JP6281233B2 - Resin composition - Google Patents
Resin composition Download PDFInfo
- Publication number
- JP6281233B2 JP6281233B2 JP2013214005A JP2013214005A JP6281233B2 JP 6281233 B2 JP6281233 B2 JP 6281233B2 JP 2013214005 A JP2013214005 A JP 2013214005A JP 2013214005 A JP2013214005 A JP 2013214005A JP 6281233 B2 JP6281233 B2 JP 6281233B2
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- resin
- insulating layer
- mass
- curing agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000011342 resin composition Substances 0.000 title claims description 109
- 239000003795 chemical substances by application Substances 0.000 claims description 75
- 239000003822 epoxy resin Substances 0.000 claims description 60
- 229920000647 polyepoxide Polymers 0.000 claims description 60
- 239000011256 inorganic filler Substances 0.000 claims description 42
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 42
- 150000002148 esters Chemical class 0.000 claims description 37
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 31
- 238000007747 plating Methods 0.000 claims description 24
- 239000004643 cyanate ester Substances 0.000 claims description 23
- 239000012756 surface treatment agent Substances 0.000 claims description 18
- 239000002648 laminated material Substances 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 14
- 239000004065 semiconductor Substances 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 229920005992 thermoplastic resin Polymers 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 5
- 238000001723 curing Methods 0.000 description 81
- -1 naphthylene ether Chemical compound 0.000 description 43
- 238000000034 method Methods 0.000 description 41
- 229920005989 resin Polymers 0.000 description 38
- 239000011347 resin Substances 0.000 description 38
- 239000000243 solution Substances 0.000 description 25
- 239000004020 conductor Substances 0.000 description 23
- 239000002313 adhesive film Substances 0.000 description 21
- 238000007788 roughening Methods 0.000 description 20
- 239000002966 varnish Substances 0.000 description 20
- 239000000047 product Substances 0.000 description 19
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 18
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 17
- 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 15
- 239000004593 Epoxy Substances 0.000 description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 14
- 238000010030 laminating Methods 0.000 description 14
- 229920003986 novolac Polymers 0.000 description 14
- 239000007787 solid Substances 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
- 239000007822 coupling agent Substances 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000003960 organic solvent Substances 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 206010042674 Swelling Diseases 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 11
- 239000000758 substrate Substances 0.000 description 11
- 230000008961 swelling Effects 0.000 description 11
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 10
- 239000006087 Silane Coupling Agent Substances 0.000 description 10
- 238000005259 measurement Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 8
- 230000001681 protective effect Effects 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 230000003014 reinforcing effect Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 238000004381 surface treatment Methods 0.000 description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 125000001624 naphthyl group Chemical group 0.000 description 5
- 230000003472 neutralizing effect Effects 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 5
- 239000013034 phenoxy resin Substances 0.000 description 5
- 229920006287 phenoxy resin Polymers 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 4
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 4
- IZSHZLKNFQAAKX-UHFFFAOYSA-N 5-cyclopenta-2,4-dien-1-ylcyclopenta-1,3-diene Chemical group C1=CC=CC1C1C=CC=C1 IZSHZLKNFQAAKX-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
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000005553 drilling Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 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
- 238000003475 lamination Methods 0.000 description 4
- 230000000670 limiting effect Effects 0.000 description 4
- 238000000691 measurement method Methods 0.000 description 4
- GLTDLAUASUFHNK-UHFFFAOYSA-N n-silylaniline Chemical compound [SiH3]NC1=CC=CC=C1 GLTDLAUASUFHNK-UHFFFAOYSA-N 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 3
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920002799 BoPET Polymers 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
- 239000012670 alkaline solution Substances 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000011889 copper foil Substances 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
- 238000005530 etching Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 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
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-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
- YTTFFPATQICAQN-UHFFFAOYSA-N 2-methoxypropan-1-ol Chemical compound COC(C)CO YTTFFPATQICAQN-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-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
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-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
- 229930185605 Bisphenol Natural products 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
- AEMRFAOFKBGASW-UHFFFAOYSA-M Glycolate Chemical compound OCC([O-])=O AEMRFAOFKBGASW-UHFFFAOYSA-M 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
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- AHZMUXQJTGRNHT-UHFFFAOYSA-N [4-[2-(4-cyanatophenyl)propan-2-yl]phenyl] cyanate Chemical compound C=1C=C(OC#N)C=CC=1C(C)(C)C1=CC=C(OC#N)C=C1 AHZMUXQJTGRNHT-UHFFFAOYSA-N 0.000 description 2
- NOKSMMGULAYSTD-UHFFFAOYSA-N [SiH4].N=C=O Chemical compound [SiH4].N=C=O NOKSMMGULAYSTD-UHFFFAOYSA-N 0.000 description 2
- MHRNQQUEUYMEEH-UHFFFAOYSA-N [[[ethyl(dimethyl)silyl]amino]-dimethylsilyl]ethane Chemical compound CC[Si](C)(C)N[Si](C)(C)CC MHRNQQUEUYMEEH-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
- 125000000217 alkyl group Chemical group 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 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
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000012943 hotmelt Substances 0.000 description 2
- 150000002440 hydroxy compounds Chemical class 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-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
- 238000006386 neutralization reaction Methods 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-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
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 229920000642 polymer 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
- 238000003825 pressing Methods 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 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
- 230000007261 regionalization Effects 0.000 description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DEQUKPCANKRTPZ-UHFFFAOYSA-N (2,3-dihydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1O DEQUKPCANKRTPZ-UHFFFAOYSA-N 0.000 description 1
- SDUWQMDIQSWWIE-UHFFFAOYSA-N (3-cyanato-5-methylidenecyclohexa-1,3-dien-1-yl) cyanate Chemical compound C=C1CC(OC#N)=CC(OC#N)=C1 SDUWQMDIQSWWIE-UHFFFAOYSA-N 0.000 description 1
- LTQBNYCMVZQRSD-UHFFFAOYSA-N (4-ethenylphenyl)-trimethoxysilane Chemical compound CO[Si](OC)(OC)C1=CC=C(C=C)C=C1 LTQBNYCMVZQRSD-UHFFFAOYSA-N 0.000 description 1
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- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 229910021523 barium zirconate Inorganic materials 0.000 description 1
- DQBAOWPVHRWLJC-UHFFFAOYSA-N barium(2+);dioxido(oxo)zirconium Chemical compound [Ba+2].[O-][Zr]([O-])=O DQBAOWPVHRWLJC-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002115 bismuth titanate Inorganic materials 0.000 description 1
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- XSEUMFJMFFMCIU-UHFFFAOYSA-N buformin Chemical compound CCCC\N=C(/N)N=C(N)N XSEUMFJMFFMCIU-UHFFFAOYSA-N 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- DAQREMPZDNTSMS-UHFFFAOYSA-M butyl(triphenyl)phosphanium;thiocyanate Chemical compound [S-]C#N.C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCC)C1=CC=CC=C1 DAQREMPZDNTSMS-UHFFFAOYSA-M 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- DEKLIKGLDMCMJG-UHFFFAOYSA-M decanoate;tetrabutylphosphanium Chemical compound CCCCCCCCCC([O-])=O.CCCC[P+](CCCC)(CCCC)CCCC DEKLIKGLDMCMJG-UHFFFAOYSA-M 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- 125000006222 dimethylaminomethyl group Chemical group [H]C([H])([H])N(C([H])([H])[H])C([H])([H])* 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- HTDKEJXHILZNPP-UHFFFAOYSA-N dioctyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OCCCCCCCC HTDKEJXHILZNPP-UHFFFAOYSA-N 0.000 description 1
- XMQYIPNJVLNWOE-UHFFFAOYSA-N dioctyl hydrogen phosphite Chemical compound CCCCCCCCOP(O)OCCCCCCCC XMQYIPNJVLNWOE-UHFFFAOYSA-N 0.000 description 1
- VTIXMGZYGRZMAW-UHFFFAOYSA-N ditridecyl hydrogen phosphite Chemical compound CCCCCCCCCCCCCOP(O)OCCCCCCCCCCCCC VTIXMGZYGRZMAW-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- FRCAGVUKJQCWBD-UHFFFAOYSA-L iodine green Chemical compound [Cl-].[Cl-].C1=CC(N(C)C)=CC=C1C(\C=1C=CC(=CC=1)[N+](C)(C)C)=C/1C=C(C)C(=[N+](C)C)C=C\1 FRCAGVUKJQCWBD-UHFFFAOYSA-L 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229940001447 lactate Drugs 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 125000005439 maleimidyl group Chemical class C1(C=CC(N1*)=O)=O 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- XFFPIAQRIDTSIZ-UHFFFAOYSA-N n'-[3-(dimethoxymethylsilyl)propyl]ethane-1,2-diamine Chemical compound COC(OC)[SiH2]CCCNCCN XFFPIAQRIDTSIZ-UHFFFAOYSA-N 0.000 description 1
- XJEJSMCUIKZVAW-UHFFFAOYSA-N n-silylmethanamine Chemical compound CN[SiH3] XJEJSMCUIKZVAW-UHFFFAOYSA-N 0.000 description 1
- FZZQNEVOYIYFPF-UHFFFAOYSA-N naphthalene-1,6-diol Chemical compound OC1=CC=CC2=CC(O)=CC=C21 FZZQNEVOYIYFPF-UHFFFAOYSA-N 0.000 description 1
- MNZMMCVIXORAQL-UHFFFAOYSA-N naphthalene-2,6-diol Chemical compound C1=C(O)C=CC2=CC(O)=CC=C21 MNZMMCVIXORAQL-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- SLYCYWCVSGPDFR-UHFFFAOYSA-N octadecyltrimethoxysilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OC)(OC)OC SLYCYWCVSGPDFR-UHFFFAOYSA-N 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 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 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- JTQPTNQXCUMDRK-UHFFFAOYSA-N propan-2-olate;titanium(2+) Chemical compound CC(C)O[Ti]OC(C)C JTQPTNQXCUMDRK-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000009774 resonance method Methods 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- HXLWJGIPGJFBEZ-UHFFFAOYSA-N tert-butyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C(C)(C)C HXLWJGIPGJFBEZ-UHFFFAOYSA-N 0.000 description 1
- GHPYAGKTTCKKDF-UHFFFAOYSA-M tetraphenylphosphanium;thiocyanate Chemical compound [S-]C#N.C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 GHPYAGKTTCKKDF-UHFFFAOYSA-M 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- FBBATURSCRIBHN-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyldisulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSCCC[Si](OCC)(OCC)OCC FBBATURSCRIBHN-UHFFFAOYSA-N 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-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
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- 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
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Laminated Bodies (AREA)
- Manufacturing Of Printed Wiring (AREA)
Description
本発明は、樹脂組成物に関する。さらに本発明は、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, this invention relates to 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、ビルドアップ層が多層化され、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 multilayer printed wiring boards are required to have multi-layered buildup layers and finer and higher density wiring.
