JP2014177530A - Resin composition - Google Patents
Resin composition Download PDFInfo
- Publication number
- JP2014177530A JP2014177530A JP2013051478A JP2013051478A JP2014177530A JP 2014177530 A JP2014177530 A JP 2014177530A JP 2013051478 A JP2013051478 A JP 2013051478A JP 2013051478 A JP2013051478 A JP 2013051478A JP 2014177530 A JP2014177530 A JP 2014177530A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- resin composition
- resin
- mass
- inorganic filler
- 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
- 239000011342 resin composition Substances 0.000 title claims abstract description 121
- 239000003822 epoxy resin Substances 0.000 claims abstract description 150
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 150
- 150000002148 esters Chemical group 0.000 claims abstract description 81
- 239000011256 inorganic filler Substances 0.000 claims abstract description 57
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 57
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 49
- 229920005989 resin Polymers 0.000 claims abstract description 27
- 239000011347 resin Substances 0.000 claims abstract description 27
- -1 glycidyl ester Chemical class 0.000 claims description 71
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 35
- 239000002313 adhesive film Substances 0.000 claims description 30
- 239000004593 Epoxy Substances 0.000 claims description 25
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 18
- 239000002648 laminated material Substances 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 15
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- 239000004065 semiconductor Substances 0.000 claims description 13
- 239000004305 biphenyl Substances 0.000 claims description 9
- 235000010290 biphenyl Nutrition 0.000 claims description 9
- JRPRCOLKIYRSNH-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,2-dicarboxylate Chemical compound C=1C=CC=C(C(=O)OCC2OC2)C=1C(=O)OCC1CO1 JRPRCOLKIYRSNH-UHFFFAOYSA-N 0.000 claims description 8
- XFUOBHWPTSIEOV-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohexane-1,2-dicarboxylate Chemical compound C1CCCC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 XFUOBHWPTSIEOV-UHFFFAOYSA-N 0.000 claims description 8
- 239000000539 dimer Substances 0.000 claims description 8
- 125000002723 alicyclic group Chemical group 0.000 claims description 7
- 239000002952 polymeric resin Substances 0.000 claims description 7
- 229920003002 synthetic resin Polymers 0.000 claims description 7
- NIYNIOYNNFXGFN-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol;7-oxabicyclo[4.1.0]heptane-4-carboxylic acid Chemical compound OCC1CCC(CO)CC1.C1C(C(=O)O)CCC2OC21.C1C(C(=O)O)CCC2OC21 NIYNIOYNNFXGFN-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 description 40
- 239000000047 product Substances 0.000 description 28
- 239000000243 solution Substances 0.000 description 24
- 239000004020 conductor Substances 0.000 description 18
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 16
- 239000007822 coupling agent Substances 0.000 description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 15
- 239000000758 substrate Substances 0.000 description 15
- 239000002966 varnish Substances 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 14
- 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 13
- 239000000463 material Substances 0.000 description 13
- 239000003960 organic solvent Substances 0.000 description 13
- 239000012756 surface treatment agent Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000007747 plating Methods 0.000 description 12
- 238000005259 measurement Methods 0.000 description 11
- 229920003986 novolac Polymers 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 238000011282 treatment Methods 0.000 description 11
- 206010042674 Swelling Diseases 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 230000008961 swelling Effects 0.000 description 10
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 238000010030 laminating Methods 0.000 description 9
- 238000007788 roughening Methods 0.000 description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 8
- 239000006087 Silane Coupling Agent Substances 0.000 description 8
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 125000004185 ester group Chemical group 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 230000001681 protective effect Effects 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-dioxonaphthalene Natural products C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 6
- BOKGTLAJQHTOKE-UHFFFAOYSA-N 1,5-dihydroxynaphthalene Chemical compound C1=CC=C2C(O)=CC=CC2=C1O BOKGTLAJQHTOKE-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 150000001491 aromatic compounds Chemical class 0.000 description 6
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- 238000003475 lamination Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- FZZQNEVOYIYFPF-UHFFFAOYSA-N naphthalene-1,6-diol Chemical compound OC1=CC=CC2=CC(O)=CC=C21 FZZQNEVOYIYFPF-UHFFFAOYSA-N 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 230000003014 reinforcing effect Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229920001187 thermosetting polymer Polymers 0.000 description 6
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 5
- 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 5
- 230000000694 effects Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- MNZMMCVIXORAQL-UHFFFAOYSA-N naphthalene-2,6-diol Chemical compound C1=C(O)C=CC2=CC(O)=CC=C21 MNZMMCVIXORAQL-UHFFFAOYSA-N 0.000 description 5
- 125000001624 naphthyl group Chemical group 0.000 description 5
- 229920006287 phenoxy resin Polymers 0.000 description 5
- 239000013034 phenoxy resin Substances 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- 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 4
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 4
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 4
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 4
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000005553 drilling Methods 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 239000005350 fused silica glass Substances 0.000 description 4
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 230000003472 neutralizing effect Effects 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-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
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- UMHKOAYRTRADAT-UHFFFAOYSA-N [hydroxy(octoxy)phosphoryl] octyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OP(O)(=O)OCCCCCCCC UMHKOAYRTRADAT-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000007772 electroless plating Methods 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 3
- 229960001553 phloroglucinol Drugs 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 3
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 2
- WGGNJZRNHUJNEM-UHFFFAOYSA-N 2,2,4,4,6,6-hexamethyl-1,3,5,2,4,6-triazatrisilinane Chemical compound C[Si]1(C)N[Si](C)(C)N[Si](C)(C)N1 WGGNJZRNHUJNEM-UHFFFAOYSA-N 0.000 description 2
- 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 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- YTTFFPATQICAQN-UHFFFAOYSA-N 2-methoxypropan-1-ol Chemical compound COC(C)CO YTTFFPATQICAQN-UHFFFAOYSA-N 0.000 description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 2
- 229940123208 Biguanide Drugs 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
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- YFONAHAKNVIHPT-UHFFFAOYSA-N [methyl-[[methyl(diphenyl)silyl]amino]-phenylsilyl]benzene Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(C)N[Si](C)(C=1C=CC=CC=1)C1=CC=CC=C1 YFONAHAKNVIHPT-UHFFFAOYSA-N 0.000 description 2
- 239000011354 acetal resin Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- NEPKLUNSRVEBIX-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,4-dicarboxylate Chemical compound C=1C=C(C(=O)OCC2OC2)C=CC=1C(=O)OCC1CO1 NEPKLUNSRVEBIX-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical group C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000012943 hotmelt Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-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
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 2
- GLTDLAUASUFHNK-UHFFFAOYSA-N n-silylaniline Chemical compound [SiH3]NC1=CC=CC=C1 GLTDLAUASUFHNK-UHFFFAOYSA-N 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- RMVRSNDYEFQCLF-UHFFFAOYSA-N phenyl mercaptan Natural products SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 2
- LYKRPDCJKSXAHS-UHFFFAOYSA-N phenyl-(2,3,4,5-tetrahydroxyphenyl)methanone Chemical compound OC1=C(O)C(O)=CC(C(=O)C=2C=CC=CC=2)=C1O LYKRPDCJKSXAHS-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000008569 process Effects 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
- 230000009467 reduction Effects 0.000 description 2
- 230000007261 regionalization Effects 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
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- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- VMYXFDVIMUEKNP-UHFFFAOYSA-N trimethoxy-[5-(oxiran-2-yl)pentyl]silane Chemical compound CO[Si](OC)(OC)CCCCCC1CO1 VMYXFDVIMUEKNP-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/12—Mountings, e.g. non-detachable insulating substrates
- H01L23/14—Mountings, e.g. non-detachable insulating substrates characterised by the material or its electrical properties
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
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- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
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- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/46—Manufacturing multilayer circuits
- H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
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Abstract
Description
本発明は、樹脂組成物に関する。さらに当該樹脂組成物を含有する、シート状積層材料、多層プリント配線板、半導体装置に関する。 The present invention relates to a resin composition. Furthermore, it is related with the sheet-like laminated material, multilayer printed wiring board, and semiconductor device containing the said resin composition.
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が求められている。 2. Description of the Related Art In recent years, electronic devices have been reduced in size and performance, and in multilayer printed wiring boards, build-up layers have been multilayered, and miniaturization and high density of wiring have been demanded.
これに対して様々な取組みがなされてきた。例えば、特許文献1には、(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が記載され、更に線膨張率を低下させる目的で無機充填材を含有させても良いことが記載されている。そして、該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り、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、ということが開示されている。 Various approaches have been made against this. For example, Patent Document 1 discloses an epoxy containing (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. A resin composition is described, and it is further described that an inorganic filler may be contained for the purpose of lowering the linear expansion coefficient. And the hardened | cured material obtained by hardening | curing this resin composition forms the conductor layer which has high adhesiveness by plating, even when the roughness of the roughening surface which roughened the surface of this hardened | cured material is comparatively 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, and the cured product has a low linear expansion coefficient. Therefore, it is disclosed that cracks due to the difference in linear expansion coefficient between the conductor layer and the insulating layer are hardly generated.
本発明者等の知見によれば、更なる低熱膨張、高密着性、低誘電正接を図るために活性エステル化合物や大量の無機充填材を含む樹脂組成物を用いて多層プリント配線板を作製していたところ、これら樹脂組成物の硬化物のピール強度が低くなりやすく、樹脂組成物をシート状形態にしたときに脆くなりやすいことが分かってきた。 According to the knowledge of the present inventors, a multilayer printed wiring board was produced using a resin composition containing an active ester compound and a large amount of an inorganic filler in order to achieve further low thermal expansion, high adhesion, and low dielectric loss tangent. As a result, it has been found that the peel strength of the cured product of these resin compositions tends to be low, and the resin composition tends to become brittle when it is made into a sheet form.
従って、本発明が解決しようとする課題は、樹脂組成物の硬化物の誘電正接が低く、ピール強度が高くなり、かつシート状形態の可とう性に優れた樹脂組成物を提供することを目的とする。 Therefore, the problem to be solved by the present invention is to provide a resin composition having a low dielectric loss tangent of a cured product of the resin composition, a high peel strength, and excellent flexibility in a sheet form. And
本発明者らは、上記課題を解決すべく鋭意検討した結果、(A)エステル骨格を有するエポキシ樹脂、(B)活性エステル型硬化剤及び(C)無機充填材を含有する樹脂組成物であって、前記樹脂組成物中の不揮発成分を100質量%とした場合、(C)無機充填材の含有量が50質量%以上であり、(C)無機充填材を100質量部とした場合、(A)エステル骨格を有するエポキシ樹脂が1〜20質量部であることを特徴とする樹脂組成物において、本発明を完成するに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found a resin composition containing (A) an epoxy resin having an ester skeleton, (B) an active ester type curing agent, and (C) an inorganic filler. When the nonvolatile component in the resin composition is 100% by mass, the content of (C) the inorganic filler is 50% by mass or more, and (C) the inorganic filler is 100 parts by mass, A) The resin composition characterized in that the epoxy resin having an ester skeleton is 1 to 20 parts by mass, and the present invention has been completed.
すなわち、本発明は以下の内容を含むものである。
〔1〕 (A)エステル骨格を有するエポキシ樹脂、(B)活性エステル型硬化剤及び(C)無機充填材を含有する樹脂組成物であって、前記樹脂組成物中の不揮発成分を100質量%とした場合、(C)無機充填材の含有量が50質量%以上であり、(C)無機充填材を100質量部とした場合、(A)エステル骨格を有するエポキシ樹脂が1〜20質量部であることを特徴とする樹脂組成物。
〔2〕 (A)エステル骨格を有するエポキシ樹脂が、グリシジルエステル型エポキシ樹脂、ダイマー酸変性エポキシ樹脂及びエステル骨格を有する脂環式エポキシ樹脂から選択される1種以上である〔1〕記載の樹脂組成物。
〔3〕 (A)エステル骨格を有するエポキシ樹脂が、フタル酸ジグリシジルエステル型エポキシ樹脂、ヘキサヒドロフタル酸ジグリシジルエステル型エポキシ樹脂及び3',4'-エポキシシクロヘキシルメチル3,4-エポキシシクロヘキサンカルボキシレートから選択される1種以上から選択される1種以上である〔1〕又は〔2〕記載の樹脂組成物。
〔4〕 (A)エステル骨格を有するエポキシ樹脂のエポキシ当量が、100〜1000である〔1〕〜〔3〕のいずれか記載の樹脂組成物。
〔5〕 (C)無機充填材の平均粒径が、0.01〜5μmである〔1〕〜〔4〕のいずれか記載の樹脂組成物。
〔6〕 (A)エステル骨格を有するエポキシ樹脂と他のエポキシ樹脂を併用し、(A)エステル骨格を有するエポキシ樹脂としてグリシジルエステル型エポキシ樹脂を含み、他のエポキシ樹脂としてビフェニル型エポキシ樹脂を含み、(C)無機充填材としてシリカを含む、〔1〕〜〔5〕のいずれか記載の樹脂組成物。
〔7〕 (A)エステル骨格を有するエポキシ樹脂と他のエポキシ樹脂を併用し、(A)エステル骨格を有するエポキシ樹脂としてフタル酸ジグリシジルエステル型エポキシ樹脂又はヘキサヒドロフタル酸ジグリシジルエステル型エポキシ樹脂を含み、他のエポキシ樹脂としてビフェニル型エポキシ樹脂を含み、(C)無機充填材として平均粒径0.01〜5μmのシリカを含む、〔1〕〜〔6〕のいずれか記載の樹脂組成物。
〔8〕 さらに(D)硬化促進剤を含有する〔1〕〜〔7〕のいずれか記載の樹脂組成物。
〔9〕 さらに(E)高分子樹脂を含有する〔1〕〜〔8〕のいずれか記載の樹脂組成物。
〔10〕 多層プリント配線板のビルドアップ層用樹脂組成物である〔1〕〜〔9〕のいずれか記載の樹脂組成物。
〔11〕 〔1〕〜〔10〕のいずれか記載の樹脂組成物を含有することを特徴とするシート状積層材料。
〔12〕 〔1〕〜〔10〕のいずれか記載の樹脂組成物を含有する接着フィルム又はプリプレグ。
〔13〕 〔1〕〜〔10〕のいずれか記載の樹脂組成物を熱硬化して絶縁層が形成された多層プリント配線板。
〔14〕 〔13〕記載の多層プリント配線板を用いることを特徴とする半導体装置。
That is, the present invention includes the following contents.
[1] A resin composition containing (A) an epoxy resin having an ester skeleton, (B) an active ester type curing agent and (C) an inorganic filler, wherein 100% by mass of the non-volatile component in the resin composition When (C) inorganic filler content is 50 mass% or more, and (C) inorganic filler is 100 mass parts, (A) 1-20 mass parts of epoxy resin having an ester skeleton A resin composition characterized by the above.
[2] (A) The resin according to [1], wherein the epoxy resin having an ester skeleton is at least one selected from a glycidyl ester type epoxy resin, a dimer acid-modified epoxy resin, and an alicyclic epoxy resin having an ester skeleton. Composition.
