JP5630241B2 - Insulating resin, wiring board, and method of manufacturing wiring board - Google Patents
Insulating resin, wiring board, and method of manufacturing wiring board Download PDFInfo
- Publication number
- JP5630241B2 JP5630241B2 JP2010265610A JP2010265610A JP5630241B2 JP 5630241 B2 JP5630241 B2 JP 5630241B2 JP 2010265610 A JP2010265610 A JP 2010265610A JP 2010265610 A JP2010265610 A JP 2010265610A JP 5630241 B2 JP5630241 B2 JP 5630241B2
- Authority
- JP
- Japan
- Prior art keywords
- insulating resin
- equivalent
- active ester
- wiring board
- epoxy
- 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.)
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- 229920005989 resin Polymers 0.000 title claims description 150
- 239000011347 resin Substances 0.000 title claims description 150
- 238000004519 manufacturing process Methods 0.000 title claims description 29
- 239000003822 epoxy resin Substances 0.000 claims description 89
- 229920000647 polyepoxide Polymers 0.000 claims description 89
- 239000011342 resin composition Substances 0.000 claims description 81
- 125000004185 ester group Chemical group 0.000 claims description 74
- 229920001187 thermosetting polymer Polymers 0.000 claims description 72
- 150000001875 compounds Chemical class 0.000 claims description 71
- 238000000034 method Methods 0.000 claims description 52
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 43
- 239000005011 phenolic resin Substances 0.000 claims description 42
- 238000007788 roughening Methods 0.000 claims description 34
- 238000001723 curing Methods 0.000 claims description 28
- 229920001568 phenolic resin Polymers 0.000 claims description 27
- 239000000758 substrate Substances 0.000 claims description 27
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 26
- 239000004020 conductor Substances 0.000 claims description 26
- 150000002148 esters Chemical class 0.000 claims description 23
- 238000007747 plating Methods 0.000 claims description 21
- 239000004593 Epoxy Substances 0.000 claims description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 20
- 238000007772 electroless plating Methods 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 15
- 230000001678 irradiating effect Effects 0.000 claims description 12
- 230000001590 oxidative effect Effects 0.000 claims description 11
- 125000003700 epoxy group Chemical group 0.000 claims description 10
- 238000009713 electroplating Methods 0.000 claims description 8
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 6
- 230000005855 radiation Effects 0.000 claims description 3
- 238000001029 thermal curing Methods 0.000 claims 1
- 239000010410 layer Substances 0.000 description 109
- 239000000243 solution Substances 0.000 description 29
- 239000007788 liquid Substances 0.000 description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 239000000853 adhesive Substances 0.000 description 22
- 230000001070 adhesive effect Effects 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 21
- -1 ester compounds Chemical class 0.000 description 16
- 239000002904 solvent Substances 0.000 description 16
- 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 15
- 229920003986 novolac Polymers 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- JYLNVJYYQQXNEK-UHFFFAOYSA-N 3-amino-2-(4-chlorophenyl)-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(CN)C1=CC=C(Cl)C=C1 JYLNVJYYQQXNEK-UHFFFAOYSA-N 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- 239000011256 inorganic filler Substances 0.000 description 9
- 229910003475 inorganic filler Inorganic materials 0.000 description 9
- 229910000679 solder Inorganic materials 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 8
- 238000005530 etching Methods 0.000 description 8
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 229930003836 cresol Natural products 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 150000002989 phenols Chemical class 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000009413 insulation Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 5
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical group CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 5
- 229910001507 metal halide Inorganic materials 0.000 description 5
- 150000005309 metal halides Chemical class 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- QQOWHRYOXYEMTL-UHFFFAOYSA-N triazin-4-amine Chemical group N=C1C=CN=NN1 QQOWHRYOXYEMTL-UHFFFAOYSA-N 0.000 description 5
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 4
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000007822 coupling agent Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 239000002966 varnish Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 3
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- 239000005751 Copper oxide Substances 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 229910000431 copper oxide Inorganic materials 0.000 description 3
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-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
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NJYZCEFQAIUHSD-UHFFFAOYSA-N acetoguanamine Chemical compound CC1=NC(N)=NC(N)=N1 NJYZCEFQAIUHSD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 description 2
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 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
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 2
- 239000004843 novolac epoxy resin Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 235000013824 polyphenols Nutrition 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
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- 238000003756 stirring Methods 0.000 description 2
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- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
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- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
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- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
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- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-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
- 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
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
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- LVACOMKKELLCHJ-UHFFFAOYSA-N 3-trimethoxysilylpropylurea Chemical compound CO[Si](OC)(OC)CCCNC(N)=O LVACOMKKELLCHJ-UHFFFAOYSA-N 0.000 description 1
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- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
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- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
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- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- UHKJHMOIRYZSTH-UHFFFAOYSA-N ethyl 2-ethoxypropanoate Chemical compound CCOC(C)C(=O)OCC UHKJHMOIRYZSTH-UHFFFAOYSA-N 0.000 description 1
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- 238000004898 kneading Methods 0.000 description 1
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- CMIAIUZBKPLIOP-YZLZLFLDSA-N methyl (1r,4ar,4br,10ar)-7-(2-hydroperoxypropan-2-yl)-4a-methyl-2,3,4,4b,5,6,10,10a-octahydro-1h-phenanthrene-1-carboxylate Chemical group C1=C(C(C)(C)OO)CC[C@@H]2[C@]3(C)CCC[C@@H](C(=O)OC)[C@H]3CC=C21 CMIAIUZBKPLIOP-YZLZLFLDSA-N 0.000 description 1
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- LIBWSLLLJZULCP-UHFFFAOYSA-N n-(3-triethoxysilylpropyl)aniline Chemical compound CCO[Si](OCC)(OCC)CCCNC1=CC=CC=C1 LIBWSLLLJZULCP-UHFFFAOYSA-N 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical class C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
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- LYKRPDCJKSXAHS-UHFFFAOYSA-N phenyl-(2,3,4,5-tetrahydroxyphenyl)methanone Chemical class OC1=C(O)C(O)=CC(C(=O)C=2C=CC=CC=2)=C1O LYKRPDCJKSXAHS-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
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- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 1
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- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
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- 239000001488 sodium phosphate Substances 0.000 description 1
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- SYZCZDCAEVUSPM-UHFFFAOYSA-M tetrahexylazanium;bromide Chemical compound [Br-].CCCCCC[N+](CCCCCC)(CCCCCC)CCCCCC SYZCZDCAEVUSPM-UHFFFAOYSA-M 0.000 description 1
- FBEVECUEMUUFKM-UHFFFAOYSA-M tetrapropylazanium;chloride Chemical compound [Cl-].CCC[N+](CCC)(CCC)CCC FBEVECUEMUUFKM-UHFFFAOYSA-M 0.000 description 1
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- 125000005270 trialkylamine group Chemical group 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
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- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、絶縁樹脂、配線板及び配線板の製造方法に関する。さらに詳しくは、本発明は、絶縁樹脂層表面の凹凸形状が小さい状態でも、配線導体に対して容易に高い接着力を発現し得る絶縁樹脂、配線板及び配線板の製造方法に関するものである。 The present invention relates to an insulating resin, a wiring board, and a method for manufacturing the wiring board. More specifically, the present invention relates to an insulating resin, a wiring board, and a method for manufacturing a wiring board that can easily exhibit a high adhesive force to a wiring conductor even when the uneven shape on the surface of the insulating resin layer is small.
電子機器の小型化、軽量化、多機能化が一段と進み、これに伴い、ＬＳＩやチップ部品等の高集積化が進み、その形態も多ピン化、小型化へと急速に変化している。このため、電子部品の実装密度を向上するために、微細配線化に対応できる配線板の開発が進められている。このような配線板としては、ガラスクロスを含まない絶縁樹脂をプリプレグの代わりに用い、必要な部分のみビアホールで層間接続を行い、配線層を形成するビルドアップ方式の配線板があり、軽量化や小型化、微細化に適した手法として主流になりつつある。 As electronic devices are further reduced in size, weight, and functionality, LSIs and chip components have been highly integrated, and their forms are rapidly changing to more pins and smaller sizes. For this reason, in order to improve the mounting density of electronic components, development of a wiring board that can cope with miniaturization is underway. As such a wiring board, there is a build-up type wiring board that uses an insulating resin that does not contain glass cloth instead of a prepreg, and performs interlayer connection with via holes only at necessary portions to form a wiring layer. It is becoming mainstream as a method suitable for miniaturization and miniaturization.
このビルドアップ方式の配線板は、まず、回路を有した基板上に絶縁樹脂層を形成する。そして、絶縁樹脂層を硬化した後、配線導体との接着力を確保するために、絶縁樹脂層表面を酸化性の処理液に浸して粗化処理を行う。次いで、めっき前処理を行って無電解めっきする。さらに、レジストパターンを無電解めっき層上に形成し、電解めっきで厚付けしたのち、レジストパターンを剥離し、無電解めっき層を除去して配線板とする。
しかしながら、配線の微細化に伴い、絶縁樹脂層表面を粗化して形成した絶縁樹脂層表面の凹凸が、配線形成の歩留まり低下の原因となっている。この理由は、無電解金属めっき層が絶縁樹脂層表面の凹凸に食い込み、エッチング時に除去されずに残り、配線ショートの原因となることや、絶縁樹脂層表面の凹凸に起因してレジストパターンの形成精度が低下するためである。
In this build-up type wiring board, first, an insulating resin layer is formed on a substrate having a circuit. And after hardening an insulating resin layer, in order to ensure the adhesive force with a wiring conductor, the insulating resin layer surface is immersed in an oxidizing process liquid, and a roughening process is performed. Next, electroless plating is performed by pre-plating treatment. Furthermore, after forming a resist pattern on the electroless plating layer and thickening by electroplating, the resist pattern is peeled off and the electroless plating layer is removed to obtain a wiring board.
However, with the miniaturization of wiring, the unevenness on the surface of the insulating resin layer formed by roughening the surface of the insulating resin layer causes a decrease in the yield of wiring formation. The reason for this is that the electroless metal plating layer bites into the irregularities on the surface of the insulating resin layer and remains without being removed during etching, causing a short circuit of the wiring or forming a resist pattern due to the irregularities on the surface of the insulating resin layer. This is because accuracy decreases.
したがって、絶縁樹脂層表面の凹凸を小さくすることが微細配線化の実現に重要となるが、凹凸が小さくなることによって、絶縁樹脂層と無電解金属めっき層との接着力が低下する為、この課題を解決する必要があった。また、絶縁樹脂層表面に凹凸を形成するために使用する酸化性の粗化液は、一般に過マンガン酸ナトリウムと水酸化ナトリウムの強アルカリ液が使用される。過マンガン酸ナトリウムは強アルカリ下で樹脂を溶解するが、７価のマンガンが酸化処理で消費されるため、電解再生装置によりマンガンを再生する必要がある。通常の絶縁樹脂は、絶縁信頼性や耐熱性を確保するために、粗化液への耐性を上げて設計するためマンガンの管理は重要である。しかし、溶解した樹脂は処理液内に浮遊するため、マンガンの電解再生が間に合わず、液の建浴を頻繁に行う必要が生じる。これらは、水洗処理や廃液処理といったコストが付加されるため、結果的にコストアップの要因となっていた。 Therefore, reducing the unevenness on the surface of the insulating resin layer is important for realizing fine wiring. However, since the unevenness decreases, the adhesive force between the insulating resin layer and the electroless metal plating layer decreases. There was a need to solve the problem. Further, as the oxidizing roughening liquid used for forming irregularities on the surface of the insulating resin layer, a strong alkaline liquid of sodium permanganate and sodium hydroxide is generally used. Sodium permanganate dissolves the resin under strong alkali. However, since 7-valent manganese is consumed in the oxidation treatment, it is necessary to regenerate manganese with an electrolytic regeneration device. In order to ensure insulation reliability and heat resistance of ordinary insulating resins, management of manganese is important because it is designed with increased resistance to the roughening solution. However, since the dissolved resin floats in the treatment liquid, the electrolytic regeneration of manganese is not in time, and the liquid needs to be frequently bathed. These have added costs such as water washing treatment and waste liquid treatment, resulting in a cost increase.
以上に記載したように、ビルドアップ方式の配線板に使用される絶縁樹脂層には、凹凸が小さくても接着力を確保できることが必要になっている。
また、過マンガン酸ナトリウム系の粗化液を用いて凹凸を形成する場合には、過マンガン酸ナトリウム系の粗化液に対し、厳しい管理なしで凹凸を形成できることが重要となっており、さらに粗化液を使用せずに接着力が確保できるのであれば、そのほうがより好ましいものである。
As described above, the insulating resin layer used for the build-up type wiring board needs to be able to secure an adhesive force even if the unevenness is small.
In addition, when forming irregularities using a sodium permanganate-based roughening liquid, it is important that the irregularities can be formed without strict control over the sodium permanganate-based roughening liquid. If adhesive strength can be secured without using a roughening solution, that is more preferable.
これらの要求に対して、特許文献１では、ポリフェニレンエーテル樹脂を用いた絶縁樹脂層に紫外線を照射し、過マンガン酸ナトリウム系の粗化液を使用せず、凹凸が小さい状態で高い接着力を発現する技術が開示されている。
また、特許文献２には、オゾン溶液下で絶縁樹脂層を紫外線処理する技術が開示されている。
さらに、特許文献３及び４には、活性エステル基含有化合物を樹脂組成物に用いる技術が開示されている。
In response to these requirements, Patent Document 1 irradiates an insulating resin layer using a polyphenylene ether resin with ultraviolet rays, does not use a sodium permanganate-based roughening solution, and has a high adhesive force with small unevenness. A technique for expressing it is disclosed.
Patent Document 2 discloses a technique for treating an insulating resin layer with an ultraviolet ray under an ozone solution.
Furthermore, Patent Documents 3 and 4 disclose techniques using an active ester group-containing compound for a resin composition.
しかしながら、特許文献１の技術においては、絶縁樹脂組成がポリフェニレンエーテル樹脂に限定されていること、通常ソルダレジストの後露光などで汎用的に用いられている紫外線ランプとは異なる３００ｎｍ以下の波長を有するキセノンエキシマーランプや低圧水銀ランプを使用せざるを得ないという課題があり、また、粗化処理をした際の接着力の強度については開示されていない。
また、特許文献２の技術においては、オゾン濃度を１００ｐｐｍ以上に限定している上、絶縁樹脂組成物については、なんら言及されていない。
一方、特許文献３及び４の技術は、誘電特性の向上を目的としたものであり、活性エステル基含有化合物をエポキシ樹脂の硬化剤として使用しているが、めっき用材料としては検討されておらず、紫外線照射の使用については、なんら言及されていない。
However, in the technique of Patent Document 1, the insulating resin composition is limited to polyphenylene ether resin, and it has a wavelength of 300 nm or less, which is different from the ultraviolet lamp generally used for post-exposure of a solder resist or the like. There is a problem that a xenon excimer lamp or a low-pressure mercury lamp must be used, and the strength of the adhesive strength when roughening is not disclosed.
In the technique of Patent Document 2, the ozone concentration is limited to 100 ppm or more, and no mention is made of the insulating resin composition.