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、フルオレン骨格を有するエポキシ化合物を含む硬化性組成物が、高耐熱性、低線膨張性、高屈折率であることが開示されているが、その性能は必ずしも十分ではなかった。 Various approaches have been made against this. For example, Patent Document 1 discloses that a curable composition containing an epoxy compound having a fluorene skeleton has high heat resistance, low linear expansion, and high refractive index, but the performance is not necessarily sufficient. There wasn't.
本発明が解決しようとする課題は、硬化して絶縁層とした後の湿式粗化工程において絶縁層表面の算術平均粗さの値が小さいのみならず、絶縁層表面の二乗平均平方根粗さの値も小さく、絶縁層上に十分なピール強度を有する導体層をメッキにより形成することができる、誘電正接が低い樹脂組成物を提供することである。 The problem to be solved by the present invention is that not only the arithmetic average roughness value of the insulating layer surface is small in the wet roughening step after curing into an insulating layer, but also the root mean square roughness of the insulating layer surface. It is to provide a resin composition having a low dielectric loss tangent, which can form a conductor layer having a small value and sufficient peel strength on an insulating layer by plating.
本発明者らは、上記課題を解決すべく鋭意検討した結果、ナフチルフルオレン構造を有するエポキシ樹脂、及び活性エステル系硬化剤及び／又はシアネートエステル系硬化剤を含有することを特徴とする樹脂組成物により、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the inventors of the present invention contain an epoxy resin having a naphthylfluorene structure, and an active ester curing agent and / or a cyanate ester curing agent. Thus, 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〕 成分（Ａ）ナフチルフルオレン構造を有するエポキシ樹脂、及び
成分（Ｂ）活性エステル系硬化剤及びシアネートエステル系硬化剤のうちのいずれか一方又は両方を含有することを特徴とする樹脂組成物。
〔２〕 前記成分（Ａ）の含有量が、樹脂組成物中の不揮発成分を１００質量％とした場合、１〜２０質量％であることを特徴とする〔１〕記載の樹脂組成物。
〔３〕 前記成分（Ｂ）の含有量が、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％であることを特徴とする〔１〕又は〔２〕記載の樹脂組成物。
〔４〕 前記成分（Ｂ）が活性エステル系硬化剤であることを特徴とする〔１〕〜〔３〕のいずれか１つに記載の樹脂組成物。
〔５〕 さらに無機充填材を含有することを特徴とする〔１〕〜〔４〕のいずれか１つに記載の樹脂組成物。
〔６〕 前記無機充填材の平均粒径が、０．０１〜５μｍであることを特徴とする〔５〕記載の樹脂組成物。
〔７〕 前記無機充填材の含有量が、樹脂組成物中の不揮発成分を１００質量％とした場合、３０〜９０質量％であることを特徴とする〔５〕又は〔６〕記載の樹脂組成物。
〔８〕 前記無機充填材が、表面処理剤で表面処理されていることを特徴とする〔５〕〜〔７〕のいずれか１つに記載の樹脂組成物。
〔９〕前記無機充填材が、シリカであることを特徴とする〔５〕〜〔８〕のいずれか１つに記載の樹脂組成物。
〔１０〕 さらに熱可塑性樹脂を含有することを特徴とする〔１〕〜〔９〕のいずれか１つに記載の樹脂組成物。
〔１１〕 樹脂組成物を硬化させて絶縁層を形成し、絶縁層表面を粗化処理した後における絶縁層表面の算術平均粗さが１０〜３５０ｎｍであり、二乗平均平方根粗さが２０〜５００ｎｍであることを特徴とする〔１〕〜〔１０〕のいずれか１つに記載の樹脂組成物。
〔１２〕 多層プリント配線板の絶縁層用樹脂組成物であることを特徴とする〔１〕〜〔１１〕のいずれか１つに記載の樹脂組成物。
〔１３〕 導体層がメッキにより形成される多層プリント配線板の絶縁層用樹脂組成物であることを特徴とする〔１〕〜〔１２〕のいずれか１つに記載の樹脂組成物。
〔１４〕 〔１〕〜〔１３〕のいずれか１つに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。
〔１５〕 〔１〕〜〔１３〕のいずれか１つに記載の樹脂組成物を絶縁層として含む多層プリント配線板。
〔１６〕 〔１５〕記載の多層プリント配線板を含む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 comprising an epoxy resin having a component (A) naphthylfluorene structure, and one or both of component (B) an active ester curing agent and a cyanate ester curing agent .
[2] The resin composition according to [1], wherein the content of the component (A) is 1 to 20% by mass when the nonvolatile component in the resin composition is 100% by mass.
[3] The resin according to [1] or [2], wherein the content of the component (B) is 1 to 30% by mass when the nonvolatile component in the resin composition is 100% by mass. Composition.
[4] The resin composition as described in any one of [1] to [3], wherein the component (B) is an active ester curing agent.
[5] The resin composition according to any one of [1] to [4], further including an inorganic filler.
[6] The resin composition according to [5], wherein the inorganic filler has an average particle size of 0.01 to 5 μm.
[7] The resin composition according to [5] or [6], wherein the content of the inorganic filler is 30 to 90% by mass when the nonvolatile component in the resin composition is 100% by mass. object.
[8] The resin composition as described in any one of [5] to [7], wherein the inorganic filler is surface-treated with a surface treatment agent.
[9] The resin composition as described in any one of [5] to [8], wherein the inorganic filler is silica.
[10] The resin composition as described in any one of [1] to [9], further including a thermoplastic resin.
[11] After the resin composition is cured to form an insulating layer and the insulating layer surface is roughened, the arithmetic average roughness of the insulating layer surface is 10 to 350 nm, and the root mean square roughness is 20 to 500 nm. The resin composition according to any one of [1] to [10], wherein
[12] The resin composition as described in any one of [1] to [11], which is a resin composition for an insulating layer of a multilayer printed wiring board.
[13] The resin composition as described in any one of [1] to [12], wherein the conductor layer is a resin composition for an insulating layer of a multilayer printed wiring board formed by plating.
[14] A sheet-like laminated material comprising the resin composition according to any one of [1] to [13].
[15] A multilayer printed wiring board comprising the resin composition according to any one of [1] to [13] as an insulating layer.
[16] A semiconductor device comprising the multilayer printed wiring board according to [15].
ナフチルフルオレン構造を有するエポキシ樹脂、及び活性エステル系硬化剤及び／又はシアネートエステル系硬化剤を含有することを特徴とする樹脂組成物を用いることにより、硬化して絶縁層とした後の湿式粗化工程において絶縁層表面の算術平均粗さの値が小さいのみならず、絶縁層表面の二乗平均平方根粗さの値も小さく、絶縁層上に十分なピール強度を有する導体層をメッキにより形成することができる、誘電正接が低い樹脂組成物を提供できるようになった。 Wet roughening after curing into an insulating layer by using a resin composition characterized by containing an epoxy resin having a naphthylfluorene structure and an active ester curing agent and / or a cyanate ester curing agent In the process, not only the arithmetic average roughness value of the insulating layer surface is small but also the root mean square roughness value of the insulating layer surface is small, and a conductor layer having sufficient peel strength is formed on the insulating layer by plating. It is possible to provide a resin composition having a low dielectric loss tangent.
本発明はナフチルフルオレン構造を有するエポキシ樹脂、及び活性エステル系硬化剤及び／又はシアネートエステル系硬化剤、すなわち活性エステル系硬化剤及びシアネートエステル系硬化剤のうちのいずれか一方又は両方を含有す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 contains an epoxy resin having a naphthylfluorene structure, and an active ester type curing agent and / or a cyanate ester type curing agent, that is, one or both of an active ester type curing agent and a cyanate ester type curing agent. It is a resin composition characterized by these. Hereinafter, the compounding components of the resin composition will be described in detail.
＜成分（Ａ）ナフチルフルオレン構造を有するエポキシ樹脂＞
本発明に使用するナフチルフルオレン構造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、フルオレン骨格とナフタレン骨格とを有するエポキシ樹脂であればよい。例えば、フルオレノンとナフタレン類とを反応させて得られたナフチルフルオレン構造を有するフェノール樹脂にエピクロルヒドリンを反応させることにより該フェノール樹脂をグリシジルエーテル化した分子構造を有するエポキシ樹脂等が挙げられる。特開２０１２−１０２２２８号公報に開示されているナフチルフルオレン構造を有するエポキシ樹脂を使用することも出来る。特に、下記一般式（１）で示される構造を含むエポキシ樹脂を用いることが好ましい。
<Component (A) Epoxy resin having naphthylfluorene structure>
The epoxy resin having a naphthylfluorene structure used in the present invention is not particularly limited, and any epoxy resin having a fluorene skeleton and a naphthalene skeleton may be used. For example, an epoxy resin having a molecular structure obtained by reacting a phenol resin having a naphthylfluorene structure obtained by reacting fluorenone and naphthalene with epichlorohydrin to form a glycidyl ether. An epoxy resin having a naphthylfluorene structure disclosed in JP2012-102228A can also be used. In particular, it is preferable to use an epoxy resin including a structure represented by the following general formula (1).
