JP2010090238A - Epoxy resin composition - Google Patents
Epoxy resin composition Download PDFInfo
- Publication number
- JP2010090238A JP2010090238A JP2008260715A JP2008260715A JP2010090238A JP 2010090238 A JP2010090238 A JP 2010090238A JP 2008260715 A JP2008260715 A JP 2008260715A JP 2008260715 A JP2008260715 A JP 2008260715A JP 2010090238 A JP2010090238 A JP 2010090238A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- resin composition
- insulating layer
- weight
- layer
- 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.)
- Granted
Links
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 143
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 133
- 239000000203 mixture Substances 0.000 title claims abstract description 78
- -1 ester compound Chemical class 0.000 claims abstract description 59
- 239000004020 conductor Substances 0.000 claims abstract description 50
- 238000007788 roughening Methods 0.000 claims abstract description 28
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000005011 phenolic resin Substances 0.000 claims abstract description 15
- 229920006287 phenoxy resin Polymers 0.000 claims abstract description 15
- 239000013034 phenoxy resin Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims description 34
- 239000002313 adhesive film Substances 0.000 claims description 32
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000003795 chemical substances by application Substances 0.000 claims description 26
- 239000011342 resin composition Substances 0.000 claims description 26
- 239000004593 Epoxy Substances 0.000 claims description 23
- 238000004519 manufacturing process Methods 0.000 claims description 18
- 238000007747 plating Methods 0.000 claims description 17
- 239000000835 fiber Substances 0.000 claims description 16
- 239000011256 inorganic filler Substances 0.000 claims description 15
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 15
- 125000003700 epoxy group Chemical group 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 10
- 238000010030 laminating Methods 0.000 claims description 9
- 229920001187 thermosetting polymer Polymers 0.000 claims description 4
- 239000010410 layer Substances 0.000 description 118
- 238000001723 curing Methods 0.000 description 48
- 239000002245 particle Substances 0.000 description 42
- 229920005989 resin Polymers 0.000 description 28
- 239000011347 resin Substances 0.000 description 28
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 27
- 229920001971 elastomer Polymers 0.000 description 19
- 239000000047 product Substances 0.000 description 18
- 239000007787 solid Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- 239000002966 varnish Substances 0.000 description 17
- 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 16
- 239000005060 rubber Substances 0.000 description 16
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 12
- 239000003960 organic solvent Substances 0.000 description 12
- 239000000377 silicon dioxide Substances 0.000 description 12
- 230000003746 surface roughness Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000003475 lamination Methods 0.000 description 9
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 230000001681 protective effect Effects 0.000 description 8
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 239000004305 biphenyl Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000007772 electroless plating Methods 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 5
- 229920000459 Nitrile rubber Polymers 0.000 description 5
- 235000010290 biphenyl Nutrition 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
- 238000001035 drying Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229920003986 novolac Polymers 0.000 description 5
- 229920003192 poly(bis maleimide) Polymers 0.000 description 5
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 5
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000009713 electroplating Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 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 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 3
- 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 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-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
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-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
- 238000000137 annealing Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000012792 core layer Substances 0.000 description 3
- 239000011258 core-shell material Substances 0.000 description 3
- 238000005553 drilling Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 239000012286 potassium permanganate Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-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
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 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
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229920000800 acrylic rubber Polymers 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 150000001412 amines Chemical class 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
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 150000005130 benzoxazines Chemical class 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 229930003836 cresol Natural products 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
- 239000000428 dust Substances 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 239000004744 fabric Substances 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
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 125000001477 organic nitrogen group Chemical group 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 150000003003 phosphines Chemical class 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
- 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 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 2
- DEQUKPCANKRTPZ-UHFFFAOYSA-N (2,3-dihydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1O DEQUKPCANKRTPZ-UHFFFAOYSA-N 0.000 description 1
- XXEYMOUSTWPDDB-OJMIUMIFSA-N (2r)-5-[(5s,7r,8s,9r)-8,9-dihydroxy-2,4-dioxo-7-(phosphonooxymethyl)-6-oxa-1,3-diazaspiro[4.4]nonan-3-yl]-2-[formyl(hydroxy)amino]pentanoic acid Chemical compound O[C@@H]1[C@H](O)[C@@H](COP(O)(O)=O)O[C@]11C(=O)N(CCC[C@@H](N(O)C=O)C(O)=O)C(=O)N1 XXEYMOUSTWPDDB-OJMIUMIFSA-N 0.000 description 1
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-dioxonaphthalene Natural products C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 1
- BOKGTLAJQHTOKE-UHFFFAOYSA-N 1,5-dihydroxynaphthalene Chemical compound C1=CC=C2C(O)=CC=CC2=C1O BOKGTLAJQHTOKE-UHFFFAOYSA-N 0.000 description 1
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 description 1
- UGJHILWNNSROJV-UHFFFAOYSA-N 1-[4-[3-[4-(2,5-dioxopyrrol-1-yl)phenoxy]phenoxy]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1OC1=CC=CC(OC=2C=CC(=CC=2)N2C(C=CC2=O)=O)=C1 UGJHILWNNSROJV-UHFFFAOYSA-N 0.000 description 1
- HTQNYBBTZSBWKL-UHFFFAOYSA-N 2,3,4-trihydroxbenzophenone Chemical compound OC1=C(O)C(O)=CC=C1C(=O)C1=CC=CC=C1 HTQNYBBTZSBWKL-UHFFFAOYSA-N 0.000 description 1
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical class CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- 150000003923 2,5-pyrrolediones Chemical class 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
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-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
- MOSSLXZUUKTULI-UHFFFAOYSA-N 3-[3-(2,5-dioxopyrrol-3-yl)-4-methylphenyl]pyrrole-2,5-dione Chemical compound CC1=CC=C(C=2C(NC(=O)C=2)=O)C=C1C1=CC(=O)NC1=O MOSSLXZUUKTULI-UHFFFAOYSA-N 0.000 description 1
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-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
- 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 1
- 101100056187 Arabidopsis thaliana WIN1 gene Proteins 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 229930185605 Bisphenol Natural products 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
- 229920000877 Melamine resin Polymers 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 238000006845 Michael addition reaction Methods 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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Production Of Multi-Layered Print Wiring Board (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
Description
本発明は、多層プリント配線板の絶縁層形成に好適なエポキシ樹脂組成物に関する。 The present invention relates to an epoxy resin composition suitable for forming an insulating layer of a 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においては、ビルドアップ層が複層化され、配線の微細化及び高密度化も一層進んでいる。高密度の微細配線を形成するのに適した導体形成方法として、絶縁層表面を粗化処理後、無電解めっきで導体層を形成するアディティブ法と、無電解めっきと電解めっきで導体層を形成するセミアディティブ法が知られている。これらの方法においては、絶縁層とめっき導体層との密着性は、主に粗化処理によって形成された絶縁層表面の凹凸によって確保されている。すなわち、絶縁層表面が凹凸を有することでめっき層との間にアンカー効果が得られる。従って、密着力を高めるには、絶縁層表面の凹凸の程度（粗度）をより大きくすることが考えられる。 In recent years, electronic devices have become smaller and higher in performance, and in multilayer printed wiring boards, the build-up layer has been multilayered, and the miniaturization and higher density of the wiring are further advanced. As a conductor formation method suitable for forming high-density fine wiring, an additive method in which a conductor layer is formed by electroless plating after the surface of the insulating layer is roughened, and a conductor layer is formed by electroless plating and electrolytic plating. A semi-additive method is known. In these methods, the adhesion between the insulating layer and the plated conductor layer is ensured mainly by the irregularities on the surface of the insulating layer formed by roughening treatment. That is, an anchor effect is obtained between the plating layer and the insulating layer surface having irregularities. Therefore, to increase the adhesion, it is conceivable to increase the degree of roughness (roughness) on the surface of the insulating layer.
しかしながら、配線のさらなる高密度化のためには絶縁層表面の粗度は小さい方が好ましい。即ち、無電解めっき、電解めっきにより導体層を形成後、フラッシュエッチングにより薄膜のめっき層を取り除いて配線形成を完了させる際、絶縁層表面の粗度が大きいと、凹部に潜り込んだ導体層を取り除くために長時間のフラッシュエッチが必要となり、フラッシュエッチを長時間行うと、その影響で微細配線が損傷または断線する危険性が高くなってしまう。従って、高信頼性の高密度配線を形成するためには、絶縁層表面には粗化処理後の粗度が小さくてもめっき導体との密着性に優れることが要求される。 However, in order to further increase the density of the wiring, it is preferable that the surface roughness of the insulating layer is small. That is, after forming a conductor layer by electroless plating or electrolytic plating, and removing the thin plating layer by flash etching to complete wiring formation, if the roughness of the surface of the insulating layer is large, the conductor layer embedded in the recess is removed. Therefore, a long flash etch is required, and if the flash etch is performed for a long time, the risk of damage or disconnection of the fine wiring increases due to the effect. Therefore, in order to form a highly reliable high-density wiring, the insulating layer surface is required to have excellent adhesion to the plated conductor even if the roughness after the roughening treatment is small.
またさらに、多層プリント基板の絶縁材には線膨張率が低いことが要求される。線膨張率が高いと、導体層と有機絶縁層との間の線膨張率の差が大きくなるため、導体層と有機絶縁層との界面においてクラックが発生する等の問題が生じやすくなる。 Furthermore, the insulating material of the multilayer printed board is required to have a low coefficient of linear expansion. If the coefficient of linear expansion is high, the difference in coefficient of linear expansion between the conductor layer and the organic insulating layer becomes large, and problems such as the occurrence of cracks at the interface between the conductor layer and the organic insulating layer are likely to occur.
特許文献１には、エポキシ樹脂、特定のフェノール系硬化剤、フェノキシ樹脂、ゴム粒子を含むエポキシ樹脂組成物が開示され、また特許文献２には、エポキシ樹脂、特定のフェノール系硬化剤、ポリビニルアセタール樹脂を含むエポキシ樹脂組成物されており、これらの組成物により形成される絶縁層が、低粗度かつめっきにより形成される導体層のピール強度にも優れることが開示されている。しかしながら、低線膨張率については開示されていない。 Patent Document 1 discloses an epoxy resin composition including an epoxy resin, a specific phenol-based curing agent, a phenoxy resin, and rubber particles, and Patent Document 2 discloses an epoxy resin, a specific phenol-based curing agent, and polyvinyl acetal. It is disclosed that an epoxy resin composition containing a resin is used, and an insulating layer formed by these compositions is low in roughness and excellent in peel strength of a conductor layer formed by plating. However, the low linear expansion coefficient is not disclosed.