On the other hand, the techniques of Patent Documents 3 and 4 are intended to improve dielectric properties and use an active ester group-containing compound as a curing agent for an epoxy resin, but have not been studied as a plating material. No mention is made of the use of ultraviolet radiation.
本発明は、このような状況下においてなされたものであり、絶縁樹脂層表面の凹凸形状が小さい状態でも、配線導体に対して容易に高い接着力を発現し得る上、ビアホール底のスミアを除去するために過マンガン酸ナトリウム系などの粗化液で処理しても、絶縁樹脂層表面の粗化凹凸形状が小さく、かつ配線導体に対して高い接着力を確保し得る絶縁樹脂、配線板及び配線板の製造方法を提供することを目的とする。 The present invention has been made under such circumstances, and can easily exhibit high adhesive force to the wiring conductor even when the uneven shape of the surface of the insulating resin layer is small, and removes smear at the bottom of the via hole. Insulating resin, wiring board, and surface roughness of the insulating resin layer are small even when treated with a roughening solution such as sodium permanganate, and high adhesion to the wiring conductor can be secured. It aims at providing the manufacturing method of a wiring board.
本発明者らは、前記目的を達成するために鋭意研究を重ねた結果、下記の知見を得た。
エポキシ樹脂と、活性エステル基含有化合物と、エポキシ樹脂硬化促進剤とを含む熱硬化性絶縁樹脂組成物を熱硬化し、これに紫外線を照射して得られる絶縁樹脂が前記目的に適合し得ることを見出した。
また、回路を有する基板に、前記熱硬化性絶縁樹脂組成物を用いて絶縁樹脂層を設け、該絶縁樹脂層を、熱硬化後、これに紫外線を照射する処理を施したのち、該層上に配線をめっきで形成することにより、効率よく目的の配線板が得られることを見出した。
本発明は、かかる知見に基づいて完成したものである。
As a result of intensive studies to achieve the above object, the present inventors have obtained the following knowledge.
An insulating resin obtained by thermally curing a thermosetting insulating resin composition containing an epoxy resin, an active ester group-containing compound, and an epoxy resin curing accelerator and irradiating it with ultraviolet rays can be adapted to the above purpose. I found.
In addition, an insulating resin layer is provided on a substrate having a circuit using the thermosetting insulating resin composition, and the insulating resin layer is subjected to a treatment of irradiating ultraviolet rays to the insulating resin layer after being thermally cured. It was found that the desired wiring board can be obtained efficiently by forming the wiring by plating.
The present invention has been completed based on such findings.
すなわち、本発明は、
（１）（Ａ）１分子中に２個以上のエポキシ基を有するエポキシ樹脂、（Ｂ）活性エステル基含有化合物、及び（Ｄ）エポキシ樹脂硬化促進剤を含む熱硬化性絶縁樹脂組成物を熱硬化し、これに紫外線を照射して得られる絶縁樹脂、
（２）熱硬化性絶縁樹脂組成物の（Ｂ）活性エステル基含有化合物が、１分子中にエステル基１個以上を有する樹脂である、上記（１）に記載の絶縁樹脂、
（３）さらに、熱硬化性絶縁樹脂組成物に（Ｃ）トリアジン骨格含有フェノール系樹脂を含む、上記（１）または（２）に記載の絶縁樹脂、
（４）熱硬化性絶縁樹脂組成物の（Ｃ）トリアジン骨格含有フェノール系樹脂が、１分子中の窒素原子含有量１２〜２２質量％のものである、上記（３）に記載の絶縁樹脂、
（５）熱硬化性絶縁樹脂組成物の（Ｂ）活性エステル基含有化合物の活性エステル当量、または（Ｂ）活性エステル基含有化合物の活性エステル当量と、（Ｃ）トリアジン骨格含有フェノール系樹脂の水酸基当量との合計当量が、（Ａ）エポキシ樹脂のエポキシ１当量に対して、０．９５〜１．２５当量である、上記（１）〜（４）のいずれかに記載の絶縁樹脂、
（６）熱硬化性絶縁樹脂組成物の（Ｂ）活性エステル基含有化合物の活性エステル当量と、（Ｃ）トリアジン骨格含有フェノール系樹脂の水酸基当量との合計当量のうちの（Ｂ）活性エステル基含有化合物の活性エステル当量が、（Ａ）エポキシ樹脂のエポキシ１当量に対して、０．１〜０．９当量である、上記（５）に記載の絶縁樹脂、
（７）配線導体の回路を有する基板上に、（Ａ）１分子中に２個以上のエポキシ基を有するエポキシ樹脂、（Ｂ）活性エステル基含有化合物、及び（Ｄ）エポキシ樹脂硬化促進剤を含む熱硬化性絶縁樹脂組成物によって設けられた絶縁樹脂層を熱硬化し、これに紫外線を照射後、この絶縁樹脂層上に、配線をめっきで形成して得られる配線板、
（８）熱硬化性絶縁樹脂組成物の（Ｂ）活性エステル基含有化合物が、１分子中にエステル基１個以上を有する樹脂である、上記（７）に記載の配線板、
（９）さらに、熱硬化性絶縁樹脂組成物に（Ｃ）トリアジン骨格含有フェノール系樹脂を含む、上記（７）または（８）に記載の配線板、
（１０）熱硬化性絶縁樹脂組成物の（Ｃ）トリアジン骨格含有フェノール系樹脂が、１分子中の窒素原子含有量１２〜２２質量％のものである、上記（９）に記載の配線板、
（１１）熱硬化性絶縁樹脂組成物の（Ｂ）活性エステル基含有化合物の活性エステル当量、または（Ｂ）活性エステル基含有化合物の活性エステル当量と、（Ｃ）トリアジン骨格
含有フェノール系樹脂の水酸基当量との合計当量が、（Ａ）エポキシ樹脂のエポキシ１当量に対して、０．９５〜１．２５当量である、上記（７）〜（１０）のいずれかに記載の配線板、
（１２）熱硬化性絶縁樹脂組成物の（Ｂ）活性エステル基含有化合物の活性エステル当量と、（Ｃ）トリアジン骨格含有フェノール系樹脂の水酸基当量との合計当量のうちの（Ｂ）活性エステル基含有化合物の活性エステル当量が、（Ａ）エポキシ樹脂のエポキシ１当量に対して、０．１〜０．９当量である、上記（１１）に記載の配線板、
（１３）紫外線の照射を、大気圧雰囲気下、最大波長３００〜４５０ｎｍの範囲で放射する紫外線ランプを用い、光量が１０００〜５０００ｍＪ／ｃｍ2になるように行う、上記（７）〜（１２）のいずれかに記載の配線板、
（１４）（ａ）配線導体の回路を有する基板上に、（Ａ）１分子中に２個以上のエポキシ基を有するエポキシ樹脂、（Ｂ）活性エステル基含有化合物、及び（Ｄ）エポキシ樹脂硬化促進剤を含む熱硬化性絶縁樹脂組成物を用いて絶縁樹脂層を形成する工程、（ｂ）前記絶縁樹脂層を熱硬化処理する工程、（ｃ）熱硬化処理された絶縁樹脂層を紫外線照射処理する工程、（ｄ）紫外線照射処理された絶縁樹脂層に、無電解めっき処理を施す工程、を含む配線板の製造方法、
（１５）熱硬化性絶縁樹脂組成物の（Ｂ）活性エステル基含有化合物が、１分子中にエステル基１個以上を有する樹脂である、上記（１４）に記載の配線板の製造方法、
（１６）さらに、熱硬化性絶縁樹脂組成物に（Ｃ）トリアジン骨格含有フェノール系樹脂を含む、上記（１４）または（１５）に記載の配線板の製造方法、
（１７）熱硬化性絶縁樹脂組成物の（Ｃ）トリアジン骨格含有フェノール系樹脂が、１分子中の窒素原子含有量１２〜２２質量％のものである、上記（１６）に記載の配線板の製造方法、
（１８）熱硬化性絶縁樹脂組成物の（Ｂ）活性エステル基含有化合物の活性エステル当量、または（Ｂ）活性エステル基含有化合物の活性エステル当量と、（Ｃ）トリアジン骨格含有フェノール系樹脂の水酸基当量との合計当量が、（Ａ）エポキシ樹脂のエポキシ１当量に対して、０．９５〜１．２５当量である、上記（１４）〜（１７）のいずれかに記載の配線板の製造方法、
（１９）熱硬化性絶縁樹脂組成物の（Ｂ）活性エステル基含有化合物の活性エステル当量と、（Ｃ）トリアジン骨格含有フェノール系樹脂の水酸基当量との合計当量のうちの（Ｂ）活性エステル基含有化合物の活性エステル当量が、（Ａ）エポキシ樹脂のエポキシ１当量に対して、０．１〜０．９当量である、上記（１８）に記載の配線板の製造方法、
（２０）さらに、（ｅ）無電解めっきの上に、電気めっき処理を施す工程を含む、上記（１４）〜（１９）のいずれかに記載の配線板の製造方法、
（２１）（ｃ）工程と（ｄ）工程との間に、（ｃ’）紫外線照射処理された絶縁樹脂層表面を、酸化性粗化液で粗化処理する工程を含む、上記（１４）〜（２０）のいずれかに記載の配線板の製造方法、
（２２）（ｃ）紫外線照射する工程において、大気圧雰囲気下、最大波長３００〜４５０ｎｍの範囲で放射する紫外線ランプを用い、光量が１０００〜５０００ｍＪ／ｃｍ2になるように、紫外線を照射する、上記（１４）〜（２１）のいずれかに記載の配線板の製造方法、
を提供するものである。
That is, the present invention
(1) A thermosetting insulating resin composition containing (A) an epoxy resin having two or more epoxy groups in one molecule, (B) an active ester group-containing compound, and (D) an epoxy resin curing accelerator is heated. Insulating resin obtained by curing and irradiating it with ultraviolet rays,
(2) The insulating resin according to (1), wherein the (B) active ester group-containing compound of the thermosetting insulating resin composition is a resin having one or more ester groups in one molecule;
(3) The insulating resin according to (1) or (2), further including (C) a triazine skeleton-containing phenolic resin in the thermosetting insulating resin composition,
(4) The insulating resin according to (3), wherein the (C) triazine skeleton-containing phenolic resin of the thermosetting insulating resin composition has a nitrogen atom content of 12 to 22% by mass in one molecule,
(5) The active ester equivalent of the (B) active ester group-containing compound of the thermosetting insulating resin composition, or (B) the active ester equivalent of the active ester group-containing compound, and (C) the hydroxyl group of the triazine skeleton-containing phenolic resin. Insulating resin in any one of said (1)-(4) whose total equivalent with an equivalent is 0.95-1.25 equivalent with respect to 1 equivalent of epoxy of (A) epoxy resin,
(6) (B) active ester group of the total equivalent of (B) active ester group-containing compound (B) active ester group-containing compound and (C) hydroxyl group equivalent of triazine skeleton-containing phenolic resin in the thermosetting insulating resin composition The insulating resin according to (5) above, wherein the active compound equivalent of the containing compound is 0.1 to 0.9 equivalent with respect to 1 equivalent of epoxy of (A) the epoxy resin,
(7) On a substrate having a wiring conductor circuit, (A) an epoxy resin having two or more epoxy groups in one molecule, (B) an active ester group-containing compound, and (D) an epoxy resin curing accelerator. A wiring board obtained by thermosetting the insulating resin layer provided by the thermosetting insulating resin composition comprising, irradiating the insulating resin layer with ultraviolet rays, and then forming a wiring on the insulating resin layer by plating;
(8) The wiring board according to (7), wherein the (B) active ester group-containing compound of the thermosetting insulating resin composition is a resin having one or more ester groups in one molecule,
(9) The wiring board according to (7) or (8), further including (C) a triazine skeleton-containing phenolic resin in the thermosetting insulating resin composition,
(10) The wiring board according to (9), wherein the (C) triazine skeleton-containing phenolic resin of the thermosetting insulating resin composition has a nitrogen atom content of 12 to 22% by mass in one molecule,
(11) The active ester equivalent of the (B) active ester group-containing compound of the thermosetting insulating resin composition, or (B) the active ester equivalent of the active ester group-containing compound, and (C) the hydroxyl group of the triazine skeleton-containing phenolic resin. The wiring board according to any one of the above (7) to (10), wherein the total equivalent weight to the equivalent weight is 0.95 to 1.25 equivalents relative to 1 equivalent of epoxy of (A) the epoxy resin,
(12) (B) Active ester group of the total equivalent of (B) active ester group-containing compound (B) active ester group-containing compound and (C) triazine skeleton-containing phenolic resin hydroxyl group equivalent of the thermosetting insulating resin composition The wiring board according to (11), wherein the active compound equivalent of the containing compound is 0.1 to 0.9 equivalent with respect to 1 equivalent of epoxy of (A) epoxy resin,
(13) The above (7) to (12), wherein irradiation with ultraviolet rays is performed using an ultraviolet lamp that radiates in an atmospheric pressure atmosphere at a maximum wavelength of 300 to 450 nm so that the light amount is 1000 to 5000 mJ / cm 2. A wiring board according to any one of
(14) (a) On a substrate having a circuit of a wiring conductor, (A) an epoxy resin having two or more epoxy groups in one molecule, (B) an active ester group-containing compound, and (D) epoxy resin curing A step of forming an insulating resin layer using a thermosetting insulating resin composition containing an accelerator, (b) a step of thermosetting the insulating resin layer, and (c) ultraviolet irradiation of the thermosetting insulating resin layer. A method of manufacturing a wiring board, including a step of processing, and (d) a step of performing an electroless plating process on the insulating resin layer subjected to the ultraviolet irradiation treatment,
(15) The method for producing a wiring board according to (14) above, wherein the (B) active ester group-containing compound of the thermosetting insulating resin composition is a resin having one or more ester groups in one molecule,
(16) The method for producing a wiring board according to (14) or (15), further including (C) a triazine skeleton-containing phenolic resin in the thermosetting insulating resin composition,
(17) The wiring board according to (16), wherein the (C) triazine skeleton-containing phenol resin of the thermosetting insulating resin composition has a nitrogen atom content of 12 to 22% by mass in one molecule. Production method,
(18) Active ester equivalent of (B) active ester group-containing compound of thermosetting insulating resin composition, or (B) Active ester equivalent of active ester group-containing compound, and (C) Hydroxyl group of triazine skeleton-containing phenolic resin The method for producing a wiring board according to any one of (14) to (17), wherein a total equivalent weight to an equivalent weight is 0.95 to 1.25 equivalents relative to 1 equivalent of epoxy of (A) epoxy resin. ,
(19) (B) active ester group in the total equivalent of (B) active ester group-containing compound (B) active ester group-containing compound of the thermosetting insulating resin composition and (C) triazine skeleton-containing phenolic resin The manufacturing method of the wiring board according to (18), wherein the active ester equivalent of the containing compound is 0.1 to 0.9 equivalent with respect to 1 equivalent of epoxy of (A) the epoxy resin,
(20) Furthermore, the manufacturing method of the wiring board in any one of said (14)-(19) including the process of performing an electroplating process on (e) electroless plating,
(21) Between the step (c) and the step (d), (c ′) including the step of roughening the surface of the insulating resin layer subjected to the ultraviolet irradiation treatment with an oxidizing roughening solution (14) A manufacturing method of the wiring board according to any one of to (20),
(22) (c) In the step of irradiating with ultraviolet rays, using an ultraviolet lamp that radiates in an atmospheric pressure atmosphere at a maximum wavelength of 300 to 450 nm, irradiating the ultraviolet rays so that the light amount is 1000 to 5000 mJ / cm 2 . The method for producing a wiring board according to any one of (14) to (21),
Is to provide.