市販されているナフチルフルオレン構造を有するエポキシ樹脂としては、ＣＧ−５００（大阪ガスケミカル（株）製、上記一般式（１）で示される構造を有する。）などが挙げられる。 Examples of commercially available epoxy resins having a naphthylfluorene structure include CG-500 (manufactured by Osaka Gas Chemical Co., Ltd., having a structure represented by the above general formula (1)).
樹脂組成物中のナフチルフルオレン構造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、湿式粗化工程において絶縁層表面の低粗度化とメッキにより形成される導体層の高ピール強度とを両立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、１〜２０質量％が好ましく、３〜１５質量％がより好ましく、５〜１０質量％が更に好ましい。 The content of the epoxy resin having a naphthylfluorene structure in the resin composition is not particularly limited, but a high peel of the conductor layer formed by lowering the roughness of the insulating layer surface and plating in the wet roughening step. From the viewpoint of achieving both strength and strength, when the nonvolatile component in the resin composition is 100% by mass, 1 to 20% by mass is preferable, 3 to 15% by mass is more preferable, and 5 to 10% by mass is even 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、必要に応じてナフチルフルオレン構造を有するエポキシ樹脂と他のエポキシ樹脂とを併用してもよい。このような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、グリシジルエステル型エポキシ樹脂、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。これらを１種又は２種以上組み合わせて他のエポキシ樹脂として使用してもよい。 In the resin composition of the present invention, an epoxy resin having a naphthylfluorene structure and another epoxy resin may be used in combination within the range in which the effects of the present invention are exhibited. Examples of such other epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, phenol novolac type epoxy resins, and tert-butyl-catechol type epoxy resins. , Naphthol type epoxy resin, naphthalene type epoxy resin, naphthylene ether type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester 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, toner Methylol type epoxy resins, and halogenated epoxy resins. These may be used alone or in combination of two or more as other epoxy resins.
エポキシ樹脂として、ナフチルフルオレン構造を有するエポキシ樹脂と他のエポキシ樹脂とを併用する場合、湿式粗化工程において絶縁層表面の低粗度化とメッキにより形成される導体層の高ピール強度とを両立させるという観点から、エポキシ樹脂全体の固形分を１００質量部とした場合、ナフチルフルオレン構造を有するエポキシ樹脂が３０〜９０質量部であることが好ましく、３５〜８０質量部であることがより好ましく、４０〜７０質量部であることが更に好ましい。 When an epoxy resin having a naphthylfluorene structure and another epoxy resin are used in combination as an epoxy resin, both the low roughness of the insulating layer surface and the high peel strength of the conductor layer formed by plating are compatible in the wet roughening process. From the viewpoint of making the total content of the epoxy resin 100 parts by mass, the epoxy resin having a naphthylfluorene structure is preferably 30 to 90 parts by mass, more preferably 35 to 80 parts by mass, More preferably, it is 40-70 mass parts.
＜成分（Ｂ）活性エステル系硬化剤及び／又はシアネートエステル系硬化剤＞
本発明の樹脂組成物に使用される活性エステル系硬化剤及び／又はシアネートエステル系硬化剤としては、特に限定されないが、低い誘電正接を実現するという観点から活性エステル系硬化剤を用いることが好ましい。活性エステル系硬化剤及び／又はシアネートエステル系硬化剤として、これらを１種又は２種以上組み合わせて使用してもよい。
<Component (B) Active ester type curing agent and / or cyanate ester type curing agent>
The active ester curing agent and / or cyanate ester curing agent used in the resin composition of the present invention is not particularly limited, but it is preferable to use an active ester curing agent from the viewpoint of realizing a low dielectric loss tangent. . You may use these as an active ester type hardening | curing agent and / or a cyanate ester type hardening | curing agent 1 type, or in combination of 2 or more types.
活性エステル系硬化剤としては、特に制限はないが、一般にフェノールエステル類、チオフェノールエステル類、Ｎ−ヒドロキシアミンエステル類、複素環ヒドロキシ化合物のエステル類等の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好ましく用いられる。当該活性エステル系硬化剤は、カルボン酸化合物及び／又はチオカルボン酸化合物と、ヒドロキシ化合物及び／又はチオール化合物との縮合反応によって得られるものが好ましい。特に耐熱性向上の観点から、カルボン酸化合物とヒドロキシ化合物とから得られる活性エステル系硬化剤が好ましく、カルボン酸化合物と、フェノール化合物及び／又はナフトール化合物とから得られる活性エステル系硬化剤がより好ましい。カルボン酸化合物としては、例えば安息香酸、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。フェノール化合物又はナフトール化合物としては、ハイドロキノン、レゾルシン、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、フェノールフタリン、メチル化ビスフェノールＡ、メチル化ビスフェノールＦ、メチル化ビスフェノールＳ、フェノール、ｏ−クレゾール、ｍ−クレゾール、ｐ−クレゾール、カテコール、α−ナフトール、β−ナフトール、１，５−ジヒドロキシナフタレン、１，６−ジヒドロキシナフタレン、２，６−ジヒドロキシナフタレン、ジヒドロキシベンゾフェノン、トリヒドロキシベンゾフェノン、テトラヒドロキシベンゾフェノン、フロログルシン、ベンゼントリオール、ジシクロペンタジエニルジフェノール、フェノールノボラック等が挙げられる。本発明における活性エステル系硬化剤として１種又は２種以上を使用してもよい。活性エステル系硬化剤として、具体的にはジシクロペンタジエニル型ジフェノール縮合構造を含む活性エステル系硬化剤、ナフタレン構造を含む活性エステル系硬化剤、フェノールノボラックのアセチル化物である活性エステル系硬化剤、フェノールノボラックのベンゾイル化物である活性エステル系硬化剤等が好ましく、なかでもピール強度の向上に優れるという点で、ジシクロペンタジエニル型ジフェノール縮合構造を含む活性エステル系硬化剤、ナフタレン構造を含む活性エステル系硬化剤がより好ましい。活性エステル系硬化剤としては、特開２００４−２７７４６０号公報に開示されている活性エステル系硬化剤を用いてもよく、また市販のものを用いることもできる。市販品としてはジシクロペンタジエニル型ジフェノール縮合構造を含むものとしてＥＸＢ９４５１、ＥＸＢ９４６０、ＥＸＢ９４６０Ｓ−６５Ｔ、ＨＰＣ８０００−６５Ｔ（ＤＩＣ（株）製、活性基当量約２２３）、フェノールノボラックのアセチル化物である活性エステル系硬化剤としてＤＣ８０８（三菱化学（株）製、活性基当量約１４９）、フェノールノボラックのベンゾイル化物である活性エステル系硬化剤としてＹＬＨ１０２６（三菱化学（株）製、活性基当量約２００）、ＹＬＨ１０３０（三菱化学（株）製、活性基当量約２０１）、ＹＬＨ１０４８（三菱化学（株）製、活性基当量約２４５）等が挙げられる。 Although there is no restriction | limiting in particular as an active ester type hardening | curing agent, Generally ester groups with high reaction activity, such as phenol ester, thiophenol ester, N-hydroxyamine ester, ester of heterocyclic hydroxy compound, are in 1 molecule. A compound having two or more in the above is preferably used. The active ester curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. . 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. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol , Dicyclopentadienyl diphenol, phenol novolac and the like. You may use 1 type (s) or 2 or more types as an active ester type hardening | curing agent in this invention. Specific examples of the active ester curing agent include an active ester curing agent having a dicyclopentadienyl type diphenol condensation structure, an active ester curing agent having a naphthalene structure, and an active ester curing which is an acetylated product of phenol novolac. Active ester hardeners, which are benzoylated compounds of phenol novolac, and the like. Among them, active ester hardeners containing dicyclopentadienyl type diphenol condensation structure, naphthalene structure An active ester curing agent containing is more preferred. As the active ester curing agent, an active ester curing agent disclosed in JP-A-2004-277460 may be used, or a commercially available one may be used. Commercially available products include EXB9451, EXB9460, EXB9460S-65T, HPC8000-65T (manufactured by DIC Corporation, active group equivalent of about 223), and acetylated products of phenol novolac as those containing a dicyclopentadienyl type diphenol condensation structure. DC808 as an active ester type curing agent (Mitsubishi Chemical Corporation, active group equivalent of about 149), YLH1026 as an active ester type curing agent which is a benzoylated phenol novolak (Mitsubishi Chemical Corporation, active group equivalent of about 200) YLH1030 (Mitsubishi Chemical Corporation, active group equivalent of about 201), YLH1048 (Mitsubishi Chemical Corporation, active group equivalent of about 245) and the like.
ジシクロペンタジエニル型ジフェノール縮合構造を含む活性エステル系硬化剤として、より具体的には下記一般式（２）で表される化合物が挙げられる。 More specifically, examples of the active ester curing agent containing a dicyclopentadienyl type diphenol condensation structure include compounds represented by the following general formula (2).
樹脂組成物の硬化物の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、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 of the cured product of the resin composition and improving the heat resistance, R is preferably a naphthyl group, k is preferably 0, and n is preferably 0.25 to 1.5.
