JP4725704B2 - Resin composition for interlayer insulation of multilayer printed wiring board, adhesive film and prepreg - Google Patents
Resin composition for interlayer insulation of multilayer printed wiring board, adhesive film and prepreg Download PDFInfo
- Publication number
- JP4725704B2 JP4725704B2 JP2004158247A JP2004158247A JP4725704B2 JP 4725704 B2 JP4725704 B2 JP 4725704B2 JP 2004158247 A JP2004158247 A JP 2004158247A JP 2004158247 A JP2004158247 A JP 2004158247A JP 4725704 B2 JP4725704 B2 JP 4725704B2
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- Prior art keywords
- resin
- component
- resin composition
- adhesive film
- epoxy resin
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- 239000011342 resin composition Substances 0.000 title claims description 104
- 239000002313 adhesive film Substances 0.000 title claims description 56
- 239000011229 interlayer Substances 0.000 title description 6
- 238000009413 insulation Methods 0.000 title description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 69
- 229920005989 resin Polymers 0.000 claims description 65
- 239000011347 resin Substances 0.000 claims description 65
- 239000003822 epoxy resin Substances 0.000 claims description 64
- 239000004020 conductor Substances 0.000 claims description 37
- 239000011256 inorganic filler Substances 0.000 claims description 32
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 32
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 26
- 125000003118 aryl group Chemical group 0.000 claims description 21
- 239000004593 Epoxy Substances 0.000 claims description 20
- 238000007788 roughening Methods 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 238000010030 laminating Methods 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 125000003700 epoxy group Chemical group 0.000 claims description 15
- 238000007747 plating Methods 0.000 claims description 15
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 14
- 230000009477 glass transition Effects 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 10
- 239000007800 oxidant agent Substances 0.000 claims description 10
- 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 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 239000013034 phenoxy resin Substances 0.000 claims description 9
- 229920006287 phenoxy resin Polymers 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 7
- 239000011354 acetal resin Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 229920006324 polyoxymethylene Polymers 0.000 claims description 7
- 229920001187 thermosetting polymer Polymers 0.000 claims description 7
- 229920002554 vinyl polymer Polymers 0.000 claims description 7
- 239000004962 Polyamide-imide Substances 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- 238000005553 drilling Methods 0.000 claims description 6
- 238000007772 electroless plating Methods 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 229920002312 polyamide-imide Polymers 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 229920006122 polyamide resin Polymers 0.000 claims description 5
- 238000004381 surface treatment Methods 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 97
- 238000000034 method Methods 0.000 description 37
- 239000002966 varnish Substances 0.000 description 28
- 238000001723 curing Methods 0.000 description 22
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 14
- -1 phosphine compound Chemical class 0.000 description 13
- 238000005259 measurement Methods 0.000 description 11
- 229920003986 novolac Polymers 0.000 description 11
- 239000000758 substrate Substances 0.000 description 11
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 10
- 238000003475 lamination Methods 0.000 description 10
- 239000000155 melt Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 229920000139 polyethylene terephthalate Polymers 0.000 description 7
- 239000005020 polyethylene terephthalate Substances 0.000 description 7
- 230000001681 protective effect Effects 0.000 description 7
- 230000003014 reinforcing effect Effects 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000013557 residual solvent Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- 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 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000000137 annealing Methods 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
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- 239000012943 hotmelt Substances 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000000930 thermomechanical effect Effects 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
- 239000008096 xylene Substances 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 1
- DJOYTAUERRJRAT-UHFFFAOYSA-N 2-(n-methyl-4-nitroanilino)acetonitrile Chemical compound N#CCN(C)C1=CC=C([N+]([O-])=O)C=C1 DJOYTAUERRJRAT-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- 229920001665 Poly-4-vinylphenol Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 229910021523 barium zirconate Inorganic materials 0.000 description 1
- DQBAOWPVHRWLJC-UHFFFAOYSA-N barium(2+);dioxido(oxo)zirconium Chemical compound [Ba+2].[O-][Zr]([O-])=O DQBAOWPVHRWLJC-UHFFFAOYSA-N 0.000 description 1
- 229910002115 bismuth titanate Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
Images
Description
本発明は、回路形成された導体層と絶縁層とを交互に積み上げたビルドアップ方式の多層プリント配線板の層間絶縁材料として有用な樹脂組成物、並びに該樹脂組成物により調製される多層プリント配線板用の接着フィルムおよびプリプレグに関する。本発明は、更に、該樹脂組成物またはプリプレグの硬化物により絶縁層が形成されている多層プリント配線板および該多層プリント配線板の製造方法に関する。 The present invention relates to a resin composition useful as an interlayer insulating material for a multilayer printed wiring board of a build-up method in which circuit-formed conductor layers and insulating layers are alternately stacked, and a multilayer printed wiring prepared using the resin composition The present invention relates to an adhesive film for a plate and a prepreg. The present invention further relates to a multilayer printed wiring board in which an insulating layer is formed from a cured product of the resin composition or prepreg, and a method for producing the multilayer printed wiring board.
近年、電子機器の小型化、高性能化が進み、多層プリント配線板のビルドアップ層が複層化され、ビアホールが複数のビルドアップ絶縁層にまたがって接続されたスタッガードビア、スタックトビアと呼ばれる多段ビア構造を有する多層プリント配線板の需要が高まっている。このような多段ビア構造を有する多層プリント配線板では、ビアホールを接続する銅配線と絶縁層との熱膨張係数が大きく異なるため、サーマルサイクル等の信頼性試験を行うと銅配線または絶縁層にクラックが入る等の問題が発生していた。そこで、絶縁層を構成する樹脂組成物の熱膨張率を低く抑えることが急務となっている。 In recent years, electronic devices have become smaller and higher in performance, and the build-up layer of multilayer printed wiring boards has been made into multiple layers, and the via hole is connected to multiple build-up insulating layers and is called a staggered via or stacked via There is an increasing demand for multilayer printed wiring boards having a multistage via structure. In a multilayer printed wiring board having such a multistage via structure, the thermal expansion coefficient of the copper wiring connecting the via hole and the insulating layer is greatly different. Therefore, when a reliability test such as a thermal cycle is performed, the copper wiring or the insulating layer cracks. There was a problem such as entering. Therefore, there is an urgent need to keep the thermal expansion coefficient of the resin composition constituting the insulating layer low.
熱膨張率を抑える手段の一つとして樹脂組成物中に無機充填材を添加する方法が一般的に知られており、無機充填材の添加量が多いほど熱膨張率を低下させる効果がある。しかしながら、従来は絶縁層に多量の無機充填材が含まれると、絶縁層のビアホールの形成に主として使用されていた炭酸ガスレーザーによる熱分解温度が樹脂と無機充填材で異なるため、ビア形状の悪化や加工速度が遅くなるといった問題点があった。例えば特許文献１は無機充填材の含有量として、レーザー加工性の点から３０重量％以下が好ましいとしている。しかしながら、炭酸ガスレーザーの進展、ＵＶ−ＹＡＧレーザーの本分野への汎用化は目覚しく、現在は無機充填材が多量に含まれた樹脂組成物であってもレーザーにより大きな問題なく加工可能となっている。 As a means for suppressing the thermal expansion coefficient, a method of adding an inorganic filler to a resin composition is generally known, and there is an effect of decreasing the thermal expansion coefficient as the amount of the inorganic filler added increases. However, if the insulating layer contains a large amount of inorganic filler, the thermal decomposition temperature by the carbon dioxide laser, which was mainly used for forming the via hole in the insulating layer, differs between the resin and the inorganic filler, so the via shape deteriorated. In addition, there is a problem that the processing speed becomes slow. For example, Patent Document 1 states that the content of the inorganic filler is preferably 30% by weight or less from the viewpoint of laser workability. However, the progress of carbon dioxide gas laser and the widespread use of UV-YAG laser in this field are remarkable, and now even a resin composition containing a large amount of inorganic filler can be processed without any major problems by the laser. Yes.
一方、ビルトアップ工法において、高密度配線を形成するのに適しためっき方法として、アルカリ性過マンガン酸溶液等の酸化剤で絶縁層表面を粗化処理後、無電解めっき、または無電解めっきと電解めっきを組み合わせて導体層を形成する方法が知られている。しかしながら、この方法において、絶縁層中に無機充填材が多量に含まれると粗化処理後の表面に無機充填材が剥き出しとなる部分が多くなり、めっきにより形成される導体層のピール（peel）強度（引き剥がし強度）が低下するという問題があった。特に本発明者ら経験によれば、従来、樹脂組成物中に３５重量％以上、特に４０重量％以上無機充填材が含まれると、多層プリント配線板に要求されるピール強度を安定的に得る事は極めて困難であった。 On the other hand, as a plating method suitable for forming high-density wiring in the build-up method, the surface of the insulating layer is roughened with an oxidizing agent such as an alkaline permanganate solution, and then electroless plating or electroless plating and electrolysis are used. A method of forming a conductor layer by combining plating is known. However, in this method, if the inorganic layer contains a large amount of the inorganic filler, the portion where the inorganic filler is exposed on the surface after the roughening treatment increases and the peel of the conductor layer formed by plating There was a problem that strength (peeling strength) was lowered. In particular, according to the experience of the present inventors, when the inorganic filler is conventionally contained in the resin composition in an amount of 35% by weight or more, particularly 40% by weight or more, the peel strength required for the multilayer printed wiring board can be stably obtained. Things were extremely difficult.
本発明の目的は、熱膨張率が低く、かつ導体層のピール強度に優れる絶縁層が形成可能な、多層プリント配線板の層間絶縁用樹脂組成物、並びに該樹脂組成物より調製される多層プリント配線板用の接着フィルムおよびプリプレグを提供することである。また、本発明の目的は、該接着フィルムまたはプリプレグにより絶縁層を導入する多層プリント配線板の製造方法、および該樹脂組成物または該プリプレグの硬化物により絶縁層が形成されている多層プリント配線板を提供することである。 An object of the present invention is to provide an interlayer insulating resin composition for a multilayer printed wiring board capable of forming an insulating layer having a low coefficient of thermal expansion and excellent peel strength of a conductor layer, and a multilayer print prepared from the resin composition It is providing the adhesive film and prepreg for wiring boards. Another object of the present invention is to produce a multilayer printed wiring board in which an insulating layer is introduced by the adhesive film or prepreg, and a multilayer printed wiring board in which an insulating layer is formed from the resin composition or a cured product of the prepreg. Is to provide.