本発明によれば、絶縁樹脂層表面の凹凸形状が小さい状態でも、配線導体に対して容易に高い接着力を発現し得る上、ビアホール底のスミアを除去するために過マンガン酸ナトリウム系などの粗化液で処理しても、絶縁樹脂層表面の粗化凹凸形状が小さく、かつ配線導体に対して高い接着力を確保し得る絶縁樹脂、配線板及び配線板の製造方法を提供することができる。 According to the present invention, even when the uneven shape on the surface of the insulating resin layer is small, a high adhesive force can be easily expressed with respect to the wiring conductor, and a sodium permanganate type or the like can be used to remove smear at the bottom of the via hole. To provide an insulating resin, a wiring board, and a method for manufacturing a wiring board, which have a small roughened uneven shape on the surface of the insulating resin layer and can ensure high adhesion to a wiring conductor even when treated with a roughening liquid. it can.
本発明に用いる熱硬化性絶縁樹脂組成物（以下、単に「樹脂組成物」と称することがある。）は、（Ａ）１分子中に２個以上のエポキシ基を有するエポキシ樹脂、（Ｂ）活性エステル基含有化合物、及び（Ｄ）エポキシ樹脂硬化促進剤を含むものである。また、必要により、さらに（Ｃ）トリアジン骨格含有フェノール系樹脂を含むものである。 The thermosetting insulating resin composition used in the present invention (hereinafter sometimes simply referred to as “resin composition”) is (A) an epoxy resin having two or more epoxy groups in one molecule, (B) It contains an active ester group-containing compound and (D) an epoxy resin curing accelerator. Further, if necessary, it further contains (C) a phenol resin containing a triazine skeleton.
［絶縁樹脂］
（（Ａ）エポキシ樹脂）
本発明に用いる樹脂組成物において、（Ａ）成分として用いられるエポキシ樹脂は、１分子中に２個以上のエポキシ基を有するものであればよく、特に制限されず、例えば、クレゾールノボラック型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、ナフトールノボラック型エポキシ樹脂、ビフェニルノボラック型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、ビスフェノールＴ型エポキシ樹脂、ビスフェノールＺ型エポキシ樹脂、テトラブロモビスフェノールＡ型エポキシ樹脂、ビフェニル型エポキシ樹脂、テトラメチルビフェニル型エポキシ樹脂、トリフェニル型エポキシ樹脂、テトラフェニル型エポキシ樹脂、ナフトールアラルキル型エポキシ樹脂、ナフタレンジオールアラルキル型エポキシ樹脂、ナフトールアラルキル型エポキシ樹脂、フルオレン型エポキシ樹脂、ジシクロペンタジエン骨格を有するエポキシ樹脂、エチレン性不飽和化合物を骨格に有するエポキシ樹脂、脂環式型エポキシ樹脂などが挙げられる。
[Insulating resin]
((A) Epoxy resin)
In the resin composition used in the present invention, the epoxy resin used as the component (A) is not particularly limited as long as it has two or more epoxy groups in one molecule. For example, a cresol novolac type epoxy resin , Phenol novolac type epoxy resin, naphthol novolac type epoxy resin, biphenyl novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol T type epoxy resin, bisphenol Z type epoxy resin, tetra Bromobisphenol A type epoxy resin, biphenyl type epoxy resin, tetramethyl biphenyl type epoxy resin, triphenyl type epoxy resin, tetraphenyl type epoxy resin, naphthol aralkyl type epoxy resin, naphtho Diols aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, fluorene epoxy resin, an epoxy resin having a dicyclopentadiene skeleton, epoxy resins having an ethylenically unsaturated compound in the backbone, an alicyclic type epoxy resins.
なお、ビアホール底のスミアを除去するために過マンガン酸ナトリウム系などの粗化液で絶縁樹脂を処理した際に、スミアが簡単に除去できて、さらに緻密な粗化凹凸形状が絶縁樹脂表面に均一に形成できる観点から、エポキシ樹脂の骨格に炭化水素を含んだものが好ましく、クレゾールノボラック型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＺ型エポキシ樹脂、エチレン性不飽和化合物を骨格に有するエポキシ樹脂、ヘキサンジオール骨格を有するエポキシ樹脂が好ましい。特に、分子骨格中に、ヘキサンジオール骨格を有するエポキシ樹脂が特に好ましい。
なお、エチレン性不飽和化合物を骨格に有するエポキシ樹脂としては、例えば、ＥＸＡ４８１６（ＤＩＣ株式会社社製、商品名）などが挙げられる。
前記エポキシ樹脂は、絶縁信頼性や耐熱性の観点から、二種以上を組み合わせて用いてもよい。
In addition, when the insulating resin is treated with a roughening solution such as sodium permanganate to remove the smear at the bottom of the via hole, the smear can be easily removed, and a finer rough uneven shape is formed on the surface of the insulating resin. From the viewpoint of uniform formation, those containing hydrocarbons in the epoxy resin skeleton are preferred. Cresol novolac epoxy resin, phenol novolac epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol Z epoxy resin An epoxy resin having an ethylenically unsaturated compound in its skeleton and an epoxy resin having a hexanediol skeleton are preferable. In particular, an epoxy resin having a hexanediol skeleton in the molecular skeleton is particularly preferable.
In addition, as an epoxy resin which has an ethylenically unsaturated compound in frame | skeleton, EXA4816 (DIC Corporation make, brand name) etc. are mentioned, for example.
The epoxy resin may be used in combination of two or more from the viewpoint of insulation reliability and heat resistance.
（（Ｂ）活性エステル基含有化合物）
本発明に用いる樹脂組成物において、（Ｂ）成分の活性エステル基含有化合物は、前記（Ａ）成分のエポキシ樹脂の硬化剤として用いられる成分であり、１分子中に１個以上のエステル基を含み、水酸基を含まずエポキシ樹脂を硬化させることができるものであれば特に制限なく使用することができる。例えば、脂肪族又は、芳香族カルボン酸と脂肪族又は芳香族ヒドロキシ化合物から得られるエステル化合物などが挙げられる。これらの中でも、脂肪族カルボン酸や脂肪族ヒドロキシ化合物などで構成されるエステル化合物は、脂肪族鎖を含むことにより有機溶媒への可溶性やエポキシ樹脂との相溶性を高くできることが知られている。芳香族カルボン酸や芳香族ヒドロキシ化合物などで構成されるエステル化合物は、芳香族環を有することで耐熱性を高められる。
((B) active ester group-containing compound)
In the resin composition used in the present invention, the active ester group-containing compound as the component (B) is a component used as a curing agent for the epoxy resin as the component (A), and has one or more ester groups in one molecule. It can be used without any particular limitation as long as it contains no hydroxyl group and can cure the epoxy resin. Examples thereof include ester compounds obtained from aliphatic or aromatic carboxylic acids and aliphatic or aromatic hydroxy compounds. Among these, it is known that an ester compound composed of an aliphatic carboxylic acid, an aliphatic hydroxy compound, or the like can increase the solubility in an organic solvent and the compatibility with an epoxy resin by including an aliphatic chain. An ester compound composed of an aromatic carboxylic acid, an aromatic hydroxy compound, or the like can improve heat resistance by having an aromatic ring.
当該活性エステル基含有化合物の好適なものとしては、ベンゼン、ナフタレン、ビフェニル、ジフェニルプロパン、ジフェニルメタン、ジフェニルエーテル、ジフェニルスルホン、ベンゾフェノン等の芳香環の水素原子の２〜４個をカルボキシ基で置換したものから選ばれる芳香族カルボン酸成分と、前記した芳香環の水素原子の１個を水酸基で置換した１価フェノール系化合物と芳香環の水素原子の２〜４個を水酸基で置換した多価フェノール系化合物との混合物を原材料として、芳香族カルボン酸とフェノール性水酸基との縮合反応にて得られる芳香族エステルが挙げられる。
１価フェノール系化合物としては、例えばフェノール、各種クレゾール、α−ナフトール、β−ナフトールなどが挙げられ、多価フェノール系化合物としては、例えばハイドロキノン、レゾルシン、カテコール、４，４’−ビフェノール、４，４’−ジヒドロキシジフェニルエーテル、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、ビスフェノールＺ、臭素化ビスフェノールＡ、臭素化ビスフェノールＦ、臭素化ビスフェノールＳ、メチル化ビスフェノールＳ、各種ジヒドロキシナフタレン、各種ジヒドロキシベンゾフェノン、各種トリヒドロキシベンゾフェノン、各種テトラヒドロキシベンゾフェノン、フロログリシンなどが挙げられる。
一方、芳香族カルボンとしては、例えばフタル酸、イソフタル酸、テレフタル酸、ベンゼントリカルボン酸などが挙げられる。
当該活性エステル基含有化合物は、１分子中にエステル基１個以上を有する樹脂を用いてもよく、また市販品としても入手可能であり、例えば、ＤＩＣ株式会社製の「ＥＸＢ−９４６０」、「ＥＸＢ−９４６０Ｓ」、「ＥＸＢ−９４７０」、「ＥＸＢ−９４８０」、「ＥＸＢ−９４２０」、三井化学株式会社製の「ＢＰＮ８０」などが挙げられる。
前記活性エステル基含有化合物は、一種を単独で用いてもよく、二種以上を組み合わせて用いてもよい。
Preferred examples of the active ester group-containing compound include compounds in which 2 to 4 hydrogen atoms of an aromatic ring such as benzene, naphthalene, biphenyl, diphenylpropane, diphenylmethane, diphenyl ether, diphenylsulfone, and benzophenone are substituted with carboxy groups. A selected aromatic carboxylic acid component, a monovalent phenol compound in which one of the hydrogen atoms of the aromatic ring is substituted with a hydroxyl group, and a polyhydric phenol compound in which 2 to 4 hydrogen atoms of the aromatic ring are substituted with a hydroxyl group And aromatic esters obtained by condensation reaction of aromatic carboxylic acid and phenolic hydroxyl group.
Examples of monohydric phenol compounds include phenol, various cresols, α-naphthol, β-naphthol, and the like. Examples of polyhydric phenol compounds include hydroquinone, resorcin, catechol, 4,4′-biphenol, 4, 4'-dihydroxydiphenyl ether, bisphenol A, bisphenol F, bisphenol S, bisphenol Z, brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, methylated bisphenol S, various dihydroxynaphthalenes, various dihydroxybenzophenones, various trihydroxybenzophenones And various tetrahydroxybenzophenones and phloroglycines.
On the other hand, examples of the aromatic carboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, and benzenetricarboxylic acid.
The active ester group-containing compound may use a resin having one or more ester groups in one molecule, and is also available as a commercial product. For example, “EXB-9460”, “ EXB-9460S "," EXB-9470 "," EXB-9480 "," EXB-9420 "," BPN80 "manufactured by Mitsui Chemicals, and the like.
The said active ester group containing compound may be used individually by 1 type, and may be used in combination of 2 or more type.
（（Ｃ）トリアジン骨格含有フェノール系樹脂）
本発明に用いる樹脂組成物において、（Ｃ）成分のトリアジン骨格含有フェノール系樹脂は、前記（Ｂ）成分の活性エステル基含有化合物と共に、前述した（Ａ）成分のエポキシ樹脂の硬化剤として、必要により、さらに用いられる成分であって、フェノールノボラック型樹脂やクレゾールノボラック型樹脂のメチレン鎖にトリアジン環を反応させて得られるものである。
トリアジン骨格含有フェノール系樹脂としては、難燃性と密着性に優れる観点から、アミノトリアジン変性ノボラック型樹脂が好ましい。このアミノトリアジン変性ノボラック型樹脂とは、アミノトリアジン環構造とフェノール系化合物構造とがメチレン基を介しランダムに結合したアミノトリアジン変性ノボラック樹脂を表し、特に限定されないが、例えば、メラミン、ベンゾグアナミン、アセトグアナミン等のアミノトリアジン化合物類とフェノール、ビスフェノールＡ、クレゾール、ブチルフェノール、フェニルフェノール等のフェノール類とホルムアルデヒドとをアルキルアミン類等の弱アルカリ性触媒の存在下または無触媒において中性付近で共縮合反応させるか、メチルエーテル化メラミン等のアミノトリアジン化合物のアルキルエーテル化物と前記フェノール類とを反応させる等により得られるアミノトリアジン構造とフェノール系化合物構造とそれらを結合するメチレン基とを１分子中に有し、メチロール基を実質的に有していないノボラック樹脂が挙げられる。アミノトリアジン構造のみがメチレン結合した分子やフェノール系化合物構造のみがメチレン結合した分子や、若干量の未反応モノマーが特に意図せず含有されていてもさしつかえない。また、上記のアミノトリアジン変性ノボラック樹脂におけるフェノール系化合物構造としては、フェノール残基、クレゾール残基、ビスフェノールＡ残基、ブチルフェノール残基、フェニルフェノール残基、ナフトール残基、レゾルシン残基の群から選ばれる構造が好ましい。上記のアミノトリアジン変性ノボラック樹脂におけるトリアジン骨格としては、特に限定されないが、例えば、メラミン、ベンゾグアナミン、アセトグアナミン等のアミノトリアジン化合物類の構造を持つことが好ましい。
((C) Triazine skeleton-containing phenolic resin)
In the resin composition used in the present invention, the triazine skeleton-containing phenolic resin as the component (C) is necessary as a curing agent for the epoxy resin as the component (A) together with the active ester group-containing compound as the component (B). Therefore, it is a component further used and obtained by reacting a methylene chain of a phenol novolac resin or a cresol novolac resin with a triazine ring.
The triazine skeleton-containing phenolic resin is preferably an aminotriazine-modified novolak resin from the viewpoint of excellent flame retardancy and adhesion. The aminotriazine-modified novolak type resin is an aminotriazine-modified novolak resin in which an aminotriazine ring structure and a phenolic compound structure are randomly bonded via a methylene group, and is not particularly limited. For example, melamine, benzoguanamine, acetoguanamine Whether or not aminotriazine compounds such as phenol and phenols such as phenol, bisphenol A, cresol, butylphenol, and phenylphenol and formaldehyde are co-condensed in the presence of a weak alkaline catalyst such as alkylamines or in the absence of a catalyst near neutrality An aminotriazine structure obtained by reacting an alkyl etherified product of an aminotriazine compound such as methyl etherified melamine with the above phenols and the like, and a phenolic compound structure are combined with each other. And a styrene group in one molecule, novolak resins substantially devoid of methylol groups. A molecule in which only the aminotriazine structure is methylene-bonded, a molecule in which only the phenolic compound structure is methylene-bonded, or a slight amount of unreacted monomer may be included unintentionally. The phenolic compound structure in the aminotriazine-modified novolak resin is selected from the group consisting of phenol residue, cresol residue, bisphenol A residue, butylphenol residue, phenylphenol residue, naphthol residue, and resorcin residue. The structure is preferred. The triazine skeleton in the aminotriazine-modified novolak resin is not particularly limited, but preferably has a structure of aminotriazine compounds such as melamine, benzoguanamine, and acetoguanamine.