シアネートエステル系硬化剤としては、特に制限はないが、ノボラック型（フェノールノボラック型、アルキルフェノールノボラック型など）シアネートエステル系硬化剤、ジシクロペンタジエン型シアネートエステル系硬化剤、ビスフェノール型（ビスフェノールＡ型、ビスフェノールＦ型、ビスフェノールＳ型など）シアネートエステル系硬化剤、及びこれらが一部トリアジン化したプレポリマーなどが挙げられる。シアネートエステル系硬化剤の重量平均分子量は、特に限定されるものではないが、５００〜４５００が好ましく、６００〜３０００がより好ましい。シアネートエステル系硬化剤の具体例としては、例えば、ビスフェノールＡジシアネート、ポリフェノールシアネート（オリゴ（３−メチレン−１，５−フェニレンシアネート））、４，４’−メチレンビス（２，６−ジメチルフェニルシアネート）、４，４’−エチリデンジフェニルジシアネート、ヘキサフルオロビスフェノールＡジシアネート、２，２−ビス（４−シアネート）フェニルプロパン、１，１−ビス（４−シアネートフェニルメタン）、ビス（４−シアネート−３，５−ジメチルフェニル）メタン、１，３−ビス（４−シアネートフェニル−１−（メチルエチリデン））ベンゼン、ビス（４−シアネートフェニル）チオエーテル、ビス（４−シアネートフェニル）エーテル等の２官能シアネート樹脂、フェノールノボラック、クレゾールノボラック、ジシクロペンタジエン型構造含有フェノール樹脂等から誘導される多官能シアネート樹脂、これらシアネート樹脂が一部トリアジン化したプレポリマーなどが挙げられる。これらを１種又は２種以上組み合わせて使用してもよい。市販されているシアネートエステル樹脂としては、下記式（３）で表されるフェノールノボラック型多官能シアネートエステル樹脂（ロンザジャパン（株）製、ＰＴ３０Ｓ、シアネート当量１２４）、下記式（４）で表されるビスフェノールＡジシアネートの一部又は全部がトリアジン化され三量体となったプレポリマー（ロンザジャパン（株）製、ＢＡ２３０Ｓ、シアネート当量２３２）、下記式（５）で表されるジシクロペンタジエン型構造含有シアネートエステル樹脂（ロンザジャパン（株）製、ＤＴ−４０００、ＤＴ−７０００）等が挙げられる。 Although there is no restriction | limiting in particular as cyanate ester type hardening | curing agent, Novolac type (phenol novolak type, alkylphenol novolak type, etc.) cyanate ester type hardening agent, dicyclopentadiene type cyanate ester type hardening agent, bisphenol type (bisphenol A type, bisphenol) Fate, bisphenol S type, etc.) cyanate ester curing agents, and prepolymers in which these are partially triazines. Although the weight average molecular weight of a cyanate ester hardening | curing agent is not specifically limited, 500-4500 are preferable and 600-3000 are more preferable. Specific examples of the cyanate ester-based curing agent include, for example, bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate)), and 4,4′-methylenebis (2,6-dimethylphenyl cyanate). 4,4′-ethylidenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3) , 5-dimethylphenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, bis (4-cyanatephenyl) ether, etc. Resin, phenol novolac Cresol novolac, a polyfunctional cyanate resins derived from dicyclopentadiene structure-containing phenol resin, these cyanate resins and partially triazine of prepolymer. These may be used alone or in combination of two or more. As a commercially available cyanate ester resin, a phenol novolak type polyfunctional cyanate ester resin represented by the following formula (3) (Lonza Japan Co., Ltd., PT30S, cyanate equivalent 124), represented by the following formula (4) Bisphenol A dicyanate, part or all of which is a trimerized prepolymer (Lonza Japan KK, BA230S, cyanate equivalent 232), dicyclopentadiene type structure represented by the following formula (5) Containing cyanate ester resins (Lonza Japan Co., Ltd., DT-4000, DT-7000) and the like.
樹脂組成物中の活性エステル系硬化剤及び／又はシアネートエステル系硬化剤の含有量は、特に限定されるものではないが、湿式粗化工程において絶縁層表面の低粗度化とメッキにより形成される導体層の高ピール強度とを両立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、１〜３０質量％が好ましく、３〜２５質量％がより好ましく、５〜２０質量％が更に好ましい。 The content of the active ester-based curing agent and / or cyanate ester-based curing agent in the resin composition is not particularly limited, but is formed by lowering the roughness of the insulating layer surface and plating in the wet-roughening step. From the viewpoint of achieving both a high peel strength of the conductive layer, when the nonvolatile component in the resin composition is 100% by mass, 1 to 30% by mass is preferable, 3 to 25% by mass is more preferable, and 5 to 20 More preferred is mass%.
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、必要に応じて活性エステル系硬化剤及び／又はシアネートエステル系硬化剤と他の硬化剤とを併用してもよい。このような他の硬化剤としては、例えば、フェノール系硬化剤、ベンゾオキサジン系硬化剤等が挙げられる。フェノール系硬化剤としては、特に制限はないが、ビフェニル型硬化剤、ナフタレン型硬化剤、フェノールノボラック型硬化剤、ナフチレンエーテル型硬化剤、トリアジン骨格含有フェノール系硬化剤から選択される１種以上を用いることが好ましい。ベンゾオキサジン系硬化剤としては、特に制限はないが、具体例としては、Ｆ−ａ、Ｐ−ｄ（四国化成（株）製）、ＨＦＢ２００６Ｍ（昭和高分子（株）製）などが挙げられる。これらは１種又は２種以上を併用してもよい。 In the resin composition of the present invention, an active ester-based curing agent and / or a cyanate ester-based curing agent and another curing agent may be used in combination within the range in which the effects of the present invention are exhibited. Examples of such other curing agents include phenol-based curing agents and benzoxazine-based curing agents. Although there is no restriction | limiting in particular as a phenol type hardening | curing agent, One or more types selected from a biphenyl type hardening | curing agent, a naphthalene type hardening | curing agent, a phenol novolak type hardening | curing agent, a naphthylene ether type hardening | curing agent, and a triazine skeleton containing phenol type hardening | curing agent. Is preferably used. Although there is no restriction | limiting in particular as a benzoxazine type hardening | curing agent, As a specific example, Fa, Pd (made by Shikoku Kasei Co., Ltd.), HFB2006M (made by Showa Polymer Co., Ltd.), etc. are mentioned. These may be used alone or in combination of two or more.
硬化剤として、活性エステル系硬化剤及び／又はシアネートエステル系硬化剤と他の硬化剤とを併用する場合、湿式粗化工程において絶縁層表面の低粗度化とメッキにより形成される導体層の高ピール強度とを両立させるという観点から、硬化剤全体の固形分を１００質量部とした場合、活性エステル系硬化剤及び／又はシアネートエステル系硬化剤が３０〜１００質量部であることが好ましく、４０〜９５質量部であることがより好ましく、５０〜９０質量部であることが更に好ましい。 When the active ester type curing agent and / or the cyanate ester type curing agent and another curing agent are used in combination as the curing agent, the conductive layer formed by lowering the roughness of the insulating layer surface and plating in the wet roughening step. From the viewpoint of achieving both high peel strength, when the solid content of the entire curing agent is 100 parts by mass, the active ester curing agent and / or the cyanate ester curing agent is preferably 30 to 100 parts by mass, More preferably, it is 40-95 mass parts, and it is still more preferable that it is 50-90 mass parts.
また、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、全てのエポキシ樹脂におけるエポキシ基の合計数と、全ての硬化剤における反応基の合計数との比が、１：０．２〜１：２であることが好ましく、１：０．３〜１：１．５であることがより好ましく、１：０．４〜１：１であることが更に好ましい。なお樹脂組成物中に存在する全てのエポキシ樹脂における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、全ての硬化剤における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 total number of epoxy groups in all epoxy resins and the total of reactive groups in all curing agents The ratio to the number is preferably 1: 0.2 to 1: 2, more preferably 1: 0.3 to 1: 1.5, and 1: 0.4 to 1: 1. More preferably. The total number of epoxy groups in all epoxy resins 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 all cured The total number of reactive groups in the agent is a value obtained by adding the values obtained by dividing the solid content mass of each curing agent by the reactive group equivalent for all the curing agents.
＜無機充填材＞
本発明の樹脂組成物は、さらに無機充填材を含有することにより、樹脂組成物の硬化物の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、特に限定されず、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。
<Inorganic filler>
The resin composition of the present invention can further reduce the dielectric loss tangent and thermal expansion coefficient of the cured product of the resin composition by further 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、絶縁層表面に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以下が特に好ましい。他方、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することにより、取り扱い性が低下するのを防止するという観点から、無機充填材の平均粒径は、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。測定サンプルとして、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、（株）堀場製作所製 ＬＡ−９５０等を使用することができる。 Although the average particle diameter of the inorganic filler is not particularly limited, it is preferably 5 μm or less, more preferably 3 μm or less from the viewpoint that the surface of the insulating layer has low roughness and enables fine wiring to be formed on the surface of the insulating layer. It is preferably 2 μm or less, more preferably 1 μm or less, still more preferably 0.8 μm or less, and particularly preferably 0.6 μm or less. On the other hand, when the resin composition is a resin varnish, the average particle size of the inorganic filler is preferably 0.01 μm or more from the viewpoint of preventing the handleability from decreasing due to an increase in the viscosity of the varnish. 0.03 μm or more is more preferable, 0.05 μm or more is further 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 a 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、線熱膨張係数を低下させる点や多層プリント配線板のクラックの発生を抑制するという点から、樹脂組成物中の不揮発成分を１００質量％とした場合、３０質量％以上が好ましく、４０質量％以上がより好ましく、５０質量％以上が更に好ましく、６０質量％以上が更に一層好ましい。他方、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、無機充填材の含有量は、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。 The content of the inorganic filler is 30% by mass when the nonvolatile component in the resin composition is 100% by mass in terms of reducing the coefficient of linear thermal expansion and suppressing the occurrence of cracks in the multilayer printed wiring board. The above is preferable, 40 mass% or more is more preferable, 50 mass% or more is further preferable, and 60 mass% or more is still more preferable. On the other hand, the content of the inorganic filler is preferably 90% by mass or less, more preferably 85% by mass or less, and more preferably 80% by mass or less from the viewpoint of preventing the cured product from becoming brittle or preventing the peel strength from being lowered. Further preferred.
無機充填材は、表面処理剤で表面処理されていることが好ましく、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, One or more selected from acrylate silane coupling agents, isocyanate silane coupling agents, sulfide silane coupling agents, vinyl silane coupling agents, silane coupling agents, organosilazane compounds and titanate coupling agents. It is more preferable to perform surface treatment with a surface treatment agent. Thereby, the dispersibility and moisture resistance of an inorganic filler can be improved.