本発明者等は、前記課題を解決すべく鋭意検討した結果、（Ａ）１分子中に２以上のエポキシ基を有し、温度２０℃で液状であるエポキシ樹脂、（Ｂ）１分子中に３以上のエポキシ基を有し、エポキシ当量が２００以下である芳香族系エポキシ樹脂、（Ｃ）フェノール系硬化剤、（Ｄ）ガラス転移温度が１００℃以上である、フェノキシ樹脂、ポリビニルアセタール樹脂、ポリアミド樹脂およびポリアミドイミド樹脂からなる群より選ばれる一種以上の樹脂を特定割合で配合し、更に無機充填材（Ｅ）を３５重量％以上配合した樹脂組成物によって、絶縁層における低熱膨張率と高いピール強度が同時に達成されることを見いだし、本発明を完成させた。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have (A) an epoxy resin having two or more epoxy groups in one molecule and being liquid at a temperature of 20 ° C., and (B) in one molecule. An aromatic epoxy resin having 3 or more epoxy groups and having an epoxy equivalent of 200 or less, (C) a phenolic curing agent, (D) a glass transition temperature of 100 ° C. or higher, a phenoxy resin, a polyvinyl acetal resin, One or more resins selected from the group consisting of polyamide resin and polyamideimide resin are blended at a specific ratio, and further, the resin composition blended with 35% by weight or more of the inorganic filler (E) has a low coefficient of thermal expansion and high in the insulating layer. It was found that peel strength was achieved at the same time, and the present invention was completed.
すなわち本発明は以下の内容を含むものである。 That is, the present invention includes the following contents.
［１］下記成分（Ａ）〜（Ｅ）：
（Ａ）１分子中に２以上のエポキシ基を有し、温度２０℃で液状であるエポキシ樹脂、
（Ｂ）１分子中に３以上のエポキシ基を有し、エポキシ当量が２００以下である芳香族系エポキシ樹脂、
（Ｃ）フェノール系硬化剤、
（Ｄ）ガラス転移温度が１００℃以上である、フェノキシ樹脂、ポリビニルアセタール樹脂、ポリアミド樹脂およびポリアミドイミド樹脂からなる群より選ばれる一種以上の樹脂、及び
（Ｅ）シランカップリング剤で表面処理してある無機充填材
を含み、シランカップリング剤で表面処理してある無機充填材（Ｅ）の含有割合が樹脂組成物の３５重量％以上であり、成分（Ａ）と成分（Ｂ）のエポキシ樹脂の割合が重量比で１：０．３乃至１：２であり、樹脂組成物中のエポキシ基と成分（Ｃ）のフェノール系硬化剤のフェノール性水酸基の割合が１：０．５乃至１：１．５であり、成分（Ｄ）の樹脂の含有割合が樹脂組成物の２乃至２０重量％である多層プリント配線板の層間絶縁用樹脂組成物。
［２］ 成分（Ｅ）の無機充填材が球形シリカであることを特徴とする上記[１]に記載の樹脂組成物。
［３］ 成分（Ｅ）の無機充填材が平均粒径５μｍ以下であることを特徴とする上記[１]又は[２]に記載の樹脂組成物。
［４］ 成分（Ａ）のエポキシ樹脂が芳香族系エポキシ樹脂である［１］に記載の樹脂組成物。
［５］ 成分（Ｂ）の芳香族系エポキシ樹脂のエポキシ当量が１５０〜２００である［１］に記載の樹脂組成物。
［６］ 成分（Ｂ）の芳香族系エポキシ樹脂が２０℃で固体である芳香族系エポキシ樹脂である［１］に記載の樹脂組成物。
［７］ 成分（Ｅ）の無機充填材の含有割合が樹脂組成物の３５乃至７０重量％である［１］記載の樹脂組成物。
［８］ 樹脂組成物中の成分（Ａ）と成分（Ｂ）の合計量が１０〜５０重量％である［１］に記載の樹脂組成物。
［９］ ［１］乃至［８］記載の樹脂組成物からなる樹脂組成物層が支持フィルム上に形成されている多層プリント配線板用の接着フィルム。
［１０］ 樹脂組成物が、これを測定開始温度６０℃、昇温速度５℃／分及び振動数１Ｈｚ／ｄｅｇで動的粘弾性を測定した場合の溶融粘度が、９０℃で４，０００乃至５０，０００ポイズ、１００℃で２，０００乃至２１，０００ポイズ、１１０℃で９００乃至１２，０００ポイズ、１２０℃で５００乃至９，０００ポイズ、１３０℃で３００乃至１５，０００である［９］記載の接着フィルム。
［１１］ ［１］乃至［８］記載の樹脂組成物が繊維からなるシート状補強基材中に含浸されていることを特徴とする多層プリント配線板用のプリプレグ。
［１２］ ［１］乃至［８］記載の樹脂組成物の硬化物により絶縁層が形成されている多層プリント配線板。
［１３］ ［１１］記載のプリプレグの硬化物により絶縁層が形成されている多層プリント配線板。
［１４］ 下記の工程（ａ）乃至（ｇ）を含むことを特徴とする多層プリント配線板の製造方法：
（ａ）［９］記載の接着フィルムを回路基板の片面又は両面にラミネートし、支持フィルムを剥離するか又は剥離しない工程、
（ｂ）ラミネートされた樹脂組成物を熱硬化し絶縁層を形成する工程、
（ｃ）支持フィルムが存在する場合に該支持フィルムを剥離する行程、
（ｄ）絶縁層が形成された回路基板に穴あけする行程、
（ｅ）絶縁層の表面を酸化剤により粗化処理する工程、
（ｆ）粗化された絶縁層の表面にめっきにより導体層を形成させる工程、および
（ｇ）導体層に回路形成する工程。
［１５］ 下記の工程（ｈ）乃至（ｍ）を含むことを特徴とする多層プリント配線板の製造方法。
（ｈ）［１１］記載のプリプレグを回路基板の片面又は両面にラミネートする工程、
（ｉ）ラミネートされたプリプレグを熱硬化し絶縁層を形成する工程、
（ｊ）絶縁層が形成された回路基板に穴あけする行程、
（ｋ）絶縁層の表面を酸化剤により粗化処理する工程、
（ｌ）粗化された絶縁層の表面にめっきにより導体層を形成させる工程、および
（ｍ）導体層に回路形成する工程。
[1] The following components (A) to (E):
(A) an epoxy resin having two or more epoxy groups in one molecule and being liquid at a temperature of 20 ° C.,
(B) an aromatic epoxy resin having 3 or more epoxy groups in one molecule and an epoxy equivalent of 200 or less,
(C) a phenolic curing agent,
(D) Surface treatment with one or more resins selected from the group consisting of phenoxy resin, polyvinyl acetal resin, polyamide resin and polyamideimide resin, and (E) silane coupling agent having a glass transition temperature of 100 ° C. or higher. It includes certain inorganic fillers, and the content of the inorganic filler that is surface treated with a silane coupling agent (E) is more than 35 wt% of the resin composition, the epoxy resin of component (a) and component (B) The ratio of the epoxy group in the resin composition to the phenolic hydroxyl group of the phenolic curing agent of component (C) is 1: 0.5 to 1: 2. The resin composition for interlayer insulation of the multilayer printed wiring board which is 1.5 and the content rate of resin of a component (D) is 2 to 20 weight% of a resin composition.
[2] The resin composition as described in [1] above, wherein the inorganic filler of component (E) is spherical silica.
[3] The resin composition as described in [1] or [2] above, wherein the inorganic filler of component (E) has an average particle size of 5 μm or less.
[ 4 ] The resin composition according to [1] , wherein the epoxy resin of component (A) is an aromatic epoxy resin.
[ 5 ] The resin composition according to [1] , wherein the epoxy equivalent of the aromatic epoxy resin of component (B) is 150 to 200.
[ 6 ] The resin composition according to [1] , wherein the aromatic epoxy resin of component (B) is an aromatic epoxy resin that is solid at 20 ° C.
[ 7 ] The resin composition according to [1], wherein the content of the inorganic filler of component (E) is 35 to 70% by weight of the resin composition .
[8] The resin composition according to [1] , wherein the total amount of component (A) and component (B) in the resin composition is 10 to 50% by weight.
[9] An adhesive film for a multilayer printed wiring board in which a resin composition layer comprising the resin composition according to [1] to [8] is formed on a support film.
[10] The resin composition has a melt viscosity of 4,000 to 9000 at 90 ° C. when dynamic viscoelasticity is measured at a measurement start temperature of 60 ° C., a heating rate of 5 ° C./min, and a frequency of 1 Hz / deg. 50,000 poise, 2,000 to 21,000 poise at 100 ° C, 900 to 12,000 poise at 110 ° C, 500 to 9,000 poise at 120 ° C, and 300 to 15,000 at 130 ° C [9] The adhesive film as described.
[11] A prepreg for a multilayer printed wiring board, wherein the resin composition according to any one of [1] to [8] is impregnated in a sheet-like reinforcing substrate made of fibers.
[12] A multilayer printed wiring board in which an insulating layer is formed of a cured product of the resin composition according to [1] to [8].
[13] A multilayer printed wiring board in which an insulating layer is formed of a cured product of the prepreg according to [11].
[14] A method for producing a multilayer printed wiring board comprising the following steps (a) to (g):
(A) Laminating the adhesive film according to [9] on one or both sides of a circuit board, and peeling or not peeling the support film;
(B) a step of thermosetting the laminated resin composition to form an insulating layer;
(C) a step of peeling the support film when the support film is present;
(D) a step of drilling a circuit board on which an insulating layer is formed;
(E) a step of roughening the surface of the insulating layer with an oxidizing agent;
(F) A step of forming a conductor layer by plating on the surface of the roughened insulating layer, and (g) a step of forming a circuit on the conductor layer.
[15] A method for producing a multilayer printed wiring board, comprising the following steps (h) to (m):
(H) A step of laminating the prepreg according to [11] on one side or both sides of a circuit board,
(I) a step of thermosetting the laminated prepreg to form an insulating layer;
(J) a step of drilling a circuit board on which an insulating layer is formed;
(K) a step of roughening the surface of the insulating layer with an oxidizing agent;
(L) A step of forming a conductor layer on the surface of the roughened insulating layer by plating, and (m) a step of forming a circuit on the conductor layer.
本発明によれば、熱膨張率が低く、かつ導体層のピール強度に優れる絶縁層を多層プリント配線板に簡便に導入することが可能である。該絶縁層は破断強度にも優れている。 According to the present invention, an insulating layer having a low coefficient of thermal expansion and excellent peel strength of a conductor layer can be easily introduced into a multilayer printed wiring board. The insulating layer is also excellent in breaking strength.