当該トリアジン骨格含有フェノール系樹脂は、市販品として入手可能であり、例えば、ＤＩＣ株式会社製のフェノールノボラッック型トリアジン含有フェノール樹脂である、「フェノライトＬＡ−７０５４」（窒素含有量１２質量％）、「フェノライトＬＡ−７７５１」（窒素含有量１４質量％）、「フェノライトＬＡ−１３５６」（窒素含有量１９質量％）、「フェノライトＬＡ−１３９８」（窒素含有量２２質量％）や、ＤＩＣ株式会社製のクレゾールノボラッック型トリアジン含有フェノール樹脂である、「フェノライトＥＸＢ−９８０８」（窒素含有量１８質量％）が使用可能である。
これらのトリアジン骨格含有フェノール系樹脂は、分子中の窒素含有量が１２〜２２質量％の範囲のものが良い。窒素含有量が１２質量％以上であると、接着力向上作用が発揮され、窒素含有量が２２質量％以下であると溶媒への溶解度が高く、ワニス中で未溶解物が残存しにくくなるからである。
The triazine skeleton-containing phenolic resin is available as a commercial product, for example, “Phenolite LA-7054” (a nitrogen content of 12 mass), which is a phenol novolac-type triazine-containing phenol resin manufactured by DIC Corporation. %), “Phenolite LA-7551” (nitrogen content 14% by mass), “Phenolite LA-1356” (nitrogen content 19% by mass), “Phenolite LA-1398” (nitrogen content 22% by mass) Alternatively, “Phenolite EXB-9808” (nitrogen content 18% by mass), which is a cresol novolac-type triazine-containing phenol resin manufactured by DIC Corporation, can be used.
These triazine skeleton-containing phenol resins preferably have a nitrogen content in the range of 12 to 22% by mass. When the nitrogen content is 12% by mass or more, an effect of improving the adhesive strength is exhibited, and when the nitrogen content is 22% by mass or less, the solubility in the solvent is high, and the undissolved matter hardly remains in the varnish. It is.
本発明に用いる樹脂組成物における前記（Ｂ）成分の活性エステル基含有化合物、または当該（Ｂ）成分の活性エステル基含有化合物と、当該（Ｃ）成分のトリアジン骨格含有フェノール系樹脂との合計含有量としては、前記（Ａ）エポキシ樹脂のエポキシ１当量に対して０．９５〜１．２５当量になるような量であることが好ましい。この範囲以外では耐熱性が低下するからである。また、（Ｂ）活性エステル基含有化合物の活性エステル当量と、（Ｃ）トリアジン骨格含有フェノール系樹脂の水酸基当量との合計当量のうちの（Ｂ）活性エステル基含有化合物の含有量は、（Ａ）エポキシ樹脂のエポキシ１当量に対して、活性エステル当量が０．１〜０．９当量になるような量であることが好ましい。該活性エステル当量が０．１当量以上であると、良好な接着性が発揮され、０．９当量以下であると、絶縁樹脂のガラス転移温度（Ｔｇ）が低くなるのを抑制することができる。該活性当量のより好ましい範囲は０．３〜０．７当量である。
なお、硬化剤として、活性エステル基含有化合物と、トリアジン骨格含有フェノール系樹脂とを併用する理由は、それぞれ単体で用いる場合よりも接着力が高くなるからである。これは、接着官能基のエステル基と窒素化合物の官能基が相乗的に作用するためと推定される。
The total content of the active ester group-containing compound of the component (B) or the active ester group-containing compound of the component (B) and the triazine skeleton-containing phenolic resin of the component (C) in the resin composition used in the present invention. The amount is preferably such that the amount is 0.95 to 1.25 equivalents relative to 1 equivalent of epoxy of the (A) epoxy resin. It is because heat resistance falls outside this range. The content of the active ester group-containing compound (B) in the total equivalent of (B) the active ester equivalent of the active ester group-containing compound and (C) the hydroxyl equivalent of the triazine skeleton-containing phenol resin is (A It is preferable that the active ester equivalent is 0.1 to 0.9 equivalent relative to 1 equivalent of epoxy of the epoxy resin. When the active ester equivalent is 0.1 equivalent or more, good adhesiveness is exhibited, and when it is 0.9 equivalent or less, the glass transition temperature (Tg) of the insulating resin can be suppressed from being lowered. . A more preferable range of the active equivalent is 0.3 to 0.7 equivalent.
The reason why the active ester group-containing compound and the triazine skeleton-containing phenol resin are used in combination as the curing agent is that the adhesive strength is higher than that when each is used alone. This is presumably because the ester group of the adhesive functional group and the functional group of the nitrogen compound act synergistically.
（（Ｄ）エポキシ樹脂硬化促進剤）
本発明に用いる樹脂組成物において、（Ｄ）成分のエポキシ樹脂硬化促進剤としては特に制限はなく、エポキシ樹脂の硬化に用いられる一般的な硬化促進剤を使用することができる。
当該硬化促進剤の具体例としては、２−メチルイミダゾール、２−エチル−４−メチルイミダゾール、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、２−ウンデシルイミダゾール、１−シアノエチル−２−フェニルイミダゾリウムトリメリテートなどのイミダゾール系化合物、トリフェニルホスフィン、トリブチルホスフィンなどの有機ホスフィン系化合物、トリメチルホスファイト、トリエチルホスファイトなどの有機ホスファイト系化合物、エチルトリフェニルホスホニウムブロミド、テトラフェニルホスホニウムテトラフェニルボレートなどのホスホニウム塩化合物、トリエチルアミン、トリブチルアミンなどのトリアルキルアミン、４−ジメチルアミノピリジン、ベンジルジメチルアミン、２，４，６−トリス（ジメチルアミノメチル）フェノール、１，８−ジアザビシクロ（５．４．０）−ウンデセン−７（以下ＤＢＵと略称する）などのアミン系化合物及びＤＢＵとテレフタル酸や２，６−ナフタレンジカルボン酸等との塩、テトラエチルアンモニウムクロリド、テトラプロピルアンモニウムクロリド、テトラブチルアンモニウムクロリド、テトラブチルアンモニウムブロミド、テトラヘキシルアンモニウムブロミド、ベンジルトリメチルアンモニウムクロリドなどの第４級アンモニウム塩化合物等を挙げることができる。これらは一種を単独で用いてもよく、二種以上を組み合わせて用いてもよい。また、絶縁樹脂における当該硬化促進剤の含有量は、（Ａ）成分のエポキシ樹脂含有量に対して、０．０２〜１．５質量％であることが好ましい。この量が０．０２質量％以上であるとエポキシ樹脂の硬化が充分となって、耐熱性を維持することができ、一方１．５質量％以下であると絶縁樹脂の保存安定性やＢステージの絶縁樹脂の取り扱い性が良好となる。より好ましい含有量は０．０７〜１．０質量％である。
((D) Epoxy resin curing accelerator)
In the resin composition used in the present invention, the epoxy resin curing accelerator of component (D) is not particularly limited, and general curing accelerators used for curing epoxy resins can be used.
Specific examples of the curing accelerator include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 2-undecylimidazole, 1-cyanoethyl-2. -Imidazole compounds such as phenylimidazolium trimellitate, organic phosphine compounds such as triphenylphosphine and tributylphosphine, organic phosphite compounds such as trimethylphosphite and triethylphosphite, ethyltriphenylphosphonium bromide, tetraphenylphosphonium Phosphonium salt compounds such as tetraphenylborate, trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6- Amine compounds such as lis (dimethylaminomethyl) phenol, 1,8-diazabicyclo (5.4.0) -undecene-7 (hereinafter abbreviated as DBU), DBU and terephthalic acid, 2,6-naphthalenedicarboxylic acid, etc. And quaternary ammonium salt compounds such as tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrahexylammonium bromide, and benzyltrimethylammonium chloride. These may be used individually by 1 type, and may be used in combination of 2 or more types. Moreover, it is preferable that content of the said hardening accelerator in insulating resin is 0.02-1.5 mass% with respect to the epoxy resin content of (A) component. When this amount is 0.02% by mass or more, the epoxy resin is sufficiently cured and heat resistance can be maintained. On the other hand, when the amount is 1.5% by mass or less, the storage stability of the insulating resin and the B stage can be maintained. This makes the insulating resin easy to handle. A more preferable content is 0.07 to 1.0% by mass.
本発明に用いる樹脂組成物は、熱硬化後、紫外線照射を受けて、樹脂組成物が硬化した絶縁樹脂硬化物、すなわち、本発明の絶縁樹脂となる。この樹脂組成物が、熱硬化後、紫外線照射を受ける必要がある理由は以下に示すとおりである。
本発明の樹脂組成物により形成された絶縁樹脂層を後述の方法で熱硬化処理したのち、該絶縁樹脂層を、さらに下記の条件で紫外線照射処理することにより、該絶縁樹脂層表面の凹凸形状が小さいにもかかわらず、配線導体に対して高い接着力を発現する。
その機構については、必ずしも明確ではないが、該絶縁樹脂層に紫外線を照射することにより、該絶縁樹脂層表面に、（Ｂ）成分の活性エステル基含有化合物における活性エステル基の分解による酸素含有基が形成し、この酸素含有基が配線導体に対する高い接着力をもたらすものと推察される。該絶縁樹脂表面に形成された酸素含有基の酸素原子量は、Ｘ線光電子分光法により測定することができる。
前記の紫外線照射条件としては、例えば最大波長３００〜４５０ｎｍの範囲で放射する紫外線ランプを用い、大気圧雰囲気下に、光量が１０００〜５０００ｍＪ／ｃｍ2程度、好ましくは２０００〜４０００ｍＪ／ｃｍ2になるように、紫外線を照射することが望ましい。
なお、前記光量（ｍＪ／ｃｍ2）は、「照度（ｍＷ／ｃｍ2）×照射時間（秒）」で表される。
The resin composition used in the present invention is an insulating resin cured product obtained by curing the resin composition by being irradiated with ultraviolet rays after thermosetting, that is, the insulating resin of the present invention. The reason why this resin composition needs to be irradiated with ultraviolet rays after thermosetting is as follows.
After the insulating resin layer formed of the resin composition of the present invention is heat-cured by the method described later, the insulating resin layer is further subjected to ultraviolet irradiation treatment under the following conditions, whereby the uneven shape on the surface of the insulating resin layer is obtained. Despite its small size, it exhibits high adhesion to the wiring conductor.
Although the mechanism is not necessarily clear, by irradiating the insulating resin layer with ultraviolet rays, the surface of the insulating resin layer is exposed to oxygen-containing groups by decomposition of active ester groups in the active ester group-containing compound of component (B). It is presumed that this oxygen-containing group provides high adhesion to the wiring conductor. The amount of oxygen atoms of the oxygen-containing group formed on the surface of the insulating resin can be measured by X-ray photoelectron spectroscopy.
The ultraviolet irradiation conditions of the, for example, using a UV lamp emitting in the range of the maximum wavelength 300 to 450 nm, under atmospheric pressure, the amount of light is 1000~5000mJ / cm 2 or so, made preferably in 2000~4000mJ / cm 2 Thus, it is desirable to irradiate with ultraviolet rays.
The light quantity (mJ / cm 2 ) is represented by “illuminance (mW / cm 2 ) × irradiation time (seconds)”.
このように、絶縁樹脂層を熱硬化処理後、紫外線照射処理することにより、該絶縁樹脂層は、従来用いられる過マンガン酸ナトリウム系などの粗化液を用いて凹凸形状を形成しなくても、配線導体に対して高い接着力を発現し得ることから、配線形成の歩留まりの低下を抑えることができると共に、粗化液使用による水洗処理や廃液処理をなくすことができ、コスト的にも有利である。
また、ビアホール底のスミアを除去するために、過マンガン酸ナトリウム系などの粗化液で処理しても、粗化凹凸形状が小さく、かつ配線導体に対して高い接着力を確保することができる。
なお、紫外線照射時の絶縁樹脂層の温度は４０〜９０℃程度が好ましく、５０〜８０℃がより好ましい。
As described above, the insulating resin layer is not subjected to an uneven shape using a conventional roughening liquid such as sodium permanganate by performing ultraviolet irradiation treatment after the thermosetting treatment of the insulating resin layer. In addition, since high adhesive strength can be expressed with respect to the wiring conductor, it is possible to suppress a decrease in the yield of wiring formation, and it is possible to eliminate water washing processing and waste liquid processing by using a roughening liquid, which is advantageous in terms of cost. It is.
In addition, even if it is treated with a roughening solution such as sodium permanganate to remove smear at the bottom of the via hole, the roughened uneven shape is small and high adhesion to the wiring conductor can be secured. .
In addition, about 40-90 degreeC is preferable and the temperature of the insulating resin layer at the time of ultraviolet irradiation has more preferable 50-80 degreeC.
本発明の樹脂組成物には、本発明の目的が損なわれない範囲で、必要に応じ、無機フィラーや、各種添加成分、例えばレベリング剤、酸化防止剤、難燃剤、揺変性付与剤、増粘剤、溶媒などを含有させることができる。 In the resin composition of the present invention, an inorganic filler and various additive components, for example, a leveling agent, an antioxidant, a flame retardant, a thixotropic agent, a thickening agent, as necessary, as long as the object of the present invention is not impaired. An agent, a solvent, etc. can be contained.
［無機フィラー］
無機フィラーは、熱膨張率の抑制や塗膜強度を上げる目的で含有させるものであり、例えばシリカ、溶融シリカ、タルク、アルミナ、水酸化アルミニウム、硫酸バリウム、水酸化カルシウム、エーロジル、炭酸カルシウムの中から選ばれるものが使用可能であり、これらは一種を単独で用いてもよく、二種以上を組み合わせて用いてもよい。なお、誘電特性や低熱膨張の点からシリカを用いるのが良く、その含有量は溶媒を除く樹脂組成物の固形分中で５〜３５ｖｏｌ％であることが好ましく、より好ましくは、１０〜３０ｖｏｌ％である。５ｖｏｌ％以上であると熱膨張係数と誘電損失の増大を抑制することができ、一方３５ｖｏｌ％以下であると絶縁樹脂を内層回路に形成する際の必要フローが充分となり未充填箇所が発生しにくくなる。
これらの無機フィラーは、分散性を高める目的でカップリング剤で処理しても良く、ニーダー、ボールミル、ビーズミル、３本ロール等既知の混練により樹脂組成物中に均質に分散しても良い。
[Inorganic filler]
Inorganic fillers are included for the purpose of suppressing the coefficient of thermal expansion and increasing the coating strength. For example, silica, fused silica, talc, alumina, aluminum hydroxide, barium sulfate, calcium hydroxide, aerosil, calcium carbonate. What is chosen from these can be used, and these may be used individually by 1 type and may be used in combination of 2 or more type. In addition, it is good to use a silica from the point of a dielectric characteristic or low thermal expansion, It is preferable that the content is 5-35 vol% in solid content of the resin composition except a solvent, More preferably, it is 10-30 vol%. It is. If it is 5 vol% or more, an increase in the thermal expansion coefficient and dielectric loss can be suppressed. On the other hand, if it is 35 vol% or less, the necessary flow for forming the insulating resin in the inner layer circuit is sufficient, and unfilled portions are hardly generated. Become.