[3] (A) Epoxy resins having an ester skeleton are diglycidyl phthalate epoxy resin, diglycidyl hexahydrophthalate epoxy resin, and 3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxy The resin composition according to [1] or [2], which is one or more selected from one or more selected from rates.
[4] (A) The resin composition according to any one of [1] to [3], wherein the epoxy equivalent of the epoxy resin having an ester skeleton is 100 to 1000.
[5] The resin composition according to any one of [1] to [4], wherein the average particle size of the inorganic filler (C) is 0.01 to 5 μm.
[6] (A) A combination of an epoxy resin having an ester skeleton and another epoxy resin, (A) a glycidyl ester type epoxy resin as an epoxy resin having an ester skeleton, and a biphenyl type epoxy resin as another epoxy resin (C) Resin composition in any one of [1]-[5] containing a silica as an inorganic filler.
[7] (A) An epoxy resin having an ester skeleton and another epoxy resin are used in combination, and (A) an epoxy resin having an ester skeleton is a diglycidyl phthalate epoxy resin or a diglycidyl hexahydrophthalate epoxy resin The resin composition according to any one of [1] to [6], including biphenyl type epoxy resin as another epoxy resin, and (C) silica having an average particle diameter of 0.01 to 5 μm as an inorganic filler. .
[8] The resin composition according to any one of [1] to [7], further comprising (D) a curing accelerator.
[9] The resin composition according to any one of [1] to [8], further comprising (E) a polymer resin.
[10] The resin composition according to any one of [1] to [9], which is a resin composition for a buildup layer of a multilayer printed wiring board.
[11] A sheet-like laminate material comprising the resin composition according to any one of [1] to [10].
[12] An adhesive film or prepreg containing the resin composition according to any one of [1] to [10].
[13] A multilayer printed wiring board in which an insulating layer is formed by thermosetting the resin composition according to any one of [1] to [10].
[14] A semiconductor device using the multilayer printed wiring board according to [13].
本発明の樹脂組成物を用いることにより、樹脂組成物の硬化物の誘電正接が低く、ピール強度が高くなり、かつシート状形態の可とう性に優れた樹脂組成物を提供できるようになった。さらに、本発明によれば、樹脂組成物の硬化物の耐熱性を向上させることが出来る。 By using the resin composition of the present invention, it has become possible to provide a resin composition having a low dielectric loss tangent of a cured product of the resin composition, a high peel strength, and excellent flexibility in a sheet-like form. . Furthermore, according to this invention, the heat resistance of the hardened | cured material of a resin composition can be improved.
本発明は(A)エステル骨格を有するエポキシ樹脂、(B)活性エステル型硬化剤及び(C)無機充填材を含有する樹脂組成物であって、前記樹脂組成物中の不揮発成分を100質量%とした場合、(C)無機充填材の含有量が50質量%以上であり、(C)無機充填材を100質量部とした場合、(A)エステル骨格を有するエポキシ樹脂が1〜20質量部であることを特徴とする樹脂組成物である。以下、樹脂組成物の配合成分について詳述する。 The present invention is a resin composition containing (A) an epoxy resin having an ester skeleton, (B) an active ester type curing agent and (C) an inorganic filler, and 100% by mass of the nonvolatile component in the resin composition When (C) inorganic filler content is 50 mass% or more, and (C) inorganic filler is 100 mass parts, (A) 1-20 mass parts of epoxy resin having an ester skeleton It is a resin composition characterized by being. Hereinafter, the compounding components of the resin composition will be described in detail.
<(A)エステル骨格を有するエポキシ樹脂>
本発明に使用するエステル骨格を有するエポキシ樹脂としては、特に限定されるものではなく、分子内にカルボキシル基を有する化合物とエピクロロヒドリンを反応させることや、分子内にカルボキシル基を有する化合物とエポキシ樹脂を反応させることで得ることができる。とくに、エステル骨格を有するエポキシ樹脂としては、シート状形態の可とう性に優れた樹脂組成物を提供するという観点から、エステル骨格を2個以上有するエポキシ樹脂が好ましい。
<(A) Epoxy resin having ester skeleton>
The epoxy resin having an ester skeleton used in the present invention is not particularly limited, and reacts a compound having a carboxyl group in the molecule with epichlorohydrin or a compound having a carboxyl group in the molecule. It can be obtained by reacting an epoxy resin. In particular, as an epoxy resin having an ester skeleton, an epoxy resin having two or more ester skeletons is preferable from the viewpoint of providing a resin composition having excellent sheet form flexibility.
エステル骨格を有するエポキシ樹脂の具体例としては、グリシジルエステル型エポキシ樹脂、ダイマー酸変性エポキシ樹脂、エステル骨格を有する脂環式エポキシ樹脂が好ましく、ガラス転移温度が高く、硬化物の耐熱性を向上させることができる点で、グリシジルエステル型エポキシ樹脂、エステル骨格を有する脂環式エポキシ樹脂がより好ましい。 As specific examples of the epoxy resin having an ester skeleton, a glycidyl ester type epoxy resin, a dimer acid-modified epoxy resin, and an alicyclic epoxy resin having an ester skeleton are preferable, the glass transition temperature is high, and the heat resistance of the cured product is improved. The glycidyl ester type epoxy resin and the alicyclic epoxy resin having an ester skeleton are more preferable.
グリシジルエステル型エポキシ樹脂としては、フタル酸ジグリシジルエステル型エポキシ樹脂、ヘキサヒドロフタル酸ジグリシジルエステル型エポキシ樹脂、テレフタル酸ジグリシジルエステル型エポキシ樹脂、イソフタル酸ジグリシジルエステル型エポキシ樹脂、およびこれらの各種異性体などが挙げられ、耐熱性向上の点からフタル酸ジグリシジルエステル型エポキシ樹脂、ヘキサヒドロフタル酸ジグリシジルエステル型エポキシ樹脂が好ましい。 Examples of glycidyl ester type epoxy resins include diglycidyl phthalate type epoxy resins, diglycidyl hexahydrophthalate type epoxy resins, diglycidyl terephthalate type epoxy resins, diglycidyl ester type isophthalate epoxy resins, and various types thereof. Examples include isomers, and from the viewpoint of improving heat resistance, diglycidyl phthalate epoxy resin and diglycidyl hexahydrophthalate epoxy resin are preferred.
フタル酸ジグリシジルエステル型エポキシ樹脂は下記式(1)で表される。市販品としては、「エポミックR508」(三井化学(株)製)、「EX−721」(ナガセケムテックス(株)製)などが挙げられる。 The diglycidyl phthalate type epoxy resin is represented by the following formula (1). Examples of commercially available products include “Epomic R508” (manufactured by Mitsui Chemicals), “EX-721” (manufactured by Nagase ChemteX Corporation), and the like.
ヘキサヒドロフタル酸ジグリシジルエステル型エポキシ樹脂としては、下記式(2)で表される。市販品としては、「エポミックR540」(三井化学(株)製)、「AK−601」(日本化薬株式会社製)、「EX−722L」(ナガセケムテックス(株)製)などが挙げられる。 The hexahydrophthalic acid diglycidyl ester type epoxy resin is represented by the following formula (2). Examples of commercially available products include “Epomic R540” (manufactured by Mitsui Chemicals), “AK-601” (manufactured by Nippon Kayaku Co., Ltd.), “EX-722L” (manufactured by Nagase ChemteX Corporation), and the like. .
テレフタル酸ジグリシジルエステル型エポキシ樹脂としては、「EX−711」(ナガセケムテックス(株)製)などが挙げられる。 Examples of the terephthalic acid diglycidyl ester type epoxy resin include “EX-711” (manufactured by Nagase ChemteX Corporation).
ダイマー酸変性エポキシ樹脂としては、ダイマー酸のグリシジル変性化合物、ダイマー酸とビスフェノールA型ジグリシジルエーテルとの反応物等が挙げられる。ダイマー酸変性エポキシ樹脂は、下記式(3)で表される。市販品としては、「jER871」、「jER872」(三菱化学(株)製)、「YD−171」、「YD−172」(新日鐵化学(株)製)などが挙げられる。 Examples of the dimer acid-modified epoxy resin include dimer acid glycidyl-modified compounds, reaction products of dimer acid and bisphenol A diglycidyl ether, and the like. The dimer acid-modified epoxy resin is represented by the following formula (3). Examples of commercially available products include “jER871”, “jER872” (manufactured by Mitsubishi Chemical Corporation), “YD-171”, “YD-172” (manufactured by Nippon Steel Chemical Co., Ltd.), and the like.
エステル骨格を有する脂環式エポキシ樹脂としては、「セロキサイド2021P」(3',4'-エポキシシクロヘキシルメチル3,4-エポキシシクロヘキサンカルボキシレート、下記式(4)、(株)ダイセル製)、「セロキサイド2081」、「セロキサイド2000」、「セロキサイド3000」などが挙げられる。 As the alicyclic epoxy resin having an ester skeleton, “Celoxide 2021P” (3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, the following formula (4), manufactured by Daicel Corporation), “Celoxide” 2081 "," Celoxide 2000 "," Celoxide 3000 "and the like.
エステル骨格を有するエポキシ樹脂のエポキシ当量は、とくに制限されないが、100〜1000が好ましく、110〜800がより好ましく、120〜600が更に好ましく、130〜400が特に好ましい。これにより、接着フィルム形態の際に可とう性を向上させることができる点、硬化物の架橋密度が十分となり耐熱性が向上できる点などが優れることになる。なお、エポキシ当量(g/eq)は、1当量のエポキシ基を含む樹脂の質量であり、JIS K7236:2001に従って測定することができる。 The epoxy equivalent of the epoxy resin having an ester skeleton is not particularly limited, but is preferably 100 to 1000, more preferably 110 to 800, still more preferably 120 to 600, and particularly preferably 130 to 400. Thereby, the point which can improve a flexibility in the case of an adhesive film form, the crosslink density of hardened | cured material becomes sufficient, and the point which can improve heat resistance are excellent. In addition, epoxy equivalent (g / eq) is the mass of resin containing 1 equivalent of epoxy groups, and can be measured according to JIS K7236: 2001.
樹脂組成物中のエステル骨格を有するエポキシ樹脂の含有量は、特に限定されるものではないが、樹脂組成物のシート状形態の可とう性を向上させ、かつピール強度を向上させるという観点から、樹脂組成物中の不揮発成分を100質量%とした場合、2〜15質量%が好ましく、3〜12質量%がより好ましい。 The content of the epoxy resin having an ester skeleton in the resin composition is not particularly limited, but from the viewpoint of improving the flexibility of the sheet-like form of the resin composition and improving the peel strength. When the non-volatile component in a resin composition is 100 mass%, 2-15 mass% is preferable and 3-12 mass% is more preferable.
本発明の樹脂組成物においては、本発明の効果が発揮される範囲で、必要に応じてエステル骨格を有するエポキシ樹脂と他のエポキシ樹脂を併用しても良い。他のエポキシ樹脂としては、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、ビスフェノールS型エポキシ樹脂、ビスフェノールAF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、ナフトール型エポキシ樹脂、ナフタレン型エポキシ樹脂、ナフチレンエーテル型エポキシ樹脂、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、アントラセン型エポキシ樹脂、線状脂肪族エポキシ樹脂、ブタジエン構造を有するエポキシ樹脂、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等が挙げられる。なかでも、ピール強度の向上の観点から、エステル骨格を有するエポキシ樹脂とビフェニル型エポキシ樹脂を併用することが好ましい。これらは1種又は2種以上組み合わせて使用してもよい。 In the resin composition of the present invention, an epoxy resin having an ester skeleton and another epoxy resin may be used in combination within the range where the effects of the present invention are exhibited. Examples of other epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, and naphthol type. Epoxy resin, naphthalene type epoxy resin, naphthylene ether type epoxy resin, glycidylamine type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, anthracene type epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure , Alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol type epoxy resin, trimethylol type epoxy resin, halogenated epoxy Resins. Especially, it is preferable to use together the epoxy resin which has ester skeleton, and a biphenyl type epoxy resin from a viewpoint of the improvement of peel strength. These may be used alone or in combination of two or more.
エポキシ樹脂として、エステル骨格を有するエポキシ樹脂と他のエポキシ樹脂を併用する場合、シート状形態の可とう性を得るという観点から、エポキシ樹脂全体の固形分を100質量部とした場合、エステル骨格を有するエポキシ樹脂が10〜100質量部であることが好ましく、15〜90質量部であることがより好ましく、20〜80質量部であることが更に好ましい。 In the case of using an epoxy resin having an ester skeleton in combination with another epoxy resin as an epoxy resin, from the viewpoint of obtaining the flexibility of the sheet-like form, when the solid content of the entire epoxy resin is 100 parts by mass, the ester skeleton is The epoxy resin is preferably 10 to 100 parts by mass, more preferably 15 to 90 parts by mass, and still more preferably 20 to 80 parts by mass.
<(B)活性エステル型硬化剤>
本発明に使用する(B)活性エステル型硬化剤は、1分子中に活性エステル基を1個以上有する化合物であり、誘電正接を低くすることができる。ここで、「活性エステル基」とは、エポキシ樹脂と反応するエステル基を意味する。活性エステル型硬化剤は、エポキシ樹脂と反応することができ、1分子中に活性エステル基を2個以上有する化合物が好ましい。一般的には、フェノールエステル、チオフェノールエステル、N−ヒドロキシアミンエステル及び複素環ヒドロキシ化合物エステルからなる群より選択される、反応活性の高いエステル基を1分子中に2個以上有する化合物が、活性エステル型硬化剤として好ましく用いられる。
<(B) Active ester type curing agent>
The (B) active ester type curing agent used in the present invention is a compound having one or more active ester groups in one molecule, and can lower the dielectric loss tangent. Here, the “active ester group” means an ester group that reacts with an epoxy resin. The active ester type curing agent can react with the epoxy resin, and a compound having two or more active ester groups in one molecule is preferable. In general, a compound selected from the group consisting of phenol ester, thiophenol ester, N-hydroxyamine ester and heterocyclic hydroxy compound ester and having two or more ester groups with high reaction activity in one molecule is active. It is preferably used as an ester type curing agent.
