copper-clad 6-layer laminates D1 to D4, and the copper-clad 6-layer laminates E1 to E3 was measured with a stylus type surface roughness meter. The measurement location was on a straight line with a length of 25 mm from the portion where the inner layer wiring circuit was present immediately below to the portion where the inner layer wiring circuit was not present, and the 10-point average roughness of the step between the portion where the inner layer wiring circuit was present and not present was measured. The results are shown in Table 1.
Further, the copper-clad 6-layer laminates B1 to B4, the copper-clad 6-layer laminates D1 to D4, and the copper-clad 6-layer laminates E1 to E3 were floated in a solder bath at 260 ° C. for 30 seconds to evaluate solder heat resistance. The results are shown in Table 1.
[0070]
[Table 1]
As shown in Table 1, since the resin sheet of the present invention does not dissolve in the etching solution even when cured at a low temperature, it has solder heat resistance even in the state of the copper-clad 6-layer laminate B or the copper-clad 6-layer laminate E. It can also be seen that the circuit embedding property is excellent and the solder heat resistance is excellent.
[0072]
【The invention's effect】
By using a resin that does not decompose against chemicals such as etching solution even when it is not completely cured, the present invention can serve as an insulating layer and allows wiring to be embedded in the resin sheet during molding. Thus, since the influence of the convexity by the inner layer wiring circuit is small after molding, the surface can be flattened, and a resin material suitable for fine wiring can be provided.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view showing an example of a resin material with a wiring circuit of the present invention.
FIG. 2 is a cross-sectional view showing an example of a resin material with a wiring circuit according to the present invention.
FIG. 3 is a cross-sectional view showing a copper-clad 6-layer laminate produced using the resin material with a wiring circuit of the present invention.
[Explanation of symbols]
1,1 ', 1' '. Resin layer (derived from resin sheet with copper foil)
2, 2 '. Wiring conductor (derived from resin sheet with copper foil)
3. Inner layer circuit board insulation layer
4). Circuit wiring of inner circuit board
5. Copper layer (derived from resin sheet with copper foil)
Claims (11)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001190565A JP4487448B2 (en) | 2001-06-25 | 2001-06-25 | Resin material with wiring circuit, manufacturing method thereof and multilayer printed wiring board |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001190565A JP4487448B2 (en) | 2001-06-25 | 2001-06-25 | Resin material with wiring circuit, manufacturing method thereof and multilayer printed wiring board |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2003008212A JP2003008212A (en) | 2003-01-10 |
| JP4487448B2 true JP4487448B2 (en) | 2010-06-23 |
Family
ID=19029316
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001190565A Expired - Fee Related JP4487448B2 (en) | 2001-06-25 | 2001-06-25 | Resin material with wiring circuit, manufacturing method thereof and multilayer printed wiring board |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4487448B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4110170B2 (en) | 2003-02-13 | 2008-07-02 | 株式会社フジクラ | Multilayer substrate and manufacturing method thereof |
| JP2005072187A (en) * | 2003-08-22 | 2005-03-17 | Denso Corp | Multilayer circuit board and manufacturing method thereof |
| JP6166614B2 (en) * | 2013-07-23 | 2017-07-19 | Ｊｘ金属株式会社 | Surface-treated copper foil, copper foil with carrier, substrate, printed wiring board, printed circuit board, copper-clad laminate, and printed wiring board manufacturing method |
| JP7147223B2 (en) * | 2018-03-30 | 2022-10-05 | 住友ベークライト株式会社 | Method for manufacturing coreless substrate and method for manufacturing printed wiring board |
-
2001
- 2001-06-25 JP JP2001190565A patent/JP4487448B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2003008212A (en) | 2003-01-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5545194B2 (en) | Method for producing novel silicone polymer, silicone polymer produced by the method, thermosetting resin composition, resin film, metal foil with insulating material, insulating film with double-sided metal foil, metal-clad laminate, multilayer metal-clad Laminated board and multilayer printed wiring board | |
| JP5370333B2 (en) | Low thermal expansion thermosetting resin composition and resin film | |
| JPWO2001074927A1 (en) | Novel method for producing silicone polymers, silicone polymers produced by said method, thermosetting resin compositions, resin films, metal foils with insulating material, insulating films with metal foils on both sides, metal-clad laminates, multi-layer metal-clad laminates, and multi-layer printed wiring boards | |
| TW200848257A (en) | Prepreg and laminate | |
| TWI290816B (en) | Wiring board and method for producing the same | |
| TWI264448B (en) | Prepreg, metal-clad laminated board and printed wiring board using these | |
| WO2003099952A1 (en) | Adhesive film and prepreg | |
| JP2006143973A (en) | Epoxy resin composition, prepreg, laminated board, printed wiring board | |
| JP4572423B2 (en) | Method for producing copper-clad laminate, printed wiring board using the same, and multilayer printed wiring board | |
| JP4487448B2 (en) | Resin material with wiring circuit, manufacturing method thereof and multilayer printed wiring board | |
| JP3615906B2 (en) | Adhesive film for multilayer wiring boards | |
| JP2000301534A (en) | Prepreg, metal-clad laminated board, and printed wiring board using prepreg and laminated board | |
| JP4899280B2 (en) | Composite material for wiring board and manufacturing method thereof | |
| JP5251949B2 (en) | PCB and printed circuit board | |
| JP2010258462A (en) | Composite material for wiring board and production method thereof | |
| JP2005048036A (en) | Prepreg and metal foil-clad laminate board using the same | |
| JP2003007138A (en) | Inter-layer insulating varnish for multi-layer interconnection board, inter-layer insulating material using it, multi-layer interconnection board, manufacturing method therefor | |
| JP4734781B2 (en) | Substrate, printed circuit board, and manufacturing method thereof | |
| JP2008111188A (en) | Copper foil for printed circuit board | |
| WO2025183004A1 (en) | Resin composition, prepreg, metal-clad laminate, wiring board, metal foil with resin, and film with resin | |
| JP2012084923A (en) | Composite material for wiring board and manufacturing method thereof | |
| JP2014009356A (en) | Epoxy resin composition, insulating film made of the same, and multilayer printed board comprising the same | |
| JP2002012834A (en) | Thermosetting adhesive film | |
| JP2004175936A (en) | Prepreg and metal foil-clad laminate | |
| JP2001106811A (en) | Prepreg and laminate for printed wiring board |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20080530 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20091015 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20091203 |
|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20091203 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20100309 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20100322 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130409 Year of fee payment: 3 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 4487448 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130409 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130409 Year of fee payment: 3 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140409 Year of fee payment: 4 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| LAPS | Cancellation because of no payment of annual fees |