These inorganic fillers may be treated with a coupling agent for the purpose of enhancing dispersibility, or may be uniformly dispersed in the resin composition by known kneading such as a kneader, a ball mill, a bead mill, or a three roll.
（カップリング剤）
無機フィラーの分散性を高める目的で、該無機フィラーの表面処理に用いられるカップリング剤としては、シラン系、チタネート系、アルミニウム系カップリング剤などが挙げられる。その中でも、シラン系カップリング剤が好ましい。例えば、Ｎ−フェニル−γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、γ−（２−アミノエチル）アミノプロピルトリメトキシシラン、γ−（２−アミノエチル）アミノプロピルトリエトキシシラン、γ−アニリノプロピルトリメトキシシラン、γ−アニリノプロピルトリエトキシシラン、Ｎ−β−（Ｎ−ビニルベンジルアミノエチル）−γ−アミノプロピルトリメトキシシランおよびＮ−β−（Ｎ−ビニルベンジルアミノエチル）−γ−アミノプロピルトリエトキシシランなどのアミノシラン化合物、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルトリエトキシシランおよびβ−（３，４−エポキシシクロヘキシル）エチルトリメトキシシランなどのエポキシシラン化合物、その他として、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルビニルエトキシシラン、γ−メルカトプロピルトリメトキシシラン、γ−メルカトプロピルトリエトキシシラン、γ−ウレイドプロピルトリメトキシシラン、γ−ウレイドプロピルトリエトキシシラン、γ−メタクロキシプロピルトリメトキシシランなどが挙げられる。
(Coupling agent)
For the purpose of enhancing the dispersibility of the inorganic filler, examples of the coupling agent used for the surface treatment of the inorganic filler include silane-based, titanate-based, and aluminum-based coupling agents. Among these, a silane coupling agent is preferable. For example, N-phenyl-γ-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-amino Ethyl) aminopropyltriethoxysilane, γ-anilinopropyltrimethoxysilane, γ-anilinopropyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane and N-β Aminosilane compounds such as-(N-vinylbenzylaminoethyl) -γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane and β- (3,4-epoxy (Cyclohexyl) ethyltrimethoxysila As other epoxy silane compounds such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylvinylethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ- Examples include ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, and γ-methacryloxypropyltrimethoxysilane.
［溶媒］
本発明の樹脂組成物は、溶媒に希釈して用いることができる。この溶媒としては、例えばメチルエチルケトン、キシレン、トルエン、アセトン、エチレングリコールモノエチルエーテル、シクロヘキサノン、エチルエトキシプロピオネート、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド等を挙げることができる。これらは一種を単独で用いてもよく、二種以上を混合して用いてもよい。この溶媒の前記樹脂組成物に対する使用割合は、従来使用されている割合でよく、目的とする絶縁樹脂の塗膜形成の設備に合わせて使用量を調整するのがよい。
[solvent]
The resin composition of the present invention can be used after diluted in a solvent. Examples of the solvent include methyl ethyl ketone, xylene, toluene, acetone, ethylene glycol monoethyl ether, cyclohexanone, ethyl ethoxypropionate, N, N-dimethylformamide, N, N-dimethylacetamide and the like. These may be used individually by 1 type, and 2 or more types may be mixed and used for them. The use ratio of this solvent to the resin composition may be a conventionally used ratio, and the use amount may be adjusted according to the facility for forming a coating film of the target insulating resin.
［熱硬化性絶縁樹脂組成物の調製］
本発明の熱硬化性絶縁樹脂組成物の調製方法には、特に制限はなく、従来公知の調製方法を用いることができる。
例えば、前記溶媒中に、前述した（Ａ）成分のエポキシ樹脂、（Ｂ）成分の活性エステル基含有化合物、及び（Ｄ）成分のエポキシ樹脂硬化促進剤を加えると共に、必要により、さらに（Ｃ）トリアジン骨格含有フェノール系樹脂を加え、さらに、必要に応じて用いられる無機フィラーや各種添加成分を加えたのち、超音波分散方式、高圧衝突式分散方式、高速回転分散方式、ビーズミル方式、高速せん断分散方式、及び自転公転式分散方式などの各種混合機を用いて混合・攪拌することにより、ワニスとして調製することができる。
このワニス中の溶媒を除く固形分濃度は４０〜７０質量％であることが、塗工性などの観点から好ましい。
[Preparation of thermosetting insulating resin composition]
There is no restriction | limiting in particular in the preparation method of the thermosetting insulating resin composition of this invention, A conventionally well-known preparation method can be used.
For example, the epoxy resin of component (A), the active ester group-containing compound of component (B), and the epoxy resin curing accelerator of component (D) described above are added to the solvent, and if necessary, (C) After adding triazine skeleton-containing phenolic resin and adding inorganic fillers and various additional components as needed, ultrasonic dispersion method, high-pressure collision dispersion method, high-speed rotation dispersion method, bead mill method, high-speed shear dispersion It can be prepared as a varnish by mixing and stirring using various mixers such as a method and a rotation and revolution dispersion method.
The solid content concentration excluding the solvent in the varnish is preferably 40 to 70% by mass from the viewpoint of coating property and the like.
［配線板］
本発明の配線板は、配線導体の回路を有する基板上に、前述した熱硬化性絶縁樹脂組成物によって設けられた絶縁樹脂層を熱硬化し、これに紫外線を照射後、この絶縁樹脂層上に、配線をめっきで形成してなることを特徴とする。
（絶縁樹脂層付キャリアフィルムの作製）
本発明の配線板において、配線回路を有する基板上に絶縁樹脂層を形成するには、まず、前述した熱硬化性絶縁樹脂組成物（ワニス）をキャリアフィルムに塗工したのち、８０〜１１０℃程度の温度で、１〜１０分間程度乾燥処理して、絶縁樹脂層付キャリアフィルムを作製する。乾燥処理の温度が８０℃以上であり、かつ時間が１分以上である場合、乾燥が充分に進行し、絶縁樹脂層内にボイドが発生するのを抑制することができ、一方乾燥処理の温度が１１０℃以下で、かつ時間が１０分以下であると、乾燥が進みすぎて樹脂フロー量が低下するのを抑制することができる。
絶縁樹脂層の厚み（乾燥後の厚み）に関しては、絶縁性の観点から、最小絶縁距離が確保できる最小膜厚以上であることが好ましく、この最小絶縁距離は絶縁樹脂の組成により変わるものであるが、一般的には、３０μｍ以上であることが好ましい。絶縁樹脂層の膜厚を厚くすることは絶縁性の点では有利になるが、一方で、経済性の観点から、通常は６０μｍ以下程度とすることが好ましい。
前記キャリアフィルムの厚さとしては特に制限はないが、１０〜２００μｍ程度が好ましく、２０〜１００μｍがより好ましい。また、キャリアフィルムとしては、ポリエチレンテレフタレート（ＰＥＴ）フィルムがよく用いられる。
[Wiring board]
The wiring board of the present invention thermally cures the insulating resin layer provided by the above-described thermosetting insulating resin composition on a substrate having a circuit of a wiring conductor, and after irradiating it with ultraviolet rays, Further, the wiring is formed by plating.
(Preparation of carrier film with insulating resin layer)
In the wiring board of the present invention, in order to form an insulating resin layer on a substrate having a wiring circuit, first, the thermosetting insulating resin composition (varnish) described above is applied to a carrier film, and then 80 to 110 ° C. A carrier film with an insulating resin layer is prepared by drying at a temperature of about 1 to 10 minutes. When the temperature of the drying process is 80 ° C. or more and the time is 1 minute or more, the drying can sufficiently proceed and the generation of voids in the insulating resin layer can be suppressed, while the temperature of the drying process When the temperature is 110 ° C. or lower and the time is 10 minutes or shorter, it is possible to prevent the resin flow from decreasing due to excessive drying.
The thickness of the insulating resin layer (thickness after drying) is preferably at least the minimum film thickness that can ensure the minimum insulation distance from the viewpoint of insulation, and this minimum insulation distance varies depending on the composition of the insulating resin. However, in general, it is preferably 30 μm or more. Increasing the thickness of the insulating resin layer is advantageous in terms of insulation, but on the other hand, it is usually preferable to set the thickness to about 60 μm or less from the viewpoint of economy.
Although there is no restriction | limiting in particular as thickness of the said carrier film, About 10-200 micrometers is preferable and 20-100 micrometers is more preferable. As the carrier film, a polyethylene terephthalate (PET) film is often used.
（配線回路を有する基板）
本発明の配線板に用いられる配線回路を有する基板（以下、回路付絶縁基板と称することがある。）としては、少なくとも一方の面に回路を備えた絶縁基板であれば特に限定するものではなく、片面にのみ回路を形成したものや両面銅張積層板を用いて得られるような、絶縁基板の両面に回路が形成されたものであってもよい。この回路付絶縁基板は、通常の配線板において用いられている公知の積層板、たとえば、ガラス布−エポキシ樹脂、紙−フェノール樹脂、紙−エポキシ樹脂、ガラス布・ガラス紙−エポキシ樹脂等を使用することができる。回路は公知のいずれの方法により形成されていてもよく、銅箔と上記絶縁基板を張り合わせた銅張り積層板を用い、銅箔の不要な部分をエッチング除去するサブトラクティブ法や、上記絶縁基板の必要な箇所に無電解めっきによって回路を形成するアディティブ法等、公知の配線板の製造法を用いることができる。
また、この回路表面には、接着性を向上させるための回路表面処理を行ってもよい。この処理方法も、特に制限されることはなく、例えば、次亜塩素酸ナトリウムのアルカリ水溶液により回路表面に酸化銅の針状結晶を形成し、形成した酸化銅の針状結晶をジメチルアミンボラン水溶液に浸漬して還元するなどの公知の方法を採用することができる。
(Board with wiring circuit)
The substrate having a wiring circuit used for the wiring board of the present invention (hereinafter sometimes referred to as an insulating substrate with circuit) is not particularly limited as long as it is an insulating substrate having a circuit on at least one surface. The circuit may be formed on both sides of the insulating substrate, such as a circuit formed only on one side or a double-sided copper-clad laminate. As this insulating substrate with circuit, a known laminated board used in a normal wiring board, for example, glass cloth-epoxy resin, paper-phenol resin, paper-epoxy resin, glass cloth / glass paper-epoxy resin, etc. is used. can do. The circuit may be formed by any known method, using a copper-clad laminate in which a copper foil and the insulating substrate are bonded together, using a subtractive method for etching away unnecessary portions of the copper foil, A known method for manufacturing a wiring board such as an additive method for forming a circuit by electroless plating at a necessary location can be used.
Moreover, you may perform the circuit surface treatment for improving adhesiveness to this circuit surface. This treatment method is also not particularly limited. For example, a copper oxide needle crystal is formed on the circuit surface with an alkaline aqueous solution of sodium hypochlorite, and the formed copper oxide needle crystal is converted into a dimethylamine borane aqueous solution. It is possible to employ a known method such as dipping in a reducing solution.
（回路付絶縁基板の回路上への絶縁樹脂層の形成）
次に、前述した回路付絶縁基板の回路上に絶縁樹脂層を形成する方法としては、前記で得られた絶縁樹脂層付キャリアフィルムを用い、ラミネート方式やプレス方式で絶縁樹脂層を形成することができる。
ラミネート方式は、回路付絶縁基板の回路に、絶縁樹脂層付キャストフィルムを、その絶縁樹脂層が対面するように接触させ、例えば真空加圧ラミネータ積層装置を用いて、該絶縁樹脂層を積層したのち、キャリアフィルムを剥離する方法である。
真空加圧ラミネータ積層装置を用いる場合、温度は５０〜１７０℃程度、圧力０．２ＭＰａ以上であることが好ましい。好ましい圧力値も、加熱温度と同様に、基板の厚みや残存銅率などにより変化するが、圧力が高すぎると基板が変形する恐れがあるため、１．０ＭＰａ以下であることが好ましい。また、真空度は、１５ｈＰａ以下であると内層回路板への埋め込み性が良好となり、一方で真空度は低ければ低い方が好ましいが、装置の能力や所定値への到達までの待ち時間等が生産性に及ぼす影響などを考慮すると、５〜１０ｈＰａの範囲で行うことが好ましい。熱圧着時間は１０〜９０秒程度が好ましい。１０秒以上であると内層回路への樹脂の流動に要する時間が充分となり、９０秒以下では生産性が良好となる。より好ましい熱圧着時間は２０〜６０秒である。
(Formation of an insulating resin layer on the circuit of an insulating substrate with circuit)
Next, as a method of forming the insulating resin layer on the circuit of the above-mentioned insulating substrate with circuit, the insulating resin layer is formed by a laminate method or a press method using the carrier film with the insulating resin layer obtained above. Can do.
In the laminating method, a cast film with an insulating resin layer is brought into contact with a circuit of an insulating substrate with a circuit so that the insulating resin layer faces, and the insulating resin layer is laminated using, for example, a vacuum pressure laminator laminator. Thereafter, the carrier film is peeled off.
When using a vacuum pressurizing laminator laminator, the temperature is preferably about 50 to 170 ° C. and the pressure is 0.2 MPa or more. The preferred pressure value also varies depending on the thickness of the substrate, the remaining copper ratio, etc., as with the heating temperature. However, if the pressure is too high, the substrate may be deformed, so it is preferably 1.0 MPa or less. In addition, when the degree of vacuum is 15 hPa or less, the embedding property to the inner layer circuit board is good. On the other hand, it is preferable that the degree of vacuum is low, but the ability of the apparatus and the waiting time until reaching the predetermined value are reduced. Considering the influence on productivity, it is preferable to carry out in the range of 5 to 10 hPa. The thermocompression bonding time is preferably about 10 to 90 seconds. If it is 10 seconds or more, the time required for the resin to flow to the inner layer circuit is sufficient, and if it is 90 seconds or less, the productivity is good. A more preferable thermocompression bonding time is 20 to 60 seconds.