耐熱性向上の観点から、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を縮合反応させたものから得られる活性エステル型硬化剤がより好ましい。フェノール化合物、ナフトール化合物及びチオール化合物とから選択される1種又は2種以上と、カルボン酸化合物とを反応させたものから得られる活性エステル型硬化剤が更に好ましい。カルボン酸化合物とフェノール性水酸基を有する芳香族化合物とを反応させたものから得られる1分子中に2個以上の活性エステル基を有する芳香族化合物が更に一層好ましい。少なくとも2個以上のカルボン酸を1分子中に有する化合物と、フェノール性水酸基を有する芳香族化合物とを反応させたものから得られる芳香族化合物であり、かつ該芳香族化合物の1分子中に2個以上の活性エステル基を有する芳香族化合物が殊更好ましい。活性エステル型硬化剤は、直鎖状または多分岐状であってもよい。また、少なくとも2個以上のカルボン酸を1分子中に有する化合物が脂肪族鎖を含む化合物であれば樹脂組成物との相溶性を高くすることができ、芳香族環を有する化合物であれば耐熱性を高くすることができる。 From the viewpoint of improving heat resistance, an active ester type curing agent obtained from a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound is more preferable. An active ester type curing agent obtained by reacting one or more selected from a phenol compound, a naphthol compound and a thiol compound with a carboxylic acid compound is more preferred. An aromatic compound having two or more active ester groups in one molecule obtained by reacting a carboxylic acid compound with an aromatic compound having a phenolic hydroxyl group is even more preferable. An aromatic compound obtained by reacting a compound having at least two or more carboxylic acids in one molecule with an aromatic compound having a phenolic hydroxyl group, and 2 in one molecule of the aromatic compound Particularly preferred are aromatic compounds having one or more active ester groups. The active ester type curing agent may be linear or hyperbranched. In addition, if the compound having at least two carboxylic acids in one molecule is a compound containing an aliphatic chain, the compatibility with the resin composition can be increased, and if it is a compound having an aromatic ring, it is heat resistant. Sexuality can be increased.
上記カルボン酸化合物としては、具体的には、安息香酸、酢酸、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。なかでも耐熱性の観点からコハク酸、マレイン酸、イタコン酸、フタル酸、イソフタル酸、テレフタル酸が好ましく、イソフタル酸、テレフタル酸がより好ましい。チオカルボン酸化合物としては、具体的には、チオ酢酸、チオ安息香酸等が挙げられる。 Specific examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Of these, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid and terephthalic acid are preferred, and isophthalic acid and terephthalic acid are more preferred from the viewpoint of heat resistance. Specific examples of the thiocarboxylic acid compound include thioacetic acid and thiobenzoic acid.
上記フェノール化合物又はナフトール化合物としては、具体的には、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。なかでも耐熱性向上、溶解性向上の観点から、ビスフェノールA、ビスフェノールF、ビスフェノールS、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、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が好ましく、カテコール、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がより好ましく、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、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が更に好ましく、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が更に一層好ましく、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、ジシクロペンタジエニルジフェノールが殊更好ましく、ジシクロペンタジエニルジフェノールが特に好ましい。チオール化合物としては、具体的には、ベンゼンジチオール、トリアジンジチオール等が挙げられる。活性エステル型硬化剤は1種又は2種以上を併用してもよい。 Specific 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, tetrahydroxy Examples include benzophenone, phloroglucin, benzenetriol, dicyclopentadienyl diphenol, and phenol novolac. Among them, from the viewpoint of improving heat resistance and solubility, bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, catechol, α-naphthol, β-naphthol, 1,5 -Dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadienyl diphenol, phenol novolac are preferred, catechol, 1 , 5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophene Non-tetrahydrobenzophenone, phloroglucin, benzenetriol, dicyclopentadienyl diphenol, and phenol novolak are more preferable. 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxy More preferred are hydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyl diphenol, phenol novolac, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadienyl diphenol, Phenol novolac is even more preferred, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthal Emissions, dicyclopentadienyl diphenol especially preferred, dicyclopentadienyl diphenol is particularly preferred. Specific examples of the thiol compound include benzenedithiol and triazinedithiol. The active ester type curing agent may be used alone or in combination of two or more.
活性エステル型硬化剤としては、具体的には、ジシクロペンタジエニルジフェノール構造を含む活性エステル型硬化剤、ナフタレン構造を含む活性エステル型硬化剤、フェノールノボラックのアセチル化物を含む活性エステル型硬化剤、フェノールノボラックのベンゾイル化物を含む活性エステル型硬化剤が好ましく、なかでもナフタレン構造を含む活性エステル型硬化剤、ジシクロペンタジエニルジフェノール構造を含む活性エステル型硬化剤がより好ましい。市販品としては、ジシクロペンタジエニルジフェノール構造を含む活性エステル型硬化剤として、EXB9451、EXB9460、EXB9460S、HPC8000−65T(DIC(株)製)、ナフタレン構造を含む活性エステル型硬化剤としてEXB9416−70BK(DIC(株)製)、フェノールノボラックのアセチル化物を含む活性エステル型硬化剤としてDC808(三菱化学(株)製)、フェノールノボラックのベンゾイル化物を含む活性エステル型硬化剤としてYLH1026(三菱化学(株)製)、などが挙げられる。 Specific examples of the active ester type curing agent include an active ester type curing agent containing a dicyclopentadienyl diphenol structure, an active ester type curing agent containing a naphthalene structure, and an active ester type curing containing a phenol novolac acetylated product. An active ester type curing agent containing a benzoylated product of a phenol novolac is preferable, and an active ester type curing agent containing a naphthalene structure and an active ester type curing agent containing a dicyclopentadienyl diphenol structure are more preferable. Commercially available products include EXB9451, EXB9460, EXB9460S, HPC8000-65T (manufactured by DIC Corporation) as an active ester type curing agent containing a dicyclopentadienyl diphenol structure, and EXB9416 as an active ester type curing agent containing a naphthalene structure. -70BK (manufactured by DIC Corporation), DC808 (manufactured by Mitsubishi Chemical Corporation) as an active ester type curing agent containing an acetylated product of phenol novolac, YLH1026 (Mitsubishi Chemical) as an active ester type curing agent containing a benzoylated product of phenol novolac Etc.).
ジシクロペンタジエニルジフェノール構造を含む活性エステル型硬化剤として、より具体的には下式(5)の化合物が挙げられる。 More specifically, an active ester type curing agent containing a dicyclopentadienyl diphenol structure includes a compound represented by the following formula (5).
誘電正接を低下させ、耐熱性を向上させるという観点から、Rはナフチル基が好ましく、一方、kは0が好ましく、また、nは0.25〜1.5が好ましい。 From the viewpoint of reducing the dielectric loss tangent and improving the heat resistance, R is preferably a naphthyl group, while k is preferably 0 and n is preferably 0.25 to 1.5.
活性エステル型硬化剤の含有量は、硬化物の誘電正接を低下させつつ、ピール強度を向上させることができるという点から、樹脂組成物中の不揮発成分を100質量%とした場合、1〜30質量%であることが好ましく、1.5〜20質量%であることがより好ましく、2〜10質量%がさらに好ましい。 The content of the active ester type curing agent is 1 to 30 when the nonvolatile component in the resin composition is 100% by mass from the viewpoint that the peel strength can be improved while reducing the dielectric loss tangent of the cured product. It is preferable that it is mass%, it is more preferable that it is 1.5-20 mass%, and 2-10 mass% is further more preferable.
本発明の樹脂組成物においては、本発明の効果が発揮される範囲で、必要に応じてフェノール型硬化剤、シアネートエステル型硬化剤等の硬化剤を添加しても良い。硬化剤全体の固形分を100質量部とした場合、活性エステル型硬化剤の合計量が30〜100質量部であることが好ましく、50〜100質量部であることがより好ましい。 In the resin composition of this invention, you may add hardening | curing agents, such as a phenol type hardening | curing agent and a cyanate ester type hardening | curing agent, as needed in the range by which the effect of this invention is exhibited. When the solid content of the entire curing agent is 100 parts by mass, the total amount of the active ester type curing agent is preferably 30 to 100 parts by mass, and more preferably 50 to 100 parts by mass.
本発明の樹脂組成物において、樹脂組成物の硬化物の機械強度や耐水性を向上させるという観点から、エポキシ樹脂のエポキシ基の合計数と、硬化剤の反応基の合計数との比が、1:0.2〜1:2が好ましく、1:0.3〜1:1.5がより好ましく、1:0.4〜1:1が更に好ましい。なお樹脂組成物中に存在するエポキシ樹脂のエポキシ基の合計数とは、各エポキシ樹脂の固形分質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、硬化剤の反応基の合計数とは、各硬化剤の固形分質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。 In the resin composition of the present invention, from the viewpoint of improving the mechanical strength and water resistance of the cured product of the resin composition, the ratio of the total number of epoxy groups of the epoxy resin and the total number of reactive groups of the curing agent is: 1: 0.2-1: 2 is preferable, 1: 0.3-1: 1.5 is more preferable, and 1: 0.4-1: 1 is still more preferable. The total number of epoxy groups of the epoxy resin present in the resin composition is a value obtained by dividing the solid content mass of each epoxy resin by the epoxy equivalent for all epoxy resins, and the reactive group of the curing agent. The total number of is a value obtained by adding the values obtained by dividing the solid mass of each curing agent by the reactive group equivalent for all curing agents.
<(C)無機充填材>
本発明の樹脂組成物は、無機充填材を含有することにより、誘電正接や熱膨張係数を低下させることができる。無機充填材としては、特に限定されないが、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る。なかでも、無定形シリカ、粉砕シリカ、溶融シリカ、結晶シリカ、合成シリカ、中空シリカ、球状シリカ等のシリカが好ましく、とくに絶縁層の表面粗さを低下させるという点で溶融シリカ、球状シリカがより好ましく、球状溶融シリカが更に好ましい。これらは1種または2種以上組み合わせて使用してもよい。市販されている球状溶融シリカとして、(株)アドマテックス製「SOC2」、「SOC1」等が挙げられる。
<(C) Inorganic filler>
The resin composition of this invention can reduce a dielectric loss tangent and a thermal expansion coefficient by containing an inorganic filler. The inorganic filler is not particularly limited. For example, silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate , Barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate and the like. Of these, silica such as amorphous silica, pulverized silica, fused silica, crystalline silica, synthetic silica, hollow silica, and spherical silica is preferable. In particular, fused silica and spherical silica are more preferable in terms of reducing the surface roughness of the insulating layer. Preferably, spherical fused silica is more preferable. You may use these 1 type or in combination of 2 or more types. Examples of commercially available spherical fused silica include “SOC2” and “SOC1” manufactured by Admatechs Co., Ltd.
無機充填材の平均粒径は、特に限定されないが、絶縁層表面が低粗度となり、微細配線形成を行うことを可能にするという観点から、5μm以下が好ましく、3μm以下がより好ましく、2μm以下が更に好ましく、1μm以下が更に一層好ましく、0.8μm以下が殊更好ましく、0.6μm以下が特に好ましく、0.4μm以下がとりわけ好ましい。一方、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のを防止するという観点から、0.01μm以上が好ましく、0.03μm以上がより好ましく、0.05μm以上が更に好ましく、0.07μm以上が更に一層好ましく、0.1μm以上が殊更好ましい。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散乱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。レーザー回折散乱式粒度分布測定装置としては、(株)堀場製作所製 LA−950等を使用することができる。 The average particle size of the inorganic filler is not particularly limited, but is preferably 5 μm or less, more preferably 3 μm or less, and more preferably 2 μm or less from the viewpoint that the surface of the insulating layer has low roughness and enables fine wiring formation. Is more preferably 1 μm or less, still more preferably 0.8 μm or less, particularly preferably 0.6 μm or less, and particularly preferably 0.4 μm or less. On the other hand, when the resin composition is a resin varnish, it is preferably 0.01 μm or more, more preferably 0.03 μm or more, from the viewpoint of preventing the viscosity of the varnish from increasing and handling properties from decreasing. 05 μm or more is more preferable, 0.07 μm or more is further more preferable, and 0.1 μm or more is particularly preferable. 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 prepared on a volume basis by a laser diffraction / scattering particle size distribution measuring apparatus, 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 scattering type particle size distribution measuring apparatus, LA-950 manufactured by Horiba, Ltd. or the like can be used.
無機充填材の含有量は、誘電正接を低下させる点や多層プリント配線板のクラックを防止するという点から、樹脂組成物中の不揮発成分を100質量%とした場合、50質量%以上となる。本発明の樹脂組成物はシート状形態の可とう性に優れるため、無機充填材の含有量を60質量%以上又は70質量%以上とすることが出来る。一方、硬化物が脆くなるのを防止する点やピール強度低下を防止する点から、90質量%以下が好ましく、85質量%以下がより好ましく、80質量%以下が更に好ましい。 In view of reducing the dielectric loss tangent and preventing cracks in the multilayer printed wiring board, the content of the inorganic filler is 50% by mass or more when the nonvolatile component in the resin composition is 100% by mass. Since the resin composition of this invention is excellent in the flexibility of a sheet form form, content of an inorganic filler can be 60 mass% or more or 70 mass% or more. On the other hand, 90 mass% or less is preferable, 85 mass% or less is more preferable, and 80 mass% or less is still more preferable from the point which prevents hardened | cured material from becoming weak and the point which prevents a peeling strength fall.
また、無機充填材とエステル骨格を有するエポキシ樹脂は、ピール強度の低下を防止し、シート状形態の可とう性を高めるために、(C)無機充填材を100質量部とした場合、(A)エステル骨格を有するエポキシ樹脂が1〜20質量部となり、好ましくは2〜17質量部、より好ましくは3〜14質量部、更に好ましくは4〜10質量部となる。 In addition, the epoxy resin having an inorganic filler and an ester skeleton prevents the decrease in peel strength and increases the flexibility of the sheet-like form when (C) the inorganic filler is 100 parts by mass, (A ) The epoxy resin having an ester skeleton is 1 to 20 parts by mass, preferably 2 to 17 parts by mass, more preferably 3 to 14 parts by mass, and still more preferably 4 to 10 parts by mass.
無機充填材は、表面処理剤で表面処理することが好ましく、具体的には、アミノシラン系カップリング剤、エポキシシラン系カップリング剤、メルカプトシラン系カップリング剤、スチリルシラン系カップリング剤、アクリレートシラン系カップリング剤、イソシアネートシラン系カップリング剤、スルフィドシラン系カップリング剤、ビニルシラン系カップリング剤、シラン系カップリング剤、オルガノシラザン化合物及びチタネート系カップリング剤より選択される1種以上の表面処理剤で表面処理することがより好ましい。これにより、無機充填材の分散性や耐湿性を向上させることが出来る。 The inorganic filler is preferably surface-treated with a surface treatment agent. Specifically, an aminosilane coupling agent, an epoxysilane coupling agent, a mercaptosilane coupling agent, a styrylsilane coupling agent, and an acrylate silane. One or more surface treatments selected from a series coupling agent, an isocyanate silane coupling agent, a sulfide silane coupling agent, a vinyl silane coupling agent, a silane coupling agent, an organosilazane compound and a titanate coupling agent More preferably, the surface treatment is performed with an agent. Thereby, the dispersibility and moisture resistance of an inorganic filler can be improved.