具体的には、表面処理剤として、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、メタクリロイルオ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, as the surface treatment agent, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, N-phenyl-3-aminopropyltrimethoxysilane, N-methyl Aminosilane coupling agents such as aminopropyltrimethoxysilane, N-2 (-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyldimethoxymethylsilane, 3-glycidyl Oxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyl (dimethoxy) methylsilane, glycidylbutyltrimethoxysilane, 2- (3,4-epoxy (Cicyclohexyl) Epoxysilane coupling agents such as ethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 11-mercaptoundecyltrimethoxysilane, etc. Mercaptosilane coupling agents, styrylsilane coupling agents such as p-styryltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyldimethoxysilane, 3- Acrylate silane coupling agents such as methacryloxypropyltriethoxysilane and 3-methacryloxypropyldiethoxysilane, 3-isocyanatopropyltrimethoxy Isocyanate silane coupling agents such as run, sulfide silane coupling agents such as bis (triethoxysilylpropyl) disulfide, bis (triethoxysilylpropyl) tetrasulfide, methyltrimethoxysilane, octadecyltrimethoxysilane, phenyltrimethoxy Silane coupling agents such as silane, methacryloyloxypropyltrimethoxysilane, imidazolesilane, triazinesilane, t-butyltrimethoxysilane, hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyl Disilazane, hexaphenyldisilazane, trisilazane, cyclotrisilazane, 2,2,4,4,6,6-hexamethylcyclotrisilazane, octamethylcyclotetrasilazane, hexabutyldisilazane, f Saoctyldisilazane, 1,3-diethyltetramethyldisilazane, 1,3-di-n-octyltetramethyldisilazane, 1,3-diphenyltetramethyldisilazane, 1,3-dimethyltetraphenyldisilazane, 1 , 3-diethyltetramethyldisilazane, 1,1,3,3-tetraphenyl-1,3-dimethyldisilazane, 1,3-dipropyltetramethyldisilazane, hexamethylcyclotrisilazane, dimethylaminotrimethylsilazane, Organosilazane compounds such as tetramethyldisilazane, tetra-n-butyl titanate dimer, titanium-i-propoxyoctylene glycolate, tetra-n-butyl titanate, titanium octylene glycolate, diisopropoxytitanium bis (triethanolaminate) ), Dihydroxychi Tanbis lactate, dihydroxybis (ammonium lactate) titanium, bis (dioctyl pyrophosphate) ethylene titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, tri-n-butoxy titanium monostearate, tetra-n-butyl titanate, tetra ( 2-ethylhexyl) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, isopropyl Trioctanoyl titanate, isopropyl tricumyl phenyl titanate, isopropyl triisostearoyl titanate, isopropyl isostear Titanates such as ildiacryl titanate, isopropyldimethacrylisostearoyl titanate, isopropyltri (dioctylphosphate) titanate, isopropyltridodecylbenzenesulfonyl titanate, isopropyltris (dioctylpyrophosphate) titanate, isopropyltri (N-amidoethylaminoethyl) titanate A coupling agent etc. are 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は、溶剤（例えば、メチルエチルケトン：ＭＥＫと略す。）により洗浄処理した後の無機充填材の単位重量当たりのカーボン量を測定することができる。ここで、「無機充填材の単位重量当たりのカーボン量」とは、無機充填材１ｇに結合しているカーボン量（ｇ）を百分率で表したものである。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固形分を分析することにより、無機充填材の単位重量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, the inorganic filler surface-treated with the surface treatment agent can measure the amount of carbon per unit weight of the inorganic filler after being washed with a solvent (for example, methyl ethyl ketone: abbreviated as MEK). Here, “the amount of carbon per unit weight of the inorganic filler” is the percentage of the amount of carbon (g) bonded to 1 g of the inorganic filler. 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 content per unit weight of the inorganic filler can be measured by analyzing the solid content using a carbon analyzer. As the carbon analyzer, “EMIA-320V” manufactured by HORIBA, Ltd. can be used.
無機充填材の単位重量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二乗平均平方根粗さを安定させるという点で、０．０２％以上が好ましく、０．０５％以上がより好ましく、０．１％以上が更に好ましい。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、３％以下が好ましく、２％以下がより好ましく、１％以下が更に好ましい。 The carbon amount per unit weight of the inorganic filler is preferably 0.02% or more from the viewpoint of improving the dispersibility of the inorganic filler and stabilizing the root mean square roughness after the wet roughening step of the cured product. 0.05% or more is more preferable, and 0.1% or more is still more preferable. On the other hand, it is preferably 3% or less, more preferably 2% or less, and even more preferably 1% or less from the viewpoint of preventing an increase in the melt viscosity of the resin varnish or the adhesive film.
表面処理剤で表面処理されている無機充填材を樹脂組成物に含有させる場合、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。 When the resin composition contains an inorganic filler that has been surface-treated with a surface treatment agent, it is preferable to add the inorganic filler to the resin composition after the surface treatment with the surface treatment agent. In this case, the dispersibility of the inorganic filler can be further enhanced.
無機充填材を表面処理剤で表面処理する際の表面処理方法は、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、加熱処理して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表面処理されている無機充填材を得ることができる。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、加熱処理して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、表面処理されている無機充填材を得ることができる。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表面処理を行うことが可能である。 The surface treatment method for treating the surface of the inorganic filler 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. Then, the surface-treated inorganic filler can be obtained by subjecting the surface treatment agent and the inorganic filler to dehydration condensation by heat treatment. 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. Then, the surface-treated inorganic filler can be obtained by heat-treating and dehydrating and condensing the surface treatment agent and the inorganic filler. Further, the surface treatment can be performed by an integral blend method in which a surface treatment agent is added to the resin composition.
＜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と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。
<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, 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-methylguanidine, 1-ethylguanidine, 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、及びこれら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-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, - dodecyl-2-methyl-3-benzyl-imidazolium chloride, 2-methyl-imidazoline, 2-phenyl-imidazoline, etc. imidazole compounds, and adducts of these imidazole compounds and epoxy resins. 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.
本発明の樹脂組成物に硬化促進剤を配合する場合には、硬化促進剤は、エポキシ樹脂と硬化剤との合計を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。硬化促進剤が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 a curing accelerator is blended in the resin composition of the present invention, the curing accelerator is preferably in the range of 0.005 to 1 part by mass when the total of the epoxy resin and the curing agent is 100 parts by mass. The range of 0.01-0.5 mass part is more preferable. When the curing accelerator is within this range, thermal curing can be more efficiently performed and the storage stability of the resin varnish is also improved.
＜熱可塑性樹脂＞
本発明の樹脂組成物には、さらに熱可塑性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、更に樹脂組成物を接着フィルムの形態で使用する場合の、樹脂組成物のフィルム成型能を向上させることもできる。熱可塑性樹脂としては、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。これらの熱可塑性樹脂は各々単独で用いてもよく、２種以上を組み合わせて使用してもよい。熱可塑性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。
<Thermoplastic resin>
The resin composition of the present invention can further improve the mechanical strength of the cured product by further containing a thermoplastic resin, and further the resin composition when the resin composition is used in the form of an adhesive film. The film forming ability can also be improved. Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, polyetheretherketone resin, and polyester resin. In particular, phenoxy resin and polyvinyl acetal resin are preferable. These thermoplastic resins may be used alone or in combination of two or more. The weight average molecular weight of the thermoplastic resin is preferably in the range of 8,000 to 200,000, and more preferably in the range of 12,000 to 100,000. 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熱可塑性樹脂を配合する場合には、熱可塑性樹脂の配合率は、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。熱可塑性樹脂の配合率がこの範囲内であると、樹脂組成物のフィルム成型能や硬化物の機械強度を向上させる効果が発揮され、更に溶融粘度の上昇を抑制し、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 the thermoplastic resin is blended with the resin composition of the present invention, the blending ratio of the thermoplastic resin is preferably 0.1 to 10% by mass when the nonvolatile component in the resin composition is 100% by mass, 0.5-5 mass% is more preferable. When the blending ratio of the thermoplastic resin is within this range, the effect of improving the film molding ability of the resin composition and the mechanical strength of the cured product is exhibited, and further, the increase in melt viscosity is suppressed, and after the wet roughening step The roughness of the surface of the insulating layer 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、フッ素化合物パウダー、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、イミダゾール系、チアゾール系、トリアゾール系、シランカップリング剤等の、密着性付与剤、フタロシアニン・ブルー、フタロシアニン・グリーン、アイオジン・グリーン、ジスアゾイエロー、カーボンブラック等の着色剤、水酸化アルミニウム、リン系化合物等の難燃剤、等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 vinyl benzyl compounds, acrylic compounds, maleimide compounds, thermosetting resins such as blocked isocyanate compounds, silicon powder, nylon powder, fluorine compound powder, organic fillers such as rubber particles, orbene, benton, etc. Thickener, silicone-based, fluorine-based, polymer-based antifoaming agent or leveling agent, imidazole-based, thiazole-based, triazole-based, silane coupling agent, etc., adhesion imparting agent, phthalocyanine blue, phthalocyanine green, Colorants such as Iodine Green, Disazo Yellow, and Carbon Black, and flame retardants such as aluminum hydroxide and phosphorus compounds can be used.
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製することができる。また、さらに樹脂組成物に有機溶剤を加えることで樹脂ワニスとしても調製することができる。 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. Can be prepared. Further, it can be prepared as a resin varnish by adding an organic solvent to the resin composition.
本発明の樹脂組成物は、硬化させて絶縁層を形成した場合に、粗化処理（湿式粗化）した後における絶縁層表面の算術平均粗さの値が小さいのみならず、絶縁層表面の二乗平均平方根粗さの値も小さく、絶縁層表面上に十分なピール強度を有する導体層をメッキにより形成することができ、硬化物の誘電正接が低いので、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、本発明の樹脂組成物は、メッキにより導体層を形成するための樹脂組成物（導体層がメッキにより形成され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。 When the resin composition of the present invention is cured to form an insulating layer, the arithmetic average roughness of the insulating layer surface after roughening treatment (wet roughening) is not only small, but the insulating layer surface The value of the root mean square roughness is small, and a conductive layer having sufficient peel strength can be formed on the surface of the insulating layer by plating, and the dielectric loss tangent of the cured product is low. It can be suitably used as a resin composition for an insulating layer of a printed wiring board. Furthermore, the resin composition of the present invention can be suitably used as a resin composition for forming a conductor layer by plating (a resin composition for an insulating layer of a multilayer printed wiring board in which the conductor layer is formed by plating). Furthermore, it is suitable as a resin composition for buildup layers of multilayer printed wiring boards.