本発明は、エポキシ樹脂組成物の硬化物表面を粗化処理した粗化面の粗度が比較的小さいにもかかわらず、該粗化面がめっき導体に対して高い密着力を示し、かつ線膨張率が小さい絶縁層を達成し得るエポキシ樹脂組成物を提供することを目的とする。 In the present invention, although the roughness of the roughened surface obtained by roughening the cured product surface of the epoxy resin composition is relatively small, the roughened surface exhibits high adhesion to the plated conductor, and It aims at providing the epoxy resin composition which can achieve the insulating layer with a small expansion coefficient.
本発明者は、上記課題を解決すべく鋭意研究した結果、エポキシ樹脂、活性エステル化合物、ビスマレイミド樹脂及びフェノキシ樹脂を配合したエポキシ樹脂組成物において、該エポキシ樹脂組成物を硬化して得られる硬化物が低線膨張率性に優れ、かつ該硬化物表面を粗化処理した粗化面の粗度が比較的小さい場合でも、めっき導体と高い密着力で密着し得ることを見出し、本発明を完成するに至った。 As a result of diligent research to solve the above-mentioned problems, the present inventor has found that an epoxy resin composition containing an epoxy resin, an active ester compound, a bismaleimide resin, and a phenoxy resin can be obtained by curing the epoxy resin composition. It has been found that the product is excellent in low linear expansion coefficient and can be adhered to the plated conductor with high adhesion even when the roughness of the roughened surface obtained by roughening the surface of the cured product is relatively small. It came to be completed.
すなわち、本発明は以下の内容を含むものである。
［１］ （Ａ）エポキシ樹脂、（Ｂ）活性エステル化合物、（Ｃ）トリアジン構造含有フェノール樹脂、（Ｄ）マレイミド化合物及び（Ｅ）フェノキシ樹脂を含有することを特徴とするエポキシ樹脂組成物。
［２］ エポキシ樹脂組成物の不揮発成分を１００重量％とした場合、成分（Ａ）の含有量が１０〜５０重量％、成分（Ｄ）の含有量が１〜２０重量％、成分（Ｅ）の含有量が１〜２０重量％であり、エポキシ樹脂組成物中に存在するエポキシ基とエポキシ硬化剤の反応基の比率が１：０．４〜１：１．１である、上記［１］に記載のエポキシ樹脂組成物。
［３］ さらに（Ｆ）無機充填材を含有する、上記［１］又は［２］記載のエポキシ樹脂組成物。
［４］ エポキシ樹脂組成物の不揮発成分を１００重量％とした場合、（Ｆ）無機充填材の含有量が１０〜７０重量％である、上記［３］記載のエポキシ樹脂組成物。
［５］ さらに（Ｇ）硬化促進剤を含有する、上記［１］〜［４］のいずれかに記載のエポキシ樹脂組成物。
［６］ エポキシ樹脂組成物中に含まれるエポキシ樹脂とフェノール性硬化剤の総量を１００重量％とした場合、（Ｇ）硬化促進剤の含有量が０．１〜５重量％である、上記［５］記載のエポキシ樹脂組成物。
［７］ 上記［１］〜［６］のいずれかに記載のエポキシ樹脂組成物が支持フィルム上に層形成されている接着フィルム。
［８］ 上記［１］〜［６］のいずれかに記載のエポキシ樹脂組成物が繊維からなるシート状繊維基材中に含浸されていることを特徴とするプリプレグ。
［９］ 上記［１］〜［６］のいずれかに記載のエポキシ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。
［１０］ 内層回路基板上に絶縁層を形成する工程及び該絶縁層上に導体層を形成する工程を含む多層プリント配線板の製造方法であって、該絶縁層が、上記［１］〜［６］のいずれかに記載のエポキシ樹脂組成物を熱硬化して形成され、該導体層が、該絶縁層表面を粗化処理した粗化面にめっきにより形成されることを特徴とする、多層プリント配線板の製造方法。
［１１］ 内層回路基板上に絶縁層を形成する工程及び該絶縁層上に導体層を形成する工程を含む多層プリント配線板の製造方法であって、絶縁層が、上記［７］記載の接着フィルムを内層回路基板上にラミネートし、支持フィルムを剥離するか又は剥離しないで、エポキシ樹脂組成物を熱硬化し、硬化後に支持フィルムが存在する場合に支持フィルムを剥離して形成され、該導体層が、該絶縁層表面を粗化処理した粗化面にめっきにより形成されることを特徴とする、多層プリント配線板の製造方法。
［１２］ 内層回路基板上に絶縁層を形成する工程及び該絶縁層上に導体層を形成する工程を含む多層プリント配線板の製造方法であって、絶縁層が、上記［８］記載のプリプレグを内層回路基板上にラミネートし、エポキシ樹脂組成物を熱硬化して形成され、該導体層が、該絶縁層表面を粗化処理した粗化面にめっきにより形成されることを特徴とする、多層プリント配線板の製造方法。
［１３］ 粗化処理が、アルカリ性過マンガン酸溶液を使用して行われる、上記［１０］〜［１２］のいずれかに記載の製造方法。
That is, the present invention includes the following contents.
[1] An epoxy resin composition comprising (A) an epoxy resin, (B) an active ester compound, (C) a triazine structure-containing phenol resin, (D) a maleimide compound and (E) a phenoxy resin.
[2] When the nonvolatile component of the epoxy resin composition is 100% by weight, the content of the component (A) is 10 to 50% by weight, the content of the component (D) is 1 to 20% by weight, and the component (E) 1 to 20% by weight, and the ratio of the epoxy group present in the epoxy resin composition to the reactive group of the epoxy curing agent is 1: 0.4 to 1: 1.1 [1] The epoxy resin composition described in 1.
[3] The epoxy resin composition according to the above [1] or [2], further comprising (F) an inorganic filler.
[4] The epoxy resin composition according to the above [3], wherein the content of the inorganic filler (F) is 10 to 70% by weight when the nonvolatile component of the epoxy resin composition is 100% by weight.
[5] The epoxy resin composition according to any one of [1] to [4], further including (G) a curing accelerator.
[6] When the total amount of the epoxy resin and the phenolic curing agent contained in the epoxy resin composition is 100% by weight, the content of the (G) curing accelerator is 0.1 to 5% by weight. 5] The epoxy resin composition according to the above.
[7] An adhesive film in which the epoxy resin composition according to any one of [1] to [6] is layered on a support film.
[8] A prepreg characterized in that the epoxy resin composition according to any one of [1] to [6] is impregnated in a sheet-like fiber base material composed of fibers.
[9] A multilayer printed wiring board in which an insulating layer is formed of a cured product of the epoxy resin composition according to any one of [1] to [6].
[10] A method for producing a multilayer printed wiring board, comprising a step of forming an insulating layer on an inner circuit board and a step of forming a conductor layer on the insulating layer, wherein the insulating layer comprises the above-mentioned [1] to [ 6], wherein the epoxy resin composition is heat-cured and the conductor layer is formed by plating on a roughened surface obtained by roughening the surface of the insulating layer. Manufacturing method of printed wiring board.
[11] A method for producing a multilayer printed wiring board, comprising a step of forming an insulating layer on an inner circuit board and a step of forming a conductor layer on the insulating layer, wherein the insulating layer is an adhesive according to the above [7] The film is laminated on the inner layer circuit board, the epoxy resin composition is heat-cured with or without peeling off the support film, and the support film is peeled off when the support film is present after curing. A method for producing a multilayer printed wiring board, wherein the layer is formed by plating on a roughened surface obtained by roughening the surface of the insulating layer.
[12] A method for producing a multilayer printed wiring board, comprising a step of forming an insulating layer on an inner circuit board and a step of forming a conductor layer on the insulating layer, wherein the insulating layer comprises the prepreg according to the above [8] Is formed by thermosetting an epoxy resin composition, and the conductor layer is formed by plating on a roughened surface obtained by roughening the surface of the insulating layer. A method for producing a multilayer printed wiring board.
[13] The production method according to any one of [10] to [12], wherein the roughening treatment is performed using an alkaline permanganate solution.
本発明のエポキシ樹脂組成物を硬化して得られる硬化物は、該硬化物表面を粗化処理した粗化面の粗度が比較的小さい場合でも、めっきにより高い密着性を有する導体層を形成することができ、例えば、多層プリント配線板の絶縁層として使用した場合、該絶縁層上に形成する導体層の微細配線化に極めて有利な材料となる。さらに、該硬化物は低線膨張率性にも優れるため、導体層と絶縁層との線膨張率の差によるクラックも発生しにくい。このように、本発明のエポキシ樹脂組成物は、多層プリント配線板の絶縁層形成材料として非常に優れたものとなる。 The cured product obtained by curing the epoxy resin composition of the present invention forms a conductor layer having high adhesion by plating even when the roughness of the roughened surface obtained by roughening the surface of the cured product is relatively small. For example, when it is used as an insulating layer of a multilayer printed wiring board, it becomes a material that is extremely advantageous for miniaturization of a conductor layer formed on the insulating layer. Furthermore, since the cured product is also excellent in low linear expansion coefficient, cracks due to the difference in linear expansion coefficient between the conductor layer and the insulating layer hardly occur. Thus, the epoxy resin composition of the present invention is extremely excellent as an insulating layer forming material for multilayer printed wiring boards.
［成分（Ａ）のエポキシ樹脂］
本発明における成分（Ａ）のエポキシ樹脂は特に限定はされず、例えば、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、クレゾールノボラック型エポキシ樹脂、ビフェニル型エポキシ樹脂、線状脂肪族エポキシ樹脂、脂環式エポキシ樹脂、複素環式エポキシ樹脂、スピロ環含有エポキシ樹脂、シクロヘキサンジメタノール型エポキシ樹脂、トリメチロール型エポキシ樹脂、ハロゲン化エポキシ樹脂などが挙げられる。
[Epoxy resin of component (A)]
The epoxy resin of component (A) in the present invention is not particularly limited. For example, 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, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol type epoxy resin, Trimethylol type epoxy resin, halogenated epoxy resin, etc. are mentioned.