具体的には、3−アミノプロピルトリメトキシシラン、3−アミノプロピルトリエトキシシラン、3−アミノプロピルジエトキシメチルシラン、N−フェニル−3−アミノプロピルトリメトキシシラン、N−メチルアミノプロピルトリメトキシシラン、N−2(−アミノエチル)−3−アミノプロピルトリメトキシシラン、N−(2−アミノエチル)−3−アミノプロピルジメトキシメチルシラン等のアミノシラン系カップリング剤、3−グリシジルオキシプロピルトリメトキシシラン、3−グリシジルオキシプロピルトリエトキシシラン、3−グリシジルオキシプロピルメチルジエトキシシラン、3−グリシジルオキシプロピル(ジメトキシ)メチルシラン、グリシジルブチルトリメトキシシラン、2−(3,4−エポキシシクロヘキシル)エチルトリメトキシシラン等のエポキシシラン系カップリング剤、3−メルカプトプロピルトリメトキシシラン、3−メルカプトプロピルトリエトキシシラン、3−メルカプトプロピルメチルジメトキシシラン、11−メルカプトウンデシルトリメトキシシラン等のメルカプトシラン系カップリング剤、p−スチリルトリメトキシシラン等のスチリルシラン系カップリング剤、3−アクリルオキシプロピルトリメトキシシラン、3−メタクリルオキシプロピルトリメトキシシラン、3−メタクリルオキシプロピルジメトキシシラン、3−メタクリルオキシプロピルトリエトキシシラン、3−メタクリルオキシプロピルジエトキシシラン等のアクリレートシラン系カップリング剤、3−イソシアネートプロピルトリメトキシシラン等のイソシアネートシラン系カップリング剤、ビス(トリエトキシシリルプロピル)ジスルフィド、ビス(トリエトキシシリルプロピル)テトラスルフィド等のスルフィドシラン系カップリング剤、メチルトリメトキシシラン、オクタデシルトリメトキシシラン、フェニルトリメトキシシラン、メタクロキシプロピルトリメトキシシラン、イミダゾールシラン、トリアジンシラン、t-ブチルトリメトキシシラン等のシラン系カップリング剤、ヘキサメチルジシラザン、1,3−ジビニル−1,1,3,3−テトラメチルジシラザン、ヘキサフェニルジシラザン、トリシラザン、シクロトリシラザン、2,2,4,4,6,6−ヘキサメチルシクロトリシラザン、オクタメチルシクロテトラシラザン、ヘキサブチルジシラザン、ヘキサオクチルジシラザン、1,3−ジエチルテトラメチルジシラザン、1,3−ジ−n−オクチルテトラメチルジシラザン、1,3−ジフェニルテトラメチルジシラザン、1,3−ジメチルテトラフェニルジシラザン、1,3−ジエチルテトラメチルジシラザン、1,1,3,3−テトラフェニル−1,3−ジメチルジシラザン、1,3−ジプロピルテトラメチルジシラザン、ヘキサメチルシクロトリシラザン、ジメチルアミノトリメチルシラザン、テトラメチルジシラザン等のオルガノシラザン化合物、テトラ-n-ブチルチタネートダイマー、チタニウム-i-プロポキシオクチレングリコレート、テトラ−n−ブチルチタネート、チタンオクチレングリコレート、ジイソプロポキシチタンビス(トリエタノールアミネート)、ジヒドロキシチタンビスラクテート、ジヒドロキシビス(アンモニウムラクテート)チタニウム、ビス(ジオクチルパイロホスフェート)エチレンチタネート、ビス(ジオクチルパイロホスフェート)オキシアセテートチタネート、トリ−n−ブトキシチタンモノステアレート、テトラ−n−ブチルチタネート、テトラ(2−エチルヘキシル)チタネート、テトライソプロピルビス(ジオクチルホスファイト)チタネート、テトラオクチルビス(ジトリデシルホスファイト)チタネート、テトラ(2,2−ジアリルオキシメチル−1−ブチル)ビス(ジトリデシル)ホスファイトチタネート、イソプロピルトリオクタノイルチタネート、イソプロピルトリクミルフェニルチタネート、イソプロピルトリイソステアロイルチタネート、イソプロピルイソステアロイルジアクリルチタネート、イソプロピルジメタクリルイソステアロイルチタネート、イソプロピルトリ(ジオクチルホスフェート)チタネート、イソプロピルトリドデシルベンゼンスルホニルチタネート、イソプロピルトリス(ジオクチルパイロホスフェート)チタネート、イソプロピルトリ(N−アミドエチル・アミノエチル)チタネート等のチタネート系カップリング剤等が挙げられる。これらのなかでもアミノシラン系カップリング剤、エポキシシラン系カップリング剤、メルカプトシラン系カップリング剤、オルガノシラザン化合物が好ましい。市販品としては、信越化学工業(株)製「KBM403」(3−グリシドキシプロピルトリメトキシシラン)、信越化学工業(株)製「KBM803」(3−メルカプトプロピルトリメトキシシラン)、信越化学工業(株)製「KBE903」(3−アミノプロピルトリエトキシシラン)、信越化学工業(株)製「KBM573」(N−フェニル−3−アミノプロピルトリメトキシシラン)、信越化学工業(株)製「SZ−31」(ヘキサメチルジシラザン)等が挙げられる。 Specifically, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, N-phenyl-3-aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane Aminosilane coupling agents such as N-2 (-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyldimethoxymethylsilane, 3-glycidyloxypropyltrimethoxysilane , 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyl (dimethoxy) methylsilane, glycidylbutyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) Epoxysilane coupling agents such as ethyltrimethoxysilane, mercaptosilanes such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 11-mercaptoundecyltrimethoxysilane Coupling agents, styrylsilane coupling agents such as p-styryltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyldimethoxysilane, 3-methacryloxypropyl Acrylate silane coupling agents such as triethoxysilane and 3-methacryloxypropyldiethoxysilane, and isocyanates such as 3-isocyanatopropyltrimethoxysilane Silane coupling agents, sulfide silane coupling agents such as bis (triethoxysilylpropyl) disulfide, bis (triethoxysilylpropyl) tetrasulfide, methyltrimethoxysilane, octadecyltrimethoxysilane, phenyltrimethoxysilane, methacloxy Silane coupling agents such as propyltrimethoxysilane, imidazolesilane, triazinesilane, t-butyltrimethoxysilane, hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, hexa Phenyldisilazane, trisilazane, cyclotrisilazane, 2,2,4,4,6,6-hexamethylcyclotrisilazane, octamethylcyclotetrasilazane, hexabutyldisilazane, hexaoctyldisilazane, 1 3-diethyltetramethyldisilazane, 1,3-di-n-octyltetramethyldisilazane, 1,3-diphenyltetramethyldisilazane, 1,3-dimethyltetraphenyldisilazane, 1,3-diethyltetramethyldi Organos such as silazane, 1,1,3,3-tetraphenyl-1,3-dimethyldisilazane, 1,3-dipropyltetramethyldisilazane, hexamethylcyclotrisilazane, dimethylaminotrimethylsilazane, tetramethyldisilazane Silazane compound, tetra-n-butyl titanate dimer, titanium-i-propoxy octylene glycolate, tetra-n-butyl titanate, titanium octylene glycolate, diisopropoxy titanium bis (triethanolaminate), dihydroxy titanium bis lactate, dihydroxy Cis (ammonium lactate) titanium, bis (dioctyl pyrophosphate) ethylene titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, tri-n-butoxytitanium monostearate, tetra-n-butyl titanate, tetra (2-ethylhexyl) titanate Tetraisopropylbis (dioctylphosphite) titanate, tetraoctylbis (ditridecylphosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, isopropyltrioctanoyl titanate, Isopropyl tricumyl phenyl titanate, isopropyl triisostearoyl titanate, isopropyl isostearoyl diacryl titanate, Titanate coupling agents such as propyldimethacrylisostearoyl titanate, isopropyltri (dioctylphosphate) titanate, isopropyltridodecylbenzenesulfonyl titanate, isopropyltris (dioctylpyrophosphate) titanate, isopropyltri (N-amidoethyl / aminoethyl) titanate, etc. Is mentioned. Of these, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, and organosilazane compounds are preferred. Commercially available products include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM803” (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane) manufactured by Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "SZ" manufactured by Shin-Etsu Chemical Co., Ltd. -31 "(hexamethyldisilazane) and the like.
無機充填材を表面処理剤で表面処理する際の、該表面処理剤の量は、特に限定されないが、無機充填材100質量部に対して、表面処理剤を0.05〜5質量部で表面処理するのが好ましく、0.1〜4質量部で表面処理するのがより好ましく、0.2〜3質量部で表面処理するのが更に好ましく、0.3〜2質量部で表面処理するのが更に一層好ましい。 The amount of the surface treatment agent when the inorganic filler is surface-treated with the surface treatment agent is not particularly limited, but the surface treatment agent is 0.05 to 5 parts by mass with respect to 100 parts by mass of the inorganic filler. It is preferable to treat, more preferably 0.1 to 4 parts by mass, and more preferably 0.2 to 3 parts by mass, and more preferably 0.3 to 2 parts by mass. Is even more preferred.
また、表面処理剤で表面処理された無機充填材においては、該無機充填材の表面組成を分析することによって、炭素原子の存在を確認し、該無機充填材の単位表面積当たりのカーボン量を求めることができる。具体的には、溶剤として十分な量のMEKを表面処理剤で表面処理された無機充填材に加えて、25℃で5分間超音波洗浄する。上澄液を除去し、固形分を乾燥させた後、カーボン分析計を用いて該無機充填材の単位表面積当たりのカーボン量を測定することができる。カーボン分析計としては、堀場製作所製「EMIA−320V」等を使用することができる。 Moreover, in the inorganic filler surface-treated with the surface treatment agent, the presence of carbon atoms is confirmed by analyzing the surface composition of the inorganic filler, and the amount of carbon per unit surface area of the inorganic filler is obtained. be able to. Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with the surface treatment agent and ultrasonically cleaned at 25 ° C. for 5 minutes. After removing the supernatant and drying the solid content, the carbon amount per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, “EMIA-320V” manufactured by HORIBA, Ltd. can be used.
無機充填材の単位表面積当たりのカーボン量は、無機充填材の分散性向上や硬化物の湿式粗化工程後の算術平均粗さ、二乗平均平方根粗さを安定させるという点で、0.05mg/m2以上が好ましく、0.1mg/m2以上がより好ましく、0.15mg/m2以上が更に好ましく、0.2mg/m2以上が更に一層好ましい。一方、樹脂ワニスの溶融粘度や接着フィルム形態での溶融粘度の上昇を防止するという点で、1mg/m2以下が好ましく、0.75mg/m2以下がより好ましく、0.5mg/m2以下が更に好ましい。 The amount of carbon per unit surface area of the inorganic filler is 0.05 mg / square in terms of improving the dispersibility of the inorganic filler and stabilizing the arithmetic average roughness and the root mean square roughness after the wet roughening step of the cured product. m 2 or more preferably, 0.1 mg / m 2 or more, and further preferably 0.15 mg / m 2 or more, 0.2 mg / m 2 or more is even more preferred. On the other hand, in terms of preventing an increase in the melt viscosity at the melt viscosity and the adhesive film forms of the resin varnish is preferably 1 mg / m 2 or less, more preferably 0.75 mg / m 2 or less, 0.5 mg / m 2 or less Is more preferable.
表面処理剤で表面処理された無機充填材は、無機充填材を表面処理剤により表面処理した後、樹脂組成物に添加することが好ましい。この場合には、無機充填材の分散性をより一層高めることが出来る。 The inorganic filler surface-treated with the surface treatment agent is preferably added to the resin composition after the inorganic filler is surface-treated with the surface treatment agent. In this case, the dispersibility of the inorganic filler can be further enhanced.
表面処理剤で表面処理された無機充填材への表面処理方法は、特に限定されないが、乾式法や湿式法が挙げられる。乾式法としては、回転ミキサーに無機充填材を仕込んで、攪拌しながら表面処理剤のアルコール溶液又は水溶液を滴下又は噴霧した後、さらに攪拌し、ふるいにより分級する。その後、加熱により表面処理剤と無機充填材とを脱水縮合させることにより得ることができる。湿式法としては、無機充填材と有機溶媒とのスラリーを攪拌しながら表面処理剤を添加し、攪拌した後、濾過、乾燥及びふるいによる分級を行う。その後、加熱により表面処理剤と無機充填材とを脱水縮合させることにより得ることができる。さらに、樹脂組成物中に表面処理剤を添加するインテグラルブレンド法でも可能である。 The surface treatment method for the inorganic filler surface-treated with the surface treatment agent is not particularly limited, and examples thereof include a dry method and a wet method. As a dry method, an inorganic filler is charged in a rotary mixer, and an alcohol solution or an aqueous solution of a surface treatment agent is dropped or sprayed while stirring, followed by further stirring and classification with a sieve. Thereafter, the surface treatment agent and the inorganic filler can be dehydrated and condensed by heating. As a wet method, a surface treatment agent is added while stirring a slurry of an inorganic filler and an organic solvent, and after stirring, classification is performed by filtration, drying, and sieving. Thereafter, the surface treatment agent and the inorganic filler can be dehydrated and condensed by heating. Furthermore, an integral blend method in which a surface treating agent is added to the resin composition is also possible.
本発明の樹脂組成物の好適な一実施態様は、樹脂組成物の硬化物の誘電正接が低く、ピール強度が高くなり、かつシート状形態の可とう性に優れた樹脂組成物を提供するという点から、(A)エステル骨格を有するエポキシ樹脂、(B)活性エステル型硬化剤及び(C)無機充填材を含有する樹脂組成物であって、前記樹脂組成物中の不揮発成分を100質量%とした場合、(C)無機充填材の含有量が50質量%以上であり、(C)無機充填材を100質量部とした場合、(A)エステル骨格を有するエポキシ樹脂が1〜20質量部であり、(A)エステル骨格を有するエポキシ樹脂と他のエポキシ樹脂を併用し、(A)エステル骨格を有するエポキシ樹脂としてグリシジルエステル型エポキシ樹脂(より好ましくはフタル酸ジグリシジルエステル型エポキシ樹脂又はヘキサヒドロフタル酸ジグリシジルエステル型エポキシ樹脂)を含み、他のエポキシ樹脂としてビフェニル型エポキシ樹脂を含み、(C)無機充填材としてシリカ(より好ましくは平均粒径0.01〜5μmのシリカ)を含む樹脂組成物の態様が好ましい。 One preferred embodiment of the resin composition of the present invention is to provide a resin composition having a low dielectric loss tangent of a cured product of the resin composition, a high peel strength, and an excellent flexibility in a sheet form. From the point, it is a resin composition containing (A) an epoxy resin having an ester skeleton, (B) an active ester type curing agent, and (C) an inorganic filler, and 100% by mass of the nonvolatile component in the resin composition When (C) inorganic filler content is 50 mass% or more, and (C) inorganic filler is 100 mass parts, (A) 1-20 mass parts of epoxy resin having an ester skeleton (A) An epoxy resin having an ester skeleton and another epoxy resin are used in combination, and (A) a glycidyl ester type epoxy resin (more preferably diglycidyl phthalate) as an epoxy resin having an ester skeleton. Steal type epoxy resin or hexahydrophthalic acid diglycidyl ester type epoxy resin), biphenyl type epoxy resin as other epoxy resin, and silica as inorganic filler (more preferably, average particle size 0.01- An embodiment of a resin composition containing 5 μm silica) is preferred.