成分（Ａ）である「１分子中に２以上のエポキシ基を有し、温度２０℃で液状であるエポキシ樹脂」としては、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、フェノールノボラック型エポキシ樹脂、ｔｅｒｔ−ブチル−カテコール型エポキシ樹脂、ナフタレン型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、脂環式エポキシ樹脂等が挙げられる。またエポキシ樹脂としては硬化物の好ましい物性等の観点から芳香族系エポキシ樹脂が好ましい。なお本発明において芳香族系エポキシ樹脂とは、その分子内に芳香環骨格を有するエポキシ樹脂を意味する。従って成分（Ａ）としては「１分子中に２以上のエポキシ基を有し、温度２０℃で液状である芳香族系エポキシ樹脂」がより好ましい。これらのエポキシ樹脂は各々単独で用いてもよく、２種以上を組み合わせて使用してもよい。なお成分（Ａ）のエポキシ樹脂は温度２０℃未満で液状であってもよい。成分（Ａ）として温度２０℃で固体のものを用いた場合、接着フィルムを取り扱う常温（２０〜３０℃程度）で接着フィルムの十分な可とう性が得られにくく、接着フィルムの取り扱い性が低下する傾向にある。また回路基板へのラミネートの際に、ビアホールやスルーホール内を充填するだけの樹脂組成物の十分な流動性が得られない傾向にある。 The component (A) “epoxy resin having two or more epoxy groups in one molecule and being liquid at a temperature of 20 ° C.” includes bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin. Tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, glycidylamine type epoxy resin, alicyclic epoxy resin and the like. The epoxy resin is preferably an aromatic epoxy resin from the viewpoint of preferable physical properties of the cured product. In the present invention, the aromatic epoxy resin means an epoxy resin having an aromatic ring skeleton in the molecule. Therefore, as the component (A), “an aromatic epoxy resin having two or more epoxy groups in one molecule and being liquid at a temperature of 20 ° C.” is more preferable. These epoxy resins may be used alone or in combination of two or more. The component (A) epoxy resin may be liquid at a temperature of less than 20 ° C. When a solid component (A) is used at a temperature of 20 ° C., it is difficult to obtain sufficient flexibility of the adhesive film at room temperature (about 20 to 30 ° C.) for handling the adhesive film, and the handleability of the adhesive film is lowered. Tend to. In addition, when laminating to a circuit board, there is a tendency that sufficient fluidity of the resin composition sufficient to fill the via hole or the through hole is not obtained.
成分（Ｂ）である「１分子中に３以上のエポキシ基を有し、エポキシ当量が２００以下である芳香族系エポキシ樹脂」としては、ナフタレン型エポキシ樹脂、フェノール類とフェノール性水酸基を有する芳香族アルデヒドとの縮合物のエポキシ化物（トリスフェノール型エポキシ樹脂）が挙げられ、具体的には大日本インキ化学工業（株）製ＥＸＡ４７００（４官能ナフタレン型エポキシ樹脂）、日本化薬（株）ＥＰＰＮ−５０２Ｈ（トリスフェノールエポキシ樹脂）等がある。これらのエポキシ樹脂は各々単独で用いてもよく、２種以上を組み合わせて使用してもよい。成分（Ｂ）において、エポキシ当量は好ましくは１５０〜２００であり、温度２０℃で固体であるものがより好ましい。すなわち成分（Ｂ）としては、「１分子中に３以上のエポキシ基を有し、エポキシ当量が１５０〜２００である芳香族系エポキシ樹脂」が好ましく、「１分子中に３以上のエポキシ基を有し、エポキシ当量が１５０〜２００であり、温度２０℃で固体の芳香族系エポキシ樹脂」がより好ましい。成分（Ｂ）は樹脂組成物の硬化物の破断強度を向上させ、また硬化物の架橋密度を向上させ、無機充填材が３５ｗｔ％以上、更には４０ｗｔ％以上存在しても粗化処理後の硬化物表面に無機充填材が剥き出しになるのを抑制し、安定して高いめっきピール強度を得るための重要な役割を果たす。エポキシ当量が１５０〜２００、温度２０℃で固体であるものはこのような機能を十分発揮する上で好ましい。 The component (B) “aromatic epoxy resin having 3 or more epoxy groups in one molecule and having an epoxy equivalent of 200 or less” includes naphthalene type epoxy resins, aromatics having phenols and phenolic hydroxyl groups. Epoxidation product (trisphenol type epoxy resin) of a condensate with a group aldehyde, specifically, EXA4700 (tetrafunctional naphthalene type epoxy resin) manufactured by Dainippon Ink & Chemicals, Inc., Nippon Kayaku Co., Ltd. EPPN -502H (trisphenol epoxy resin). These epoxy resins may be used alone or in combination of two or more. In the component (B), the epoxy equivalent is preferably 150 to 200, and more preferably a solid at a temperature of 20 ° C. That is, as the component (B), “an aromatic epoxy resin having 3 or more epoxy groups in one molecule and an epoxy equivalent of 150 to 200” is preferable, and “3 or more epoxy groups in one molecule are contained. Having an epoxy equivalent of 150 to 200 and being a solid aromatic epoxy resin at a temperature of 20 ° C. is more preferable. Component (B) improves the breaking strength of the cured product of the resin composition, improves the crosslink density of the cured product, and even after the roughening treatment even if the inorganic filler is present in an amount of 35 wt% or more, further 40 wt% or more. It suppresses the inorganic filler from being exposed on the surface of the cured product, and plays an important role for stably obtaining high plating peel strength. Those having an epoxy equivalent of 150 to 200 and a solid at a temperature of 20 ° C. are preferable for sufficiently exhibiting such a function.
本発明の樹脂組成物における成分（Ａ）と成分（Ｂ）の配合割合は１：０．３乃至１：２の範囲とする。特に１：０．５乃至１：１の範囲とするのが好ましい。成分（Ａ）がこの配合割合を超えて多すぎると、樹脂組成物の粘着性が高くなり、真空ラミネート時の脱気性が低下してボイドが発生しやすくなる、あるいは硬化後の耐熱性が不十分となるなどの問題が発生する。一方、成分（Ｂ）がこの配合割合を超えて多すぎると、樹脂組成物が常温において脆くなり、接着フィルムに用いた場合の取り扱いが困難となる。 The blending ratio of component (A) and component (B) in the resin composition of the present invention is in the range of 1: 0.3 to 1: 2. In particular, the range of 1: 0.5 to 1: 1 is preferable. If the amount of component (A) exceeds this blending ratio, the adhesiveness of the resin composition will increase, degassing during vacuum lamination will decrease, and voids will tend to occur, or heat resistance after curing will be poor. Problems such as becoming sufficient occur. On the other hand, when there are too many components (B) exceeding this compounding ratio, a resin composition will become weak at normal temperature, and the handling at the time of using for an adhesive film will become difficult.
樹脂組成物（不揮発分１００重量％）中における成分（Ａ）と成分（Ｂ）の合計量は通常１０〜５０重量％、好ましくは２０〜４０重量％とする。 The total amount of component (A) and component (B) in the resin composition (non-volatile content: 100% by weight) is usually 10-50% by weight, preferably 20-40% by weight.
なお、本発明の樹脂組成物には本発明の効果を損なわない程度に（Ａ）または（Ｂ）以外の多官能エポキシ樹脂、または単官能エポキシ樹脂を含んでいてもよい。 The resin composition of the present invention may contain a polyfunctional epoxy resin other than (A) or (B) or a monofunctional epoxy resin to the extent that the effects of the present invention are not impaired.
成分（Ｃ）である「フェノール系硬化剤」としては、例えばフェノールノボラック樹脂、アルキルフェノールノボラック樹脂、トリアジン構造含有ノボラック樹脂、ビスフェノールＡノボラック樹脂、ジシクロペンタジエン型フェノール樹脂、ザイロック（Ｘｙｌｏｋ）型フェノール樹脂、テルペン変性フェノール樹脂、ポリビニルフェノール類等のフェノール系硬化剤、ナフタレン系硬化剤、フルオレン系硬化剤を挙げることができる。これらのフェノール系硬化剤は各々単独で用いてもよく、２種以上を組み合わせて使用してもよい。 Examples of the “phenolic curing agent” as the component (C) include phenol novolak resins, alkylphenol novolak resins, triazine structure-containing novolak resins, bisphenol A novolak resins, dicyclopentadiene type phenol resins, xylok type phenol resins, Mention may be made of phenolic curing agents such as terpene-modified phenolic resins and polyvinylphenols, naphthalene-based curing agents and fluorene-based curing agents. These phenolic curing agents may be used alone or in combination of two or more.
フェノール系硬化剤は、樹脂組成物中に存在するエポキシ基の合計数と成分（Ｃ）のフェノール系硬化剤のフェノール性水酸基の合計数の割合が１：０．５乃至１：１．５となるように配合する。なお、樹脂組成物中に成分（Ａ）および成分（Ｂ）以外のエポキシ樹脂が含まれる場合、これらのエポキシ樹脂のエポキシ基を含めて上記割合が決定される。フェノール系硬化剤の配合割合がこの範囲を外れると、樹脂組成物の硬化物の耐熱性が不十分となる場合がある。 In the phenolic curing agent, the ratio of the total number of epoxy groups present in the resin composition and the total number of phenolic hydroxyl groups in the phenolic curing agent of component (C) is 1: 0.5 to 1: 1.5. It mix | blends so that it may become. In addition, when epoxy resins other than a component (A) and a component (B) are contained in a resin composition, the said ratio is determined including the epoxy group of these epoxy resins. When the blending ratio of the phenolic curing agent is out of this range, the heat resistance of the cured product of the resin composition may be insufficient.
上記フェノール系硬化剤に加え、トリフェニルホスフィンなどの有機ホスフィン系化合物、２−エチル４−メチルイミダゾールなどのイミダゾール系化合物等を硬化促進剤として添加してもよい。硬化促進剤を使用する場合、配合量はフェノール系硬化剤の配合量を１００重量％とした場合に０．５乃至２重量％の範囲で用いるのが好ましい。 In addition to the phenolic curing agent, an organic phosphine compound such as triphenylphosphine, an imidazole compound such as 2-ethyl 4-methylimidazole, and the like may be added as a curing accelerator. When a curing accelerator is used, the blending amount is preferably in the range of 0.5 to 2% by weight when the blending amount of the phenolic curing agent is 100% by weight.
次に、成分（Ｄ）の「ガラス転移温度が１００℃以上である、フェノキシ樹脂、ポリビニルアセタール樹脂、ポリアミド樹脂およびポリアミドイミド樹脂からなる群より選ばれる一種以上の樹脂」について説明する。 Next, the component (D) “one or more resins selected from the group consisting of phenoxy resin, polyvinyl acetal resin, polyamide resin, and polyamideimide resin having a glass transition temperature of 100 ° C. or higher” will be described.
フェノキシ樹脂の具体例としては東都化成（株）製ＦＸ２８０、ＦＸ２９３、ジャパンエポキシレジン（株）製ＹＸ８１００、ＹＬ６９５４、ＹＬ６９７４等が挙げられる。ポリビニルアセタール樹脂の具体例としては、積水化学工業（株）製エスレックＫＳシリーズ、ポリアミド樹脂としては日立化成工業（株）製ＫＳ５０００シリーズ、日本化薬（株）製ＢＰシリーズ、さらにポリアミドイミド樹脂としては日立化成工業（株）製ＫＳ９０００シリーズ等が挙げられる。これらの樹脂は各々単独で用いてもよく、２種以上を組み合わせて使用してもよい。成分（Ｄ）の樹脂としては特にフェノキシ樹脂、ポリビニルアセタール樹脂が好ましい。 Specific examples of the phenoxy resin include FX280, FX293 manufactured by Toto Kasei Co., Ltd., YX8100, YL6954, YL6974 manufactured by Japan Epoxy Resin Co., Ltd., and the like. Specific examples of the polyvinyl acetal resin include SLECK KS series manufactured by Sekisui Chemical Co., Ltd., as the polyamide resin, KS5000 series manufactured by Hitachi Chemical Co., Ltd., BP series manufactured by Nippon Kayaku Co., Ltd., and further as polyamideimide resin Examples include KS9000 series manufactured by Hitachi Chemical Co., Ltd. These resins may be used alone or in combination of two or more. As the resin of component (D), phenoxy resin and polyvinyl acetal resin are particularly preferable.