エポキシ樹脂は２種以上を併用してもよいが、通常、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が含有される。エポキシ樹脂組成物の不揮発成分を１００重量％とした場合に、少なくとも５０重量％以上は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であるのが好ましい。またさらに、１分子中に２以上のエポキシ基を有し、温度２０℃で液状の芳香族系エポキシ樹脂であるエポキシ樹脂、および１分子中に３以上エポキシ基を有し、温度２０℃で固体状の芳香族系エポキシ樹脂を含有する態様が好ましい。なお、本発明でいう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。またエポキシ当量（ｇ／ｅｑ）は、エポキシ基１個当たりの分子量のことである。エポキシ樹脂として、液状エポキシ樹脂と固形エポキシ樹脂を使用することで、エポキシ樹脂組成物を接着フィルムの形態で使用する場合に、十分な可撓性を示し、取扱い性に優れた接着フィルムを形成できると同時に、エポキシ樹脂組成物の硬化物の破断強度が向上し、多層プリント配線板の耐久性が向上する。 Two or more epoxy resins may be used in combination, but usually an epoxy resin having two or more epoxy groups in one molecule is contained. When the nonvolatile component of the epoxy resin composition is 100% by weight, at least 50% by weight or more is preferably an epoxy resin having two or more epoxy groups in one molecule. Furthermore, an epoxy resin that is an aromatic epoxy resin that has two or more epoxy groups in one molecule and is liquid at a temperature of 20 ° C, and a solid that has three or more epoxy groups in one molecule and has a temperature of 20 ° C. The aspect which contains a shape-like aromatic epoxy resin is preferable. The aromatic epoxy resin in the present invention means an epoxy resin having an aromatic ring skeleton in the molecule. The epoxy equivalent (g / eq) is the molecular weight per epoxy group. By using a liquid epoxy resin and a solid epoxy resin as an epoxy resin, when using an epoxy resin composition in the form of an adhesive film, an adhesive film that exhibits sufficient flexibility and excellent handling properties can be formed. At the same time, the breaking strength of the cured product of the epoxy resin composition is improved, and the durability of the multilayer printed wiring board is improved.
また、エポキシ樹脂として、液状エポキシ樹脂と固形エポキシ樹脂を併用する場合、その配合割合（液状：固形）は重量比で１：０．１〜１：２の範囲が好ましい。かかる範囲を超えて液状エポキシ樹脂の割合が多すぎると、エポキシ樹脂組成物の粘着性が高くなり、接着フィルムの形態で使用する場合に、真空ラミネート時の脱気性が低下しボイドが発生しやすくなる傾向にある。また真空ラミネート時に保護フィルムや支持フィルムの剥離性の低下や、硬化後の耐熱性が低下する傾向にある。また、エポキシ樹脂組成物の硬化物において十分な破断強度が得られにくい傾向にある。一方、かかる範囲を超えて固形エポキシ樹脂の割合が多すぎると、接着フィルムの形態で使用する場合に、十分な可撓性が得られず、取り扱い性が低下する、ラミネートの際の十分な流動性が得られにくいなどの傾向がある。 Moreover, when using together a liquid epoxy resin and a solid epoxy resin as an epoxy resin, the mixture ratio (liquid: solid) has the preferable range of 1: 0.1-1: 2 by weight ratio. If the ratio of the liquid epoxy resin is too large beyond this range, the tackiness of the epoxy resin composition becomes high, and when used in the form of an adhesive film, the degassing property during vacuum lamination is reduced and voids are likely to occur. Tend to be. Moreover, there exists a tendency for the peelability of a protective film and a support film to fall at the time of vacuum lamination, and the heat resistance after hardening to fall. Moreover, it exists in the tendency for sufficient breaking strength to be hard to be obtained in the hardened | cured material of an epoxy resin composition. On the other hand, if the proportion of the solid epoxy resin is too large beyond this range, sufficient flexibility cannot be obtained when using it in the form of an adhesive film, and the handleability is lowered. There is a tendency that it is difficult to obtain.
本発明のエポキシ樹脂組成物において、エポキシ樹脂組成物の不揮発成分を１００重量％とした場合、エポキシ樹脂の含有量は１０〜５０重量％であるのが好ましく、より好ましくは２０〜４０重量％であり、とりわけ好ましくは２０〜３５重量％である。エポキシ樹脂（Ａ）の含有量がこの範囲から外れると、樹脂組成物の硬化性が低下する傾向にある。 In the epoxy resin composition of the present invention, when the nonvolatile component of the epoxy resin composition is 100% by weight, the content of the epoxy resin is preferably 10 to 50% by weight, more preferably 20 to 40% by weight. Yes, particularly preferably 20 to 35% by weight. When the content of the epoxy resin (A) is out of this range, the curability of the resin composition tends to decrease.
[成分（Ｂ）の活性エステル化合物]
本発明における（Ｂ）活性エステル化合物は、エポキシ樹脂の硬化剤として機能し、また耐薬品性に優れることから粗化後の絶縁樹脂表面の表面粗さを抑える機能も持ち、一般に１分子中に２個以上の活性エステル基を有する化合物が好ましく用いられる。活性エステル化合物は、一般に、カルボン酸化合物及び／又はチオカルボン酸化合物とヒドロキシ化合物及び／又はチオール化合物との縮合反応によって得ることができる。特に耐熱性等の観点から、カルボン酸化合物とフェノール化合物又はナフトール化合物とから得られる活性エステル化合物が好ましい。カルボン酸化合物としては、例えば酢酸、安息香酸、コハク酸、マレイン酸、イタコン酸、フタル酸、イソフタル酸、テレフタル酸、ピロメリット酸等が挙げられる。フェノール化合物又はナフトール化合物としては、ハイドロキノン、レゾルシン、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、フェノールフタリン、メチル化ビスフェノールＡ、メチル化ビスフェノールＦ、メチル化ビスフェノールＳ、フェノール、ｏ−クレゾール、ｍ−クレゾール、ｐ−クレゾール、カテコール、α−ナフトール、β−ナフトール、１，５−ジヒドロキシナフタレン、１，６−ジヒドロキシナフタレン、２，６−ジヒドロキシナフタレン、ジヒドロキシベンゾフェノン、トリヒドロキシベンゾフェノン、テトラヒドロキシベンゾフェノン、フロログルシン、ベンゼントリオール、ジシクロペンタジエニルジフェノール、フェノールノボラック等が挙げられる。活性エステル化合物は２種以上を併用してもよい。活性エステル化合物は市販のものを用いても、特開２００４−４２７７６１号公報に開示されているような方法で合成したものを用いても良く、市販されている活性エステル化合物としては、例えば、ジシクロペンタジエニル構造を含むものとして、ＥＸＢ−９４５１、ＥＸＢ−９４６０（ＤＩＣ（株）製）、フェノールノボラックのアセチル化物として、ＤＣ８０８、フェノールノボラックのベンゾイル化物として、ＹＬＨ１０３０（ジャパンエポキシレジン（株）製）などが挙げられる。
[Active ester compound of component (B)]
The (B) active ester compound in the present invention functions as a curing agent for epoxy resin, and also has a function of suppressing the surface roughness of the insulating resin surface after roughening because of its excellent chemical resistance, and generally in one molecule. A compound having two or more active ester groups is preferably used. The active ester compound can be generally obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of heat resistance and the like, an active ester compound obtained from a carboxylic acid compound and a phenol compound or a naphthol compound is preferable. Examples of the carboxylic acid compound include acetic acid, benzoic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol , Dicyclopentadienyl diphenol, phenol novolac and the like. Two or more active ester compounds may be used in combination. The active ester compound may be a commercially available one, or one synthesized by a method as disclosed in JP-A No. 2004-427761, and examples of commercially available active ester compounds include diesters. EXB-9451, EXB-9460 (manufactured by DIC Corporation) as a cyclopentadienyl structure, DC808 as an acetylated product of phenol novolac, YLH1030 (manufactured by Japan Epoxy Resin Co., Ltd.) as a benzoylated product of phenol novolac ) And the like.
［成分（Ｃ）のトリアジン構造含有フェノール樹脂］
本発明における（Ｃ）トリアジン構造含有フェノール樹脂は、フェノール部位がエポキシ樹脂の硬化剤として機能し、トリアジン部位が（Ｄ）マレイミド樹脂とマイケル付加反応し硬化系に取り込む機能を有する。トリアジン構造含有フェノール樹脂は一般にフェノールやクレゾール、ナフトールなどの芳香族ヒドロキシ化合物とメラミン、ベンゾグアナミンなどのトリアジン環を有する化合物とホルムアルデヒドの縮合により製造される。市販されているものとしてはＬＡ７０５２、ＬＡ７０５４、ＬＡ３０１８、ＬＡ１３５６（ＤＩＣ（株）製）などが挙げられる。トリアジン構造含有フェノール樹脂は２種以上を併用してもよい。
[Triazine structure-containing phenol resin of component (C)]
In the (C) triazine structure-containing phenol resin in the present invention, the phenol moiety functions as a curing agent for the epoxy resin, and the triazine moiety has a function of Michael addition reaction with the (D) maleimide resin and incorporated into the curing system. The triazine structure-containing phenol resin is generally produced by condensation of an aromatic hydroxy compound such as phenol, cresol or naphthol with a compound having a triazine ring such as melamine or benzoguanamine and formaldehyde. Examples of commercially available products include LA7052, LA7054, LA3018, LA1356 (manufactured by DIC Corporation). Two or more triazine structure-containing phenol resins may be used in combination.
本発明の効果を達成し得る範囲で、その他のエポキシ硬化剤を任意で併用しても良い。活性エステル以外のエポキシ硬化剤としては、ＴＤ２０９０、ＴＤ２１３１（ＤＩＣ（株）製）、ＭＥＨ−７６００、ＭＥＨ−７８５１、ＭＥＨ−８０００Ｈ（明和化成（株）製）、ＮＨＮ、ＣＢＮ、ＧＰＨ−６５、ＧＰＨ−１０３（日本化薬（株）製）、ＳＮ１７０、ＳＮ１８０、ＳＮ１９０、ＳＮ４７５、ＳＮ４８５、ＳＮ４９５、ＳＮ３７５、ＳＮ３９５（東都化成（株）製）などのフェノール系硬化剤、Ｆ−ａ、Ｐ−ｄ（四国化成（株）製）、ＨＦＢ２００６Ｍ（昭和高分子（株）製）などのベンゾオキサジン化合物、メチルヘキサヒドロ無水フタル酸、メチルナジック酸無水物、水素化メチルナジック酸無水物などの酸無水物などが挙げられる。 Other epoxy curing agents may be optionally used in combination as long as the effects of the present invention can be achieved. As epoxy curing agents other than the active ester, TD2090, TD2131 (manufactured by DIC Corporation), MEH-7600, MEH-7851, MEH-8000H (manufactured by Meiwa Kasei Co., Ltd.), NHN, CBN, GPH-65, GPH -103 (manufactured by Nippon Kayaku Co., Ltd.), SN170, SN180, SN190, SN475, SN485, SN495, SN375, SN395 (manufactured by Tohto Kasei Co., Ltd.), F-a, Pd Benzoxazine compounds such as Shikoku Kasei Co., Ltd.), HFB2006M (manufactured by Showa Polymer Co., Ltd.), acid anhydrides such as methylhexahydrophthalic anhydride, methyl nadic anhydride, hydrogenated methyl nadic anhydride, etc. Is mentioned.