<(D)硬化促進剤>
本発明の樹脂組成物には、さらに硬化促進剤を含有させることにより、エポキシ樹脂と硬化剤を効率的に硬化させることができる。硬化促進剤としては、特に限定されないが、アミン系硬化促進剤、グアニジン系硬化促進剤、イミダゾール系硬化促進剤、ホスホニウム系硬化促進剤、金属系硬化促進剤等が挙げられる。これらは1種又は2種以上組み合わせて使用してもよい。
<(D) Curing accelerator>
When the resin composition of the present invention further contains a curing accelerator, the epoxy resin and the curing agent can be efficiently cured. Although it does not specifically limit as a hardening accelerator, An amine hardening accelerator, a guanidine hardening accelerator, an imidazole hardening accelerator, a phosphonium hardening accelerator, a metal hardening accelerator, etc. are mentioned. These may be used alone or in combination of two or more.
アミン系硬化促進剤としては、特に限定されるものではないが、トリエチルアミン、トリブチルアミンなどのトリアルキルアミン、4−ジメチルアミノピリジン、ベンジルジメチルアミン、2,4,6,−トリス(ジメチルアミノメチル)フェノール、1,8−ジアザビシクロ(5,4,0)−ウンデセン(以下、DBUと略記する。)などのアミン化合物などが挙げられる。これらは1種または2種以上組み合わせて使用してもよい。 The amine curing accelerator is not particularly limited, but trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl). And amine compounds such as phenol and 1,8-diazabicyclo (5,4,0) -undecene (hereinafter abbreviated as DBU). You may use these 1 type or in combination of 2 or more types.
グアニジン系硬化促進剤としては、特に限定されるものではないが、ジシアンジアミド、1−メチルグアニジン、1−エチルグアニジン、1−シクロヘキシルグアニジン、1−フェニルグアニジン、1−(o−トリル)グアニジン、ジメチルグアニジン、ジフェニルグアニジン、トリメチルグアニジン、テトラメチルグアニジン、ペンタメチルグアニジン、1,5,7−トリアザビシクロ[4.4.0]デカ−5−エン、7−メチル−1,5,7−トリアザビシクロ[4.4.0]デカ−5−エン、1−メチルビグアニド、1−エチルビグアニド、1−n−ブチルビグアニド、1−n−オクタデシルビグアニド、1,1−ジメチルビグアニド、1,1−ジエチルビグアニド、1−シクロヘキシルビグアニド、1−アリルビグアニド、1−フェニルビグアニド、1−(o−トリル)ビグアニド等が挙げられる。これらは1種または2種以上組み合わせて使用してもよい。 Although it does not specifically limit as a guanidine type hardening accelerator, Dicyandiamide, 1-methyl guanidine, 1-ethyl guanidine, 1-cyclohexyl guanidine, 1-phenyl guanidine, 1- (o-tolyl) guanidine, dimethyl guanidine , Diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl Rubiguanido, 1-(o-tolyl) biguanide, and the like. You may use these 1 type or in combination of 2 or more types.
イミダゾール系硬化促進剤としては、特に限定されるものではないが、2−メチルイミダゾール、2−ウンデシルイミダゾール、2−ヘプタデシルイミダゾール、1,2−ジメチルイミダゾール、2−エチル−4−メチルイミダゾール、1,2−ジメチルイミダゾール、2−エチル−4−メチルイミダゾール、2−フェニルイミダゾール、2−フェニル−4−メチルイミダゾール、1−ベンジル−2−メチルイミダゾール、1−ベンジル−2−フェニルイミダゾール、1−シアノエチル−2−メチルイミダゾール、1−シアノエチル−2−ウンデシルイミダゾール、1−シアノエチル−2−エチル−4−メチルイミダゾール、1−シアノエチル−2−フェニルイミダゾール、1−シアノエチル−2−ウンデシルイミダゾリウムトリメリテイト、1−シアノエチル−2−フェニルイミダゾリウムトリメリテイト、2,4−ジアミノ−6−[2’−メチルイミダゾリル−(1’)]−エチル−s−トリアジン、2,4−ジアミノ−6−[2’−ウンデシルイミダゾリル−(1’)]−エチル−s−トリアジン、2,4−ジアミノ−6−[2’−エチル−4’−メチルイミダゾリル−(1’)]−エチル−s−トリアジン、2,4−ジアミノ−6−[2’−メチルイミダゾリル−(1’)]−エチル−s−トリアジンイソシアヌル酸付加物、2−フェニルイミダゾールイソシアヌル酸付加物、2−フェニル−4,5−ジヒドロキシメチルイミダゾール、2−フェニル−4−メチル−5ヒドロキシメチルイミダゾール、2,3−ジヒドロ−1H−ピロロ[1,2−a]ベンズイミダゾール、1−ドデシル−2−メチル−3−ベンジルイミダゾリウムクロライド、2−メチルイミダゾリン、2−フェニルイミダゾリン等のイミダゾール化合物及びイミダゾール化合物とエポキシ樹脂とのアダクト体が挙げられる。これらは1種または2種以上組み合わせて使用してもよい。 The imidazole curing accelerator is not particularly limited, but 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1- Cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium tri Meritate 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2 '-Undecylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethyl Imidazole, 2-phenyl-4-methyl-5hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1 Dodecyl-2-methyl-3-benzyl-imidazolium chloride, 2-methyl-imidazoline, adduct of 2-phenyl-imidazo imidazole compounds such as phosphorus and imidazole compound and an epoxy resin. You may use these 1 type or in combination of 2 or more types.
ホスホニウム系硬化促進剤としては、特に限定されるものではないが、トリフェニルホスフィン、ホスホニウムボレート化合物、テトラフェニルホスホニウムテトラフェニルボレート、n−ブチルホスホニウムテトラフェニルボレート、テトラブチルホスホニウムデカン酸塩、(4−メチルフェニル)トリフェニルホスホニウムチオシアネート、テトラフェニルホスホニウムチオシアネート、ブチルトリフェニルホスホニウムチオシアネート等が挙げられる。これらは1種または2種以上組み合わせて使用してもよい。 Although it does not specifically limit as a phosphonium type hardening accelerator, Triphenylphosphine, a phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4- Methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, and the like. You may use these 1 type or in combination of 2 or more types.
金属系硬化促進剤としては、特に限定されるものではないが、コバルト、銅、亜鉛、鉄、ニッケル、マンガン、スズ等の金属の、有機金属錯体又は有機金属塩が挙げられる。有機金属錯体の具体例としては、コバルト(II)アセチルアセトナート、コバルト(III)アセチルアセトナート等の有機コバルト錯体、銅(II)アセチルアセトナート等の有機銅錯体、亜鉛(II)アセチルアセトナート等の有機亜鉛錯体、鉄(III)アセチルアセトナート等の有機鉄錯体、ニッケル(II)アセチルアセトナート等の有機ニッケル錯体、マンガン(II)アセチルアセトナート等の有機マンガン錯体などが挙げられる。有機金属塩としては、オクチル酸亜鉛、オクチル酸錫、ナフテン酸亜鉛、ナフテン酸コバルト、ステアリン酸スズ、ステアリン酸亜鉛などが挙げられる。これらは1種又は2種以上組み合わせて使用してもよい。 Although it does not specifically limit as a metal type hardening accelerator, The organometallic complex or organometallic salt of metals, such as cobalt, copper, zinc, iron, nickel, manganese, tin, is mentioned. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Organic zinc complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate. These may be used alone or in combination of two or more.
本発明の樹脂組成物に硬化促進剤を配合する場合には、エポキシ樹脂と硬化剤の合計を100質量部とした場合、0.005〜1質量部の範囲が好ましく、0.01〜0.5質量部の範囲がより好ましい。この範囲内であると、熱硬化をより効率的にでき、樹脂ワニスの保存安定性も向上する。 When mix | blending a hardening accelerator with the resin composition of this invention, the range of 0.005-1 mass part is preferable when the sum total of an epoxy resin and a hardening | curing agent is 100 mass parts, 0.01-0. The range of 5 parts by mass is more preferable. Within this range, thermosetting can be performed more efficiently, and the storage stability of the resin varnish is improved.
<(E)高分子樹脂>
本発明の樹脂組成物には、さらに(E)高分子樹脂を含有させることにより、硬化物の機械強度を向上させることができ、更に接着フィルムの形態で使用する場合のフィルム成型能を向上させることもできる。(E)高分子樹脂としては、フェノキシ樹脂、ポリビニルアセタール樹脂、ポリイミド樹脂、ポリアミドイミド樹脂、ポリエーテルイミド樹脂、ポリスルホン樹脂、ポリエーテルスルホン樹脂、ポリフェニレンエーテル樹脂、ポリカーボネート樹脂、ポリエーテルエーテルケトン樹脂、ポリエステル樹脂を挙げることができ、特にフェノキシ樹脂、ポリビニルアセタール樹脂が好ましい。これらは各々単独で用いてもよく、2種以上を組み合わせて使用してもよい。(E)高分子樹脂の重量平均分子量は8000〜200000の範囲であるのが好ましく、12000〜100000の範囲がより好ましく、20000〜60000の範囲が更に好ましい。なお本発明における重量平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)法(ポリスチレンン換算)で測定される。GPC法による重量平均分子量は、具体的には、測定装置として(株)島津製作所製LC−9A/RID−6Aを、カラムとして昭和電工(株)社製Shodex K−800P/K−804L/K−804Lを、移動相としてクロロホルム等を用いて、カラム温度40℃にて測定し、標準ポリスチレンの検量線を用いて算出することができる。
<(E) polymer resin>
When the resin composition of the present invention further contains (E) a polymer resin, the mechanical strength of the cured product can be improved, and further the film molding ability when used in the form of an adhesive film is improved. You can also. (E) As polymer resin, phenoxy resin, polyvinyl acetal resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, polyetheretherketone resin, polyester Examples of the resin include phenoxy resin and polyvinyl acetal resin. These may be used alone or in combination of two or more. (E) The weight average molecular weight of the polymer resin is preferably in the range of 8000 to 200000, more preferably in the range of 12000 to 100,000, and still more preferably in the range of 20000 to 60000. In addition, the weight average molecular weight in this invention is measured by the gel permeation chromatography (GPC) method (polystyrene conversion). Specifically, the weight average molecular weight by the GPC method is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K-804L / K manufactured by Showa Denko KK as a column. -804L can be measured at a column temperature of 40 ° C. using chloroform or the like as a mobile phase, and can be calculated using a standard polystyrene calibration curve.
本発明の樹脂組成物に(E)高分子樹脂を配合する場合には、樹脂組成物中の不揮発成分を100質量%とした場合、0.1〜10質量%が好ましく、0.5〜5質量%がより好ましい。この範囲内であると、フィルム成型能や機械強度向上の効果が発揮され、更に溶融粘度の上昇や湿式粗化工程後の絶縁層表面の粗度を低下させることができる。 When (E) polymer resin is mix | blended with the resin composition of this invention, 0.1-10 mass% is preferable when the non-volatile component in a resin composition is 100 mass%, 0.5-5 The mass% is more preferable. Within this range, the effect of improving the film forming ability and mechanical strength can be exhibited, and the melt viscosity can be increased and the roughness of the insulating layer surface after the wet roughening step can be reduced.
<他の成分>
本発明の樹脂組成物には、本発明の効果を阻害しない範囲で、必要に応じて他の成分を配合することができる。他の成分としては、ビニルベンジル化合物、アクリル化合物、マレイミド化合物、ブロックイソシアネート化合物のような熱硬化性樹脂、シリコンパウダー、ナイロンパウダー、フッ素パウダー、ゴム粒子等の有機充填剤、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、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、リン系化合物、金属水酸化物等の難燃剤、を挙げることができる。
<Other ingredients>
In the resin composition of the present invention, other components can be blended as necessary within a range not inhibiting the effects of the present invention. Other components include thermosetting resins such as vinyl benzyl compounds, acrylic compounds, maleimide compounds, and blocked isocyanate compounds, organic fillers such as silicon powder, nylon powder, fluorine powder, and rubber particles; Adhesives, silicone-based, fluorine-based, polymer-based defoamers or leveling agents, phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, carbon black and other colorants, phosphorus compounds, metal hydroxides And flame retardants.
本発明の樹脂組成物は、上記成分を適宜混合し、また、必要に応じて三本ロール、ボールミル、ビーズミル、サンドミル等の混練手段、あるいはスーパーミキサー、プラネタリーミキサー等の撹拌手段により混練または混合することにより調整することができる。また、上記成分を有機溶剤に溶解して樹脂組成物中に添加してもよいし、樹脂組成物中にさらに有機溶剤を加えることで樹脂ワニスとして調整することもできる。 The resin composition of the present invention is appropriately mixed with the above components and, if necessary, kneaded or mixed by a kneading means such as a three-roll, ball mill, bead mill, or sand mill, or a stirring means such as a super mixer or a planetary mixer. It can be adjusted by doing. Moreover, the said component may be melt | dissolved in the organic solvent and you may add in a resin composition, and it can also adjust as a resin varnish by adding an organic solvent further in a resin composition.
本発明においては、樹脂組成物の硬化物の誘電正接が低く、ピール強度が高くなり、かつシート状形態の可とう性に優れた樹脂組成物を提供できるので、多層プリント配線板の製造において、多層プリント配線板の絶縁層用樹脂組成物として好適に使用することができる。更に、メッキにより導体層を形成するための樹脂組成物(メッキにより導体層を形成する多層プリント配線板の絶縁層用樹脂組成物)として好適に使用することができ、更に多層プリント配線板のビルドアップ層用樹脂組成物として好適である。 In the present invention, since the dielectric loss tangent of the cured product of the resin composition is low, the peel strength is high, and a resin composition excellent in flexibility of the sheet form can be provided. It can be suitably used as a resin composition for an insulating layer of a multilayer printed wiring board. Furthermore, it can be suitably used as a resin composition for forming a conductor layer by plating (resin composition for an insulating layer of a multilayer printed wiring board on which a conductor layer is formed by plating), and further building a multilayer printed wiring board It is suitable as a resin composition for an up layer.
本発明の樹脂組成物の硬化物の誘電正接は、後述する〔誘電正接の測定〕に記載の測定方法により把握することができる。誘電正接は、電気信号ロスを軽減させるという点から、0.007以下が好ましい。誘電正接は低いほどよく、特に下限値は無いが、一般的に0.002以上、0.003以上などとなる。 The dielectric loss tangent of the cured product of the resin composition of the present invention can be grasped by the measurement method described in [Measurement of dielectric loss tangent] described later. The dielectric loss tangent is preferably 0.007 or less from the viewpoint of reducing electric signal loss. The lower the dielectric loss tangent, the better. There is no particular lower limit, but generally it is 0.002 or more, 0.003 or more, and the like.