ガラス転移温度は、ＪＩＳ（日本工業規格） Ｋ ７１９７に記載の方法に従って決定される。なお、ガラス転移温度が分解温度よりも高いため実際にはガラス転移温度が観測されない場合も本発明に言う「ガラス転移温度が１００℃以上である」の定義内に含まれる。なお、分解温度とは、ＪＩＳ Ｋ ７１２０に記載の方法に従って測定したときの質量減少率が５％となる温度で定義される。 The glass transition temperature is determined according to the method described in JIS (Japanese Industrial Standard) K 7197. In addition, since the glass transition temperature is higher than the decomposition temperature, the case where the glass transition temperature is not actually observed is also included in the definition of “the glass transition temperature is 100 ° C. or higher” in the present invention. The decomposition temperature is defined as the temperature at which the mass reduction rate is 5% when measured according to the method described in JIS K 7120.
成分（Ｄ）は、樹脂組成物のラミネート時における熱流動性と、酸化剤による硬化物の粗化性に重要な影響を及ぼす。また成分（Ｄ）のガラス転移温度が１００℃未満であると、硬化物の機械強度が十分でなく、粗化後の硬化物表面に無機充填材が析出しやすく、十分なめっきピール強度を得る事が困難となる。 The component (D) has an important influence on the thermal fluidity at the time of laminating the resin composition and the roughening property of the cured product by the oxidizing agent. Further, when the glass transition temperature of the component (D) is less than 100 ° C., the mechanical strength of the cured product is not sufficient, and the inorganic filler is likely to precipitate on the surface of the cured product after roughening, thereby obtaining sufficient plating peel strength. Things will be difficult.
成分（Ｄ）の樹脂組成物（不揮発分１００重量％）に対する含有割合は２〜２０重量％とする。２重量％未満であると樹脂組成物のラミネート時の熱流動性が大きくなりすぎて絶縁層厚が不均一となる、あるいは硬化物の十分な粗化性が得られない等の問題を生じることがある。一方、２０重量％を超えると、熱流動性が低すぎて回路基板に存在するビアホールやスルーホールに十分に樹脂組成物が充填されないなどの問題を生じることがある。 The content ratio of the component (D) to the resin composition (non-volatile content: 100% by weight) is 2 to 20% by weight. If it is less than 2% by weight, the heat fluidity at the time of laminating the resin composition becomes too large and the insulating layer thickness becomes non-uniform, or the roughening property of the cured product cannot be obtained. There is. On the other hand, if it exceeds 20% by weight, the thermal fluidity is too low, and there may be a problem that the resin composition is not sufficiently filled in via holes and through holes existing in the circuit board.
成分（Ｅ）無機充填材の樹脂組成物（不揮発分１００重量％）に対する含有割合は樹脂組成物に要求される特性によっても異なるが、３５重量％以上又は４０重量％以上である。より好ましい範囲は３５〜７５重量％又は４０〜７５重量％である。３５重量％未満であると、熱膨張率が高くなり本発明の効果が得られない。なお７５重量％以上である場合はピール強度が低下する傾向にある。 The content ratio of the component (E) inorganic filler to the resin composition (non-volatile content: 100% by weight) varies depending on the properties required for the resin composition, but is 35% by weight or more or 40% by weight or more. A more preferable range is 35 to 75% by weight or 40 to 75% by weight. If it is less than 35% by weight, the coefficient of thermal expansion increases and the effect of the present invention cannot be obtained. In addition, when it is 75 weight% or more, there exists a tendency for peel strength to fall.
無機充填材としては、シリカ、アルミナ、硫酸バリウム、タルク、クレー、雲母粉、水酸化アルミニウム、水酸化マグネシウム、炭酸カルシウム、炭酸マグネシウム、酸化マグネシウム、窒化ホウ素、ホウ酸アルミニウム、チタン酸バリウム、チタン酸ストロンチウム、チタン酸カルシウム、チタン酸マグネシウム、チタン酸ビスマス、酸化チタン、ジルコン酸バリウム、ジルコン酸カルシウムなどが挙げられる。特にシリカが好ましい。無機充填材は平均粒径５μｍ以下のものが好ましい。平均粒径が５μｍを超える場合、導体層に回路パターンを形成する際にファインパターンの形成を安定的行うのが困難になる場合がある。また無機充填材は耐湿性を向上させるため、シランカップリング剤等の表面処理剤で表面処理してあるものが好ましい。 Inorganic fillers include silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, titanate Examples include strontium, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate. Silica is particularly preferable. The inorganic filler preferably has an average particle size of 5 μm or less. When the average particle diameter exceeds 5 μm, it may be difficult to stably form the fine pattern when forming the circuit pattern on the conductor layer. The inorganic filler is preferably surface-treated with a surface treatment agent such as a silane coupling agent in order to improve moisture resistance.
本発明の樹脂組成物には上記成分の他、本発明の効果を阻害しない範囲で、熱硬化性樹脂、添加剤等の他の成分を配合することもできる。熱硬化性樹脂としては、例えば、ブロックイソシアネート樹脂、キシレン樹脂、ラジカル発生剤と重合性樹脂などが挙げられる。添加剤としては、例えばシリコンパウダー、ナイロンパウダー、フッ素パウダー等の有機充填剤、オルベン、ベントン等の増粘剤、シリコーン系、フッ素系、高分子系の消泡剤又はレベリング剤、イミダゾール系、チアゾール系、トリアゾール系、シランカップリング剤等の密着性付与剤、フタロシアニン・ブルー、フタロシアニン・グリーン、アイオジン・グリーン、ジスアゾイエロー、カーボンブラック等の着色剤等を挙げることができる。 In the resin composition of the present invention, in addition to the above components, other components such as a thermosetting resin and an additive can also be blended within a range that does not impair the effects of the present invention. Examples of the thermosetting resin include a blocked isocyanate resin, a xylene resin, a radical generator and a polymerizable resin. Examples of additives include organic fillers such as silicon powder, nylon powder, and fluorine powder, thickeners such as olben and benton, silicone-based, fluorine-based, and polymer-based antifoaming agents or leveling agents, imidazole-based, and thiazole. Examples thereof include adhesion imparting agents such as phthalocyanine, triazole, and silane coupling agents, and colorants such as phthalocyanine / blue, phthalocyanine / green, iodin / green, disazo yellow, and carbon black.
本発明の樹脂組成物は、支持フィルム上に塗布し樹脂組成物層を形成させて多層プリント配線板用の接着フィルムとするか、または繊維からなるシート状補強基材中に該樹脂組成物を含浸させて多層プリント配線板の層間絶縁層用のプリプレグとすることができる。本発明の樹脂組成物は回路基板に塗布して絶縁層を形成することもできるが、工業的には、一般に、接着フィルムまたはプリプレグの形態として絶縁層形成に用いられる。 The resin composition of the present invention is applied on a support film to form a resin composition layer to form an adhesive film for a multilayer printed wiring board, or the resin composition is contained in a sheet-like reinforcing substrate made of fibers. It can be impregnated to form a prepreg for an interlayer insulating layer of a multilayer printed wiring board. The resin composition of the present invention can be applied to a circuit board to form an insulating layer, but industrially, it is generally used for forming an insulating layer in the form of an adhesive film or a prepreg.
本発明の接着フィルムにおいて樹脂組成物層を構成する樹脂組成物は、真空ラミネート法におけるラミネートの温度条件（通常７０℃〜１４０℃）で軟化し、回路基板のラミネートと同時に、回路基板に存在するビアホール或いはスルーホール内の樹脂充填が可能な流動性（樹脂流れ）を示すものであるものが好ましい。多層プリント配線板のスルホールの直径は通常０．１〜０．５ｍｍ、深さは通常０．１〜１．２ｍｍであり、通常この範囲で樹脂充填を可能とするのが好ましい。なお回路基板の両面をラミネートする場合はスルーホールの１／２が充填されればよい。このような物性は、樹脂組成物の動的粘弾性の測定による温度−溶融粘度曲線によって特徴づけることができる。 The resin composition constituting the resin composition layer in the adhesive film of the present invention is softened under the lamination temperature condition (usually 70 ° C. to 140 ° C.) in the vacuum laminating method, and is present on the circuit board simultaneously with the lamination of the circuit board. Those exhibiting fluidity (resin flow) capable of filling the via hole or through hole with resin are preferable. The diameter of the through hole of the multilayer printed wiring board is usually from 0.1 to 0.5 mm, and the depth is usually from 0.1 to 1.2 mm. It is usually preferable to allow resin filling in this range. When laminating both sides of the circuit board, it is sufficient that half of the through holes are filled. Such physical properties can be characterized by a temperature-melt viscosity curve obtained by measuring the dynamic viscoelasticity of the resin composition.
後掲実施例１で得られた樹脂組成物の動的粘弾性を測定し、温度−溶融粘度（η）の関係を図４に示した。図４は測定開始温度を６０℃、振動数を１Ｈｚ／ｄｅｇとし、５℃／分の昇温速度で加熱したときの樹脂組成物の溶融粘度を曲線図として表したものである。このように、本発明の樹脂組成物は、測定開始温度６０℃、昇温速度５℃／分及び振動数を１Ｈｚ／ｄｅｇの条件で測定した場合の溶融粘度が、９０℃で４，０００乃至５０，０００ポイズ、１００℃で２，０００乃至２１，０００ポイズ、１１０℃で９００乃至１２，０００ポイズ、１２０℃で５００乃至９，０００ポイズ、１３０℃で３００乃至１５，０００となるものを用いるのが好ましい。 The dynamic viscoelasticity of the resin composition obtained in Example 1 described later was measured, and the relationship between temperature and melt viscosity (η) is shown in FIG. FIG. 4 is a curve diagram showing the melt viscosity of the resin composition when the measurement start temperature is 60 ° C., the frequency is 1 Hz / deg, and the sample is heated at a rate of temperature increase of 5 ° C./min. Thus, the resin composition of the present invention has a melt viscosity of 4,000 to 90 ° C. at 90 ° C. when the measurement start temperature is 60 ° C., the heating rate is 5 ° C./min, and the frequency is 1 Hz / deg. Use 50,000 poise, 2,000 to 21,000 poise at 100 ° C, 900 to 12,000 poise at 110 ° C, 500 to 9,000 poise at 120 ° C, and 300 to 15,000 at 130 ° C. Is preferred.