本発明の樹脂組成物を硬化して絶縁層を形成し、絶縁層表面を粗化処理した後における絶縁層表面の算術平均粗さ（Ｒａ値）、二乗平均平方根粗さ（Ｒｑ値）は、後述する〔メッキにより形成された導体層の引き剥がし強さ（ピール強度）の測定、算術平均粗さ（Ｒａ値）、二乗平均平方根粗さ（Ｒｑ値）の測定〕に記載の測定方法により把握することができる。 The resin composition of the present invention is cured to form an insulating layer, and after the surface of the insulating layer is roughened, the arithmetic average roughness (Ra value) and root mean square roughness (Rq value) of the insulating layer surface are: Grasped by the measurement method described later in [Measurement of peel strength (peel strength) of conductor layer formed by plating, arithmetic average roughness (Ra value), root mean square roughness (Rq value)]. can do.
絶縁層表面の算術平均粗さ（Ｒａ値）の上限値は、微細配線形成の観点から、３５０ｎｍ以下が好ましく、３００ｎｍ以下がより好ましく、２５０ｎｍ以下が更に好ましく、２００ｎｍ以下が更に一層好ましく、１５０ｎｍ以下が殊更好ましく、１００ｎｍ以下が特に好ましい。絶縁層表面の算術平均粗さ（Ｒａ値）の下限値は、特に制限は無く、１０ｎｍ以上などとなる。 The upper limit of the arithmetic average roughness (Ra value) of the insulating layer surface is preferably 350 nm or less, more preferably 300 nm or less, still more preferably 250 nm or less, still more preferably 200 nm or less, and even more preferably 150 nm or less, from the viewpoint of fine wiring formation. Is particularly preferable, and 100 nm or less is particularly preferable. The lower limit value of the arithmetic average roughness (Ra value) on the surface of the insulating layer is not particularly limited and is 10 nm or more.
絶縁層表面の二乗平均平方根粗さ（Ｒｑ値）には絶縁層表面の局所的な状態が反映されるため、Ｒｑ値の把握により、緻密で平滑な絶縁層表面になっているか否かが確認でき、緻密で平滑な絶縁層表面になっている場合、ピール強度が安定することを見出した。絶縁層表面の二乗平均平方根粗さ（Ｒｑ値）の上限値は、緻密で平滑な絶縁層表面とするために、５００ｎｍ以下が好ましく、４００ｎｍ以下がより好ましく、３００ｎｍ以下が更に好ましく、２００ｎｍ以下が更に一層好ましい。絶縁層表面の二乗平均平方根粗さ（Ｒｑ値）の下限値は、ピール強度を安定させるという観点から、２０ｎｍ以上が好ましく、４０ｎｍ以上がより好ましい。 Since the root mean square roughness (Rq value) of the insulating layer surface reflects the local state of the insulating layer surface, it is confirmed whether the surface of the insulating layer is dense and smooth by grasping the Rq value. It was found that the peel strength is stable when the surface of the insulating layer is dense and smooth. The upper limit of the root mean square roughness (Rq value) of the insulating layer surface is preferably 500 nm or less, more preferably 400 nm or less, even more preferably 300 nm or less, and even more preferably 200 nm or less in order to obtain a dense and smooth insulating layer surface. Even more preferred. The lower limit of the root mean square roughness (Rq value) of the insulating layer surface is preferably 20 nm or more, and more preferably 40 nm or more, from the viewpoint of stabilizing the peel strength.
本発明の樹脂組成物を硬化させて絶縁層を形成し、絶縁層表面を粗化処理し、さらにメッキにより形成さ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、算術平均粗さ（Ｒａ値）、二乗平均平方根粗さ（Ｒｑ値）の測定〕に記載の測定方法により把握することができる。 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 formed by plating is described later [Plating conductor layer pulling]. Measurement of peeling strength (peel strength), arithmetic average roughness (Ra value), root mean square roughness (Rq value)].
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０．３７ｋｇｆ／ｃｍ以上が好ましく、０．４ｋｇｆ／ｃｍ以上がより好ましく、０．４３ｋｇｆ／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 peel strength is preferably 0.37 kgf / cm or more, more preferably 0.4 kgf / cm or more, and further preferably 0.43 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以下が好ましく、０．００６以下がより好ましい。誘電正接は低いほどよく、特に下限値は無いが、一般的に０．００１以上、０．００２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, more preferably 0.006 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 0.001 or more, 0.002 or more, and the like.
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、樹脂ワニスとして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。 Although it does not specifically limit as a form of the resin composition of this invention, It can apply to sheet-like laminated materials, such as an adhesive film and a prepreg, and a circuit board (a laminated board use, a multilayer printed wiring board use, etc.). The resin composition of the present invention can be applied to a circuit board as a resin varnish 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、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する方法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 is prepared by a method known to those skilled in the art, for example, by preparing a resin varnish in which a resin composition is dissolved in an organic solvent, and applying the resin varnish to a support using a die coater or the like. It can be produced by a method of forming the resin composition layer by drying the organic solvent by heating or blowing hot air.
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。有機溶剤を２種以上組み合わせて用いてもよい。 Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate, and carbitols such as cellosolve and butyl carbitol. Examples thereof include aromatic hydrocarbons such as tols, 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。例えば、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％以下となるように樹脂ワニスを乾燥させる。樹脂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％の有機溶剤を含む樹脂ワニスを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。 Drying conditions are not particularly limited. For example, the resin varnish is dried 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 the organic solvent in the resin varnish and the boiling point of the organic solvent, the resin varnish containing, for example, 30 to 60% by mass of the organic solvent is dried at 50 to 150 ° C. for about 3 to 10 minutes to obtain a resin composition layer. Can be formed.
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。また支持体として、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、支持体は、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、支持体及び後述する保護フィルムには、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 metal foils, such as release paper, copper foil, and aluminum foil, as a support body. Among them, the support is preferably a plastic film and more preferably a polyethylene terephthalate film from the viewpoint of versatility. The support and a protective film described later may be subjected to surface treatment such as mud treatment or corona treatment. The support and the protective film described later may be subjected to a release treatment 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、支持体と同様の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。以上のように形成された接着フィルムを、ロール状に巻きとって貯蔵することもできる。 A protective film similar 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 formed as described above can be wound and stored in a roll shape.
（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された状態であ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。このプリプレグが支持体上に設けられる構成が好適である。
(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, a prepreg in a state where the resin composition of the present invention is impregnated in a sheet-like reinforcing base material can be obtained. 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. A configuration in which this prepreg is provided on a support is preferred.
ホットメルト法は、樹脂組成物を有機溶剤に溶解させることなく、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か、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。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、この樹脂ワニスにシート状補強基材を浸漬し、樹脂ワニスをシート状補強基材に含浸させ、その後乾燥させる方法である。また、加熱、加圧条件下で、接着フィルムをシート状補強基材の両面に、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 temporarily coated on a support without being dissolved in an organic solvent and then laminated to a sheet-like reinforcing base, or directly applied to a sheet-like reinforcing base by a die coater. This is a method for manufacturing a prepreg. 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 substrate is immersed in the resin varnish, and then the sheet-like reinforcing substrate is impregnated. It is a method of drying. It can also be prepared by continuously heat laminating the adhesive film on both sides of the sheet-like reinforcing base material 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（ラミネート工程）。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、銅エッチング等の粗化処理が予め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 (laminating step). 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 subjected to roughening treatment such as blackening treatment or copper etching.
上記ラミネート工程において、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を用いる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 laminating step, 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 laminating to the 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. Examples of commercially available vacuum laminators include 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. Examples thereof include a vacuum laminator.
シート状積層材料を回路基板にラミネートした後、室温程度に冷却してから、支持体を剥離する場合には支持体を剥離し、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には、必要により硬化後に支持体を剥離することもできる。 After laminating the sheet-like laminated material on the circuit board, after cooling to about room temperature, when peeling the support, the support is peeled off, and the resin composition is thermally cured to form a cured product, An insulating layer can be formed on the circuit board. 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. If the support is not peeled off after curing after the insulating layer is formed, the support can be peeled off after curing 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、温度を７０〜１５０℃とし、圧力を１〜１５ｋｇｆ／ｃｍ２の範囲として行い、２段階目のプレスを、温度を１５０〜２００℃とし、圧力を１〜４０ｋｇｆ／ｃｍ２の範囲として行うのが好ましい。各段階は、時間を３０〜１２０分間として行うのが好ましい。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 is performed at 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 is performed at a temperature of 150 to 200 ° C. and the pressure is 1 to 40 kgf. / Cm 2 is preferable. Each stage is preferably performed for 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 Co., Ltd.), 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手段により、また必要によりこれらの手段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、穴あけ加工後に支持体を剥離することができる。 Next, a hole is formed in the insulating layer formed on the circuit board to form a via hole and a through hole. The drilling can be performed, for example, by known means such as a drill, a laser, or a plasma, or a combination of these means if necessary, but drilling by a laser such as a carbon dioxide laser or a YAG laser is the most common. Is the method. When the support is not peeled off before drilling, the support can be peeled off after drilling.
次いで、絶縁層表面に対して粗化処理を行う。乾式の粗化処理の方法としてはプラズマ処理等が挙げられ、湿式の粗化処理の方法として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または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. Examples of the dry roughening treatment include plasma treatment, and the wet roughening treatment includes a swelling treatment using a swelling liquid, a roughening treatment using an oxidizing agent, and a neutralization treatment using a neutralizing solution in this order. Is mentioned. 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 or sodium permanganate is 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を形成することができる。本発明の樹脂組成物は、硬化し、粗化処理した後に、低粗度、高ピール強度であるため、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 A printed wiring board can be formed. Since the resin composition of the present invention has low roughness and high peel strength after being cured and roughened, 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。すなわち、この半導体装置は本発明の多層プリント配線板を含んでいる。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. That is, this semiconductor device includes 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、実施例及び比較例を用いて本発明をより詳細に説明するが、これらは本発明をいかなる意味においても制限するものではない。なお、以下の記載において、「部」は「質量部」を意味する。 EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example and a comparative example, these do not restrict | limit this invention in any meaning. In the following description, “part” means “part by mass”.