本発明の樹脂組成物を硬化して絶縁層を形成し、その絶縁層表面を粗化処理し、メッキして得られる導体層と絶縁層とのピール強度は、後述する〔メッキ導体層の引き剥がし強さ(ピール強度)の測定〕に記載の測定方法により把握することができる。ピール強度は、絶縁層と導体層とを十分に密着させておくために0.45kgf/cm以上が好ましく、0.5kgf/cm以上がより好ましく、0.55kgf/cm以上が更に好ましい。ピール強度の上限値は高いほどよく、特に制限は無いが、一般的に1.5kgf/cm以下、1.2kgf/cm以下、1.0kgf/cm以下、0.8kgf/cm以下などとなる。 The resin composition of the present invention is cured to form an insulating layer, the surface of the insulating layer is roughened, and the peel strength between the conductor layer and the insulating layer obtained by plating is described later in [Plating conductor layer drawing]. It can be grasped by the measuring method described in [Measurement of Peeling Strength (Peel Strength)]. The peel strength is preferably 0.45 kgf / cm or more, more preferably 0.5 kgf / cm or more, and further preferably 0.55 kgf / cm or more in order to keep the insulating layer and the conductor layer in close contact with each other. The upper limit of the peel strength is preferably as high as possible and is not particularly limited, but is generally 1.5 kgf / cm or less, 1.2 kgf / cm or less, 1.0 kgf / cm or less, 0.8 kgf / cm or less.
本発明の樹脂組成物のガラス転移温度は、後述する〔ガラス転移温度の測定〕に記載の測定方法により把握することができる。ガラス転移温度は、耐熱性向上という点から、150℃以上が好ましく155℃以上がより好ましい。特に上限値は無いが、一般的に300℃以下となる。 The glass transition temperature of the resin composition of this invention can be grasped | ascertained by the measuring method as described in [Measurement of glass transition temperature] described later. The glass transition temperature is preferably 150 ° C. or higher and more preferably 155 ° C. or higher from the viewpoint of improving heat resistance. Although there is no particular upper limit, it is generally 300 ° C. or lower.
本発明の樹脂組成物は、多層プリント配線板の絶縁層用樹脂組成物として特に適した組成であるが、ソルダーレジスト、アンダ−フィル材、ダイボンディング材、半導体封止材、穴埋め樹脂、部品埋め込み樹脂等、樹脂組成物が必要とされる用途の広範囲に使用できる。また、本発明の樹脂組成物の形態としては、特に限定されないが、接着フィルム、プリプレグ等のシート状積層材料、回路基板(積層板用途、多層プリント配線板用途等)に適用することが出来る。本発明の樹脂組成物は、ワニス状態で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、プリプレグ等のシート状積層材料の形態で用いるのが好ましい。樹脂組成物の軟化点は、シート状積層材料のラミネート性の観点から40〜150℃が好ましい。 The resin composition of the present invention is a composition particularly suitable as a resin composition for an insulating layer of a multilayer printed wiring board. However, a solder resist, an underfill material, a die bonding material, a semiconductor sealing material, a hole filling resin, and a component filling It can be used in a wide range of applications where a resin composition is required, such as a resin. In addition, the form of the resin composition of the present invention is not particularly limited, but it can be applied to sheet-like laminated materials such as adhesive films and prepregs, and circuit boards (for laminated boards and multilayer printed wiring boards). The resin composition of the present invention can be applied to a circuit board in a varnish state to form an insulating layer, but in general, it is preferably used in the form of a sheet-like laminated material such as an adhesive film or a prepreg. . The softening point of the resin composition is preferably 40 to 150 ° C. from the viewpoint of the laminate property of the sheet-like laminated material.
<シート状積層材料>
(接着フィルム)
本発明の接着フィルムは、支持体上に樹脂組成物層が形成されたものであり、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、この樹脂ワニスを、ダイコーターなどを用いて、支持体に塗布し、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。
<Sheet laminated material>
(Adhesive film)
The adhesive film of the present invention has a resin composition layer formed on a support, and is prepared by a method known to those skilled in the art, for example, a resin varnish in which a resin composition is dissolved in an organic solvent. Can be produced by applying the composition to a support using a die coater or the like, and further drying the organic solvent by heating or blowing hot air 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種以上を組みわせて用いてもよい。 Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, and carbitols such as cellosolve and butyl carbitol. And aromatic hydrocarbons such as toluene and xylene, 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量が10質量%以下、好ましくは5質量%以下となるように乾燥させる。ワニス中の有機溶剤量、有機溶剤の沸点によっても異なるが、例えば30〜60質量%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により、樹脂組成物層を形成することができる。 The drying conditions are not particularly limited, but the drying is performed so that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Depending on the amount of organic solvent in the varnish and the boiling point of the organic solvent, for example, a resin composition layer is formed by drying a varnish containing 30 to 60% by mass of an organic solvent at 50 to 150 ° C. for about 3 to 10 minutes. can do.
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、導体層の厚さ以上とするのが好ましい。回路基板が有する導体層の厚さは通常5〜70μmの範囲であるので、樹脂組成物層は10〜100μmの厚さを有するのが好ましい。薄膜化の観点から、15〜80μmがより好ましい。 The thickness of the resin composition layer formed in the adhesive film is preferably equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, the resin composition layer preferably has a thickness of 10 to 100 μm. From the viewpoint of thinning, 15 to 80 μm is more preferable.
支持体としては、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のフィルム、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のフィルム、ポリカーボネートフィルム、ポリイミドフィルムなどの各種プラスチックフィルムが挙げられる。また離型紙や銅箔、アルミニウム箔等の金属箔などを使用してもよい。中でも、汎用性の点から、プラスチックフィルムが好ましく、ポリエチレンテレフタレートフィルムがより好ましい。支持体及び後述する保護フィルムには、マッド処理、コロナ処理等の表面処理が施してあってもよい。また、シリコーン樹脂系離型剤、アルキッド樹脂系離型剤、フッ素樹脂系離型剤等の離型剤で離型処理が施してあってもよい。 Examples of the support include polyolefin films such as polyethylene, polypropylene, and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyester films such as polyethylene naphthalate, polycarbonate films, and polyimide films. Various plastic films are listed. Moreover, you may use release foil, metal foil, such as copper foil and aluminum foil. Among these, from the viewpoint of versatility, a plastic film is preferable, and a polyethylene terephthalate film is more preferable. The support and a protective film described later may be subjected to surface treatment such as mud treatment or corona treatment. The release treatment may be performed with a release agent such as a silicone resin release agent, an alkyd resin release agent, or a fluororesin release agent.
支持体の厚さは特に限定されないが、10〜150μmが好ましく、25〜50μmがより好ましい。 Although the thickness of a support body is not specifically limited, 10-150 micrometers is preferable and 25-50 micrometers is more preferable.
樹脂組成物層の支持体が密着していない面には、支持体に準じた保護フィルムをさらに積層することができる。保護フィルムの厚みは、特に限定されるものではないが、例えば、1〜40μmである。保護フィルムを積層することにより、樹脂組成物層の表面へのゴミ等の付着やキズを防止することができる。接着フィルムは、ロール状に巻きとって貯蔵することもできる。 A protective film according to the support can be further laminated on the surface of the resin composition layer on which the support is not in close contact. Although the thickness of a protective film is not specifically limited, For example, it is 1-40 micrometers. By laminating the protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches. The adhesive film can also be stored in a roll.
(プリプレグ)
本発明のプリプレグは、本発明の樹脂組成物をシート状補強基材にホットメルト法又はソルベント法により含浸させ、加熱して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シート状補強基材に含浸した状態となるプリプレグとすることができる。シート状補強基材としては、例えば、ガラスクロスやアラミド繊維等のプリプレグ用繊維として常用されている繊維からなるものを用いることができる。そして支持体上にプリプレグが形成されたものが好適である。
(Prepreg)
The prepreg of the present invention can be produced by impregnating the resin composition of the present invention into a sheet-like reinforcing base material by a hot melt method or a solvent method, and heating and semi-curing it. That is, it can be set as the prepreg which will be in the state which impregnated the sheet-like reinforcement base material with the resin composition of this invention. As a sheet-like reinforcement base material, what consists of a fiber currently used as prepreg fibers, such as glass cloth and an aramid fiber, can be used, for example. And what formed the prepreg on the support body is suitable.
ホットメルト法は、樹脂組成物を有機溶剤に溶解することなく、支持体上に一旦コーティングし、それをシート状補強基材にラミネートする、あるいはダイコーターによりシート状補強基材に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にして樹脂を有機溶剤に溶解して樹脂ワニスを調製し、このワニスにシート状補強基材を浸漬し、樹脂ワニスをシート状補強基材に含浸させ、その後乾燥させる方法である。また、接着フィルムをシート状補強基材の両面から加熱、加圧条件下、連続的に熱ラミネートすることで調製することもできる。支持体や保護フィルム等も接着フィルムと同様に用いることができる。 In the hot melt method, the resin composition is once coated on a support without being dissolved in an organic solvent, and then laminated on a sheet-like reinforcing substrate, or directly applied to a sheet-like reinforcing substrate by a die coater. Thus, a prepreg is manufactured. In the solvent method, a resin varnish is prepared by dissolving a resin in an organic solvent in the same manner as the adhesive film, and a sheet-like reinforcing base material is immersed in the varnish, and then the resin-like varnish is impregnated into the sheet-like reinforcing base material. It is a method of drying. Alternatively, the adhesive film can be prepared by continuously laminating the adhesive film from both sides of the sheet-like reinforcing substrate under heating and pressure conditions. A support, a protective film, and the like can be used in the same manner as the adhesive film.
<シート状積層材料を用いた多層プリント配線板>
次に、上記のようにして製造したシート状積層材料を用いて多層プリント配線板を製造する方法の一例を説明する。
<Multilayer printed wiring board using sheet-like laminated material>
Next, an example of a method for producing a multilayer printed wiring board using the sheet-like laminated material produced as described above will be described.
まず、シート状積層材料を、真空ラミネーターを用いて回路基板の片面又は両面にラミネート(積層)する。回路基板に用いられる基板としては、例えば、ガラスエポキシ基板、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が挙げられる。なお、ここで回路基板とは、上記のような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とを交互に積層してなる多層プリント配線板において、該多層プリント配線板の最外層の片面又は両面がパターン加工された導体層(回路)となっているものも、ここでいう回路基板に含まれる。なお導体層表面には、黒化処理、銅エッチング等により予め粗化処理が施されていてもよい。 First, a sheet-like laminated material is laminated (laminated) on one side or both sides of a circuit board using a vacuum laminator. Examples of the substrate used for the circuit substrate include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like. In addition, a circuit board means here that the conductor layer (circuit) patterned was formed in the one or both surfaces of the above boards. Also, in a multilayer printed wiring board in which conductor layers and insulating layers are alternately laminated, one of the outermost layers of the multilayer printed wiring board is a conductor layer (circuit) in which one or both sides are patterned. It is included in the circuit board. The surface of the conductor layer may be previously roughened by blackening, copper etching, or the like.
上記ラミネートにおいて、シート状積層材料が保護フィルムを有している場合には該保護フィルムを除去した後、必要に応じてシート状積層材料及び回路基板をプレヒートし、シート状積層材料を加圧及び加熱しながら回路基板にラミネートする。本発明のシート状積層材料においては、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。ラミネートの条件は、特に限定されるものではないが、例えば、圧着温度(ラミネート温度)を好ましくは70〜140℃、圧着圧力(ラミネート圧力)を好ましくは1〜11kgf/cm2(9.8×104〜107.9×104N/m2)とし、圧着時間(ラミネート時間)を好ましくは5〜180秒とし、空気圧20mmHg(26.7hPa)以下の減圧下でラミネートするのが好ましい。また、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。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。 In the above laminate, when the sheet-like laminate material has a protective film, after removing the protective film, the sheet-like laminate material and the circuit board are preheated as necessary, and the sheet-like laminate material is pressurized and Laminate to circuit board while heating. In the sheet-like laminated material of the present invention, a method of laminating on a circuit board under reduced pressure by a vacuum laminating method is suitably used. Lamination conditions are not particularly limited. For example, the pressure bonding temperature (laminating temperature) is preferably 70 to 140 ° C., and the pressure bonding pressure (laminating pressure) is preferably 1 to 11 kgf / cm 2 (9.8 × 10 4 to 107.9 × 10 4 N / m 2 ), the pressure bonding time (laminating time) is preferably 5 to 180 seconds, and the lamination is preferably performed under reduced pressure with an air pressure of 20 mmHg (26.7 hPa) or less. The laminating method may be a batch method or a continuous method using a roll. 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 Co., Ltd., a roll dry coater manufactured by Hitachi Industries, Ltd., and Hitachi AIC Co., Ltd. ) Made vacuum laminator and the like.
シート状積層材料を回路基板にラミネートした後、室温付近に冷却してから、支持体を剥離する場合は剥離し、樹脂組成物を熱硬化して硬化物を形成することで、回路基板上に絶縁層を形成することができる。熱硬化の条件は、樹脂組成物中の樹脂成分の種類、含有量などに応じて適宜選択すればよいが、好ましくは150℃〜220℃で20分〜180分、より好ましくは160℃〜210℃で30〜120分の範囲で選択される。絶縁層を形成した後、硬化前に支持体を剥離しなかった場合は、必要によりここで剥離することもできる。 After laminating the sheet-like laminated material on the circuit board, after cooling to near room temperature, if the support is peeled off, it is peeled off, and the resin composition is thermally cured to form a cured product, thereby forming a cured product on the circuit board. An insulating layer can be formed. The thermosetting conditions may be appropriately selected according to the type and content of the resin component in the resin composition, but preferably 150 ° C. to 220 ° C. for 20 minutes to 180 minutes, more preferably 160 ° C. to 210 ° C. It is selected in the range of 30 to 120 minutes at ° C. After the insulating layer is formed, if the support is not peeled before curing, it can be peeled off here if necessary.
また、シート状積層材料を、真空プレス機を用いて回路基板の片面又は両面に積層することもできる。減圧下、加熱及び加圧を行う積層工程は、一般の真空ホットプレス機を用いて行うことが可能である。例えば、加熱されたSUS板等の金属板を支持体層側からプレスすることにより行うことができる。プレス条件は、減圧度を通常1×10−2MPa以下、好ましくは1×10−3MPa以下の減圧下とする。加熱及び加圧は、1段階で行うことも出来るが、樹脂のしみだしを制御する観点から2段階以上に条件を分けて行うのが好ましい。例えば、1段階目のプレスを、温度が70〜150℃、圧力が1〜15kgf/cm2の範囲、2段階目のプレスを、温度が150〜200℃、圧力が1〜40kgf/cm2の範囲で行うのが好ましい。各段階の時間は30〜120分で行うのが好ましい。このように樹脂組成物層を熱硬化することにより回路基板上に絶縁層を形成することができる。市販されている真空ホットプレス機としては、例えば、MNPC−V−750−5−200(株)名機製作所製)、VH1−1603(北川精機(株)製)等が挙げられる。 Moreover, a sheet-like laminated material can also be laminated | stacked on the single side | surface or both surfaces of a circuit board using a vacuum press machine. The lamination process for heating and pressurizing under reduced pressure can be performed using a general vacuum hot press machine. For example, it can be performed by pressing a metal plate such as a heated SUS plate from the support layer side. The pressing condition is that the degree of vacuum is usually 1 × 10 −2 MPa or less, preferably 1 × 10 −3 MPa or less. Although heating and pressurization can be carried out in one stage, it is preferable to carry out the conditions separately in two or more stages from the viewpoint of controlling the oozing of the resin. For example, the first stage press has a temperature of 70 to 150 ° C. and the pressure is in the range of 1 to 15 kgf / cm 2, and the second stage press has the temperature of 150 to 200 ° C. and the pressure is in the range of 1 to 40 kgf / cm 2 It is preferred to do so. The time for each stage is preferably 30 to 120 minutes. Thus, an insulating layer can be formed on a circuit board by thermosetting the resin composition layer. Examples of commercially available vacuum hot press machines include MNPC-V-750-5-200 (manufactured by Meiki Seisakusho), VH1-1603 (manufactured by Kitagawa Seiki Co., Ltd.), and the like.