本発明において、エポキシ樹脂組成物中の成分（B）活性エステル化合物及びトリアジン構造含有フェノール樹脂を含むエポキシ硬化剤の量は、通常、エポキシ樹脂組成物中に存在するエポキシ基の合計数とエポキシ硬化剤の反応基の合計数の比率が１：０．４〜１：１．１となる量にするのが好ましい。なおエポキシ樹脂組成物中に存在するエポキシ基の合計数とは、各エポキシ樹脂の固形分重量をエポキシ当量で除した値をすべてのエポキシ樹脂について合計した値であり、エポキシ硬化剤の反応基（活性エステル基、活性水酸基等）の合計数とは、各硬化剤の固形分重量を反応基当量で除した値をすべての硬化剤について合計した値である。硬化剤の含有量がかかる好ましい範囲を外れると、エポキシ樹脂組成物を硬化して得られる硬化物の耐熱性が不十分となる場合がある。
活性エステル化合物は、エポキシ樹脂組成物中のすべてのエポキシ硬化剤（活性エステル化合物及びトリアジン構造含有フェノール樹脂を含む）を重量１００％とすると、活性エステル化合物の重量％が１０〜１００％であるのが好ましく、２０〜１００％であるのがさらに好ましい。活性エステル化合物の含有量が少なすぎると、絶縁層表面の粗度が大きくなる傾向にある。また、トリアジン構造含有フェノール樹脂は、エポキシ樹脂組成物中のすべてのエポキシ硬化剤（活性エステル化合物及びトリアジン構造含有フェノール樹脂を含む）を重量１００％とすると、１０〜９０％であるのが好ましく、２０〜８０％であるのがさらに好ましい。トリアジン構造含有フェノール樹脂の含有量が多すぎると、絶縁層表面の粗度が大きくなる傾向にあり、少なすぎるとマレイミド化合物の硬化が不十分になり、エポキシ樹脂組成物を硬化して得られる硬化物が脆くなる、絶縁層表面の粗度が大きくなる傾向にある。
In the present invention, the amount of the epoxy curing agent containing the component (B) active ester compound and the triazine structure-containing phenol resin in the epoxy resin composition is usually the total number of epoxy groups present in the epoxy resin composition and epoxy curing. It is preferable that the ratio of the total number of reactive groups in the agent is 1: 0.4 to 1: 1.1. The total number of epoxy groups present in the epoxy resin composition is a value obtained by dividing the solid content weight of each epoxy resin by the epoxy equivalent for all epoxy resins, and the reactive group ( The total number of active ester groups, active hydroxyl groups and the like) is a value obtained by totaling the values obtained by dividing the solid content weight of each curing agent by the reactive group equivalent for all curing agents. If the content of the curing agent is outside the preferable range, the heat resistance of the cured product obtained by curing the epoxy resin composition may be insufficient.
The active ester compound is 10% to 100% by weight of the active ester compound when all the epoxy curing agents (including the active ester compound and the triazine structure-containing phenol resin) in the epoxy resin composition are 100% by weight. Is preferable, and it is further more preferable that it is 20 to 100%. If the content of the active ester compound is too small, the roughness of the insulating layer surface tends to increase. Further, the triazine structure-containing phenol resin is preferably 10 to 90% when the weight of all epoxy curing agents (including the active ester compound and the triazine structure-containing phenol resin) in the epoxy resin composition is 100%, More preferably, it is 20 to 80%. If the content of the triazine structure-containing phenol resin is too large, the surface roughness of the insulating layer tends to increase, and if it is too small, the maleimide compound is insufficiently cured, resulting in curing obtained by curing the epoxy resin composition. Things tend to be brittle, and the surface roughness of the insulating layer tends to increase.
［成分（Ｄ）のマレイミド化合物］
本発明における（Ｄ）マレイミド化合物は、無水マレイン酸と各種アミン化合物から得られるものであり、一般に一分子中に２個以上のマレイミド基を含むビスマレイミド化合物が好ましく使用される。具体例としては４，４’−ジフェニルメタンビスマレイミド（大和化成工業（株）製ＢＭＩ−１０００、ケイ・アイ化成（株）製ＢＭＩ）、ＢＭＩ−２０００、m−フェニレンビスマレイミドＢＭＩ３０００、ビスフェノール A ジフェニルエーテルビスマレイミド（大和化成工業（株）製ＢＭＩ４０００、ケイ・アイ化成（株）製ＢＭＩ−８０）、３，３’−ジメチル−５，５’−ジエチル−４，４’−ジフェニルメタンビスマレイミド（大和化成工業（株）製ＢＭＩ５１００、ケイ・アイ化成（株）製ＢＭＩ−７０）、４−メチル−１，３−フェニレンビスマレイミド（大和化成工業（株）製ＢＭＩ−７０００）、１，６’−ビスマレイミド−（２，２，４−トリメチル)ヘキサン（大和化成工業（株）製ＢＭＩ−ＴＭＨ）、４，４’−ジフェニルエーテルビスマレイミド（大和化成工業（株）製ＢＭＩ−６０００）、４，４’−ジフェニルスルフォンビスマレイミド（ＢＭＩ−８０００）大和化成工業（株）製）、１，３−ビス（３−マレイミドフェノキシ)ベンゼン（大和化成工業（株）製）、１，３−ビス(４−マレイミドフェノキシ)ベンゼン（大和化成工業（株）製）、ＡＮＩＬＩＸ−ＭＩ（三井化学ファイン（株）製）等が挙げられる。マレイミド化合物は２種以上を併用してもよい。
[Maleimide compound of component (D)]
The (D) maleimide compound in the present invention is obtained from maleic anhydride and various amine compounds. Generally, a bismaleimide compound containing two or more maleimide groups in one molecule is preferably used. Specific examples include 4,4′-diphenylmethane bismaleimide (BMI-1000 manufactured by Daiwa Kasei Kogyo Co., Ltd., BMI manufactured by Kay Kasei Co., Ltd.), BMI-2000, m-phenylene bismaleimide BMI3000, bisphenol A diphenyl ether bis. Maleimide (BMI4000 manufactured by Daiwa Kasei Kogyo Co., Ltd., BMI-80 manufactured by Kay Kasei Chemical Co., Ltd.), 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide (Daiwa Kasei Kogyo) BMI5100 manufactured by BMI-70 manufactured by K.I. Kasei Co., Ltd., 4-methyl-1,3-phenylenebismaleimide (BMI-7000 manufactured by Daiwa Kasei Kogyo Co., Ltd.), 1,6′-bismaleimide -(2,2,4-trimethyl) hexane (BMI-TMH manufactured by Daiwa Kasei Kogyo Co., Ltd.), 4,4'-diphenyl ester Terbismaleimide (BMI-6000 manufactured by Daiwa Kasei Kogyo Co., Ltd.), 4,4′-diphenylsulfone bismaleimide (BMI-8000) manufactured by Daiwa Kasei Kogyo Co., Ltd., 1,3-bis (3-maleimidophenoxy) Examples include benzene (manufactured by Daiwa Kasei Kogyo Co., Ltd.), 1,3-bis (4-maleimidophenoxy) benzene (manufactured by Daiwa Kasei Kogyo Co., Ltd.), ANILIX-MI (manufactured by Mitsui Chemicals Fine Co., Ltd.), and the like. Two or more maleimide compounds may be used in combination.
本発明のエポキシ樹脂組成物において、エポキシ樹脂組成物の不揮発成分を１００重量％とした場合、当該マレイミド化合物の含有量は１〜２０重量％の範囲であることが好ましい。１重量％未満であると線膨張率があまり低くならず、２０重量％を超えると、粗化後の絶縁樹脂表面の粗度が大きくなりすぎる傾向にある。 In the epoxy resin composition of the present invention, when the nonvolatile component of the epoxy resin composition is 100% by weight, the content of the maleimide compound is preferably in the range of 1 to 20% by weight. If it is less than 1% by weight, the linear expansion coefficient is not so low, and if it exceeds 20% by weight, the roughness of the surface of the insulating resin after roughening tends to be too large.
[成分（Ｅ）のフェノキシ樹脂]
本発明でのフェノキシ樹脂は、接着フィルムに十分な可撓性を付与すること、及び粗化性の調整の目的で使用される。フェノキシ樹脂は市販のものを用いることができ，その具体例としては、ジャパンエポキシレジン（株）製１２５６、４２５０などのビスフェノールＡ骨格を有するもの、ジャパンエポキシレジン製ＹＸ８１００などのビスフェノールＳ骨格を有するもの、ジャパンエポキシレジン製ＹＸ６９５４などのビスフェノールアセトフェノン骨格を有するものや、その他東都化成（株）製ＦＸ２８０、ＦＸ２９３、ジャパンエポキシレジン（株）製ＹＬ７５５３、ＹＬ６７９４、ＹＬ７２１３、ＹＬ７２９０、ＹＬ７４８２等が挙げられる。フェノキシ樹脂は２種以上を併用してもよい。フェノキシ樹脂の重量平均分子量は１００００〜５００００の範囲であるのが好ましく、さらに好ましくは１００００〜４００００、さらに好ましくは２００００〜３５０００である。分子量が小さすぎると十分な導体層のピール強度が得られない傾向にあり、分子量が大きすぎると、粗度が大きくなりやすい、線膨張率が大きくなりやすいなどの傾向にある。
[Phenoxy resin of component (E)]
The phenoxy resin in the present invention is used for the purpose of imparting sufficient flexibility to the adhesive film and adjusting the roughening property. A commercially available phenoxy resin can be used. Specific examples thereof include those having a bisphenol A skeleton such as 1256, 4250 manufactured by Japan Epoxy Resin Co., Ltd., and those having a bisphenol S skeleton such as YX8100 manufactured by Japan Epoxy Resin. And those having a bisphenol acetophenone skeleton such as YX6954 manufactured by Japan Epoxy Resin, FX280, FX293 manufactured by Toto Kasei Co., Ltd., YL7553, YL6794, YL7213, YL7290, YL7482 manufactured by Japan Epoxy Resin Co., Ltd., and the like. Two or more phenoxy resins may be used in combination. The weight average molecular weight of the phenoxy resin is preferably in the range of 10,000 to 50,000, more preferably 10,000 to 40,000, and further preferably 20,000 to 35,000. If the molecular weight is too small, sufficient peel strength of the conductor layer tends not to be obtained. If the molecular weight is too large, the roughness tends to increase and the linear expansion coefficient tends to increase.