＜測定方法・評価方法＞
まずは測定方法・評価方法について説明する。
<Measurement method / Evaluation method>
First, the measurement method / evaluation method will be described.
〔メッキにより形成された導体層の引き剥がし強さ（ピール強度）の測定、算術平均粗さ（Ｒａ）、二乗平均平方根粗さ（Ｒｑ）の測定〕
（１）積層板の下地処理
内層回路の形成されたガラス布基材エポキシ樹脂両面銅張積層板（銅箔の厚さ１８μｍ、残銅率６０％、基板厚み０．３ｍｍ、松下電工（株）製Ｒ５７１５ＥＳ）両面をメック（株）製ＣＺ８１００に浸漬して銅箔表面の粗化処理を行った。
[Measurement of peel strength (peel strength) of conductor layer formed by plating, arithmetic average roughness (Ra), root mean square roughness (Rq)]
(1) Surface treatment of laminated board Glass cloth base epoxy resin double-sided copper-clad laminated board with inner layer circuit (copper foil thickness 18μm, remaining copper ratio 60%, substrate thickness 0.3mm, Matsushita Electric Works, Ltd.) (R5715ES manufactured by R & D Co., Ltd.) Both surfaces were immersed in CZ8100 manufactured by MEC Co., Ltd. to roughen the surface of the copper foil.
（２）接着フィルムのラミネート工程
各実施例及び各比較例で作成した接着フィルムを、バッチ式真空加圧ラミネーターＭＶＬＰ-５００（（株）名機製作所製、商品名）を用いて、積層板の両面にラミネートした。ラミネート工程は、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) Laminating process of adhesive film The adhesive film created in each example and each comparative example was prepared using a batch type vacuum pressure laminator MVLP-500 (trade name, manufactured by Meiki Seisakusho Co., Ltd.). Laminated on both sides. The laminating step 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ＰＥＴフィルムを剥離し、１７０℃、３０分間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 resin composition The PET film was peeled off from the laminated adhesive film, and the resin composition was cured under curing conditions of 170 ° C for 30 minutes to form an insulating layer.
（４）粗化処理
絶縁層を形成した積層板を、膨潤液である、アトテックジャパン（株）のジエチレングリコールモノブチルエーテル含有のスエリングディップ・セキュリガンドＰに６０℃で１０分間浸漬し、次に粗化液として、アトテックジャパン（株）のコンセントレート・コンパクトＰ（ＫＭｎＯ４：６０ｇ／Ｌ、ＮａＯＨ：４０ｇ／Ｌの水溶液）に８０℃で２０分間浸漬し、最後に中和液として、アトテックジャパン（株）のリダクションショリューシン・セキュリガントＰに４０℃で５分間浸漬した。この粗化処理後の積層板をサンプルＡとした。
(4) Roughening treatment The laminated plate on which the insulating layer is formed is immersed in a swelling dip secu-ligand P containing diethylene glycol monobutyl ether of Atotech Japan Co., Ltd. for 10 minutes at 60 ° C., and then roughened. As a solution, it was immersed in an Atotech Japan Co., Ltd. Concentrate Compact P (KMnO 4 : 60 g / L, NaOH: 40 g / L aqueous solution) at 80 ° C. for 20 minutes, and finally as a neutralizing solution, Atotech Japan Co., Ltd. ) Was reduced for 5 minutes at 40 ° C. The laminate after the roughening treatment was designated as sample A.
（５）セミアディティブ工法によるメッキ
サンプルＡを、ＰｄＣｌ２を含む無電解メッキ用溶液に浸漬し、次に無電解銅メッキ液に浸漬した。１５０℃にて３０分間加熱してアニール処理を行った後に、エッチングレジストを形成し、エッチングによるパターン形成の後に、硫酸銅電解メッキを行い、３０μｍの厚さで導体層を形成した。次に、アニール処理を１８０℃にて６０分間行った。この積層板をサンプルＢとした。
(5) Plating by semi-additive method Sample A was immersed in an electroless plating solution containing PdCl 2 and then immersed in an electroless copper plating solution. After annealing for 30 minutes at 150 ° C., an etching resist was formed. After pattern formation by etching, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 30 μm. Next, annealing was performed at 180 ° C. for 60 minutes. This laminate was designated as Sample B.
（６）算術平均粗さ（Ｒａ）、二乗平均平方根粗さ（Ｒｑ値）の測定
サンプルＡについて、非接触型表面粗さ計（ビーコインスツルメンツ社製ＷＹＫＯ ＮＴ３３００）を用いて、ＶＳＩコンタクトモード、５０倍レンズにより測定範囲を１２１μｍ×９２μｍとして得られる数値によりＲａ、Ｒｑ値を求めた。そして、それぞれ１０点の平均値を求め、これを測定値とした。
(6) Measurement of arithmetic average roughness (Ra) and root mean square roughness (Rq value) For sample A, using a non-contact type surface roughness meter (WYKO NT3300, manufactured by Beec Instruments), VSI contact mode, 50 Ra and Rq values were obtained from numerical values obtained with a measurement range of 121 μm × 92 μm using a double lens. And the average value of 10 points | pieces was calculated | required and each was made into the measured value.
（７）メッキにより形成された導体層の引き剥がし強さ（ピール強度）の測定
サンプルＢの導体層に、幅１０ｍｍ、長さ１００ｍｍの部分を囲む切込みをいれ、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。
(7) Measurement of peel strength (peel strength) of conductor layer formed by plating In the conductor layer of sample B, a notch surrounding a portion having a width of 10 mm and a length of 100 mm is formed, and this one end is peeled off to grasp a grip ( The load (kgf / cm) when grasping with TS Co., Ltd., Autocom type testing machine AC-50C-SL) and peeling 35mm vertically at a speed of 50mm / min at room temperature It 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分間熱硬化させ、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.
(実施例１)
液状ビスフェノールＡ型エポキシ樹脂（エポキシ当量１６５、新日鐵化学（株）製「ＺＸ１０５９」）１０部と、ナフチルフルオレン型エポキシ樹脂（エポキシ当量３００、大阪ガスケミカル（株）製「ＣＧ−５００」）１０部とをメチルエチルケトン（以下「ＭＥＫ」と略称する。）５部、シクロヘキサノン５部に撹拌しながら加熱溶解させた。そこへ、活性エステル化合物（ＤＩＣ（株）製「ＨＰＣ８０００−６５Ｔ」、活性エステル当量２２３、固形分６５％のトルエン溶液）３０部、硬化促進剤（広栄化学工業（株）製、「４−ジメチルアミノピリジン」）０．３部、球形シリカ（平均粒径０．５μｍ、フェニルアミノシラン処理付「ＳＯ−Ｃ２」、（株）アドマテックス製、単位重量あたりのカーボン量０．１８％）１３０部、フェノキシ樹脂（ＹＬ７５５３ＢＨ３０、固形分３０質量％のＭＥＫ溶液、重量平均分子量３５０００）５部を混合し、高速回転ミキサーで均一に分散して、樹脂ワニスを調製した。次に、かかる樹脂ワニスをＰＥＴフィルム（厚さ３８μｍ）上に、乾燥後の樹脂厚みが４０μｍとなるようにダイコーターにて塗布し、８０〜１２０℃（平均１００℃）で６分間乾燥させて、シート状の接着フィルムを得た。
(Example 1)
10 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 165, “ZX1059” manufactured by Nippon Steel Chemical Co., Ltd.) and naphthylfluorene type epoxy resin (epoxy equivalent 300, “CG-500” manufactured by Osaka Gas Chemical Co., Ltd.) 10 parts was dissolved by heating in 5 parts of methyl ethyl ketone (hereinafter abbreviated as “MEK”) and 5 parts of cyclohexanone with stirring. There, 30 parts of an active ester compound (“HPC8000-65T” manufactured by DIC Corporation, active ester equivalent 223, 65% solid content toluene solution), curing accelerator (manufactured by Guangei Chemical Industry Co., Ltd., “4-dimethyl) "Aminopyridine") 0.3 parts, spherical silica (average particle size 0.5 µm, "SO-C2" with phenylaminosilane treatment, manufactured by Admatechs Co., Ltd., carbon amount 0.18% per unit weight), 130 parts, 5 parts of phenoxy resin (YL7553BH30, MEK solution having a solid content of 30% by mass, weight average molecular weight 35000) was mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish. Next, this resin varnish is applied on a PET film (thickness 38 μm) with a die coater so that the resin thickness after drying is 40 μm, and dried at 80 to 120 ° C. (average 100 ° C.) for 6 minutes. A sheet-like adhesive film was obtained.