このような溶融粘度特性を有する樹脂組成物を用いることにより、真空ラミネーターを用いた真空ラミネートにより、回路基板表面への樹脂組成物の積層とビアホール及びスルーホール内への樹脂組成物の充填を同時に一括して行うことができる。溶融粘度が低すぎると、真空ラミネート法により回路基板への樹脂組成物のラミネートする際または加熱硬化する際、樹脂組成物の流動性が大きくなり過ぎ、樹脂層の厚さが不均一になる傾向にある。また溶融粘度が高すぎると樹脂組成物の流動性が小さすぎて、ビアホールやスルーホール内への樹脂充填が不十分となる傾向にある。（国際公開ＷＯ０１／９７５８２号パンフレット参照）。当業者は、本発明のエポキシ樹脂組成物と接着フィルムに関する開示、及び上記ＷＯ０１／９７５８２号公報の開示に従って、真空ラミネート法に好適な溶融粘度特性を有する接着フィルムを適宜容易に調製することができる。 By using a resin composition having such a melt viscosity characteristic, the lamination of the resin composition on the circuit board surface and the filling of the resin composition into the via hole and the through hole are simultaneously performed by vacuum lamination using a vacuum laminator. Can be done in a lump. If the melt viscosity is too low, when the resin composition is laminated to a circuit board by a vacuum laminating method or heat-cured, the fluidity of the resin composition becomes too large, and the thickness of the resin layer tends to be uneven. It is in. On the other hand, if the melt viscosity is too high, the fluidity of the resin composition is too small and the resin filling into the via hole or the through hole tends to be insufficient. (See International Publication WO01 / 97582 pamphlet). A person skilled in the art can easily and appropriately prepare an adhesive film having a melt viscosity characteristic suitable for the vacuum laminating method according to the disclosure relating to the epoxy resin composition and the adhesive film of the present invention and the disclosure of the above-mentioned WO 01/97582. .
本発明の接着フィルムは、当業者に公知の方法、例えば、有機溶剤に樹脂組成物を溶解した樹脂ワニスを調製し、支持フィルムを支持体として、この樹脂ワニスを塗布し、更に加熱、あるいは熱風吹きつけ等により有機溶剤を乾燥させて樹脂組成物層を形成させることにより製造することができる。 The adhesive film of the present invention is prepared by a method known to those skilled in the art, for example, by preparing a resin varnish in which a resin composition is dissolved in an organic solvent, applying the resin varnish using the support film as a support, and further heating or hot air. The organic solvent can be dried by spraying or the like to form a resin composition layer.
有機溶剤としては、例えば、アセトン、メチルエチルケトン、シクロヘキサノン等のケトン類、酢酸エチル、酢酸ブチル、セロソルブアセテート、プロピレングリコールモノメチルエーテルアセテート、カルビトールアセテート等の酢酸エステル類、セロソルブ、ブチルカルビトール等のカルビトール類、トルエン、キシレン等の芳香族炭化水素類、ジメチルホルムアミド、ジメチルアセトアミド、Ｎ−メチルピロリドン等を挙げることができる。有機溶剤は２種以上を組み合わせて用いてもよい。 Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, and carbitols such as cellosolve and butyl carbitol. And aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like. Two or more organic solvents may be used in combination.
乾燥条件は特に限定されないが、樹脂組成物層への有機溶剤の含有割合が通常１０重量％以下、好ましくは５重量％以下となるように乾燥させる。形成される樹脂組成物層の溶融粘度曲線は後掲の乾燥条件によっても影響を受けるため、好ましくは前記溶融粘度特性を満たすよう乾燥条件を設定する。ワニス中の有機溶媒量によっても異なるが、例えば３０〜６０重量％の有機溶剤を含むワニスを５０〜１５０℃で３〜１０分程度乾燥させることができる。当業者、簡単な実験により適宜、好適な乾燥条件を設定することができる。 The drying conditions are not particularly limited, but drying is performed so that the content of the organic solvent in the resin composition layer is usually 10% by weight or less, preferably 5% by weight or less. Since the melt viscosity curve of the resin composition layer to be formed is influenced by the drying conditions described later, the drying conditions are preferably set so as to satisfy the melt viscosity characteristics. Although it depends on the amount of organic solvent in the varnish, for example, a varnish containing 30 to 60% by weight of an organic solvent can be dried at 50 to 150 ° C. for about 3 to 10 minutes. Those skilled in the art can appropriately set suitable drying conditions through simple experiments.
形成される樹脂組成物層の厚さは、通常、導体層の厚さ以上とする。回路基板が有する導体層の厚さは通常５〜７０μｍの範囲であるので、樹脂組成物層の厚さは１０〜１００μｍの厚みを有するのが好ましい。 The thickness of the resin composition layer to be formed is usually not less than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, the thickness of the resin composition layer is preferably 10 to 100 μm.
なお、本発明における樹脂組成物層は、後述する保護フィルムで保護されていてもよい。保護フィルムで保護することにより、樹脂組成物層表面へのゴミ等の付着やキズを防止することができる。 In addition, the resin composition layer in this invention may be protected with the protective film mentioned later. By protecting with a protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches.
本発明における支持フィルム及び保護フィルムとしては、ポリエチレン、ポリプロピレン、ポリ塩化ビニル等のポリオレフィン、ポリエチレンテレフタレート（以下「ＰＥＴ」と略称することがある。）、ポリエチレンナフタレート等のポリエステル、ポリカーボネート、ポリイミド、更には離型紙や銅箔、アルミニウム箔等の金属箔などを挙げることができる。なお、支持フィルム及び保護フィルムはマッド処理、コロナ処理の他、離型処理を施してあってもよい。 Examples of the support film and protective film in the present invention include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyesters such as polyethylene naphthalate, polycarbonate, polyimide, Can include release paper, copper foil, metal foil such as aluminum foil, and the like. In addition, the support film and the protective film may be subjected to a release treatment in addition to the mud treatment and the corona treatment.
支持フィルムの厚さは特に限定されないが、通常１０〜１５０μｍであり、好ましくは２５〜５０μｍの範囲で用いられる。また保護フィルムの厚さは１〜４０μｍとするのが好ましい。なお、後述するように、接着フィルムの製造工程で支持体として用いる支持フィルムを樹脂組成物層表面を保護する保護フィルムとして使用することもできる。 Although the thickness of a support film is not specifically limited, Usually, it is 10-150 micrometers, Preferably it is used in 25-50 micrometers. Moreover, it is preferable that the thickness of a protective film shall be 1-40 micrometers. In addition, as will be described later, a support film used as a support in the production process of the adhesive film can be used as a protective film for protecting the resin composition layer surface.
本発明における支持フィルムは、回路基板にラミネートした後に、或いは加熱硬化することにより絶縁層を形成した後に、剥離される。接着フィルムを加熱硬化した後に支持フィルムを剥離すれば、硬化工程でのゴミ等の付着を防ぐことができる。硬化後に剥離する場合、通常、支持フィルムには予め離型処理が施される。なお、支持フィルム上に形成される樹脂組成物層は、層の面積が支持フィルムの面積より小さくなるように形成するのが好ましい。また接着フィルムは、ロール状に巻き取って、保存、貯蔵することができる。 The support film in the present invention is peeled after being laminated on a circuit board or after forming an insulating layer by heat curing. If the support film is peeled after the adhesive film is heat-cured, adhesion of dust and the like in the curing process can be prevented. In the case of peeling after curing, the support film is usually subjected to a release treatment in advance. In addition, it is preferable to form the resin composition layer formed on a support film so that the area of a layer may become smaller than the area of a support film. The adhesive film can be wound up in a roll shape and stored and stored.
次に、本発明の接着フィルムを用いて本発明の多層プリント配線板を製造する方法について説明する。樹脂組成物層が保護フィルムで保護されている場合はこれらを剥離した後、樹脂組成物層を回路基板に直接接するように、回路基板の片面又は両面にラミネートする。本発明の接着フィルムにおいては真空ラミネート法により減圧下で回路基板にラミネートする方法が好適に用いられる。ラミネートの方法はバッチ式であってもロールでの連続式であってもよい。またラミネートを行う前に接着フィルム及び回路基板を必要により加熱（プレヒート）しておいてもよい。 Next, a method for producing the multilayer printed wiring board of the present invention using the adhesive film of the present invention will be described. When the resin composition layer is protected with a protective film, the resin composition layer is peeled and then laminated on one or both sides of the circuit board so that the resin composition layer is in direct contact with the circuit board. In the adhesive film of the present invention, a method of laminating on a circuit board under reduced pressure by a vacuum laminating method is preferably used. The laminating method may be a batch method or a continuous method using a roll. Further, the adhesive film and the circuit board may be heated (preheated) as necessary before lamination.
ラミネートの条件は、圧着温度（ラミネート温度）を好ましくは７０〜１４０℃、圧着圧力を好ましくは１〜１１ｋｇｆ／ｃｍ２（９．８×１０４〜１０７．９×１０４Ｎ／ｍ２）とし、空気圧２０ｍｍＨｇ（２６．７ｈＰａ）以下の減圧下でラミネートするのが好ましい。 The laminating conditions are preferably a pressure bonding temperature (laminating temperature) of 70 to 140 ° C. and a pressure bonding pressure of preferably 1 to 11 kgf / cm 2 (9.8 × 10 4 to 107.9 × 10 4 N / m 2 ). Lamination is preferably performed under a reduced pressure of 20 mmHg (26.7 hPa) or less.
真空ラミネートは市販の真空ラミネーターを使用して行うことができる。市販の真空ラミネーターとしては、例えば、ニチゴー・モートン（株）製 バキュームアップリケーター、（株）名機製作所製 真空加圧式ラミネーター、（株）日立インダストリイズ製 ロール式ドライコータ、日立エーアイーシー（株）製真空ラミネーター等を挙げることができる。 The vacuum lamination can be performed using a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum applicator manufactured by Nichigo-Morton Co., Ltd., a vacuum pressurizing laminator manufactured by Meiki Seisakusho, a roll dry coater manufactured by Hitachi Industries, Ltd., and Hitachi AIC Co., Ltd. ) Made vacuum laminator and the like.
本発明における回路基板とは、主として、ガラスエポキシ、金属基板、ポリエステル基板、ポリイミド基板、ＢＴレジン基板、熱硬化型ポリフェニレンエーテル基板等の基板の片面又は両面にパターン加工された導体層（回路）が形成されたものをいう。また導体層と絶縁層が交互に層形成され、片面又は両面がパターン加工された導体層（回路）となっている多層プリント配線板も本発明にいう回路基板に含まれる。なお導体回路層表面は黒化処理等により予め粗化処理が施されていた方が絶縁層の回路基板への密着性の観点から好ましい。 The circuit board in the present invention is mainly a conductive layer (circuit) patterned on one or both sides of a substrate such as a glass epoxy, metal substrate, polyester substrate, polyimide substrate, BT resin substrate, thermosetting polyphenylene ether substrate or the like. The one formed. Also included in the circuit board of the present invention is a multilayer printed wiring board in which conductor layers and insulating layers are alternately formed and a conductor layer (circuit) is patterned on one or both sides. The surface of the conductor circuit layer is preferably roughened by blackening or the like in advance from the viewpoint of adhesion of the insulating layer to the circuit board.