本発明のエポキシ樹脂組成物において、エポキシ樹脂組成物の不揮発成分を１００重量％とした場合、当該フェノキシ樹脂の含有量は１〜２０重量％の範囲であることが好ましい。２重量％未満であると十分な可撓性が得られず、取り扱い性が低下する、メッキにより形成された導体層のピール強度が十分に得られない傾向にあり、２０重量％を超えると、ラミネートの際の十分な流動性が得られにくい、粗度が大きくなりすぎる傾向にある。 In the epoxy resin composition of the present invention, when the nonvolatile component of the epoxy resin composition is 100% by weight, the content of the phenoxy resin is preferably in the range of 1 to 20% by weight. When the amount is less than 2% by weight, sufficient flexibility cannot be obtained, and the handleability is deteriorated. Peel strength of the conductor layer formed by plating tends to be not sufficiently obtained. It is difficult to obtain sufficient fluidity during lamination, and the roughness tends to be too large.
本発明のエポキシ樹脂組成物は、さらに線膨張率を低下させる等の目的でさらに無機充填材を含有してもよい。無機充填材としては、例えば、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、これらの中でも無定形シリカ、溶融シリカ、結晶シリカ、合成シリカ等のシリカが特に好適である。シリカとしては球状のものが好ましい。無機充填材の平均粒径は１μｍ以下であるのが好ましく、０．８μｍ以下がより好ましく、０．７μｍ以下がとりわけ好ましい。平均粒径が１μｍを超える場合、メッキにより形成される導体層のピール強度が低下する傾向にある。なお、無機充填材の平均粒径が小さくなりすぎると、エポキシ樹脂組成物を樹脂ワニスとした場合に、ワニスの粘度が上昇し、取り扱い性が低下する傾向にあるため、平均粒径は０．０５μｍ以上であるのが好ましい。なお、無機充填材は耐湿性を向上させるため、エポキシシランカップリング剤、アミノシランカップリング剤、チタネート系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。無機充填材は２種以上を併用してもよい。 The epoxy resin composition of the present invention may further contain an inorganic filler for the purpose of further reducing the linear expansion coefficient. Examples of the inorganic filler 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, Examples include strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate. Among these, silica such as amorphous silica, fused silica, crystalline silica, and synthetic silica Particularly preferred. The silica is preferably spherical. The average particle size of the inorganic filler is preferably 1 μm or less, more preferably 0.8 μm or less, and particularly preferably 0.7 μm or less. When the average particle diameter exceeds 1 μm, the peel strength of the conductor layer formed by plating tends to decrease. If the average particle size of the inorganic filler is too small, when the epoxy resin composition is used as a resin varnish, the viscosity of the varnish tends to increase and the handleability tends to decrease. It is preferable that it is 05 μm or more. The inorganic filler is preferably surface-treated with a surface treatment agent such as an epoxy silane coupling agent, an aminosilane coupling agent, or a titanate coupling agent in order to improve moisture resistance. Two or more inorganic fillers may be used in combination.
上記無機充填材の平均粒径はミー（Mie）散乱理論に基づくレーザー回折・散乱法により測定することができる。具体的にはレーザー回折式粒度分布測定装置により、無機充填材の粒度分布を体積基準で作成し、そのメディアン径を平均粒径とすることで測定することができる。測定サンプルは、無機充填材を超音波により水中に分散させたものを好ましく使用することができる。レーザー回折式粒度分布測定装置としては、（株）堀場製作所製 ＬＡ−５００等を使用することができる。 The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be created on a volume basis by a laser diffraction particle size distribution measuring device, and the median diameter can be measured as the average particle diameter. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As a laser diffraction type particle size distribution measuring apparatus, LA-500 manufactured by Horiba Ltd. can be used.
当該無機充填材を配合する場合の、エポキシ樹脂組成物（不揮発成分１００重量％）中の含有量は樹脂組成物に要求される特性によっても異なるが、１０〜７０重量％であるのが好ましく、１５〜６０重量％がより好ましい。無機充填材の含有量が小さすぎると、硬化物の線膨張率が高くなる傾向にあり、含有量が大きすぎると接着フィルムを調製する際にフィルム化が困難となったり、硬化物が脆くなる傾向にある When the inorganic filler is blended, the content in the epoxy resin composition (non-volatile component 100% by weight) varies depending on the properties required for the resin composition, but is preferably 10 to 70% by weight, 15-60 wt% is more preferable. If the content of the inorganic filler is too small, the linear expansion coefficient of the cured product tends to be high. If the content is too large, film formation becomes difficult when the adhesive film is prepared, or the cured product becomes brittle. There is a tendency
本発明のエポキシ樹脂組成物は、硬化時間および硬化温度を調整する等の目的で硬化促進剤を含有してもよい。硬化促進剤としては、例えば、ＴＰＰ、ＴＰＰ−Ｋ、ＴＰＰ−Ｓ、ＴＰＴＰ−Ｓ（北興化学工業（株）商品名）などの有機ホスフィン化合物、キュアゾール２ＭＺ、２Ｅ４ＭＺ、Ｃ１１Ｚ、Ｃ１１Ｚ−ＣＮ、Ｃ１１Ｚ−ＣＮＳ、Ｃ１１Ｚ−Ａ、２ＭＺ−ＯＫ、２ＭＡ−ＯＫ、２ＰＨＺ（四国化成工業（株）商品名）などのイミダゾール化合物、ノバキュア（旭化成工業（株）商品名）、フジキュア（富士化成工業（株）商品名）などのアミンアダクト化合物、１，８−ジアザビシクロ［５，４，０］ウンデセン−７、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）フェノールなどのアミン化合物が挙げられる。硬化促進剤は２種以上を併用してもよい。本発明のエポキシ樹脂組成物において、硬化促進剤の含有量は、エポキシ樹脂組成物中に含まれるエポキシ樹脂とフェノール性硬化剤の総量を１００重量％（不揮発成分）とした場合、通常０．１〜５重量％の範囲で使用される。 The epoxy resin composition of the present invention may contain a curing accelerator for the purpose of adjusting the curing time and the curing temperature. Examples of the curing accelerator include organic phosphine compounds such as TPP, TPP-K, TPP-S, and TPTP-S (trade name of Hokuko Chemical Co., Ltd.), Curesol 2MZ, 2E4MZ, C11Z, C11Z-CN, C11Z- Imidazole compounds such as CNS, C11Z-A, 2MZ-OK, 2MA-OK, 2PHZ (trade names of Shikoku Kasei Kogyo Co., Ltd.), Novacure (trade names of Asahi Kasei Kogyo Co., Ltd.), Fuji Cure (products of Fuji Kasei Kogyo Co., Ltd.) Amine adduct compounds such as 1, 8-diazabicyclo [5,4,0] undecene-7, 4-dimethylaminopyridine, benzyldimethylamine, amines such as 2,4,6-tris (dimethylaminomethyl) phenol Compounds. Two or more curing accelerators may be used in combination. In the epoxy resin composition of the present invention, the content of the curing accelerator is usually 0.1 when the total amount of the epoxy resin and the phenolic curing agent contained in the epoxy resin composition is 100% by weight (nonvolatile component). Used in the range of ˜5% by weight.
本発明のエポキシ樹脂組成物は、硬化物の機械強度を高める、応力緩和効果等の目的で固体状のゴム粒子を含有してもよい。本発明におけるゴム粒子は、エポキシ樹脂組成物を調製する際の有機溶媒にも溶解せず、エポキシ樹脂等の樹脂組成物中の成分とも相溶せず、エポキシ樹脂組成物のワニス中では分散状態で存在するものである。このようなゴム粒子は、一般には、ゴム成分の分子量を有機溶剤や樹脂に溶解しないレベルまで大きくし、粒子状とすることで調製される。ゴム粒子は２種以上を併用してもよい。ゴム粒子としては、例えば、コアシェル型ゴム粒子、架橋アクリルニトリルブタジエンゴム粒子、架橋スチレンブタジエンゴム粒子、アクリルゴム粒子などが挙げられる。コアシェル型ゴム粒子は、粒子がコア層とシェル層を有するゴム粒子であり、例えば、外層のシェル層がガラス状ポリマー、内層のコア層がゴム状ポリマーで構成される２層構造、または外層のシェル層がガラス状ポリマー、中間層がゴム状ポリマー、コア層がガラス状ポリマーで構成される３層構造のものなどが挙げられる。ガラス層は例えば、メタクリル酸メチルの重合物などで構成され、ゴム状ポリマー層は例えば、ブチルアクリレート重合物（ブチルゴム）などで構成される。コアシェル型ゴム粒子の具体例としては、スタフィロイドＡＣ３８３２、ＡＣ３８１６Ｎ、（ガンツ化成（株）商品名）、メタブレンＷ-５５００（三菱レイヨン（株）商品名）が挙げられる。アクリロニトリルブタジエンゴム（ＮＢＲ）粒子の具体例としては、ＸＥＲ-９１（平均粒径０．５μｍ、ＪＳＲ（株）製）などが挙げられる。スチレンブタジエンゴム（ＳＢＲ）粒子の具体例としては、ＸＳＫ-５００（平均粒径０．５μｍ、ＪＳＲ（株）製）などが挙げられる。アクリルゴム粒子の具体例としては、メタブレンＷ３００Ａ（平均粒径０．１μｍ）、Ｗ４５０Ａ（平均粒径０．５μｍ）（三菱レイヨン（株）製）を挙げることができる。 The epoxy resin composition of the present invention may contain solid rubber particles for the purpose of increasing the mechanical strength of the cured product and for the purpose of stress relaxation. The rubber particles in the present invention are not dissolved in an organic solvent when preparing the epoxy resin composition, are not compatible with components in the resin composition such as an epoxy resin, and are dispersed in the varnish of the epoxy resin composition. Exist. Such rubber particles are generally prepared by increasing the molecular weight of the rubber component to a level at which it does not dissolve in an organic solvent or resin and making it into particles. Two or more rubber particles may be used in combination. Examples of the rubber particles include core-shell type rubber particles, cross-linked acrylonitrile butadiene rubber particles, cross-linked styrene butadiene rubber particles, and acrylic rubber particles. The core-shell type rubber particles are rubber particles having a core layer and a shell layer. For example, the outer shell layer is a glassy polymer and the inner core layer is a rubbery polymer. Examples include a three-layer structure in which the shell layer is a glassy polymer, the intermediate layer is a rubbery polymer, and the core layer is a glassy polymer. The glass layer is made of, for example, a polymer of methyl methacrylate, and the rubbery polymer layer is made of, for example, a butyl acrylate polymer (butyl rubber). Specific examples of the core-shell type rubber particles include Staphyloid AC3832, AC3816N, (Ganz Kasei Co., Ltd. trade name), and Metabrene W-5500 (Mitsubishi Rayon Co., Ltd. trade name). Specific examples of acrylonitrile butadiene rubber (NBR) particles include XER-91 (average particle size 0.5 μm, manufactured by JSR Corporation). Specific examples of styrene butadiene rubber (SBR) particles include XSK-500 (average particle size 0.5 μm, manufactured by JSR Corporation). Specific examples of the acrylic rubber particles include Methbrene W300A (average particle size 0.1 μm), W450A (average particle size 0.5 μm) (manufactured by Mitsubishi Rayon Co., Ltd.).