一方、プレス方式の場合、前記と同様に、回路付絶縁基板の回路に絶縁樹脂層付キャストフィルムを、その絶縁樹脂層が対面するように接触させ、使用する絶縁樹脂層に合わせた適正な条件で行うことが望ましく、例えば昇温速度３℃／分程度で、３５℃から１９０℃程度まで約５０分間を要して昇温させ、その温度にて２．０〜３．０ＭＰａ程度の圧力で、６０〜９０分間程度保持したのち、室温まで３０分間程度を要して冷却する方法を用いることで、回路付絶縁基板の回路上に、絶縁樹脂層を形成することができる。 On the other hand, in the case of the press method, as described above, the cast film with the insulating resin layer is brought into contact with the circuit of the insulating substrate with circuit so that the insulating resin layer faces, and appropriate conditions are matched to the insulating resin layer to be used. For example, at a rate of temperature increase of about 3 ° C./min, the temperature is increased from 35 ° C. to about 190 ° C. for about 50 minutes, and the pressure is about 2.0 to 3.0 MPa at that temperature. The insulating resin layer can be formed on the circuit of the insulating substrate with circuit by using a method of cooling for about 30 minutes to room temperature after holding for about 60 to 90 minutes.
（絶縁樹脂層の熱硬化処理）
本発明の配線板においては、前記のようにして回路付絶縁基板の回路上に形成された絶縁樹脂層を、まず熱硬化処理する。
この熱硬化処理は、後のめっき処理や配線導体のアニール処理などを考慮した温度や時間で行うことが望ましい。あまり硬化を進めると、後のめっき処理時に配線導体との接着性が低下する恐れがあり、反対に硬化が足りないと、めっき処理時のアルカリ処理液に浸食され、めっき液に溶解する恐れがあるからである。これらのことを考慮すると、例えば１５０〜１９０℃で３０〜９０分間程度の熱処理を施して硬化させることが好ましい。
(Thermosetting treatment of insulating resin layer)
In the wiring board of the present invention, the insulating resin layer formed on the circuit of the insulating substrate with circuit as described above is first heat-cured.
This thermosetting treatment is desirably performed at a temperature and time taking into account subsequent plating treatment or annealing treatment of the wiring conductor. If the curing is advanced too much, the adhesion to the wiring conductor may be reduced during the subsequent plating process. On the contrary, if the curing is insufficient, it may be eroded by the alkaline treatment liquid during the plating process and dissolved in the plating solution. Because there is. In consideration of these matters, it is preferable to cure by applying a heat treatment at 150 to 190 ° C. for about 30 to 90 minutes, for example.
（紫外線照射処理）
本発明の配線板においては、前記のようにして熱硬化処理された絶縁樹脂層を、紫外線照射処理する。この紫外線照射処理の目的は、前述した本発明の樹脂組成物において説明したとおりである。
紫外線照射処理の条件については、紫外線は、最大波長が３００〜４５０ｎｍの範囲を有する紫外線ランプを用い、大気圧雰囲気下に、紫外線を光量が１０００〜５０００ｍＪ／ｃｍ2の範囲になるように照射することが好ましい。絶縁樹脂層に大気圧雰囲気下で紫外線を照射する方法は、紫外線装置により異なるため特に限定はしないが、生産性を考慮すればコンベア式の紫外線照射方式が好ましい。紫外線ランプとして、最大波長が３００〜４５０ｎｍの範囲を有するものは、水銀ショートアークランプ、高圧水銀ランプ、毛細管型超高圧ランプ、高圧ランプ、メタルハライドランプなどを用いることができる。これらのランプにおいて、紫外線の波長が全域で広いメタルハライドランプが好ましい。
(UV irradiation treatment)
In the wiring board of the present invention, the insulating resin layer that has been heat-cured as described above is subjected to ultraviolet irradiation treatment. The purpose of the ultraviolet irradiation treatment is as described in the above-described resin composition of the present invention.
As for the conditions of the ultraviolet irradiation treatment, ultraviolet rays are irradiated so that the amount of light is in a range of 1000 to 5000 mJ / cm 2 under an atmospheric pressure atmosphere using an ultraviolet lamp having a maximum wavelength of 300 to 450 nm. It is preferable. A method of irradiating the insulating resin layer with ultraviolet rays under an atmospheric pressure atmosphere is not particularly limited because it differs depending on the ultraviolet device, but a conveyor type ultraviolet irradiation method is preferable in consideration of productivity. As the ultraviolet lamp, a lamp having a maximum wavelength in the range of 300 to 450 nm may be a mercury short arc lamp, a high pressure mercury lamp, a capillary type ultra high pressure lamp, a high pressure lamp, a metal halide lamp, or the like. Among these lamps, metal halide lamps having a wide ultraviolet wavelength over the entire region are preferable.
紫外線の最大波長が３００〜４５０ｎｍの範囲を有する紫外線ランプを使用する目的は、汎用性と紫外線の波長域が関係する。すなわち、最大波長が３００〜４５０ｎｍを示す紫外線ランプは、コンベア式型の紫外線照射装置、例えばソルダレジストの後露光装置として一般的に用いられているからである。さらに、メタルハライド型のコンベア照射装置は、紫外線波長領域が広く、特別な装置を必要としないでこれらの装置を代替えすることで本発明の効果を発揮できる。紫外線の光量が、１０００ｍＪ／ｃｍ2以上であると酸化性粗化液で絶縁樹脂層を処理しなくてもめっき導体との接着力が十分となり、一方５０００ｍＪ／ｃｍ2以下であると該接着力は、良好に発現され、経済的にも有利である。より好ましい光量は、２０００〜４０００ｍＪ／ｃｍ2の範囲である。
このように、熱硬化処理後の絶縁樹脂層を紫外線照射処理することにより、該絶縁樹脂層表面の凹凸形状が小さい状態でも、配線導体に対して容易に高い接着力を発現することができる。
The purpose of using an ultraviolet lamp having a maximum ultraviolet wavelength in the range of 300 to 450 nm relates to versatility and the wavelength range of ultraviolet rays. That is, an ultraviolet lamp having a maximum wavelength of 300 to 450 nm is generally used as a conveyor type ultraviolet irradiation device, for example, a solder resist post-exposure device. Furthermore, the metal halide type conveyor irradiation apparatus has a wide ultraviolet wavelength region, and the effects of the present invention can be exhibited by substituting these apparatuses without requiring a special apparatus. Amount for ultraviolet, 1000 mJ / cm 2 or more is that even without treating the insulating resin layer in an oxidizing roughening solution becomes sufficient adhesion with the plated conductor, whereas 5000 mJ / cm 2 is not more than adhesive force Is well expressed and economically advantageous. A more preferable light amount is in the range of 2000 to 4000 mJ / cm 2 .
In this way, by performing the ultraviolet irradiation treatment on the insulating resin layer after the thermosetting treatment, it is possible to easily exhibit a high adhesive force to the wiring conductor even in a state where the uneven shape on the surface of the insulating resin layer is small.
（酸化性粗化液による処理）
ビアホール底のスミアの除去が必要な場合、酸化性粗化液を用いて除去処理することができる。この酸化性粗化液としては、クロム／硫酸粗化液、アルカリ過マンガン酸粗化液、フッ化ナトリウム／クロム／硫酸粗化液、ホウフッ酸粗化液などを用いることができる。また、この酸化性粗化液で処理する際、溶媒またはアルカリ液、あるいはこれらの混合物液（一般には、膨潤液またはプリディップ液）に浸したのち、酸化性粗化液で処理しても良い。上記溶媒としては、アルコール系の溶媒例えばジエチレングリコールモノメチルエーテル、ジエチレングリコールモノブチルエーテル、イソプロピルアルコール等が使用できる。また、アルカリ液は、水に溶解した際にアルカリ性を示す液であれば特に制限はなく、水酸化ナトリウム溶液、水酸化カリウム溶液等が使用できる。さらに、溶媒またはアルカリ液を混合しても良く、例えば水酸化ナトリウム３ｇ／Ｌとジエチレングリコールモノブチルエーテル３００ｍＬ／Ｌの組成のものが使用できる。
(Treatment with oxidizing roughening solution)
When it is necessary to remove the smear on the bottom of the via hole, it can be removed using an oxidizing roughening solution. As this oxidizing roughening liquid, a chromium / sulfuric acid roughening liquid, an alkaline permanganic acid roughening liquid, a sodium fluoride / chromium / sulfuric acid roughening liquid, a borofluoric acid roughening liquid, or the like can be used. Moreover, when processing with this oxidizing roughening liquid, after immersing in a solvent or alkaline liquid, or a mixture liquid (generally swelling liquid or pre-dip liquid), you may process with an oxidizing roughening liquid. . As the solvent, alcohol solvents such as diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, isopropyl alcohol and the like can be used. Further, the alkaline solution is not particularly limited as long as it is a solution that exhibits alkalinity when dissolved in water, and a sodium hydroxide solution, a potassium hydroxide solution, or the like can be used. Furthermore, you may mix a solvent or an alkali liquid, for example, the thing of the composition of sodium hydroxide 3g / L and diethylene glycol monobutyl ether 300mL / L can be used.
（めっき処理）
本発明の配線板においては、前述のようにして処理された絶縁樹脂層の表面に、例えば以下に示すようにめっき処理が施される。
まず、上記絶縁樹脂層を塩化第１錫の塩酸水溶液に浸漬して、中和処理を行い、さらに、パラジウムを付着させるめっき触媒付与処理を行う。めっき触媒付与処理は、塩化パラジウム系のめっき触媒液に浸漬することにより行われる。次に、無電解めっき液に浸漬することにより、めっき触媒上に厚さが０．３〜１．５μｍ程度の無電解めっき層を析出させる。必要により、更に電気めっきを行うことができる。無電解めっき処理に使用する無電解めっき液は、公知の無電解めっき液を使用することができ、特に制限はない。また、電気めっき処理についても公知の方法によることができ特に制限はない。
これらの手法を繰り返して多層配線板を作製することもできる。
(Plating treatment)
In the wiring board of the present invention, the surface of the insulating resin layer treated as described above is subjected to a plating treatment as shown below, for example.
First, the insulating resin layer is immersed in an aqueous hydrochloric acid solution of stannous chloride, neutralized, and further subjected to a plating catalyst application treatment for depositing palladium. The plating catalyst application treatment is performed by immersing in a palladium chloride plating catalyst solution. Next, an electroless plating layer having a thickness of about 0.3 to 1.5 μm is deposited on the plating catalyst by being immersed in an electroless plating solution. If necessary, further electroplating can be performed. As the electroless plating solution used for the electroless plating treatment, a known electroless plating solution can be used, and there is no particular limitation. Further, the electroplating treatment can be performed by a known method and is not particularly limited.
These methods can be repeated to produce a multilayer wiring board.
［配線板の製造方法］
本発明はまた、配線板の製造方法をも提供する。
本発明の配線板の製造方法は、（ａ）配線導体の回路を有する基板上に、前述した熱硬化性絶縁樹脂組成物を用いて絶縁樹脂層を形成する工程、（ｂ）前記絶縁樹脂層を熱硬化処理する工程、（ｃ）熱硬化処理された絶縁樹脂層を紫外線照射処理する工程、（ｄ）紫外線照射処理された絶縁樹脂層に、無電解めっき処理を施す工程、を含むことを特徴とする。
本発明の配線板の製造方法においては、さらに、（ｅ）無電解めっき上に、電気めっき処理を施す工程を含むことができ、また、前記（ｃ）工程と（ｄ）工程との間に、（ｃ’）紫外線照射処理された絶縁樹脂層表面を、酸化性粗化液で粗化処理する工程を含むことができる。
前記の各工程については、前述した本発明の配線板の説明において示したとおりである。
[Method of manufacturing a wiring board]
The present invention also provides a method for manufacturing a wiring board.
The method for producing a wiring board according to the present invention includes: (a) a step of forming an insulating resin layer on a substrate having a circuit of a wiring conductor using the thermosetting insulating resin composition described above; (b) the insulating resin layer; (C) a step of subjecting the heat-cured insulating resin layer to ultraviolet irradiation treatment, and (d) a step of subjecting the insulating resin layer subjected to ultraviolet radiation treatment to electroless plating treatment. Features.
In the method for manufacturing a wiring board of the present invention, the method may further include (e) a step of performing electroplating on the electroless plating, and between the steps (c) and (d). (C ′) A step of roughening the surface of the insulating resin layer subjected to the ultraviolet irradiation treatment with an oxidizing roughening solution may be included.
Each of the above steps is as shown in the description of the wiring board of the present invention described above.
次に、本発明を実施例により、さらに詳細に説明するが、本発明は、これらの例によってなんら限定されるものではない。
なお、各例における諸特性は、以下に示す方法により求めた。
多層配線板の特性
（ｉ）多層回路との接着強度
Ｌ１回路層（第３回路層）の一部に幅１０ｍｍ、長さ１００ｍｍの部分を形成し、この一端を剥がしてつかみ具でつかみ、垂直方向に約５０ｍｍ室温中で引き剥がした際の荷重を測定した。
（ｉｉ）めっき銅エッチング除去面の絶縁樹脂層粗さ
外層回路をエッチング処理して銅を除去した試験片を作製する。この試験片を２ｍｍ角程度に切断し、（株）キーエンス社製超深度形状測定顕微鏡「ＶＫ−８５００型」を用いて、試験片中の異なる箇所３点について、測定長さ１４９μｍ、倍率２０００倍、分解能０．０５μｍの条件で測定し、測定長さ１４９μｍ中の粗さの最大部から最小部を引いた値を絶縁樹脂層の表面粗さとし、３箇所の平均値を算出した。
（ｉｉｉ）はんだ耐熱性
多層配線板を２５ｍｍ角に切断し、その直後に２８８℃±２℃に調整したはんだ浴に浮かべ、ふくれが発生するまでの時間を調べた。
EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
Various characteristics in each example were determined by the following methods.
Characteristics of the multilayer wiring board (i) Adhesive strength with the multilayer circuit A part having a width of 10 mm and a length of 100 mm is formed on a part of the L1 circuit layer (third circuit layer). The load when peeled in the direction at about 50 mm at room temperature was measured.
(Ii) Roughness of insulating resin layer on plated copper etching removal surface A test piece from which copper is removed by etching the outer layer circuit is prepared. This test piece was cut into about 2 mm square, and using a ultra deep shape measurement microscope “VK-8500 type” manufactured by Keyence Corporation, the measurement length was 149 μm and the magnification was 2000 times at three different points in the test piece. The measurement was performed under the condition of a resolution of 0.05 μm, and a value obtained by subtracting the minimum portion from the maximum portion of the roughness in the measurement length of 149 μm was defined as the surface roughness of the insulating resin layer, and the average value of the three locations was calculated.
(Iii) Solder heat resistance A multilayer wiring board was cut into a 25 mm square, and immediately after that, it was floated on a solder bath adjusted to 288 ° C. ± 2 ° C., and the time until blistering was examined.
実施例１
（１）回路板の作製
ガラス布基材エポキシ樹脂両面銅張積層板［銅箔の厚さ１８μｍ、基板厚み０．８ｍｍ、両面粗化箔を両面に有する日立化成工業株式会社製「ＭＣＬ−Ｅ−６７」］にエッチングを施して片面に回路層（以下、第１回路層とする）を有する回路板を作製した。
（２）熱硬化性絶縁樹脂組成物の調製
下記組成の熱硬化性絶縁樹脂組成物を調製した。（Ｂ）成分である活性エステル基含有化合物としては、ＤＩＣ株式会社製「ＥＸＢ−９４７０」（活性エステル当量：２２３）を用いた。「ＥＸＢ−９４７０」の活性エステル当量はエポキシ１当量に対して１当量とした。
使用した（Ａ）成分である１分子中に２個以上のエポキシ基を有するエポキシ樹脂、（Ｂ）成分である活性エステル基含有化合物、（Ｄ）成分であるエポキシ樹脂硬化促進剤及び溶媒等の種類及び含有量等を表１に示す。
Example 1
(1) Fabrication of circuit board Glass cloth base epoxy resin double-sided copper-clad laminate [HCL 18 mm, copper thickness 0.8 mm, Hitachi Chemical Co., Ltd. -67 "] was etched to produce a circuit board having a circuit layer (hereinafter referred to as a first circuit layer) on one side.