このように接着フィルムを回路基板にラミネートした後、支持フィルムを剥離する場合は剥離し、熱硬化することにより回路基板に絶縁層を形成することができる。加熱硬化の条件は１５０℃〜２２０℃で２０分〜１８０分の範囲で選択され、より好ましくは１６０℃〜２００℃で３０〜１２０分である。 Thus, after laminating the adhesive film on the circuit board, when the support film is peeled off, the insulating film can be formed on the circuit board by peeling and thermosetting. The conditions of heat curing are selected in the range of 20 to 180 minutes at 150 to 220 ° C, more preferably 30 to 120 minutes at 160 to 200 ° C.
絶縁層を形成した後、硬化前に支持フィルムを剥離しなかった場合は、ここで剥離する。次に回路基板上に形成された絶縁層に穴開けを行いビアホール、スルーホールを形成する。穴あけは例えば、ドリル、レーザー、プラズマ等の公知の方法により、また必要によりこれらの方法を組み合わせて行うことができるが、炭酸ガスレーザー、ＹＡＧレーザー等のレーザーによる穴あけがもっとも一般的な方法である。 If the support film is not peeled off after the insulating layer is formed, it is peeled off here. Next, holes are formed in the insulating layer formed on the circuit board to form via holes and through holes. Drilling can be performed by a known method such as drilling, laser, or plasma, or a combination of these methods if necessary. However, drilling by a laser such as a carbon dioxide laser or YAG laser is the most common method. .
次いで、絶縁層表面を酸化剤より粗化処理を行う。酸化剤としては、過マンガン酸塩（過マンガン酸カリウム、過マンガン酸ナトリウム等）、重クロム酸塩、オゾン、過酸化水素／硫酸、硝酸等が挙げられる。好ましくはビルトアップ工法による多層プリント配線板の製造における絶縁層の粗化に汎用されている酸化剤である、アルカリ性過マンガン酸溶液（例えば過マンガン酸カリウム、過マンガン酸ナトリウムの水酸化ナトリウム水溶液）を用いて粗化を行うのが好ましい。 Next, the surface of the insulating layer is roughened with an oxidizing agent. Examples of the oxidizing agent include permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid and the like. Preferably, an alkaline permanganate solution (eg, potassium permanganate, sodium hydroxide solution of sodium permanganate), which is an oxidizer widely used for roughening an insulating layer in the production of multilayer printed wiring boards by a built-up method. It is preferable to perform roughening using.
次に、粗化処理により凸凹のアンカーが形成された樹脂組成物層表面に、無電解めっきと電解めっきを組み合わせた方法で導体層を形成する。また導体層とは逆パターンのめっきレジストを形成し、無電解めっきのみで導体層を形成することもできる。なお導体層形成後、１５０〜２００℃で２０〜９０分アニール（anneal）処理することにより、導体層のピール強度をさらに向上、安定化させることができる。本発明によれば、多層プリント配線板として好ましい導体層のピール強度が得ることができる。多層プリント配線板に好ましいピール強度は、通常０．６ｋｇｆ／ｃｍ以上、好ましくは０．７ｋｇｆ／ｃｍ以上である。 Next, a conductor layer is formed on the surface of the resin composition layer on which uneven anchors are formed by the roughening treatment by a method combining electroless plating and electrolytic plating. Further, a plating resist having a pattern opposite to that of the conductor layer can be formed, and the conductor layer can be formed only by electroless plating. In addition, after forming the conductor layer, the peel strength of the conductor layer can be further improved and stabilized by annealing at 150 to 200 ° C. for 20 to 90 minutes. According to the present invention, a peel strength of a conductor layer preferable as a multilayer printed wiring board can be obtained. The peel strength preferable for the multilayer printed wiring board is usually 0.6 kgf / cm or more, preferably 0.7 kgf / cm or more.
また、導体層をパターン加工し回路形成する方法としては、例えば当業者に公知のサブトラクティブ法、セミアディディブ法などを用いることができる。 Moreover, as a method of patterning the conductor layer to form a circuit, for example, a subtractive method or a semi-additive method known to those skilled in the art can be used.
本発明のプリプレグは、本発明の樹脂組成物を繊維からなるシート状補強基材にホットメルト法又はソルベント法により含浸させ、加熱により半硬化させることにより製造することができる。すなわち、本発明の樹脂組成物が繊維からなるシート状補強基材に含浸した状態となるプリプレグとすることができる。 The prepreg of the present invention can be produced by impregnating the resin composition of the present invention into a sheet-like reinforcing substrate made of fibers by a hot melt method or a solvent method and semi-curing by heating. That is, it can be set as the prepreg which will be in the state which the resin composition of this invention impregnated the sheet-like reinforcement base material which consists of fibers.
繊維からなるシート状補強基材としては、例えばガラスクロスやアラミド繊維等、プリプレグ用繊維として常用されているものを用いることができる。 As the sheet-like reinforcing substrate made of fibers, for example, those commonly used as prepreg fibers such as glass cloth and aramid fibers can be used.
ホットメルト法は、樹脂を有機溶剤に溶解することなく、樹脂を樹脂と剥離性の良い塗工紙に一旦コーティングし、それをシート状補強基材にラミネートする、あるいはダイコーターにより直接塗工するなどして、プリプレグを製造する方法である。またソルベント法は、接着フィルムと同様、樹脂を有機溶剤に溶解した樹脂ワニスにシート状補強基材を浸漬し、樹脂ワニスをシート状補強基材に含浸させ、その後乾燥させる方法である。 In the hot melt method, without dissolving the resin in an organic solvent, the resin is once coated on the resin and a coated paper having good releasability, and then laminated on a sheet-like reinforcing substrate or directly applied by a die coater. Thus, a prepreg is manufactured. Similarly to the adhesive film, the solvent method is a method in which a sheet-like reinforcing base material is immersed in a resin varnish in which a resin is dissolved in an organic solvent, the resin varnish is impregnated into the sheet-like reinforcing base material, and then dried.
次に本発明のプリプレグを用いて本発明の多層プリント配線板を製造する方法について説明する。回路基板に本発明のプリプレグを１枚あるいは必要により数枚重ね、離型フィルムを介して金属プレートを挟み加圧・加熱条件下でプレス積層する。圧力は好ましくは５〜４０ｋｇｆ／ｃｍ２、温度は好ましくは１２０〜２００℃で２０〜１００分の範囲で成型するのが好ましい。また接着フィルムと同様に真空ラミネート法により回路基板にラミネートした後、加熱硬化することによっても製造可能である。その後、前に記載した方法と同様、酸化剤により硬化したプリプレグ表面を粗化した後、導体層をめっきにより形成して多層プリント配線板を製造することができる。 Next, a method for producing the multilayer printed wiring board of the present invention using the prepreg of the present invention will be described. One or several prepregs of the present invention are stacked on a circuit board, a metal plate is sandwiched through a release film, and press lamination is performed under pressure and heating conditions. The pressure is preferably 5 to 40 kgf / cm 2 , and the temperature is preferably 120 to 200 ° C. for 20 to 100 minutes. Moreover, it can also be manufactured by laminating on a circuit board by a vacuum laminating method as in the case of an adhesive film, and then curing by heating. Thereafter, similar to the method described above, the surface of the prepreg cured with an oxidizing agent is roughened, and then a conductor layer is formed by plating to produce a multilayer printed wiring board.
以下、実施例を示して本発明を具体的に説明するが、本発明はこれに限定されるものではない。 EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated concretely, this invention is not limited to this.
（Ａ）成分として液状ビスフエノールＦ型エポキシ樹脂（エポキシ当量１７０、ジャパンエポキシレジン（株）製「エピコート８０７」）２０部、（Ｂ）成分としてナフタレン型４官能エポキシ樹脂（エポキシ当量１６３、大日本インキ化学工業（株）製「ＥＸＡ−４７００」）１２部、メチルエチルケトン（以下ＭＥＫと略す）１０部、シクロヘキサノン１０部に撹拝しながら加熱溶解させた。そこへ（Ｃ）成分としてトリアジン構造含有フェノールノボラック樹脂のＭＥＫワニス（大日本インキ化学工業（株）製「フェノライトＬＡ−７０５２」、不揮発分６０％、不揮発分のフェノール性水酸基当量１２０）２５部、（Ｄ）成分としてフェノキシ樹脂ワニス（不揮発分４０重量％、東都化成（株）製「ＦＸ２９３」、ガラス転位温度１６３℃）２０部、さらに（Ｅ）成分として球形シリカ（平均粒径１μｍ、アミノシラン処理）６０部を添加し樹脂ワニスを作製した（樹脂ワニスの不揮発分に対する無機充填材含有量５２重量％）。
次に、樹脂ワニスをポリエチレンテレフタレート（厚さ３８μｍ、以下ＰＥＴと略す）上に、乾燥後の樹脂厚みが７０μｍとなるようにダイコーターにて塗布し、８０〜１２０℃（平均１００℃）で６分間乾燥した（残留溶媒量約１重量％）。次いで樹脂組成物の表面に厚さ１５μｍのポリプロピレンフィルムを貼り合わせながらロール状に巻き取った。ロール状の接着フィルムを幅５０７ｍｍにスリット（slit）し、これより５０７×３３６ｍｍサイズのシート状の接着フィルムを得た。
20 parts of liquid bisphenol F type epoxy resin (epoxy equivalent 170, “Epicoat 807” manufactured by Japan Epoxy Resin Co., Ltd.) as component (A), naphthalene type tetrafunctional epoxy resin (epoxy equivalent 163, Dainippon) as component (B) Ink Chemical Industry Co., Ltd. “EXA-4700”) 12 parts, methyl ethyl ketone (hereinafter abbreviated as MEK) 10 parts, and cyclohexanone 10 parts were heated and dissolved while stirring. There as a component (C) MEK varnish of phenol novolak resin containing triazine structure ("Phenolite LA-7052" manufactured by Dainippon Ink & Chemicals, Inc.,
Next, the resin varnish was applied onto polyethylene terephthalate (thickness 38 μm, hereinafter abbreviated as PET) with a die coater so that the resin thickness after drying was 70 μm, and the temperature was 6 at 80 to 120 ° C. (average 100 ° C.). Dried for minutes (residual solvent amount about 1% by weight). Subsequently, it wound up in roll shape, bonding a 15-micrometer-thick polypropylene film on the surface of a resin composition. The roll-like adhesive film was slit to a width of 507 mm, and a sheet-like adhesive film having a size of 507 × 336 mm was obtained therefrom.