配合するゴム粒子の平均粒径は０．００５〜１μｍの範囲が好ましく、０．２〜０．６μｍの範囲がより好ましい。本発明におけるゴム粒子の平均粒径は、動的光散乱法を用いて測定することが出来る。例えば、適当な有機溶剤にゴム粒子を超音波などにより均一に分散させ、ＦＰＲＡ−１０００（大塚電子（株）社製）を用いて、ゴム粒子の粒度分布を重量基準で作成し、そのメディアン径を平均粒径とすることで測定することができる。 The average particle size of the rubber particles to be blended is preferably in the range of 0.005 to 1 μm, and more preferably in the range of 0.2 to 0.6 μm. The average particle diameter of the rubber particles in the present invention can be measured using a dynamic light scattering method. For example, rubber particles are uniformly dispersed in a suitable organic solvent by ultrasonic waves, etc., and the particle size distribution of the rubber particles is prepared on a weight basis using FPRA-1000 (manufactured by Otsuka Electronics Co., Ltd.). The average particle size can be measured.
当該ゴム粒子を配合する場合の、エポキシ樹脂組成物の不揮発成分を１００重量％とすると、エポキシ樹脂組成物中の含有量は、０．５〜１０重量％であるのが好ましく、１〜４重量％がより好ましい。 When the non-volatile component of the epoxy resin composition when blending the rubber particles is 100% by weight, the content in the epoxy resin composition is preferably 0.5 to 10% by weight, and preferably 1 to 4% by weight. % Is more preferable.
本発明のエポキシ樹脂組成物は、本発明の効果を損なわない範囲で難燃剤を含有しても良い。難燃剤としては、例えば、有機リン系難燃剤、有機系窒素含有リン化合物、窒素化合物、シリコーン系難燃剤、金属水酸化物等が挙げられる。有機リン系難燃剤としては、三光（株）製のＨＣＡ、ＨＣＡ−ＨＱ、ＨＣＡ−ＮＱ等のホスフィン化合物、昭和高分子（株）製のＨＦＢ−２００６Ｍ等のリン含有ベンゾオキサジン化合物、味の素ファインテクノ（株）製のレオフォス３０、５０、６５、９０、１１０、ＴＰＰ、ＲＰＤ、ＢＡＰＰ、ＣＰＤ、ＴＣＰ、ＴＸＰ、ＴＢＰ、ＴＯＰ、ＫＰ１４０、ＴＩＢＰ、北興化学工業（株）製のＰＰＱ、クラリアント（株）製のＯＰ９３０、大八化学（株）製のＰＸ２００等のリン酸エステル化合物、東都化成（株）製のＦＸ２８９、ＦＸ３１０等のリン含有エポキシ樹脂、東都化成（株）製のＥＲＦ００１等のリン含有フェノキシ樹脂等が挙げられる。有機系窒素含有リン化合物としては、四国化成工業（株）製のＳＰ６７０、ＳＰ７０３等のリン酸エステルミド化合物、大塚化学（株）社製のＳＰＢ１００、ＳＰＥ１００等のホスファゼン化合物等が挙げられる。金属水酸化物としては、宇部マテリアルズ（株）製のＵＤ６５、ＵＤ６５０、ＵＤ６５３等の水酸化マグネシウム、巴工業（株）社製のＢ−３０、Ｂ−３２５、Ｂ−３１５、Ｂ−３０８、Ｂ−３０３、ＵＦＨ−２０等の水酸化アルミニウム等が挙げられる。難燃剤は２種以上を併用してもよい。 The epoxy resin composition of the present invention may contain a flame retardant as long as the effects of the present invention are not impaired. Examples of the flame retardant include an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone flame retardant, and a metal hydroxide. Examples of organophosphorus flame retardants include phosphine compounds such as HCA, HCA-HQ, and HCA-NQ manufactured by Sanko Co., Ltd., phosphorus-containing benzoxazine compounds such as HFB-2006M manufactured by Showa Polymer Co., Ltd., and Ajinomoto Fine Techno. Reefos 30, 50, 65, 90, 110, TPP, RPD, BAPP, CPD, TCP, TXP, TBP, TOP, KP140, TIBP, PPQ manufactured by Hokuko Chemical Co., Ltd., Clariant Phosphorus ester compounds such as OP930 manufactured by Daihachi Chemical Co., Ltd., PX200 manufactured by Daihachi Chemical Co., Ltd., phosphorus-containing epoxy resins such as FX289 manufactured by Toto Kasei Co., Ltd., and FX310, and phosphorus-containing phenoxy such as ERF001 manufactured by Toto Kasei Co., Ltd. Examples thereof include resins. Examples of the organic nitrogen-containing phosphorus compound include phosphate ester compounds such as SP670 and SP703 manufactured by Shikoku Kasei Kogyo Co., and phosphazene compounds such as SPB100 and SPE100 manufactured by Otsuka Chemical Co., Ltd. As the metal hydroxide, magnesium hydroxide such as UD65, UD650, UD653 manufactured by Ube Materials Co., Ltd., B-30, B-325, B-315, B-308 manufactured by Sakai Kogyo Co., Ltd. Examples thereof include aluminum hydroxide such as B-303 and UFH-20. Two or more flame retardants may be used in combination.
本発明のエポキシ樹脂組成物は、本発明の効果が発揮される範囲で、上述した以外の他の各種樹脂添加剤を任意で含有しても良い。樹脂添加剤としては、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。 The epoxy resin composition of the present invention may optionally contain various resin additives other than those described above as long as the effects of the present invention are exhibited. Examples of the resin additive include organic fillers such as silicon powder, nylon powder, and fluorine powder, thickeners such as olben and benton, silicone-based, fluorine-based, polymer-based antifoaming agents or leveling agents, imidazole-based, Examples thereof include adhesion imparting agents such as thiazole, triazole, and silane coupling agents, and coloring agents 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繊維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 fiber 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のアミド系溶媒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. , Aromatic hydrocarbons such as toluene and xylene, amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. 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。乾燥条件は、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。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。 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. As drying conditions, suitable drying conditions can be appropriately set by simple experiments. 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.
接着フィルムにおいて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５〜８０μｍ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。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。 The thickness of the resin composition layer formed in the adhesive film 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 80 μm, the thickness of the resin composition layer is preferably 10 to 100 μm. The resin composition layer may be protected by a protective film described 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も特に制限されないが、通常１〜４０μｍ、好ましくは１０〜３０μｍの範囲で用いられる。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. The thickness of the protective film is not particularly limited, but is usually 1 to 40 μm, preferably 10 to 30 μm. In addition, as will be described later, a support film used as a support in the production process of the adhesive film can also 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、また硬化後の絶縁層の表面平滑性を向上させることができる。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 step can be prevented, and the surface smoothness of the insulating layer after curing can be improved. 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、空気圧が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.
本発明における内層回路基板とは、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を製造する際に、さらに絶縁層および導体層が形成されるべき中間製造物も本発明における内層回路基板に含まれる。内層回路基板において、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内層回路基板への密着性の観点から好ましい。 The inner layer circuit board in the present invention is mainly a conductor 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, etc. The one formed by. In addition, when manufacturing a multilayer printed wiring board in which conductor layers and insulating layers are alternately formed, and one or both surfaces are patterned conductor layers (circuits), an insulating layer and a conductor layer are further formed. The intermediate product to be included is also included in the inner layer circuit board in the present invention. In the inner layer circuit board, the surface of the conductor circuit layer is preferably roughened by a blackening process or the like from the viewpoint of adhesion of the insulating layer to the inner layer 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、絶縁層表面に粗化処理を行う。本発明における粗化処理は通常、酸化剤を使用した湿式粗化方法で行うのが好ましい。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, a roughening process is performed on the surface of the insulating layer. The roughening treatment in the present invention is usually preferably carried out by a wet roughening method using 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.
絶縁層表面を粗化処理した粗化面の粗さは、微細配線を形成する上で、Ｒａ値で０．５μｍ以下であるのが好ましい。なお、Ｒａ値とは、表面粗さを表す数値の一種であり、算術平均粗さと呼ばれるものであって、具体的には測定領域内で変化する高さの絶対値を平均ラインである表面から測定して算術平均したものである。例えば、ビーコインスツルメンツ社製ＷＹＫＯ ＮＴ３３００を用いて、VSIコンタクトモード、５０倍レンズにより測定範囲を１２１μｍ×９２μｍとして得られる数値により求めることができる。 The roughness of the roughened surface obtained by roughening the surface of the insulating layer is preferably 0.5 μm or less in terms of Ra when forming fine wiring. The Ra value is a kind of numerical value representing the surface roughness, and is called arithmetic average roughness. Specifically, the absolute value of the height changing in the measurement region is determined from the surface that is the average line. Measured and arithmetically averaged. For example, using WYKO NT3300 manufactured by Becoin Instruments Co., Ltd., it can be obtained from a numerical value obtained with a measurement range of 121 μm × 92 μm using a VSI contact mode and a 50 × lens.
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、無電解メッキと電解メッキ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メッキレジストを形成し、無電解メッキ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。導体層のピール強度は、０．６ｋｇｆ／ｃｍ以上であるのが好ましい。 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. Alternatively, 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. The peel strength of the conductor layer is preferably 0.6 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繊維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繊維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 fiber 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 fiber base material which consists of fibers.
繊維からなるシート状繊維基材としては、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 fiber base material composed of fibers, for example, glass cloth and aramid fibers, which are commonly used as prepreg 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、それをシート状繊維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繊維基材を浸漬し、樹脂ワニスをシート状繊維基材に含浸させ、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 fiber 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 fiber base material is immersed in a resin varnish obtained by dissolving a resin in an organic solvent, the resin varnish is impregnated into the sheet-like fiber 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（４９×１０４〜３９２×１０４Ｎ／ｍ２）、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、前述の方法と同様、酸化剤により硬化したプリプレグ表面を粗化した後、導体層をメッキにより形成することで、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 (49 × 10 4 to 392 × 10 4 N / m 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, in the same manner as described above, the surface of the prepreg cured with an oxidizing agent is roughened, and then the conductor layer is formed by plating, whereby a multilayer printed wiring board can be manufactured.