(2) Preparation of thermosetting insulating resin composition A thermosetting insulating resin composition having the following composition was prepared. As the active ester group-containing compound as component (B), “EXB-9470” (active ester equivalent: 223) manufactured by DIC Corporation was used. The active ester equivalent of “EXB-9470” was 1 equivalent per 1 equivalent of epoxy.
The epoxy resin having two or more epoxy groups in one molecule as the component (A) used, the active ester group-containing compound as the component (B), the epoxy resin curing accelerator as the component (D), a solvent, etc. The types and contents are shown in Table 1.
（３）絶縁樹脂層の形成、及び熱硬化・紫外線照射処理
上記（２）で得られた熱硬化性絶縁樹脂組成物を、キャリアフィルムとしてのポリエチレンテレフタレート（ＰＥＴ）フィルム（厚さ２５μｍ）上に塗工し、１００℃で１０分間乾燥処理することにより、膜厚５０±３μｍの絶縁樹脂層付キャリアフィルムロールを作製した。
さらに、上記の絶縁樹脂層付キャリアフィルムを、上記（１）で得られた回路板の片面に絶縁樹脂層が回路層と接する面側にして、名機株式会社製バッチ式真空加圧ラミネータ「ＭＶＬＰ−５００」を用いて積層した。
次いで、キャリアフィルムを剥がしたのち、絶縁樹脂層を１７０℃、６０分間の硬化条件にて熱硬化処理した。
次に、上記絶縁樹脂層付き基板をランプがメタルハライドランプのコンベア式紫外線照射装置（最大波長３５０〜３８０ｎｍ）にて、紫外線を光量が３０００ｍＪ／ｃｍ2になるように照射した。
(3) Formation of insulating resin layer and thermosetting / ultraviolet irradiation treatment The thermosetting insulating resin composition obtained in (2) above is formed on a polyethylene terephthalate (PET) film (thickness 25 μm) as a carrier film. The carrier film roll with an insulating resin layer having a film thickness of 50 ± 3 μm was prepared by coating and drying at 100 ° C. for 10 minutes.
Furthermore, the above-mentioned carrier film with an insulating resin layer is placed on one side of the circuit board obtained in (1) above on the side where the insulating resin layer is in contact with the circuit layer, and a batch type vacuum pressure laminator “ The film was laminated using “MVLP-500”.
Next, after peeling off the carrier film, the insulating resin layer was heat-cured under curing conditions at 170 ° C. for 60 minutes.
Next, the substrate with the insulating resin layer was irradiated with ultraviolet rays so that the light amount was 3000 mJ / cm 2 using a conveyor type ultraviolet irradiation device (maximum wavelength 350 to 380 nm) in which the lamp was a metal halide lamp.
（４）無電解めっき処理及び電解めっき処理
無電解めっき前処理として、日立化成工業株式会社製コンディショナー液「ＣＬＣ−６０１」に上記（３）で得られた絶縁樹脂層付き基板を６０℃で５分間浸漬し、その後水洗し、日立化成工業株式会社製プリディップ液「ＰＤ−２０１」に室温にて２分間浸漬した。次にＰｄＣｌ2を含む無電解めっき用触媒である日立化成工業株式会社製「ＨＳ−２０２Ｂ」に、室温で１０分間浸漬処理したのち、水洗し、無電解銅めっき液である日立化成工業株式会社製「ＣＵＳＴ−２０１めっき液」に室温にて１５分間浸漬し、さらに硫酸銅電解めっきを行った。その後、アニール処理を１７０℃で３０分間行い絶縁樹脂層表面上に厚さ２０μｍの導体層を形成した。
(4) Electroless plating treatment and electrolytic plating treatment As an electroless plating pretreatment, the substrate with an insulating resin layer obtained in the above (3) was added to the conditioner liquid “CLC-601” manufactured by Hitachi Chemical Co., Ltd. at 5 ° C. It was immersed for 1 minute, then washed with water, and immersed in a pre-dip solution “PD-201” manufactured by Hitachi Chemical Co., Ltd. for 2 minutes at room temperature. Next, it was immersed in “HS-202B” manufactured by Hitachi Chemical Co., Ltd., which is a catalyst for electroless plating containing PdCl 2 , at room temperature for 10 minutes, washed with water, and Hitachi Chemical Co., Ltd., an electroless copper plating solution. It was immersed in a manufactured “CUST-201 plating solution” at room temperature for 15 minutes, and further subjected to copper sulfate electrolytic plating. Thereafter, annealing treatment was performed at 170 ° C. for 30 minutes to form a conductor layer having a thickness of 20 μm on the surface of the insulating resin layer.
（５）回路の形成
めっき導体層の不要な箇所をエッチング除去するために銅表面の酸化皮膜を＃６００のバフロール研磨で除去した後、エッチング用レジスト膜を形成してエッチング処理し、その後エッチング用レジスト膜を除去して、第１の回路と接続したビアホールを含む第２の回路形成を行った。さらに、多層化するために、第２の回路導体表面を、亜塩素酸ナトリウム：５０ｇ／Ｌ、ＮａＯＨ：２０ｇ／Ｌ、リン酸三ナトリウム：１０ｇ／Ｌの水溶液に８５℃で２０分間浸漬したのち、水洗し、８０℃で２０分間乾燥して第２の回路導体表面上に酸化銅の凹凸を形成した。
（６）多層配線板の作製
上記（３）〜（５）の工程を繰り返して、３層の多層配線板を作製した。
(5) Circuit formation To remove unnecessary portions of the plated conductor layer by etching, the oxide film on the copper surface is removed by buffing # 600, and then an etching resist film is formed and etched, and then for etching. The resist film was removed, and a second circuit including a via hole connected to the first circuit was formed. Furthermore, after the second circuit conductor surface was immersed in an aqueous solution of sodium chlorite: 50 g / L, NaOH: 20 g / L, and trisodium phosphate: 10 g / L at 85 ° C. for 20 minutes for multilayering. This was washed with water and dried at 80 ° C. for 20 minutes to form copper oxide irregularities on the surface of the second circuit conductor.
(6) Production of multilayer wiring board The steps (3) to (5) were repeated to produce a three-layer multilayer wiring board.
実施例２〜４
実施例１において、熱硬化性絶縁樹脂組成物の組成を表１に示すように変更した以外は、実施例１と同様な操作を行い、多層配線板を作製した。
実施例５
実施例１において、熱硬化性絶縁樹脂組成物として、下記組成の熱硬化性絶縁樹脂組成物を調製した以外は、実施例１と同様な操作を行い、多層配線板を作製した。
（Ｂ）成分である活性エステル基含有化合物としては、ＤＩＣ株式会社製「ＥＸＢ−９４７０」（活性エステル当量：２２３）を用い、（Ｃ）成分であるトリアジン骨格含有フェノール系樹脂としては、ＤＩＣ株式会社製フェノールノボラック型トリアジン含有フェノール樹脂「ＬＡ−１３５６」（窒素含有量１９質量％、水酸基当量：１４５）を用いた。「ＥＸＢ−９４７０」の活性エステル当量はエポキシ１当量に対して０．５当量とすると共に、「ＬＡ−１３５６」の水酸基当量はエポキシ１当量に対して０．５当量とし、「ＥＸＢ−９４７０」と「ＬＡ−１３５６」の合計当量は１．０当量とした。
使用した（Ａ）成分である１分子中に２個以上のエポキシ基を有するエポキシ樹脂、（Ｂ）成分である活性エステル基含有化合物、（Ｃ）成分であるトリアジン骨格含有フェノール系樹脂、（Ｄ）成分であるエポキシ樹脂硬化促進剤及び溶媒等の種類及び含有量等を表１に示す。
Examples 2-4
In Example 1, the same operation as Example 1 was performed except having changed the composition of the thermosetting insulating resin composition as shown in Table 1, and the multilayer wiring board was produced.
Example 5
In Example 1, the same operation as Example 1 was performed except having prepared the thermosetting insulating resin composition of the following composition as a thermosetting insulating resin composition, and the multilayer wiring board was produced.
As the active ester group-containing compound as component (B), “EXB-9470” (active ester equivalent: 223) manufactured by DIC Corporation is used, and as the triazine skeleton-containing phenolic resin as component (C), DIC stock A phenol novolac-type triazine-containing phenol resin “LA-1356” (nitrogen content 19% by mass, hydroxyl group equivalent: 145) manufactured by the company was used. The active ester equivalent of “EXB-9470” is 0.5 equivalent to 1 equivalent of epoxy, and the hydroxyl equivalent of “LA-1356” is 0.5 equivalent to 1 equivalent of epoxy. And “LA-1356” were 1.0 equivalent.
The epoxy resin having two or more epoxy groups in one molecule as the component (A) used, the active ester group-containing compound as the component (B), the triazine skeleton-containing phenol resin as the component (C), (D Table 1 shows the types and contents of the epoxy resin curing accelerator and solvent as the component.
実施例６〜９
実施例５において、熱硬化性絶縁樹脂組成物の組成を表１に示すように変更した以外は、実施例５と同様な操作を行い、多層配線板を作製した。
実施例１０
実施例８と同様の熱硬化性絶縁樹脂組成物を用いて、キャリアフィルム（ＰＥＴフィルム）を剥がしたのち、絶縁樹脂層を１８０℃、６０分間の硬化条件で熱硬化処理するまで同様にして行った。次に、この絶縁樹脂層付き基板に層間接続用のビアホールを、日立ビアメカニクス製ＣＯ2レーザ加工機「ＬＣＯ−１Ｂ２１型」により、ビーム径８０μｍ、周波数５００Ｈｚ、パルス幅５μｓｅｃ、ショット数７の条件で加工して作製した。その後、絶縁樹脂層付き基板をランプがメタルハライドランプのコンベア式紫外線照射装置（最大波長３５０〜３８０ｎｍ）を用い、紫外線を光量が３０００ｍＪ／ｃｍ2になるように照射した。そして、絶縁樹脂層を化学粗化するために、膨潤液として、ジエチレングリコールモノブチルエーテル：２００ｍＬ／Ｌ、ＮａＯＨ：５ｇ／Ｌの水溶液を８０℃に加温して、これに５分間浸漬処理した。次に、粗化液として、ＫＭｎＯ4：６０ｇ／Ｌ、ＮａＯＨ：４０ｇ／Ｌの水溶液を８０℃に加温して１０分間浸漬処理した。引き続き、中和液（ＳｎＣｌ2：３０ｇ／Ｌ、濃度３５質量％のＨＣｌ：３００ｍＬ／Ｌ）の水溶液に室温で５分間浸漬処理して中和した。その後は、実施例８と同様な操作を行って多層配線板を作製した。
Examples 6-9
A multilayer wiring board was produced in the same manner as in Example 5 except that the composition of the thermosetting insulating resin composition was changed as shown in Table 1 in Example 5.
Example 10
Using the same thermosetting insulating resin composition as in Example 8, after peeling off the carrier film (PET film), the insulating resin layer was subjected to the same process until the thermosetting treatment was performed at 180 ° C. for 60 minutes. It was. Next, via holes for interlayer connection are formed in this substrate with an insulating resin layer by using a CO 2 laser processing machine “LCO-1B21 type” manufactured by Hitachi Via Mechanics, with a beam diameter of 80 μm, a frequency of 500 Hz, a pulse width of 5 μsec, and a shot number of 7 It was manufactured by processing. Thereafter, the substrate with an insulating resin layer was irradiated with ultraviolet rays so that the amount of light became 3000 mJ / cm 2 using a conveyor type ultraviolet irradiation device (maximum wavelength 350 to 380 nm) in which the lamp was a metal halide lamp. Then, in order to chemically roughen the insulating resin layer, an aqueous solution of diethylene glycol monobutyl ether: 200 mL / L, NaOH: 5 g / L was heated to 80 ° C. as a swelling liquid, and immersed in this for 5 minutes. Next, as a roughening solution, an aqueous solution of KMnO 4 : 60 g / L, NaOH: 40 g / L was heated to 80 ° C. and immersed for 10 minutes. Subsequently, it was neutralized by immersing it in an aqueous solution of a neutralizing solution (SnCl 2 : 30 g / L, HCl having a concentration of 35% by mass: 300 mL / L) at room temperature for 5 minutes. Thereafter, the same operation as in Example 8 was performed to produce a multilayer wiring board.
実施例１１、１２
実施例５において、熱硬化性絶縁樹脂組成物の組成を表１に示すように変更した以外は、実施例５と同様な操作を行い、多層配線板を作製した。
実施例１３
実施例６において、表１に示すように、無機フィラー平均粒径０．５μｍの球状シリカ、「ＳＯ−２５Ｒ」（株式会社アドマテックス製、商品名）を加えた熱硬化性絶縁樹脂組成物を用いた以外は、実施例６と同様な操作を行い、多層配線板を作製した。
Examples 11 and 12
A multilayer wiring board was produced in the same manner as in Example 5 except that the composition of the thermosetting insulating resin composition was changed as shown in Table 1 in Example 5.
Example 13
In Example 6, as shown in Table 1, a thermosetting insulating resin composition to which spherical silica having an average inorganic filler particle size of 0.5 μm and “SO-25R” (trade name, manufactured by Admatechs Co., Ltd.) were added. A multilayer wiring board was produced in the same manner as in Example 6 except that it was used.
実施例１４
実施例５において、紫外線照射のランプを高圧水銀灯のコンベア式紫外線照射装置（最大波長３１０〜３７０ｎｍ）に変更した以外は、実施例５と同様な操作を行い、多層配線板を作製した。なお、紫外線の照射は、実施例５と同様に、光量が３０００ｍＪ／ｃｍ2になるように行った。
実施例１５
実施例５において、熱硬化性絶縁樹脂組成物の組成を表１に示すように変更した以外は、実施例５と同様な操作を行い、多層配線板を作製した。
実施例１６
実施例６において、熱硬化性絶縁樹脂組成物の組成を表１に示すように変更した以外は、実施例６と同様な操作を行い、多層配線板を作製した。
Example 14
A multilayer wiring board was manufactured in the same manner as in Example 5 except that the ultraviolet irradiation lamp was changed to a conveyor type ultraviolet irradiation device (maximum wavelength of 310 to 370 nm) of a high-pressure mercury lamp in Example 5. In addition, the irradiation of ultraviolet rays was performed so that the amount of light was 3000 mJ / cm 2 as in Example 5.
Example 15
A multilayer wiring board was produced in the same manner as in Example 5 except that the composition of the thermosetting insulating resin composition was changed as shown in Table 1 in Example 5.