（Ａ）成分として液状ビスフエノールＡ型エポキシ樹脂（エポキシ当量１８５、ジャパンエポキシレジン（株）製「エピコート８２８ＥＬ」）１５部、（Ｂ）成分としてトリスフェノール型エポキシ樹脂（エポキシ当量１７６、日本化薬（株）製「ＥＰＰＮ−５０２Ｈ」）１５部、ＭＥＫ１０部、シクロヘキサノン１０部に撹拝しながら加熱溶解させた。そこへ（Ｃ）成分としてトリアジン構造含有フェノールノボラック樹脂のＭＥＫワニス（大日本インキ化学工業（株）製「フェノライトＬＡ−７０５２」）２５部、（Ｄ）成分としてポリアミドイミド樹脂ワニス（不揮発分３３重量％、日立化成工業（株）製「ＫＳ９３００」、ガラス転位温度１８０℃）２５部、さらに（Ｅ）成分として球形シリカ（平均粒径１μｍ、アミノシラン処理）３０部、カオリン（平均粒径３μｍ、アミノシラン処理）１０部を添加し樹脂ワニスを作製した（樹脂ワニスの不揮発分に対する無機充填材含有量４３重量％）。
次に、樹脂ワニスを実施例１と同様にＰＥＴ上に、乾燥後の樹脂厚みが７０μｍとなるようにダイコーターにて塗布し、８０〜１２０℃（平均１００℃）で６分間乾燥した（残留溶媒量約２重量％）。次いで樹脂組成物の表面に厚さ１５μｍのポリプロピレンフィルムを貼り合わせながらロール状に巻き取った。ロール状の接着フィルムを幅５０７ｍｍにスリットし、これより５０７×３３６ｍｍサイズのシート状の接着フィルムを得た。
(A) Liquid bisphenol A type epoxy resin (epoxy equivalent 185, "Epicoat 828EL" manufactured by Japan Epoxy Resin Co., Ltd.) 15 parts as component (B) Trisphenol type epoxy resin (epoxy equivalent 176, Nippon Kayaku) as component (B) “EPPN-502H” manufactured by Co., Ltd.) was dissolved in 15 parts, 10 parts of MEK, and 10 parts of cyclohexanone while stirring. There, 25 parts of MEK varnish (“Phenolite LA-7052” manufactured by Dainippon Ink & Chemicals, Inc.), a phenol novolac resin containing triazine structure as component (C), and polyamideimide resin varnish (nonvolatile content 33) as component (D) % By weight, 25 parts by Hitachi Chemical Co., Ltd. “KS9300”,
Next, the resin varnish was coated on PET in the same manner as in Example 1 so that the resin thickness after drying was 70 μm, and dried at 80 to 120 ° C. (average 100 ° C.) for 6 minutes (residual) Solvent amount of about 2% by weight). Subsequently, it wound up in roll shape, bonding a 15-micrometer-thick polypropylene film on the surface of a resin composition. The roll-like adhesive film was slit to a width of 507 mm, and a sheet-like adhesive film having a size of 507 × 336 mm was obtained therefrom.
（Ａ）成分として液状ビスフエノールＦ型エポキシ樹脂（エポキシ当量１７０、ジャパンエポキシレジン（株）製「エピコート８０７」）２０部、（Ｂ）成分としてナフタレン型４官能エポキシ樹脂（エポキシ当量１６３、大日本インキ化学工業（株）製「ＥＸＡ−４７００」）１２部、さらにクレゾールノボラック型エポキシ樹脂１０部（エポキシ当量２２０、大日本インキ化学工業（株）製「Ｎ−６９０」）をＭＥＫ２０部、シクロヘキサノン１０部に撹拝しながら加熱溶解させた。そこへ（Ｃ）成分としてトリアジン構造含有フェノールノボラック樹脂のＭＥＫワニス（大日本インキ化学工業（株）製「フェノライトＬＡ−７０５２」、不揮発分６０％、不揮発分のフェノール性水酸基当量１２０）３０部、（Ｄ）成分としてフェノキシ樹脂ワニス（不揮発分４０重量％、東都化成（株）製「ＦＸ２９３」、ガラス転位温度１６３℃）２０部、ポリビニルアセタール樹脂ワニス（不揮発分１５重量％、積水化学工業製「ＫＳ１」、ガラス転位温度１０７℃）１５部、さらに（Ｅ）成分として球形シリカ（平均粒径１μｍ、アミノシラン処理）４０部を添加し樹脂ワニスを作製した（樹脂ワニスの不揮発分に対する無機充填材含有量３６重量％）。
次に、樹脂ワニスをＰＥＴ（厚さ３８μｍ）上に、乾燥後の樹脂厚みが７０μｍとなるようにダイコーターにて塗布し、８０〜１２０℃（平均１００℃）で６分間乾燥した（残留溶媒量約１重量％）。次いで樹脂組成物の表面に厚さ１５μｍのポリプロピレンフィルムを貼り合わせながらロール状に巻き取った。ロール状の接着フィルムを幅５０７ｍｍにスリット（slit）し、これより５０７×３３６ｍｍサイズのシート状の接着フィルムを得た。
20 parts of liquid bisphenol F type epoxy resin (epoxy equivalent 170, “Epicoat 807” manufactured by Japan Epoxy Resin Co., Ltd.) as component (A), naphthalene type tetrafunctional epoxy resin (epoxy equivalent 163, Dainippon) as component (B) 12 parts of “EXA-4700” manufactured by Ink Chemical Industry Co., Ltd., 10 parts of cresol novolac type epoxy resin (epoxy equivalent 220, “N-690” manufactured by Dainippon Ink & Chemicals, Inc.), 20 parts of MEK, and cyclohexanone 10 The solution was heated and dissolved while stirring. Then, as a component (C), 30 parts of a triazine structure-containing phenol novolak resin MEK varnish (“Phenolite LA-7052” manufactured by Dainippon Ink & Chemicals, Inc.,
Next, the resin varnish was applied on PET (thickness 38 μm) with a die coater so that the resin thickness after drying was 70 μm, and dried at 80 to 120 ° C. (average 100 ° C.) for 6 minutes (residual solvent) Amount about 1% by weight). Subsequently, it wound up in roll shape, bonding a 15-micrometer-thick polypropylene film on the surface of a resin composition. The roll-like adhesive film was slit to a width of 507 mm, and a sheet-like adhesive film having a size of 507 × 336 mm was obtained therefrom.
実施例１の樹脂ワニスをガラスクロスに含浸し、８０〜１２０℃（平均１００℃）で６分間乾燥させ、樹脂含量４５重量％で厚みが０．１ｍｍのプリプレグを得た。 The resin varnish of Example 1 was impregnated into a glass cloth and dried at 80 to 120 ° C. (average 100 ° C.) for 6 minutes to obtain a prepreg having a resin content of 45% by weight and a thickness of 0.1 mm.
＜比較例１＞
液状ビスフエノールＦ型エポキシ樹脂（エポキシ当量１７０、ジャパンエポキシレジン（株）製 「エピコート８０７」）２０部、クレゾールノボラック型エポキシ樹脂（エポキシ当量２１０、大日本インキ化学工業（株）製「Ｎ６７３」）１２部をＭＥＫ１０部、シクロヘキサノン１０部に撹拝しながら加熱溶解させた。そこへトリアジン構造含有フェノールノボラック樹脂のＭＥＫワニス（大日本インキ化学工業（株）製「フェノライトＬＡ−７０５２」）２５重量、フェノキシ樹脂ワニス（不揮発分３５重量％、東都化成（株）製「ＹＢ−５０−ＥＫ３５」、ガラス転位温度８４℃）２３部、さらに球型シリカ６０部（平均粒径１μｍ、アミノシラン処理）を添加し樹脂ワニスを作製した（樹脂ワニスの不揮発分に対する無機充填材含有量５２重量％）。
次に樹脂ワニスを実施例１と同様にＰＥＴ上に、乾燥後の樹脂厚みが７０μｍとなるようにダイコーターにて塗布し、８０〜１２０℃（平均１００℃）で６分間乾燥した。（残留溶媒量約１重量％）次いで樹脂組成物の表面に厚さ１５μｍのポリプロピレンフィルムを貼り合わせながらロール状に巻き取った。ロール状の接着フィルムを幅５０７ｍｍにスリットし、これより５０７×３３６ｍｍサイズのシート状の接着フィルムを得た。
<Comparative Example 1>
20 parts of liquid bisphenol F type epoxy resin (epoxy equivalent 170, “Epicoat 807” manufactured by Japan Epoxy Resin Co., Ltd.), cresol novolac type epoxy resin (epoxy equivalent 210, “N673” manufactured by Dainippon Ink & Chemicals, Inc.) 12 parts were heated and dissolved while stirring in 10 parts of MEK and 10 parts of cyclohexanone. Thereto, 25 weights of MEK varnish ("Phenolite LA-7052" manufactured by Dainippon Ink & Chemicals, Inc.) of phenol novolac resin containing triazine structure, 35% by weight of phenoxy resin varnish ("YB" manufactured by Toto Kasei Co., Ltd.) −50-EK35 ”, glass transition temperature 84 ° C.) 23 parts, and further
Next, the resin varnish was applied onto PET in the same manner as in Example 1 with a die coater so that the resin thickness after drying was 70 μm, and dried at 80 to 120 ° C. (average 100 ° C.) for 6 minutes. (Residual solvent amount: about 1% by weight) Then, a 15 μm-thick polypropylene film was wound on the surface of the resin composition in a roll shape. The roll-like adhesive film was slit to a width of 507 mm, and a sheet-like adhesive film having a size of 507 × 336 mm was obtained therefrom.
銅箔１８μｍ、板厚０．３ｍｍのＦＲ４両面銅張積層板から内層回路基板を作製し（直径０．２ｍｍのスルーホールあり）、実施例１で得られた接着フィルムのポリプロピレンフィルムを剥離した後、樹脂組成物層を回路面にして（株）名機製真空ラミネーターにより、温度１１０℃、圧力７ｋｇｆ／ｃｍ２、気圧５ｍｍＨｇ（１．３３ｈＰａ）以下の条件で両面にラミネートした。次いでＰＥＴフィルムを剥離し、１８０℃で３０分加熱硬化させた。その後、レーザーにより穴開けを行いビアホールを形成させ、次いで過マンガン酸塩のアルカリ性酸化剤で硬化した樹脂組成物層表面を粗化処理し、無電解及び電解めっきを行いサブトラクティブ法に従って回路を形成し、４層プリント配線板を得た。その後、さらに１８０℃で３０分アニール処理を行った。得られた導体層の導体めっき厚は約３０μｍであり、スルーホールは完全に樹脂充填されており、ピール強度は０．９ｋｇｆ／ｃｍであった。なお、ピール強度測定は日本工業規格(ＪＩＳ) Ｃ６４８１に準じて評価した。 After producing an inner circuit board from a FR4 double-sided copper-clad laminate with a copper foil of 18 μm and a thickness of 0.3 mm (with a through hole with a diameter of 0.2 mm), and peeling off the polypropylene film of the adhesive film obtained in Example 1 The resin composition layer was made into a circuit surface and laminated on both surfaces with a vacuum laminator manufactured by Meiki Co., Ltd. under conditions of a temperature of 110 ° C., a pressure of 7 kgf / cm 2 , and an atmospheric pressure of 5 mmHg (1.33 hPa) or less. Next, the PET film was peeled off and cured by heating at 180 ° C. for 30 minutes. Then, drill holes with laser to form via holes, then roughen the surface of the resin composition layer cured with an alkaline oxidizer of permanganate, perform electroless and electrolytic plating, and form a circuit according to the subtractive method A four-layer printed wiring board was obtained. Thereafter, an annealing treatment was further performed at 180 ° C. for 30 minutes. The obtained conductor layer had a conductor plating thickness of about 30 μm, the through hole was completely filled with resin, and the peel strength was 0.9 kgf / cm. The peel strength measurement was evaluated according to Japanese Industrial Standard (JIS) C6481.