以下、実施例及び比較例を用いて本発明をより詳細に説明するが、これらは本発明をいかなる意味においても制限するものではない。なお、以下の記載において、「部」は「重量部」を意味する。 EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example and a comparative example, these do not restrict | limit this invention in any meaning. In the following description, “parts” means “parts by weight”.
液状ビスフェノールＡ型エポキシ樹脂（エポキシ当量１８０、ジャパンエポキシレジン（株）製「ｊＥＲ８２８ＥＬ」）３０部と、ビフェニル型エポキシ樹脂（エポキシ当量２９１、日本化薬（株）製「ＮＣ３０００Ｈ」）３０部、マレイミド化合物として３，３’−ジメチル−５，５’−ジエチル−４，４’−ジフェニルメタンビスマレイミド（ケイ・アイ化成（株）製ＢＭＩ−７０）５部とをメチルエチルケトン（以下「ＭＥＫ」と略称する。）１５部、シクロヘキサノン１５部に撹拌しながら加熱溶解させた。そこへ、活性エステル化合物（ＤＩＣ（株）製「ＥＸＢ９４６０−６５Ｔ」、活性エステル当量２２３、固形分６５％のトルエン溶液）４０部、トリアジン構造を有するフェノール樹脂（ＤＩＣ（株）製「ＬＡ７０５２」、フェノール水酸基当量１２０、固形分６０％のＭＥＫ溶液）１５部、硬化触媒（広栄化学工業（株）製、「４−ジメチルアミノピリジン」）０．５部、球形シリカ（平均粒径０．５μｍ、アミノシラン処理付「ＳＯ−Ｃ２」（株）アドマテックス製）１１０部、フェノキシ樹脂（ジャパンエポキシレジン（株）製「ＹＸ６９５４ＢＨ３０」不揮発分３０重量％のＭＥＫとシクロヘキサノンの１：１溶液）４０部を混合し、高速回転ミキサーで均一に分散して、樹脂ワニスを作製した（固形分２２２部、シリカ５０重量％、エポキシ基と硬化剤の反応基の比率１：０．７２）。
次に、かかる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」と略称する。）上に、乾燥後の樹脂厚みが４０μｍ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（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。
30 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, “jER828EL” manufactured by Japan Epoxy Resin Co., Ltd.), 30 parts biphenyl type epoxy resin (epoxy equivalent 291; “NC3000H” manufactured by Nippon Kayaku Co., Ltd.), maleimide As a compound, 5 parts of 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide (BMI-70 manufactured by Kay Kasei Co., Ltd.) and methyl ethyl ketone (hereinafter “MEK”) are abbreviated. .) 15 parts and 15 parts of cyclohexanone were heated and dissolved with stirring. There, 40 parts of active ester compound (“EXB 9460-65T” manufactured by DIC Corporation, active ester equivalent 223, 65% solid content toluene solution), phenol resin having triazine structure (“LA 7052” manufactured by DIC Corporation), Phenol hydroxyl group equivalent 120, MEK solution 60% solid content 15 parts, curing catalyst (manufactured by Guangei Chemical Industry Co., Ltd., “4-dimethylaminopyridine”) 0.5 part, spherical silica (average particle size 0.5 μm, 110 parts of "SO-C2" (manufactured by Admatechs Co., Ltd.) with aminosilane treatment and 40 parts of phenoxy resin ("YX6954BH30" manufactured by Japan Epoxy Resin Co., Ltd., a 30% non-volatile MEK and cyclohexanone 1: 1 solution) are mixed. And uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish (solid content 222 parts, silica 50 wt% The ratio of the reactive groups of the epoxy group and the curing agent 1: 0.72).
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 40 μm, and 80 to 120 ° C. (average (100 ° C.) for 6 minutes (residual solvent amount: 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.
（比較例１）
液状ビスフェノールＡ型エポキシ樹脂（エポキシ当量１８０、ジャパンエポキシレジン（株）製「ｊＥＲ８２８ＥＬ」）３０部と、ビフェニル型エポキシ樹脂（エポキシ当量２９１、日本化薬（株）製「NＣ３０００H」）３０部、マレイミド化合物として３，３’−ジメチル−５，５’−ジエチル−４，４’−ジフェニルメタンビスマレイミド（ケイ・アイ化成（株）製ＢＭＩ−７０）５部とをメチルエチルケトン（以下「ＭＥＫ」と略称する。）１５部、シクロヘキサノン１５部に撹拌しながら加熱溶解させた。そこへ、トリアジン構造を有するフェノール樹脂（ＤＩＣ（株）製「ＬＡ７０５２」、フェノール水酸基当量１２０、固形分６０％のＭＥＫ溶液）４０部、硬化触媒（広栄化学工業（株）製、「４−ジメチルアミノピリジン」）０．５部、球形シリカ（平均粒径０．５μｍ、アミノシラン処理付「ＳＯ−Ｃ２」（株）アドマテックス製）１００部、フェノキシ樹脂（ジャパンエポキシレジン（株）製「ＹＸ６９５４ＢＨ３０」不揮発分３０重量％のＭＥＫ溶液）４０部を混合し、高速回転ミキサーで均一に分散して、樹脂ワニスを作製した（固形分２０１部、シリカ５０重量％、エポキシ基と硬化剤の反応基の比率１：０．７５）。次に、かかる樹脂ワニスを使用し、実施例１と全く同様にして接着フィルムを得た。
(Comparative Example 1)
30 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, “jER828EL” manufactured by Japan Epoxy Resin Co., Ltd.), 30 parts biphenyl type epoxy resin (epoxy equivalent 291; “NC3000H” manufactured by Nippon Kayaku Co., Ltd.), maleimide As a compound, 5 parts of 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide (BMI-70 manufactured by Kay Kasei Co., Ltd.) and methyl ethyl ketone (hereinafter “MEK”) are abbreviated. .) 15 parts and 15 parts of cyclohexanone were heated and dissolved with stirring. Thereto, 40 parts of a phenol resin having a triazine structure (“LA7052” manufactured by DIC Corporation, a MEK solution having a phenol hydroxyl equivalent of 120 and a solid content of 60%), a curing catalyst (manufactured by Guangei Chemical Industry Co., Ltd., “4-dimethyl "Aminopyridine") 0.5 parts, spherical silica (average particle size 0.5 µm, aminosilane-treated "SO-C2" manufactured by Admatechs) 100 parts, phenoxy resin (Japan Epoxy Resins "YX6954BH30") 40 parts of MEK solution having a nonvolatile content of 30 wt% was mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish (solid content of 201 parts, silica 50 wt%, epoxy group and curing agent reactive group) Ratio 1: 0.75). Next, using this resin varnish, an adhesive film was obtained in the same manner as in Example 1.
（比較例２）
液状ビスフェノールＡ型エポキシ樹脂（エポキシ当量１８０、ジャパンエポキシレジン（株）製「ｊＥＲ８２８ＥＬ」）３０部と、ビフェニル型エポキシ樹脂（エポキシ当量２９１、日本化薬（株）製「NＣ３０００H」）３０部とをメチルエチルケトン（以下「ＭＥＫ」と略称する。）１５部、シクロヘキサノン１５部に撹拌しながら加熱溶解させた。そこへ、活性エステル化合物（DIC（株）製「ＥＸＢ９４６０−６５Ｔ」、活性エステル当量２２３、固形分６５％のトルエン溶液）４０部、フェノール系硬化剤ＬＡ７０５２（ＤＩＣ（株）製、フェノール水酸基当量１２０、固形分６０％のＭＥＫ溶液）１５部、硬化触媒（広栄化学工業（株）製、「４−ジメチルアミノピリジン」）０．５部、球形シリカ（平均粒径０．５μｍ、アミノシラン処理付「ＳＯ−Ｃ２」（株）アドマテックス製）１００部、フェノキシ樹脂（ジャパンエポキシレジン（株）製「ＹＸ６９５４ＢＨ３０」不揮発分３０重量％のＭＥＫ溶液）４０部を混合し、高速回転ミキサーで均一に分散して、樹脂ワニスを作製した（固形分２０７部、シリカ４８重量％、エポキシ基とエポキシ硬化剤の反応基の比率１：０．７２）。次に、かかる樹脂ワニスを使用し、実施例１と全く同様にして接着フィルムを得た。
(Comparative Example 2)
30 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, "jER828EL" manufactured by Japan Epoxy Resin Co., Ltd.) and 30 parts biphenyl type epoxy resin (epoxy equivalent 291; "NC3000H" manufactured by Nippon Kayaku Co., Ltd.) The mixture was heated and dissolved in 15 parts of methyl ethyl ketone (hereinafter abbreviated as “MEK”) and 15 parts of cyclohexanone with stirring. Thereto, 40 parts of an active ester compound (“EXB 9460-65T” manufactured by DIC Corporation, active ester equivalent 223, 65% solid content toluene solution), phenolic curing agent LA7052 (manufactured by DIC Corporation, phenol hydroxyl equivalent 120) , 15 parts of MEK solution with a solid content of 60%, 0.5 parts of a curing catalyst (manufactured by Guangei Chemical Industry Co., Ltd., “4-dimethylaminopyridine”), spherical silica (average particle size 0.5 μm, with aminosilane treatment “ 100 parts of “SO-C2” (manufactured by Admatechs) and 40 parts of phenoxy resin (“YX6954BH30” manufactured by Japan Epoxy Resin Co., Ltd., MEK solution with a nonvolatile content of 30% by weight) are mixed and dispersed uniformly with a high-speed rotary mixer. Thus, a resin varnish was prepared (solid content: 207 parts, silica: 48 wt%, ratio of epoxy group to epoxy curing agent reactive group: 1: 0.7 ). Next, using this resin varnish, an adhesive film was obtained in the same manner as in Example 1.