Example 16
A multilayer wiring board was produced in the same manner as in Example 6 except that the composition of the thermosetting insulating resin composition was changed as shown in Table 1 in Example 6.
実施例１７
実施例１において、熱硬化性絶縁樹脂組成物における（Ａ）成分を、ヘキサンジオールを骨格に有するエポキシ樹脂に変更した以外は、実施例１と同様な操作を行い、多層配線板を作製した（組成については表１参照）。
Example 17
In Example 1, the same operation as in Example 1 was performed except that the component (A) in the thermosetting insulating resin composition was changed to an epoxy resin having hexanediol as a skeleton, thereby producing a multilayer wiring board ( See Table 1 for composition).
なお、ヘキサンジオールを骨格に有するエポキシ樹脂は、下記のようにして調製した。
まず、温度計及び撹拌機を取り付けたフラスコに、ビスフェノールＡ２２８ｇ（１．００モル）と１，６−ヘキサンジオールジビニルエーテル９２ｇ（０．８５モル）を仕込み、１２０℃まで１時間要して昇温した後、さらに１２０℃で６時間反応させて透明半固形の変性多価フェノール類４００ｇを得た。
次に、温度計、滴下ロート、冷却管、及び撹拌機を取り付けたフラスコに、上記変性多価フェノール類４００ｇ、エピクロルヒドリン９２５ｇ（１０モル）、ｎ−ブタノール１８５ｇを仕込み溶解させた。その後、窒素ガスパージを施しながら、６５℃に昇温した後、共沸する圧力までに減圧して、４９％水酸化ナトリウム水溶液１２２ｇ（１．５モル）を５時間かけて滴下した。次いでこの条件下で０．５時間撹拌を続けた。この間、共沸で留出してきた留出分をディーンスタークトラップで分離して、水層を除去し、有機層を反応系内に戻しながら反応した。その後、未反応のエピクロルヒドリンを減圧蒸留して留去させた。得られた粗エポキシ樹脂にメチルイソブチルケトン１０００ｇとｎ−ブタノール１００ｇを加え溶解した。さらに、この溶液に１０％水酸化ナトリウム水溶液２０ｇを添加して８０℃で２時間反応させた後に、洗浄液のｐＨが中性となるまで、３００ｇの水で水洗を３回繰り返した。次いで共沸によって系内を脱水し、精密ろ過を経た後に溶媒を減圧下で留去して、透明液体のエポキシ樹脂４５７ｇを得た。エポキシ当量は４０３であった。
In addition, the epoxy resin which has hexanediol in frame | skeleton was prepared as follows.
First, 228 g (1.00 mol) of bisphenol A and 92 g (0.85 mol) of bisphenol A and 92 g (0.85 mol) of bisphenol A were charged into a flask equipped with a thermometer and a stirrer, and the temperature was raised to 120 ° C. for 1 hour. And then reacted at 120 ° C. for 6 hours to obtain 400 g of a transparent semi-solid modified polyhydric phenol.
Next, 400 g of the modified polyphenols, 925 g (10 mol) of epichlorohydrin, and 185 g of n-butanol were charged and dissolved in a flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer. Thereafter, the temperature was raised to 65 ° C. while purging with nitrogen gas, and then the pressure was reduced to an azeotropic pressure, and 122 g (1.5 mol) of a 49% aqueous sodium hydroxide solution was added dropwise over 5 hours. Stirring was then continued under these conditions for 0.5 hour. During this time, the distillate distilled azeotropically was separated with a Dean-Stark trap, the aqueous layer was removed, and the reaction was conducted while returning the organic layer to the reaction system. Thereafter, unreacted epichlorohydrin was distilled off under reduced pressure. To the resulting crude epoxy resin, 1000 g of methyl isobutyl ketone and 100 g of n-butanol were added and dissolved. Further, 20 g of a 10% sodium hydroxide aqueous solution was added to this solution and reacted at 80 ° C. for 2 hours. Then, washing with 300 g of water was repeated three times until the pH of the washing solution became neutral. Next, the system was dehydrated by azeotropic distillation, and after passing through microfiltration, the solvent was distilled off under reduced pressure to obtain 457 g of a transparent liquid epoxy resin. The epoxy equivalent was 403.
比較例１
実施例５において、熱硬化性絶縁樹脂組成物の組成を表１に示すように、活性エステル基含有化合物を使用しない以外は、実施例５と同様な操作を行い、多層配線板を作製した。
比較例２
実施例５の熱硬化性絶縁樹脂組成物において、表１に示すように、活性エステル基含有化合物の代わりに、クレゾールノボラック型フェノール樹脂（「ＫＡ−１１６５」、ＤＩＣ株式会社製商品名、水酸基当量：１１９）を使用した以外は、実施例５と同様な操作を行い、多層配線板を作製した。
Comparative Example 1
In Example 5, as shown in Table 1, the composition of the thermosetting insulating resin composition was the same as in Example 5 except that no active ester group-containing compound was used, and a multilayer wiring board was produced.
Comparative Example 2
In the thermosetting insulating resin composition of Example 5, as shown in Table 1, instead of the active ester group-containing compound, a cresol novolac-type phenol resin ("KA-1165", a product name manufactured by DIC Corporation, hydroxyl equivalent) 119) was used, and the same operation as in Example 5 was performed to produce a multilayer wiring board.
表１中の（Ａ）成分のＡ１〜Ａ５、（Ｂ）成分のＢ１、（Ｃ）成分のＣ１、Ｃ２、（Ｄ）成分のＤ１、溶媒のＥ１及びフィラーのＦ１は、以下に示すものである。
また、表１中のＧ１（比較例２参照）は、下記に示すように、活性エステル基含有化合物ではないが、活性エステル基含有化合物の代わりに用いたことを示すために、便宜上、（Ｂ）成分の欄に記載した。
Ａ１：テトラフェニル型エポキシ樹脂、「ＪＥＲ−１０３１」（ＪＥＲ株式会社社製）
Ａ２：エチレン性不飽和化合物を骨格に有するエポキシ樹脂、「ＥＸＡ４８１６」（ＤＩＣ株式会社社製）
Ａ３：ナフタレン型エポキシ樹脂、「ＨＰ−４７００」（ＤＩＣ株式会社社製）
Ａ４：フェノールノボラック型エポキシ樹脂、「Ｎ−７７０」（ＤＩＣ株式会社社製）
Ａ５：ビフェニル型エポキシ樹脂、「ＮＣ３０００Ｈ」（日本化薬株式会社社製）
Ａ６：ヘキサンジオール骨格を有するエポキシ樹脂
Ｂ１：活性エステル基含有化合物、「ＥＸＢ−９４７０」（ＤＩＣ株式会社）
Ｃ１：トリアジン骨格含有フェノール系樹脂、「フェノライトＬＡ−１３５６」（ＤＩＣ株式会社製）
Ｃ２：トリアジン骨格含有フェノール系樹脂、「フェノライトＬＡ−１３９８」（窒素含有量２２質量％、水酸基当量１３５、ＤＩＣ株式会社製）
Ｄ１：硬化促進剤、イミダゾール誘導体化合物、１−シアノエチル−２−フェニルイミダゾリウムトリメリテート、「２ＰＺ−ＣＮＳ」（四国化成工業株式会社製）
Ｅ１：メチルエチルケトン
Ｆ１：無機フィラー、平均粒径０．５μｍの球状シリカ、「ＳＯ−２５Ｒ」（株式会社アドマテックス製）
Ｇ１：クレゾールノボラック型フェノール樹脂、「ＫＡ−１１６５」（水酸基当量：１１９、ＤＩＣ株式会社製商品名）
In Table 1, A1 to A5 of component (A), B1 of component (B), C1 and C2 of component (C), D1 of component (D), E1 of solvent and F1 of filler are as shown below. is there.
G1 (see Comparative Example 2) in Table 1 is not an active ester group-containing compound as shown below, but for the sake of convenience, (B ) Listed in the column of the component.
A1: Tetraphenyl type epoxy resin, “JER-1031” (manufactured by JER Corporation)
A2: Epoxy resin having an ethylenically unsaturated compound as a skeleton, “EXA4816” (manufactured by DIC Corporation)
A3: Naphthalene type epoxy resin, “HP-4700” (manufactured by DIC Corporation)
A4: Phenol novolac type epoxy resin, “N-770” (manufactured by DIC Corporation)
A5: Biphenyl type epoxy resin, “NC3000H” (manufactured by Nippon Kayaku Co., Ltd.)
A6: Epoxy resin having hexanediol skeleton B1: Active ester group-containing compound, “EXB-9470” (DIC Corporation)
C1: Triazine skeleton-containing phenolic resin, “Phenolite LA-1356” (manufactured by DIC Corporation)
C2: Triazine skeleton-containing phenol resin, “Phenolite LA-1398” (nitrogen content 22% by mass, hydroxyl group equivalent 135, manufactured by DIC Corporation)
D1: Curing accelerator, imidazole derivative compound, 1-cyanoethyl-2-phenylimidazolium trimellitate, “2PZ-CNS” (manufactured by Shikoku Kasei Kogyo Co., Ltd.)
E1: Methyl ethyl ketone F1: Inorganic filler, spherical silica having an average particle size of 0.5 μm, “SO-25R” (manufactured by Admatechs Co., Ltd.)
G1: Cresol novolac type phenol resin, “KA-1165” (hydroxyl equivalent: 119, trade name of DIC Corporation)
以上、実施例１〜１７及び比較例１、２における多層積層板について、外層回路との接着強度、めっき銅エッチング除去面の絶縁樹脂層粗さ及び２８８℃におけるはんだ耐熱性を求めた。その結果を表２に示す。 As mentioned above, about the multilayer laminated board in Examples 1-17 and Comparative Examples 1 and 2, the adhesive strength with an outer layer circuit, the insulating resin layer roughness of a plating copper etching removal surface, and the solder heat resistance in 288 degreeC were calculated | required. The results are shown in Table 2.
表２から、本発明に用いる熱硬化性絶縁樹脂組成物を熱硬化し、これに紫外線を照射した絶縁樹脂層を有する配線板は、実施例に示したように、絶縁樹脂層の表面粗さが小さい状態で外層銅との接着強度が良好で微細配線化に適していることが証明できた。また、２８８℃におけるはんだ耐熱性にも優れており、鉛フリーはんだ実装にも優れていることも併せて証明できた。
一方、本発明に用いる熱硬化性絶縁樹脂組成物を用いていない比較例に示す配線板は、接着強度やはんだ耐熱性に劣ることが証明された。
From Table 2, the thermosetting insulating resin composition used in the present invention was thermally cured, and the wiring board having the insulating resin layer irradiated with ultraviolet rays had the surface roughness of the insulating resin layer as shown in the Examples. It was proved that the adhesive strength with the outer layer copper was good in a small state and that it was suitable for fine wiring. It was also proved that it was excellent in solder heat resistance at 288 ° C. and also excellent in lead-free solder mounting.
On the other hand, it was proved that the wiring board shown in the comparative example not using the thermosetting insulating resin composition used in the present invention is inferior in adhesive strength and solder heat resistance.
本発明によれば、絶縁樹脂層表面の凹凸形状が小さい状態でも、配線導体に対して容易に高い接着力を発現し得る上、ビアホール底のスミアを除去するために、過マンガン酸ナトリウム系などの粗化液で処理しても、絶縁樹脂層表面の粗化凹凸形状が小さく、かつ配線導体に対して高い接着力を確保することができる。
本発明の樹脂組成物を用いて作製された配線板は回路との接着強度が良好であり、かつはんだ耐熱性にも優れている。
According to the present invention, even in a state where the surface of the insulating resin layer has a small uneven shape, a high adhesive force can be easily expressed with respect to the wiring conductor, and in order to remove smear at the bottom of the via hole, Even if it processes with this roughening liquid, the roughening uneven | corrugated shape of the insulating resin layer surface is small, and high adhesive force can be ensured with respect to a wiring conductor.
The wiring board produced using the resin composition of the present invention has good adhesive strength with a circuit and is excellent in solder heat resistance.
Claims (19)
熱硬化性絶縁樹脂組成物の（Ｂ）活性エステル基含有化合物が、１分子中にエステル基１個以上を有する樹脂である、絶縁樹脂。 (A) a thermosetting insulating resin composition comprising an epoxy resin having two or more epoxy groups in one molecule, (B) an active ester group-containing compound, and (D) an epoxy resin curing accelerator; This is an insulating resin obtained by irradiating with ultraviolet rays ,
Insulating resin whose (B) active ester group containing compound of a thermosetting insulating resin composition is resin which has one or more ester groups in 1 molecule .
熱硬化性絶縁樹脂組成物の（Ｂ）活性エステル基含有化合物が、１分子中にエステル基１個以上を有する樹脂である、配線板。 Thermal curing comprising (A) an epoxy resin having two or more epoxy groups in one molecule, (B) an active ester group-containing compound, and (D) an epoxy resin curing accelerator on a substrate having a wiring conductor circuit. A wiring board obtained by thermally curing an insulating resin layer provided by the conductive insulating resin composition, irradiating the insulating resin layer with ultraviolet rays, and then forming a wiring on the insulating resin layer by plating ;
The wiring board whose (B) active ester group containing compound of a thermosetting insulating resin composition is resin which has one or more ester groups in 1 molecule .
熱硬化性絶縁樹脂組成物の（Ｂ）活性エステル基含有化合物が、１分子中にエステル基１個以上を有する樹脂である、配線板の製造方法。 (A) On a substrate having a wiring conductor circuit, (A) an epoxy resin having two or more epoxy groups in one molecule, (B) an active ester group-containing compound, and (D) an epoxy resin curing accelerator. A step of forming an insulating resin layer using the thermosetting insulating resin composition comprising, (b) a step of thermosetting the insulating resin layer, and (c) a step of irradiating the heat-insulating insulating resin layer with an ultraviolet ray. (D) a process for producing an insulating resin layer that has been subjected to ultraviolet irradiation treatment, and a process for performing electroless plating treatment ,
The manufacturing method of a wiring board whose (B) active ester group containing compound of a thermosetting insulating resin composition is resin which has one or more ester groups in 1 molecule .
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| JPH04176189A (en) * | 1990-11-08 | 1992-06-23 | Hitachi Chem Co Ltd | Manufacture of printed wiring board |
| JP5011804B2 (en) * | 2005-09-06 | 2012-08-29 | 日立化成工業株式会社 | Circuit connection material, connection body and circuit member connection method |
| JP5101026B2 (en) * | 2005-11-04 | 2012-12-19 | 富士フイルム株式会社 | Conductive film forming method, conductive pattern forming method, and multilayer wiring board manufacturing method |
| JP5181769B2 (en) * | 2008-03-26 | 2013-04-10 | Ｄｉｃ株式会社 | Epoxy resin composition and cured product thereof |
| JP5245496B2 (en) * | 2008-03-31 | 2013-07-24 | Ｄｉｃ株式会社 | Epoxy resin composition and cured product thereof |
| JP5325462B2 (en) * | 2008-05-29 | 2013-10-23 | 太陽ホールディングス株式会社 | Thermosetting resin composition and printed wiring board |
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