実施例２で得られた接着フィルムを用いて実施例５と同様にして４層プリント配線板を得た。得られた導体層の導体めっき厚は約３０μｍであり、スルーホールは完全に樹脂充填されており、ピール強度は０．８ｋｇｆ／ｃｍであった。 Using the adhesive film obtained in Example 2, a 4-layer printed wiring board was obtained in the same manner as in Example 5. The obtained conductor layer had a conductor plating thickness of about 30 μm, the through hole was completely filled with resin, and the peel strength was 0.8 kgf / cm.
実施例３で得られた接着フィルムを用いて実施例５と同様にして４層プリント配線板を得た。得られた導体層の導体めっき厚は約３０μｍであり、スルーホールは完全に樹脂充填されており、ピール強度は０．９ｋｇｆ／ｃｍであった。 Using the adhesive film obtained in Example 3, a 4-layer printed wiring board was obtained in the same manner as in Example 5. The obtained conductor layer had a conductor plating thickness of about 30 μm, the through hole was completely filled with resin, and the peel strength was 0.9 kgf / cm.
実施例４で得られたプリプレグを実施例５と同じ回路基板上に枚葉し、離型フィルムを介して金属プレートで挟み、１２０℃、１０ｋｇｆ／ｃｍ２で１５分間真空積層プレスした後、更に１８０℃、４０ｋｇｆ／ｃｍ２で６０分間真空積層プレスした。その後、実施例５と同様にして４層プリント配線板を得た。得られた導体層のピール強度は０．８ｋｇｆ／ｃｍであった。 The prepreg obtained in Example 4 was diced onto the same circuit board as in Example 5, sandwiched between metal plates through a release film, and vacuum laminated press at 120 ° C. and 10 kgf / cm 2 for 15 minutes, and then further Vacuum lamination pressing was performed at 180 ° C. and 40 kgf / cm 2 for 60 minutes. Thereafter, a four-layer printed wiring board was obtained in the same manner as in Example 5. The peel strength of the obtained conductor layer was 0.8 kgf / cm.
＜比較例２＞
比較例１で得られた接着フィルムを用いて実施例５と同様にして４層プリント配線板を得た。得られた導体層の導体めっき厚は約３０μｍであり、スルーホールは完全に樹脂充填されており、導体層のピール強度は０．４ｋｇｆ／ｃｍであった。
<Comparative example 2>
Using the adhesive film obtained in Comparative Example 1, a 4-layer printed wiring board was obtained in the same manner as in Example 5. The conductor plating thickness of the obtained conductor layer was about 30 μm, the through hole was completely filled with resin, and the peel strength of the conductor layer was 0.4 kgf / cm.
＜粗化後樹脂表面の評価＞
実施例５、６及び比較例２における粗化処理後の樹脂表面をＳＥＭ観察した。結果を図１〜３に示す。図１〜３より、実施例５及び６においては粗化処理後、表面に樹脂層が残っているが、比較例２においては粗化処理後、樹脂組成物の硬化物（絶縁層）表面の多くの部分で無機充填剤の球形シリカが剥き出しとなっていることが分かる。
<Evaluation of resin surface after roughening>
The resin surfaces after the roughening treatment in Examples 5 and 6 and Comparative Example 2 were observed with an SEM. The results are shown in FIGS. 1-3, in Examples 5 and 6, the resin layer remains on the surface after the roughening treatment, but in Comparative Example 2, the surface of the cured product (insulating layer) of the resin composition after the roughening treatment. It can be seen that in many parts, the spherical silica of the inorganic filler is exposed.
＜機械強度の評価＞
実施例１、２及び比較例１で得られた接着フィルムの樹脂組成物面を１８０℃で９０分熱硬化させた。本サンプルをＪＩＳ Ｋ７１２７に準拠し、引張破断強度測定を行った。
<Evaluation of mechanical strength>
The resin composition surfaces of the adhesive films obtained in Examples 1 and 2 and Comparative Example 1 were thermally cured at 180 ° C. for 90 minutes. The sample was measured for tensile strength at break according to JIS K7127.
＜熱膨張係数の評価＞
実施例１、２及び比較例１で得られた接着フィルムの樹脂組成物面を１８０℃で９０分熱硬化させた。本サンプルを幅約５ｍｍ長さ約１５ｍｍの試験片とし、理学電機株式会社製熱機械分析装置（TMA）を使用して、引張モードで熱機械分析を行った。荷重１ｇ、昇温速度５℃／分で２回測定した。表２に、２回目の測定における室温（２３℃）から１５０℃までの平均線膨張率を記した。
<Evaluation of thermal expansion coefficient>
The resin composition surfaces of the adhesive films obtained in Examples 1 and 2 and Comparative Example 1 were thermally cured at 180 ° C. for 90 minutes. This sample was used as a test piece having a width of about 5 mm and a length of about 15 mm, and thermomechanical analysis was performed in a tensile mode using a thermomechanical analyzer (TMA) manufactured by Rigaku Corporation. The measurement was performed twice at a load of 1 g and a heating rate of 5 ° C./min. Table 2 shows the average linear expansion coefficient from room temperature (23 ° C.) to 150 ° C. in the second measurement.
上記各評価の結果を下記表２に示す。 The results of the above evaluations are shown in Table 2 below.
本発明の樹脂組成物を用いて形成された絶縁層は熱膨張率が低く、粗化処理後、めっきにより形成された導体層との密着性にも優れることがわかる。 It can be seen that the insulating layer formed using the resin composition of the present invention has a low coefficient of thermal expansion and is excellent in adhesion to the conductor layer formed by plating after the roughening treatment.
＜樹脂組成物の動的粘弾性測定＞
実施例１で得られた接着フィルムのエポキシ樹脂組成物を（株）ユー・ビー・エム社製型式Rheosol-G3000を用いて、動的粘弾性を測定した。測定結果を図４に示す。測定は初期温度約６０℃から昇温速度５℃／分で、測定間隔温度２．５℃、振動数１Hz/degで測定した。表３に各温度における溶融粘度値を以下に示す。
<Dynamic viscoelasticity measurement of resin composition>
The dynamic viscoelasticity of the epoxy resin composition of the adhesive film obtained in Example 1 was measured using a model Rheosol-G3000 manufactured by UBM Co., Ltd. The measurement results are shown in FIG. The measurement was performed at an initial temperature of about 60 ° C., a temperature rising rate of 5 ° C./min, a measurement interval temperature of 2.5 ° C., and a frequency of 1 Hz / deg. Table 3 shows the melt viscosity values at each temperature.
本発明の樹脂組成物、該樹脂組成物により調製される多層プリント配線板用の接着フィルムおよびプリプレグは、多層プリント配線板、特にビルドアップ方式で製造される多層プリント配線板の層間絶縁材料として好適に使用される。 The resin composition of the present invention, the adhesive film for a multilayer printed wiring board prepared by the resin composition, and the prepreg are suitable as an interlayer insulating material for a multilayer printed wiring board, particularly a multilayer printed wiring board manufactured by a build-up method. Used for.
Claims (13)
（Ａ）１分子中に２以上のエポキシ基を有し、温度２０℃で液状であるエポキシ樹脂、
（Ｂ）１分子中に３以上のエポキシ基を有し、エポキシ当量が２００以下である芳香族系エポキシ樹脂、
（Ｃ）フェノール系硬化剤、
（Ｄ）ガラス転移温度が１００℃以上である、フェノキシ樹脂、ポリビニルアセタール樹脂、ポリアミド樹脂およびポリアミドイミド樹脂からなる群より選ばれる一種以上の樹脂、及び
（Ｅ）シランカップリング剤で表面処理してある無機充填材
を含み、シランカップリング剤で表面処理してある無機充填材（Ｅ）の含有割合が樹脂組成物の３５重量％以上であり、成分（Ａ）と成分（Ｂ）のエポキシ樹脂の割合が重量比で１：０．３乃至１：２であり、樹脂組成物中のエポキシ基と成分（Ｃ）のフェノール系硬化剤のフェノール性水酸基の割合が１：０．５乃至１：１．５であり、成分（Ｄ）の樹脂の含有割合が樹脂組成物の２乃至２０重量％である樹脂組成物層が支持フィルム上に形成されている、無電解めっきで導体層を形成する多層プリント配線板用の接着フィルム。 The following components (A) to (E):
(A) an epoxy resin having two or more epoxy groups in one molecule and being liquid at a temperature of 20 ° C.,
(B) an aromatic epoxy resin having 3 or more epoxy groups in one molecule and an epoxy equivalent of 200 or less,
(C) a phenolic curing agent,
(D) Surface treatment with one or more resins selected from the group consisting of phenoxy resin, polyvinyl acetal resin, polyamide resin and polyamideimide resin, and (E) silane coupling agent having a glass transition temperature of 100 ° C. or higher. The content ratio of the inorganic filler (E) containing a certain inorganic filler and surface-treated with a silane coupling agent is 35% by weight or more of the resin composition, and the epoxy resin of the component (A) and the component (B) The ratio of the epoxy group in the resin composition to the phenolic hydroxyl group of the phenolic curing agent of component (C) is 1: 0.5 to 1: 2. A conductor layer is formed by electroless plating in which a resin composition layer having a resin content of component (D) of 2 to 20% by weight of the resin composition is formed on a support film. multilayer The adhesive film for the printed wiring board.
（ａ）請求項１〜１１のいずれか１項に記載の接着フィルムを回路基板の片面又は両面にラミネートし、支持フィルムを剥離するか又は剥離しない工程、
（ｂ）ラミネートされた樹脂組成物を熱硬化し絶縁層を形成する工程、
（ｃ）支持フィルムが存在する場合に該支持フィルムを剥離する行程、
（ｄ）絶縁層が形成された回路基板に穴あけする行程、
（ｅ）絶縁層の表面を酸化剤により粗化処理する工程、
（ｆ）粗化された絶縁層の表面にめっきにより導体層を形成させる工程、および
（ｇ）導体層に回路形成する工程。 A method for producing a multilayer printed wiring board comprising the following steps (a) to (g):
(A) Laminating the adhesive film according to any one of claims 1 to 11 on one or both sides of a circuit board and peeling or not peeling the support film;
(B) a step of thermosetting the laminated resin composition to form an insulating layer;
(C) a step of peeling the support film when the support film is present;
(D) a step of drilling a circuit board on which an insulating layer is formed;
(E) a step of roughening the surface of the insulating layer with an oxidizing agent;
(F) A step of forming a conductor layer by plating on the surface of the roughened insulating layer, and (g) a step of forming a circuit on the conductor layer.
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