次いで、回路基板上に形成された絶縁層に穴開け加工を行ってビアホール、スルーホールを形成する。穴あけ加工は、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加工が最も一般的な方法である。穴あけ加工前に支持体を剥離しなかった場合は、ここで剥離することになる。 Next, a hole is formed in the insulating layer formed on the circuit board to form a via hole and a through hole. For example, the drilling can be performed by a known method such as drilling, laser, or plasma, or a combination of these methods if necessary, but drilling by a laser such as a carbon dioxide gas laser or a YAG laser is the most common. Is the method. If the support is not peeled off before drilling, it will be peeled off here.
次いで、絶縁層表面に粗化処理を行う。乾式の粗化処理の場合はプラズマ処理等が挙げられ、湿式の粗化処理の場合は膨潤液による膨潤処理、酸化剤による粗化処理及び中和液による中和処理をこの順に行う方法が挙げられる。湿式の粗化処理の方が、絶縁層表面に凸凹のアンカーを形成しながら、ビアホール内のスミアを除去することができる点で好ましい。膨潤液による膨潤処理は、絶縁層を50〜80℃で5〜20分間(好ましくは55〜70℃で8〜15分間)、膨潤液に浸漬させることで行われる。膨潤液としてはアルカリ溶液、界面活性剤溶液等が挙げられ、好ましくはアルカリ溶液であり、該アルカリ溶液としては、例えば、水酸化ナトリウム溶液、水酸化カリウム溶液等が挙げられる。市販されている膨潤液としては、例えば、アトテックジャパン(株)製のスウェリング・ディップ・セキュリガンスP(Swelling Dip Securiganth P)、スウェリング・ディップ・セキュリガンスSBU(Swelling Dip Securiganth SBU)等を挙げることができる。酸化剤による粗化処理は、絶縁層を60〜80℃で10〜30分間(好ましくは70〜80℃で15〜25分間)、酸化剤溶液に浸漬させることで行われる。酸化剤としては、例えば、水酸化ナトリウムの水溶液に過マンガン酸カリウムや過マンガン酸ナトリウムを溶解したアルカリ性過マンガン酸溶液、重クロム酸塩、オゾン、過酸化水素/硫酸、硝酸等を挙げることができる。また、アルカリ性過マンガン酸溶液における過マンガン酸塩の濃度は5〜10重量%とするのが好ましい。市販されている酸化剤としては、例えば、アトテックジャパン(株)製のコンセントレート・コンパクト CP、ドージングソリューション セキュリガンスP等のアルカリ性過マンガン酸溶液が挙げられる。中和液による中和処理は、30〜50℃で3〜10分間(好ましくは35〜45℃で3〜8分間)、中和液に浸漬させることで行われる。中和液としては、酸性の水溶液が好ましく、市販品としては、アトテックジャパン(株)製のリダクションソリューシン・セキュリガントPが挙げられる。 Next, a roughening process is performed on the surface of the insulating layer. In the case of dry-type roughening treatment, plasma treatment or the like can be mentioned. It is done. The wet roughening treatment is preferable in that smear in the via hole can be removed while forming an uneven anchor on the surface of the insulating layer. The swelling treatment with the swelling liquid is performed by immersing the insulating layer in the swelling liquid at 50 to 80 ° C. for 5 to 20 minutes (preferably at 55 to 70 ° C. for 8 to 15 minutes). Examples of the swelling liquid include an alkaline solution and a surfactant solution, and an alkaline solution is preferable. Examples of the alkaline solution include a sodium hydroxide solution and a potassium hydroxide solution. Examples of the commercially available swelling liquid include Swelling Dip Securiganth P (Swelling Dip Securiganth P) and Swelling Dip Securiganth SBU (ABUTEC Japan). be able to. The roughening treatment with an oxidizing agent is performed by immersing the insulating layer in an oxidizing agent solution at 60 to 80 ° C. for 10 to 30 minutes (preferably at 70 to 80 ° C. for 15 to 25 minutes). Examples of the oxidizing agent include alkaline permanganate solution in which potassium permanganate and sodium permanganate are dissolved in an aqueous solution of sodium hydroxide, dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid and the like. it can. The concentration of permanganate in the alkaline permanganate solution is preferably 5 to 10% by weight. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as Concentrate Compact CP and Dosing Solution Securigans P manufactured by Atotech Japan. The neutralization treatment with the neutralizing solution is performed by immersing in a neutralizing solution at 30 to 50 ° C. for 3 to 10 minutes (preferably at 35 to 45 ° C. for 3 to 8 minutes). As the neutralizing solution, an acidic aqueous solution is preferable, and as a commercially available product, Reduction Solution / Secligant P manufactured by Atotech Japan Co., Ltd. may be mentioned.
次いで、乾式メッキ又は湿式メッキにより絶縁層上に導体層を形成する。乾式メッキとしては、蒸着、スパッタリング、イオンプレーティング等の公知の方法を使用することができる。湿式メッキとしては、無電解メッキと電解メッキとを組み合わせて導体層を形成する方法、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方法、等が挙げられる。その後のパターン形成の方法として、例えば、当業者に公知のサブトラクティブ法、セミアディティブ法などを用いることができ、上述の一連の工程を複数回繰り返すことで、ビルドアップ層を多段に積層した多層プリント配線板となる。本発明においては、低粗度、高ピールであるため、多層プリント配線板のビルドアップ層として好適に使用することができる。 Next, a conductor layer is formed on the insulating layer by dry plating or wet plating. As the dry plating, a known method such as vapor deposition, sputtering, or ion plating can be used. Examples of wet plating include a method in which a conductive layer is formed by combining electroless plating and electrolytic plating, a method in which a plating resist having a pattern opposite to that of the conductive layer is formed, and a conductive layer is formed only by electroless plating. It is done. As a pattern formation method thereafter, for example, a subtractive method or a semi-additive method known to those skilled in the art can be used. By repeating the above-described series of steps a plurality of times, a multilayer in which build-up layers are stacked in multiple stages It becomes a printed wiring board. In the present invention, since it has low roughness and high peel, it can be suitably used as a build-up layer of a multilayer printed wiring board.
<半導体装置>
本発明の多層プリント配線板を用いることで半導体装置を製造することができる。本発明の多層プリント配線板の導通箇所に、半導体チップを実装することにより半導体装置を製造することができる。「導通箇所」とは、「多層プリント配線板における電気信号を伝える箇所」であって、その場所は表面であっても、埋め込まれた箇所であってもいずれでも構わない。また、半導体チップは半導体を材料とする電気回路素子であれば特に限定されない。
<Semiconductor device>
A semiconductor device can be manufactured by using the multilayer printed wiring board of the present invention. A semiconductor device can be manufactured by mounting a semiconductor chip in a conductive portion of the multilayer printed wiring board of the present invention. The “conduction location” is a “location where an electrical signal is transmitted in a multilayer printed wiring board”, and the location may be a surface or an embedded location. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.
本発明の半導体装置を製造する際の半導体チップの実装方法は、半導体チップが有効に機能しさえすれば、特に限定されないが、具体的には、ワイヤボンディング実装方法、フリップチップ実装方法、バンプなしビルドアップ層(BBUL)による実装方法、異方性導電フィルム(ACF)による実装方法、非導電性フィルム(NCF)による実装方法、などが挙げられる。 The semiconductor chip mounting method for manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, and no bumps. Examples include a mounting method using a build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF).
以下、本発明を実施例により具体的に説明するが、本発明はこれらの実施例に限定されるものではない。なお、「部」は質量部を意味する。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. “Part” means part by mass.
<測定方法・評価方法>
まずは各種測定方法・評価方法について説明する。
<Measurement method / Evaluation method>
First, various measurement methods and evaluation methods will be described.
〔ピール強度測定用サンプルの調製〕
(1)内層回路基板の下地処理
内層回路を形成し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にて1umエッチングして銅表面の粗化処理をおこなった。
[Preparation of peel strength measurement sample]
(1) Underlayer treatment of inner layer circuit board Both sides of a glass cloth base epoxy resin double-sided copper-clad laminate (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 etching 1 μm with 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(名機(株)製商品名)を用いて、内層回路基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で圧着することにより行った。
(2) Lamination of adhesive film The adhesive film created in Examples and Comparative Examples was laminated on both surfaces of the inner layer circuit board using a batch type vacuum pressure laminator MVLP-500 (trade name, manufactured by Meiki Co., Ltd.). . Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressure bonding for 30 seconds at 100 ° C. and a pressure of 0.74 MPa.
(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ポリエチレンテレフタレート(PET)フィルムを剥離した後、100℃、30分続けて180℃、30分の硬化条件で樹脂組成物を硬化して絶縁層を形成した
(3) Curing of the resin composition After peeling the polyethylene terephthalate (PET) film from the laminated adhesive film, the resin composition is cured under curing conditions of 100 ° C for 30 minutes and then at 180 ° C for 30 minutes. Formed
(4)粗化処理
絶縁層を形成した内層回路基板を、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・セキュリガントP(グリコールエーテル類、水酸化ナトリウムの水溶液)に、60℃で10分間浸漬した。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分間浸漬した。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(硫酸の水溶液)に40℃で5分間浸漬した。その後80℃で30分乾燥した。
(4) Roughening treatment The inner layer circuit board on which the insulating layer is formed is a swelling liquid, diethylene glycol monobutyl ether-containing swelling dip securigant P (glycol ethers, aqueous solution of sodium hydroxide) of Atotech Japan Co., Ltd. And soaking at 60 ° C. for 10 minutes. Next, as a roughening liquid, it was immersed in the concentrate compact P (KMnO4: 60g / L, NaOH: 40g / L aqueous solution) of Atotech Japan Co., Ltd. for 20 minutes at 80 ° C. Finally, as a neutralizing solution, it was immersed for 5 minutes at 40 ° C. in Reduction Sholysin Securigant P (an aqueous solution of sulfuric acid) of Atotech Japan Co., Ltd. Thereafter, it was dried at 80 ° C. for 30 minutes.
(5)セミアディティブ工法によるメッキ
この基板を、PdCl2を含む無電解メッキ用溶液に40℃で5分間浸漬し、次に無電解銅メッキ液に25℃で20分間浸漬した。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、30μmの厚さで導体層を形成した。次に、アニール処理を190℃にて60分間行った。この基板を評価基板とした。
(5) Plating by semi-additive method This substrate was immersed in an electroless plating solution containing PdCl 2 at 40 ° C. for 5 minutes, and then immersed in an electroless copper plating solution at 25 ° C. for 20 minutes. 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 μm. Next, annealing treatment was performed at 190 ° C. for 60 minutes. This substrate was used as an evaluation substrate.
〔メッキ導体層の引き剥がし強さ(ピール強度)の測定〕
評価基板の導体層に、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(株式会社ティー・エス・イー、オートコム型試験機 AC−50C−SL)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(kgf/cm)を測定した。
[Measurement of peel strength (peel strength) of plated conductor layer]
In the conductor layer of the evaluation board, cut a portion of width 10 mm and length 100 mm, peel off one end, and hold it with a gripping tool (TSE Co., Ltd., Autocom type testing machine AC-50C-SL). The load (kgf / cm) when peeling 35 mm in the vertical direction at a speed of 50 mm / min at room temperature was measured.
〔誘電正接の測定〕
各実施例および各比較例で得られた接着フィルムを190℃で90分熱硬化させて、PETフィルムを剥離してシート状の硬化物を得た。その硬化物を、幅2mm、長さ80mmの試験片に切断し、関東応用電子開発(株)製空洞共振器摂動法誘電率測定装置CP521およびアジレントテクノロジー(株)製ネットワークアナライザーE8362Bを使用して、空洞共振法で測定周波数5.8GHzにて誘電正接(tanδ)の測定を行った。2本の試験片について測定を行い、平均値を算出した。
[Measurement of dielectric loss tangent]
The adhesive films obtained in each Example and each Comparative Example were thermally cured at 190 ° C. for 90 minutes, and the PET film was peeled off to obtain a sheet-like cured product. The cured product was cut into a test piece having a width of 2 mm and a length of 80 mm, and a cavity resonator perturbation method dielectric constant measuring device CP521 manufactured by Kanto Applied Electronics Development Co., Ltd. and a network analyzer E8362B manufactured by Agilent Technology Co., Ltd. were used. The dielectric loss tangent (tan δ) was measured by the cavity resonance method at a measurement frequency of 5.8 GHz. Two test pieces were measured, and the average value was calculated.
〔ガラス転移温度の測定〕
各実施例および各比較例で得られたで得られた接着フィルムを190℃で90分間加熱して樹脂組成物層を熱硬化させた。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回目の測定においてガラス転移温度を算出した。
[Measurement of glass transition temperature]
The adhesive films obtained in each Example and each Comparative Example were heated at 190 ° C. for 90 minutes to thermally cure the resin composition layer. 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 glass transition temperature was calculated in the second measurement.
〔可とう性の評価〕
各実施例および各比較例で得られた接着フィルムを90度に折り曲げ、塗膜表面の観察をおこなった。そのときの表面状態を次の基準で判断した。
○:塗膜表面にクラックが見られない
×:塗膜表面に微小なクラックが見られた
[Evaluation of flexibility]
The adhesive films obtained in each Example and each Comparative Example were bent at 90 degrees, and the coating film surface was observed. The surface condition at that time was judged according to the following criteria.