(実施例２)
液状ビスフェノールＡ型エポキシ樹脂（エポキシ当量１６５、新日鐵化学（株）製「ＺＸ１０５９」）１０部と、ナフチルフルオレン型エポキシ樹脂（エポキシ当量３００、大阪ガスケミカル（株）製「ＣＧ−５００」）１０部とをＭＥＫ５部、シクロヘキサノン５部に撹拌しながら加熱溶解させた。そこへ、活性エステル化合物（ＤＩＣ（株）製「ＨＰＣ８０００−６５Ｔ」、活性エステル当量２２３、固形分６５％のトルエン溶液）１５部、フェノール化合物（ＤＩＣ（株）製「ＬＡ３０１８−５０Ｐ」、フェノール当量１５１、固形分５０％の２−メトキシプロパノール溶液）１０部、硬化促進剤（広栄化学工業（株）製、「４−ジメチルアミノピリジン」）０．１部、球形シリカ（平均粒径０．５μｍ、フェニルアミノシラン処理付「ＳＯ−Ｃ２」、（株）アドマテックス製、単位重量あたりのカーボン量０．１８％）１３０部、フェノキシ樹脂（ＹＬ７５５３ＢＨ３０、固形分３０質量％のＭＥＫ溶液、重量平均分子量３５０００）５部を混合し、高速回転ミキサーで均一に分散して、樹脂ワニスを調製した。次に実施例１と同様にして接着フィルムを得た。
(Example 2)
10 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 165, “ZX1059” manufactured by Nippon Steel Chemical Co., Ltd.) and naphthylfluorene type epoxy resin (epoxy equivalent 300, “CG-500” manufactured by Osaka Gas Chemical Co., Ltd.) 10 parts were dissolved in 5 parts of MEK and 5 parts of cyclohexanone with heating and stirring. There, 15 parts of active ester compound (“HPC8000-65T” manufactured by DIC Corporation, active ester equivalent 223, 65% solid content toluene solution), phenol compound (“LA3018-50P” manufactured by DIC Corporation), phenol equivalent 151, 10 parts of a 2-methoxypropanol solution having a solid content of 50%, 0.1 part of a curing accelerator (manufactured by Guangei Chemical Industry Co., Ltd., “4-dimethylaminopyridine”), spherical silica (average particle size 0.5 μm) , "SO-C2" with phenylaminosilane treatment, manufactured by Admatechs Co., Ltd., 130 parts by weight of carbon per unit weight 0.18%, phenoxy resin (YL7553BH30, MEK solution with a solid content of 30% by weight, weight average molecular weight 35000 ) 5 parts were mixed and dispersed uniformly with a high-speed rotary mixer to prepare a resin varnish. Next, an adhesive film was obtained in the same manner as in Example 1.
(比較例１)
実施例２のナフチルフルオレン型エポキシ樹脂（エポキシ当量３００、大阪ガスケミカル（株）製「ＣＧ−５００」）１０部をナフタレン型エポキシ樹脂（ＤＩＣ（株）製「ＨＰ４７１０」、エポキシ当量１７１）１０部に変更したこと以外は、実施例２と全く同様にして樹脂ワニスを作製した。次に実施例１と同様にして接着フィルムを得た。
(Comparative Example 1)
10 parts of naphthylfluorene type epoxy resin of Example 2 (epoxy equivalent 300, “CG-500” manufactured by Osaka Gas Chemical Co., Ltd.) 10 parts of naphthalene type epoxy resin (“HP4710” manufactured by DIC Corporation, epoxy equivalent 171) A resin varnish was prepared in exactly the same manner as in Example 2 except that the change was made. Next, an adhesive film was obtained in the same manner as in Example 1.
(比較例２)
実施例２の活性エステル化合物（ＤＩＣ（株）製「ＨＰＣ−８０００−６５Ｔ」、活性エステル当量２２３、固形分６５％のトルエン溶液）１５部を添加せずに、フェノール化合物（ＤＩＣ（株）製「ＬＡ３０１８−５０Ｐ」、フェノール当量１５１、固形分５０％の２−メトキシプロパノール溶液）を２０部に変更し、さらに球形シリカ（平均粒径０．５μｍ、フェニルアミノシラン処理付「ＳＯ−Ｃ２」、（株）アドマテックス製、単位重量あたりのカーボン量０．１８％）を１１５部に変更したこと以外は、実施例２と全く同様にして樹脂ワニスを調製した。次に実施例１と同様にして接着フィルムを得た。
(Comparative Example 2)
A phenol compound (manufactured by DIC Corporation) was added without adding 15 parts of the active ester compound of Example 2 ("HPC-8000-65T" manufactured by DIC Corporation, active ester equivalent 223, solid content 65% toluene solution). “LA3018-50P”, phenol equivalent 151, 2-methoxypropanol solution having a solid content of 50% was changed to 20 parts, and spherical silica (average particle size 0.5 μm, “SO-C2” with phenylaminosilane treatment, ( Resin varnish was prepared in exactly the same manner as in Example 2 except that Admatechs Co., Ltd. (carbon amount 0.18% per unit weight) was changed to 115 parts. Next, an adhesive film was obtained in the same manner as in Example 1.
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１及び２では、硬化して絶縁層とした場合に、算術平均粗さの値及び二乗平均平方根粗さの値が小さく、ピール強度として十分な値が得られ、誘電正接が低いことが分かる。他方、比較例１及び２の樹脂組成物では、算術平均粗さ、二乗平均平方根粗さの値が大きくなり、ピール強度が小さく、誘電正接が高かった。 From the results of Table 1, in Examples 1 and 2, when cured into an insulating layer, the arithmetic average roughness value and the root mean square roughness value are small, and a sufficient value as the peel strength is obtained, It can be seen that the dielectric loss tangent is low. On the other hand, in the resin compositions of Comparative Examples 1 and 2, the arithmetic average roughness and root mean square roughness values were large, the peel strength was small, and the dielectric loss tangent was high.
（実施例３）
半固形状ナフタレン型エポキシ樹脂（エポキシ当量１４４、ＤＩＣ(株)製「ＨＰ４０３２」）９部とナフチルフルオレン型エポキシ樹脂（エポキシ当量３００、大阪ガスケミカル（株）製「ＣＧ−５００」）１０部とをＭＥＫ５部、シクロヘキサノン５部に撹拌しながら加熱溶解させた。そこへ、シアネートエステル化合物（シアネート当量１２４、ロンザジャパン（株）製「ＰＴ３０Ｓ」）７．６５部、硬化促進剤（広栄化学工業（株）製、「４−ジメチルアミノピリジン」）０．０２部、球形シリカ（平均粒径０．５μｍ、フェニルアミノシラン処理付「ＳＯ−Ｃ２」、（株）アドマテックス製、単位重量あたりのカーボン量０．１８％）１９０部、フェノキシ樹脂（ＹＬ７５５３ＢＨ３０、固形分３０質量％のＭＥＫ溶液、重量平均分子量３５０００）５部を混合し、高速回転ミキサーで均一に分散して、樹脂ワニスを調製した。次に実施例１と同様にして接着フィルムを得た。
(Example 3)
9 parts of semi-solid naphthalene type epoxy resin (epoxy equivalent 144, “HP4032” manufactured by DIC Corporation) and 10 parts of naphthylfluorene type epoxy resin (epoxy equivalent 300, “CG-500” manufactured by Osaka Gas Chemical Co., Ltd.) Was dissolved in 5 parts of MEK and 5 parts of cyclohexanone with stirring. There, 7.65 parts of a cyanate ester compound (cyanate equivalent 124, “PT30S” manufactured by Lonza Japan Co., Ltd.), 0.02 part of a curing accelerator (“4-dimethylaminopyridine” manufactured by Guangei Chemical Industry Co., Ltd.) , 190 parts of spherical silica (average particle size 0.5 μm, “SO-C2” with phenylaminosilane treatment, manufactured by Admatechs, carbon amount 0.18% per unit weight), phenoxy resin (YL7553BH30, solid content 30) A resin varnish was prepared by mixing 5 parts of a mass% MEK solution and a weight average molecular weight of 35,000) and uniformly dispersing with a high-speed rotary mixer. Next, an adhesive film was obtained in the same manner as in Example 1.
（比較例３）
実施例３のナフチルフルオレン型エポキシ樹脂（エポキシ当量３００、大阪ガスケミカル(株)製「ＣＧ−５００」）１０部をビフェニル型エポキシ樹脂（エポキシ当量１８５、三菱化学(株)製「ＹＸ４０００Ｈ」）６部に変更したこと以外は、実施例３と同様にして樹脂ワニスを調製した。次に実施例１と同様にして接着フィルムを得た。
(Comparative Example 3)
10 parts of naphthylfluorene type epoxy resin of Example 3 (epoxy equivalent 300, “CG-500” manufactured by Osaka Gas Chemical Co., Ltd.) 6 parts biphenyl type epoxy resin (epoxy equivalent 185, “YX4000H” manufactured by Mitsubishi Chemical Co., Ltd.) 6 A resin varnish was prepared in the same manner as in Example 3 except that the part was changed to part. Next, an adhesive film was obtained in the same manner as in Example 1.
結果を表２に示す。 The results are shown in Table 2.
表２の結果から、実施例３では、算術平均粗さ、二乗平均平方根粗さの値が小さく、ピール強度として十分な値が得られ、誘電正接が低いことが分かる。他方、比較例３では、算術平均粗さ、二乗平均平方根粗さの値が大きくなり、ピール強度が小さく、誘電正接が高かった。 From the results of Table 2, it can be seen that in Example 3, the arithmetic average roughness and the root mean square roughness are small, a sufficient peel strength is obtained, and the dielectric loss tangent is low. On the other hand, in Comparative Example 3, the arithmetic average roughness and root mean square roughness values were large, the peel strength was small, and the dielectric loss tangent was high.
硬化して絶縁層とした場合に湿式粗化工程において絶縁層表面の算術平均粗さの値が小さいのみならず、絶縁層表面の二乗平均平方根粗さの値も小さく、絶縁層上に十分なピール強度を有する導体層をメッキにより形成することができ、硬化物の誘電正接が低い樹脂組成物を提供できるようになった。更にそれを用いたシート状積層材料、多層プリント配線板、半導体装置を提供できるようになった。更にこれらを搭載した、コンピューター、携帯電話、デジタルカメラ、テレビ、等の電気製品や、自動二輪車、自動車、電車、船舶、航空機、等の乗物も提供できるようになった。 When cured to form an insulating layer, not only the arithmetic average roughness value of the insulating layer surface is small in the wet roughening process, but also the root mean square roughness value of the insulating layer surface is small and sufficient on the insulating layer. A conductor layer having peel strength can be formed by plating, and a resin composition having a low dielectric loss tangent of a cured product can be provided. Furthermore, sheet-like laminated materials, multilayer printed wiring boards, and semiconductor devices using the same can be provided. Furthermore, electric products such as computers, mobile phones, digital cameras, and televisions, and vehicles such as motorcycles, automobiles, trains, ships, and airplanes equipped with these can be provided.
Claims (16)
成分（Ｂ）活性エステル系硬化剤及びシアネートエステル系硬化剤のうちのいずれか一方又は両方を含有することを特徴とする樹脂組成物。 A resin composition comprising one or both of component (A) an epoxy resin having a naphthylfluorene structure, and component (B) an active ester curing agent and a cyanate ester curing agent.
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