（比較例３）
液状ビスフェノールＡ型エポキシ樹脂（エポキシ当量１８０、ジャパンエポキシレジン（株）製「ｊＥＲ８２８ＥＬ」）３０部と、ビフェニル型エポキシ樹脂（エポキシ当量２９１、日本化薬（株）製「NＣ３０００H」）３０部、マレイミド化合物として３，３’−ジメチル−５，５’−ジエチル−４，４’−ジフェニルメタンビスマレイミド（ケイ・アイ化成（株）製ＢＭＩ−７０）５部とをメチルエチルケトン（以下「ＭＥＫ」と略称する。）１５部、シクロヘキサノン１５部に撹拌しながら加熱溶解させた。そこへ、フェノール系硬化剤ＳＮ４８５（東都化成（株）製、フェノール水酸基当量２１５）の５０％ＭＥＫ溶液６０部、硬化触媒（広栄化学工業（株）製、「４−ジメチルアミノピリジン」）０．５部、球形シリカ（平均粒径０．５μｍ、アミノシラン処理付「ＳＯ−Ｃ２」（株）アドマテックス製）１２０部、フェノキシ樹脂（ジャパンエポキシレジン（株）製「ＹＸ６９５４ＢＨ３０」不揮発分３０質量％のＭＥＫ溶液）３０部を混合し、高速回転ミキサーで均一に分散して、樹脂ワニスを作製した（固形分２４９、シリカ４８重量％、エポキシ基とエポキシ硬化剤の反応基の比率１：０．８７）。次に、かかる樹脂ワニスを使用し、実施例１と全く同様にして接着フィルムを得た。
(Comparative Example 3)
30 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, “jER828EL” manufactured by Japan Epoxy Resin Co., Ltd.), 30 parts biphenyl type epoxy resin (epoxy equivalent 291; “NC3000H” manufactured by Nippon Kayaku Co., Ltd.), maleimide As a compound, 5 parts of 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide (BMI-70 manufactured by Kay Kasei Co., Ltd.) and methyl ethyl ketone (hereinafter “MEK”) are abbreviated. .) 15 parts and 15 parts of cyclohexanone were heated and dissolved with stirring. There, 60 parts of 50% MEK solution of phenolic curing agent SN485 (manufactured by Tohto Kasei Co., Ltd., phenol hydroxyl group equivalent 215), curing catalyst (manufactured by Guangei Chemical Industry Co., Ltd., “4-dimethylaminopyridine”) 0. 5 parts, 120 parts of spherical silica (average particle size 0.5 μm, “SO-C2” with aminosilane treatment, manufactured by Admatechs), phenoxy resin (“YX6954BH30”, manufactured by Japan Epoxy Resins Co., Ltd.) with a nonvolatile content of 30% by mass 30 parts of MEK solution) was mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish (solid content 249, silica 48% by weight, ratio of epoxy group to epoxy curing agent reactive group 1: 0.87). ). Next, using this resin varnish, an adhesive film was obtained in the same manner as in Example 1.
＜ピール強度およびRa値測定用サンプルの調製＞ <Preparation of peel strength and Ra value measurement sample>
（１）積層板の下地処理
内層回路の形成された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０．３ｍｍ、松下電工（株）製Ｒ５７１５ＥＳ］の両面をメック（株）製ＣＺ８１００に浸漬して銅表面の粗化処理をおこなった。
(1) Substrate treatment of laminated board Both sides of glass cloth base epoxy resin double-sided copper-clad laminated board [copper foil thickness 18 μm, substrate thickness 0.3 mm, Matsushita Electric Works R5715ES] on which an inner layer circuit is formed The copper surface was roughened by dipping in CZ8100 manufactured by MEC Co., Ltd.
（２）接着フィルムのラミネート
実施例及び比較例で作成した接着フィルムを、バッチ式真空加圧ラミネーターＭＶＬＰ-５００（（株）名機製作所製、商品名）を用いて、積層板の両面にラミネートした。ラミネートは、３０秒間減圧して気圧を１３ｈPa以下とし、その後３０秒間、１００℃、圧力０．７４MPaでプレスすることにより行った。
(2) Lamination of adhesive film Adhesive films created in Examples and Comparative Examples are laminated on both sides of a laminate using a batch type vacuum pressure laminator MVLP-500 (trade name, manufactured by Meiki Seisakusho Co., Ltd.). did. Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressing at 100 ° C. and a pressure of 0.74 MPa for 30 seconds.
（３）樹脂組成物の硬化
ラミネートされた接着フィルムからＰＥＴフィルムを剥離し、１８０℃、３０分の硬化条件で樹脂組成物を硬化した。
(3) Curing of resin composition The PET film was peeled from the laminated adhesive film, and the resin composition was cured under curing conditions of 180 ° C for 30 minutes.
（４）粗化処理
積層板を、膨潤液である、アトテックジャパン（株）のジエチレングリコールモノブチルエーテル含有のスエリングディップ・セキュリガンドＰに６０℃で５分間浸漬し、次に粗化液として、アトテックジャパン（株）のコンセントレート・コンパクトＰ（ＫＭｎＯ４：６０ｇ／Ｌ、ＮａＯＨ：４０ｇ／Ｌの水溶液）に８０℃で２０分間浸漬、最後に中和液として、アトテックジャパン（株）のリダクションショリューシン・セキュリガントＰに４０℃で５分間浸漬した。この粗化処理後の積層板について、絶縁層の算術表面粗さ（Ｒａ）の測定を行った。
(4) Roughening treatment The laminate is immersed in a swelling dip secu-ligand P containing diethylene glycol monobutyl ether of Atotech Japan Co., Ltd. for 5 minutes at 60 ° C., and then used as a roughening solution. Soaked in Concentrate Compact P (KMnO4: 60 g / L, NaOH: 40 g / L aqueous solution) at 80 ° C. for 20 minutes, and finally as a neutralizing solution, Atotech Japan Co., Ltd. It was immersed in securigant P at 40 ° C. for 5 minutes. About the laminated board after this roughening process, the arithmetic surface roughness (Ra) of the insulating layer was measured.
（５）セミアディティブ工法によるメッキ
絶縁層表面に回路を形成するために、積層板を、ＰｄＣｌ２を含む無電解メッキ用溶液に浸漬し、次に無電解銅メッキ液に浸漬した。１５０℃にて３０分間加熱してアニール処理を行った後に、エッチングレジストを形成し、エッチングによるパターン形成の後に、硫酸銅電解メッキを行い、３０±５μｍの厚さで導体層を形成した。次に、アニール処理を１８０℃にて６０分間行った。この積層板についてメッキ銅のピール強度の測定を行った。
(5) Plating by semi-additive method In order to form a circuit on the surface of the insulating layer, the laminate was immersed in an electroless plating solution containing PdCl 2 and then immersed in an electroless copper plating solution. After annealing for 30 minutes at 150 ° C., an etching resist was formed. After pattern formation by etching, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 30 ± 5 μm. Next, annealing was performed at 180 ° C. for 60 minutes. About this laminated board, the peel strength of the plated copper was measured.
［メッキ導体層の引き剥がし強さ（ピール強度）］
積層板の導体層に、幅１０ｍｍ、長さ１００ｍｍの部分の切込みをいれ、この一端を剥がしてつかみ具で掴み、室温中にて、５０ｍｍ／分の速度で垂直方向に３５ｍｍを引き剥がした時の荷重を測定した。
[Peeling strength of plating conductor layer (peel strength)]
When the conductor layer of the laminate is cut into a 10 mm wide and 100 mm long part, this end is peeled off and gripped with a gripping tool, and 35 mm is peeled off vertically at a speed of 50 mm / min at room temperature. The load of was measured.
［粗化後の算術表面粗さ（Ｒａ）］
非接触型表面粗さ計（ビーコインスツルメンツ社製ＷＹＫＯ ＮＴ３３００）を用いて、VSIコンタクトモード、５０倍レンズにより測定範囲を１２１μｍ×９２μｍとして得られる数値によりＲａの値を求めた。また１０点の平均粗さを求めることにより測定した。
[Arithmetic surface roughness (Ra) after roughening]
Using a non-contact type surface roughness meter (BYCO Instruments WYKO NT3300), the Ra value was obtained from a numerical value obtained with a VSI contact mode and a 50 × lens with a measurement range of 121 μm × 92 μm. Moreover, it measured by calculating | requiring the average roughness of 10 points | pieces.
［線膨張係数の評価］
実施例１〜３および比較例１〜４で得られた接着フィルムを１９０℃で９０分熱硬化させてシート状の硬化物を得た。その硬化物を、幅約５ｍｍ、長さ約１５ｍｍの試験片に切断し、（株）リガク製熱機械分析装置（Ｔｈｅｒｍｏ Ｐｌｕｓ ＴＭＡ８３１０）を使用して、引張加重法で熱機械分析を行った。試験片を前記装置に装着後、荷重１ｇ、昇温速度５℃／分の測定条件にて連続して２回測定した。２回目の測定における２５℃から１５０℃までの平均線熱膨張率を算出した。
[Evaluation of linear expansion coefficient]
The adhesive films obtained in Examples 1 to 3 and Comparative Examples 1 to 4 were thermally cured at 190 ° C. for 90 minutes to obtain sheet-like cured products. The cured product was cut into a test piece having a width of about 5 mm and a length of about 15 mm, and thermomechanical analysis was performed by a tensile load method using a thermomechanical analyzer manufactured by Rigaku Corporation (Thermo Plus TMA8310). After mounting the test piece on the apparatus, the test piece was measured twice continuously under the measurement conditions of a load of 1 g and a heating rate of 5 ° C./min. The average linear thermal expansion coefficient from 25 ° C. to 150 ° C. in the second measurement was calculated.
実施例及び比較例で得られた接着フィルムを使用した評価サンプルのメッキ導体層のピール強度及び粗化後の表面粗さ（Ｒａ値）の結果および線膨張率測定の結果について下記の表１に記載した。表１から明らかなように実施例の評価サンプルは、表面粗度が低いにもかかわらずめっき導体層が高いピール強度を示し、さらに線膨張率も低い値となっている。一方、活性エステル化合物を含まない比較例１では表面粗度が高い値となっており、マレイミド化合物を含まない比較例２では、粗度及び線膨張率もが高い値となっており、トリアジン構造含有フェノール樹脂を含まず、活性エステル化合物で代用した比較例３では、表面粗度が実施例より高い値にもかかわらずピール強度が低く、また線膨張率が高い値を示している。 Table 1 below shows the results of peel strength and surface roughness (Ra value) of the plated conductor layer of the evaluation sample using the adhesive films obtained in Examples and Comparative Examples, and the results of linear expansion coefficient measurement. Described. As is apparent from Table 1, in the evaluation samples of the examples, the plated conductor layer exhibits high peel strength and the linear expansion coefficient is low even though the surface roughness is low. On the other hand, in Comparative Example 1 containing no active ester compound, the surface roughness is high, and in Comparative Example 2 containing no maleimide compound, the roughness and linear expansion coefficient are also high. In Comparative Example 3, which did not contain a phenol resin and was substituted with an active ester compound, the peel strength was low and the linear expansion coefficient was high, although the surface roughness was higher than that in Examples.
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