○: No cracks were found on the coating film surface ×: Minute cracks were found on the coating film surface
<実施例1>
グリシジルエステル型エポキシ樹脂(ナガセケムテックス(株)製「EX−721」、エポキシ当量154)10部、結晶性2官能エポキシ樹脂(三菱化学(株)製「YX4000HK」、エポキシ当量約185)15部、ビフェニル型エポキシ樹脂(日本化薬(株)製「NC3000L」、エポキシ当量269)15部、フェノキシ樹脂(三菱化学(株)製「YL7553BH30」、固形分30質量%のMEKとシクロヘキサノンの1:1溶液)10部を、ソルベントナフサ20部に撹拌しながら加熱溶解させた。室温にまで冷却後、そこへトリアジン骨格含有フェノール系硬化剤(DIC(株)製「LA−3018−50P」水酸基当量151)の固形分50%の2-メトキシプロパノール溶液10部、活性エステル型硬化剤(DIC(株)製「HPC8000−65T」、活性基当量約223の不揮発分65質量%のトルエン溶液)10部、硬化促進剤(4−ジメチルアミノピリジン、固形分10質量%のMEK溶液)1部、フェニルアミノシラン系カップリング剤(信越化学工業(株)製、「KBM573」)で表面処理された球形シリカ(平均粒径0.5μm、(株)アドマテックス製「SOC2」、単位面積当たりのカーボン量0.39mg/m2)150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。次いで、離型処理付きポリエチレンテレフタレートフィルム(リンテック(株)製「PET501010」、厚さ50μm)の離型面上に、乾燥後の樹脂組成物層の厚みが30μmとなるように樹脂ワニスを均一に塗布し、80〜120℃(平均100℃)で4分間乾燥させて、接着フィルムを作製した。
<Example 1>
10 parts of a glycidyl ester type epoxy resin (“EX-721” manufactured by Nagase ChemteX Corporation, epoxy equivalent 154), 15 parts of a crystalline bifunctional epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185) , 15 parts of biphenyl type epoxy resin (Nippon Kayaku Co., Ltd. “NC3000L”, epoxy equivalent 269), phenoxy resin (“YL7553BH30” manufactured by Mitsubishi Chemical Corporation), 1: 1 of MEK and cyclohexanone having a solid content of 30% by mass 10 parts of the solution was dissolved in 20 parts of solvent naphtha with stirring. After cooling to room temperature, 10 parts of a 2-methoxypropanol solution having a solid content of 50% in a triazine skeleton-containing phenolic curing agent (“LA-3018-50P” hydroxyl group equivalent 151 manufactured by DIC Corporation), active ester type curing 10 parts of an agent (“HPC8000-65T” manufactured by DIC Corporation, a toluene solution having a nonvolatile content of 65% by mass having an active group equivalent of about 223), a curing accelerator (4-dimethylaminopyridine, a MEK solution having a solid content of 10% by mass) 1 part, spherical silica surface treated with phenylaminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (average particle size 0.5 μm, “SOC2” manufactured by Admatex Co., Ltd.) per unit area Of carbon of 0.39 mg / m 2 ) was mixed and uniformly dispersed with a high-speed rotating mixer to prepare a resin varnish. Next, the resin varnish is uniformly applied on the release surface of a polyethylene terephthalate film with a release treatment (“PET501010” manufactured by Lintec Corporation, thickness 50 μm) so that the thickness of the resin composition layer after drying is 30 μm. It apply | coated and dried at 80-120 degreeC (average 100 degreeC) for 4 minutes, and produced the adhesive film.
<実施例2>
実施例1のグリシジルエステル型エポキシ樹脂(ナガセケムテックス(株)製「EX−721」、エポキシ当量154)10部を、グリシジルエステル型エポキシ樹脂(ナガセケムテックス(株)製「EX−722L」、エポキシ当量151)10部に変更する以外は、実施例1と全く同様にして接着フィルムを作製した。
<Example 2>
10 parts of the glycidyl ester type epoxy resin of Example 1 (“EX-721” manufactured by Nagase ChemteX Corporation, epoxy equivalent 154) was added to the glycidyl ester type epoxy resin (“EX-722L” manufactured by Nagase ChemteX Corporation), Epoxy equivalent 151) An adhesive film was produced in the same manner as in Example 1 except that the equivalent was changed to 10 parts.
<実施例3>
実施例1のグリシジルエステル型エポキシ樹脂(ナガセケムテックス(株)製「EX−721」、エポキシ当量154)10部を、グリシジルエステル型エポキシ樹脂(新日鉄住金化学(株)製「YD172」、エポキシ当量600)10部に変更する以外は、実施例1と全く同様にして接着フィルムを作製した。
<Example 3>
10 parts of the glycidyl ester type epoxy resin (“EX-721” manufactured by Nagase ChemteX Corporation, epoxy equivalent 154) of Example 1 was added to the glycidyl ester type epoxy resin (“YD172” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), epoxy equivalent. 600) An adhesive film was produced in the same manner as in Example 1 except that the amount was changed to 10 parts.
<実施例4>
実施例1のグリシジルエステル型エポキシ樹脂(ナガセケムテックス(株)製「EX−721」、エポキシ当量154)10部を、グリシジルエステル型エポキシ樹脂(三菱化学(株)製「jER872」、一般式(3)のRがビスフェノールA型ジグリシジルエーテル構造、エポキシ当量650)10部に変更する以外は、実施例1と全く同様にして接着フィルムを作製した。
<Example 4>
10 parts of a glycidyl ester type epoxy resin (“EX-721” manufactured by Nagase ChemteX Corporation, epoxy equivalent 154) of Example 1 was added to a glycidyl ester type epoxy resin (“jER872” manufactured by Mitsubishi Chemical Corporation), a general formula ( An adhesive film was prepared in exactly the same manner as in Example 1 except that R in 3) was changed to 10 parts of bisphenol A type diglycidyl ether structure, epoxy equivalent 650).
<実施例5>
実施例1のグリシジルエステル型エポキシ樹脂(ナガセケムテックス(株)製「EX−721」、エポキシ当量154)10部を25部に変更し、更に結晶性2官能エポキシ樹脂(三菱化学(株)製「YX4000HK」、エポキシ当量185)15部を0部に変更する以外は、実施例1と全く同様にして接着フィルムを作製した。
<Example 5>
The glycidyl ester type epoxy resin of Example 1 (“EX-721” manufactured by Nagase ChemteX Corporation, epoxy equivalent 154) was changed to 10 parts, and further a crystalline bifunctional epoxy resin (manufactured by Mitsubishi Chemical Corporation). “YX4000HK”, epoxy equivalent 185) An adhesive film was produced in the same manner as in Example 1 except that 15 parts were changed to 0 parts.
<実施例6>
エステル骨格を有する脂環式エポキシ樹脂((株)ダイセル製「セロキサイド 2021P」、エポキシ当量126)8部、ジシクロペンタジエン型エポキシ樹脂(DIC(株)製「HP−7200H」、エポキシ当量275)12部、フェノキシ樹脂(三菱化学(株)製「YL7553BH30」、固形分30質量%のMEKとシクロヘキサノンの1:1溶液)10部を、ソルベントナフサ30部に撹拌しながら加熱溶解させた。室温にまで冷却後、そこへ活性エステル型硬化剤(DIC(株)製「HPC8000−65T」、活性基当量約223の不揮発分65質量%のトルエン溶液)35部、硬化促進剤(4−ジメチルアミノピリジン、固形分5質量%のMEK溶液)2.4部、難燃剤(三光(株)製「HCA−HQ」、10-(2,5-ジヒドロキシフェニル)-10-ヒドロ-9-オキサ-10-フォスファフェナンスレン-10-オキサイド、平均粒径2μm)2部、フェニルアミノシラン系カップリング剤(信越化学工業(株)製、「KBM573」)で表面処理された球形シリカ(平均粒径0.5μm、(株)アドマテックス製「SOC2」、単位面積当たりのカーボン量0.39mg/m2)150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。次いで、実施例1と同様にして、接着フィルムを作製した。
<Example 6>
Alicyclic epoxy resin having an ester skeleton ("Celoxide 2021P" manufactured by Daicel Corporation, epoxy equivalent 126) 8 parts, dicyclopentadiene type epoxy resin ("HP-7200H" manufactured by DIC Corporation, epoxy equivalent 275) 12 10 parts of a phenoxy resin ("YL7553BH30" manufactured by Mitsubishi Chemical Corporation, 1: 1 solution of MEK and cyclohexanone having a solid content of 30% by mass) was dissolved in 30 parts of solvent naphtha with stirring. After cooling to room temperature, 35 parts of an active ester-type curing agent (“HPC8000-65T” manufactured by DIC Corporation, 65% by weight non-volatile toluene solution having an active group equivalent of about 223), a curing accelerator (4-dimethyl) 2.4 parts of aminopyridine, MEK solution having a solid content of 5% by weight, flame retardant (“HCA-HQ” manufactured by Sanko Co., Ltd., 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa- 10 parts of phosphaphenanthrene-10-oxide (average particle size 2 μm), spherical silica (average particle size) surface-treated with a phenylaminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) 150 μm of 0.5 μm, “SOC2” manufactured by Admatechs Co., Ltd., and carbon amount of 0.39 mg / m 2 per unit area were mixed and dispersed uniformly with a high-speed rotary mixer to prepare a resin varnish. Next, an adhesive film was produced in the same manner as in Example 1.
<比較例1>
実施例1のグリシジルエステル型エポキシ樹脂(ナガセケムテックス(株)製「EX−721」、エポキシ当量154)10部を、ビスフェノールA型エポキシ樹脂(三菱化学(株)製「828US」、エポキシ当量180)10部に変更する以外は、実施例1と全く同様にして接着フィルムを作製した。
<Comparative Example 1>
10 parts of the glycidyl ester type epoxy resin of Example 1 (“EX-721” manufactured by Nagase ChemteX Corporation, epoxy equivalent 154) was added to bisphenol A type epoxy resin (“828 US” manufactured by Mitsubishi Chemical Corporation), epoxy equivalent 180 ) An adhesive film was produced in the same manner as in Example 1 except that the content was changed to 10 parts.
<比較例2>
実施例1のトリアジン骨格含有フェノール樹脂(DIC(株)製「LA3018−50P」、水酸基当量151の不揮発成分50%の2-メトキシプロパノール溶液)10部を20部に変更し、更に活性エステル型硬化剤(DIC(株)製「HPC8000−65T」、活性基当量約223の不揮発分65質量%のトルエン溶液)10部を0部に変更する以外は、実施例1と全く同様にして接着フィルムを作製した。
<Comparative example 2>
10 parts of the triazine skeleton-containing phenol resin of Example 1 (“LA3018-50P” manufactured by DIC Corporation, 2-methoxypropanol solution of 50% non-volatile component having a hydroxyl group equivalent of 151) was changed to 20 parts, and further active ester type curing The adhesive film was prepared in the same manner as in Example 1 except that 10 parts of the agent (“PCC8000-65T” manufactured by DIC Corporation, toluene solution with a non-volatile content of 65 mass% having an active group equivalent of about 223) was changed to 0 parts. Produced.
<比較例3>
実施例1のグリシジルエステル型エポキシ樹脂(ナガセケムテックス(株)製「EX−721」、エポキシ当量154)10部を35部に変更し、更に結晶性2官能エポキシ樹脂((株)製「YX4000HK」、エポキシ当量185)15部を0部に変更し、更にビフェニル型エポキシ樹脂(日本化薬(株)製「NC3000L」、エポキシ当量269)15部を5部に変更する以外は、実施例1と全く同様にして接着フィルムを作製した。
<Comparative Example 3>
The glycidyl ester type epoxy resin of Example 1 (“EX-721” manufactured by Nagase ChemteX Corp., epoxy equivalent 154) was changed to 35 parts, and further a crystalline bifunctional epoxy resin (“YX4000HK” manufactured by Co., Ltd.). “Epoxy equivalent 185) 15 parts in Example 1 except that 15 parts were changed to 0 parts and 15 parts in biphenyl type epoxy resin (“ NC3000L ”, Epoxy equivalent 269 manufactured by Nippon Kayaku Co., Ltd.) were changed to 5 parts. An adhesive film was prepared in the same manner as described above.
結果を表1に示す。 The results are shown in Table 1.
表1の結果から、実施例の樹脂組成物は、硬化物の誘電正接が低く、ピール強度が高くなり、かつシート状形態の可とう性に優れていることが分かる。一方、比較例1ではエステル型骨格を有するエポキシ樹脂を用いていないため誘電正接が高くなり、可とう性も劣っている。比較例2では活性エステル型硬化剤を用いていないため、誘電正接が著しく高くなっている。比較例3ではエステル骨格を有するエポキシ樹脂の配合量が多く、ピール強度が低下している。 From the results shown in Table 1, it can be seen that the resin compositions of the examples have a low dielectric loss tangent of the cured product, a high peel strength, and excellent flexibility in the sheet form. On the other hand, in Comparative Example 1, since an epoxy resin having an ester skeleton is not used, the dielectric loss tangent is increased and the flexibility is also inferior. In Comparative Example 2, since the active ester type curing agent is not used, the dielectric loss tangent is remarkably increased. In Comparative Example 3, the amount of the epoxy resin having an ester skeleton is large, and the peel strength is lowered.
Claims (14)
前記樹脂組成物中の不揮発成分を100質量%とした場合、(C)無機充填材の含有量が50質量%以上であり、
(C)無機充填材を100質量部とした場合、(A)エステル骨格を有するエポキシ樹脂が1〜20質量部であることを特徴とする樹脂組成物。 (A) an epoxy resin having an ester skeleton, (B) an active ester type curing agent and (C) a resin composition containing an inorganic filler,
When the nonvolatile component in the resin composition is 100% by mass, the content of the (C) inorganic filler is 50% by mass or more,
(C) When the inorganic filler is 100 parts by mass, (A) the epoxy resin having an ester skeleton is 1 to 20 parts by mass.
(A)エステル骨格を有するエポキシ樹脂としてグリシジルエステル型エポキシ樹脂を含み、
他のエポキシ樹脂としてビフェニル型エポキシ樹脂を含み、
(C)無機充填材としてシリカを含む、請求項1〜5のいずれか1項記載の樹脂組成物。 (A) An epoxy resin having an ester skeleton and another epoxy resin are used in combination,
(A) a glycidyl ester type epoxy resin as an epoxy resin having an ester skeleton,
Including biphenyl type epoxy resin as other epoxy resin,
(C) The resin composition of any one of Claims 1-5 containing a silica as an inorganic filler.
(A)エステル骨格を有するエポキシ樹脂としてフタル酸ジグリシジルエステル型エポキシ樹脂又はヘキサヒドロフタル酸ジグリシジルエステル型エポキシ樹脂を含み、
他のエポキシ樹脂としてビフェニル型エポキシ樹脂を含み、
(C)無機充填材として平均粒径0.01〜5μmのシリカを含む、請求項1〜6のいずれか1項記載の樹脂組成物。 (A) An epoxy resin having an ester skeleton and another epoxy resin are used in combination,
(A) As an epoxy resin having an ester skeleton, phthalic acid diglycidyl ester type epoxy resin or hexahydrophthalic acid diglycidyl ester type epoxy resin,
Including biphenyl type epoxy resin as other epoxy resin,
(C) The resin composition of any one of Claims 1-6 containing the silica with an average particle diameter of 0.01-5 micrometers as an inorganic filler.
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Also Published As
Publication number | Publication date |
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CN104045976A (en) | 2014-09-17 |
CN104045976B (en) | 2018-04-03 |
TWI627224B (en) | 2018-06-21 |
KR102132148B1 (en) | 2020-07-09 |
TW201443141A (en) | 2014-11-16 |
KR20140113409A (en) | 2014-09-24 |
JP6163803B2 (en) | 2017-07-19 |
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