JP5249903B2 - Resin composition - Google Patents
Resin composition Download PDFInfo
- Publication number
- JP5249903B2 JP5249903B2 JP2009243919A JP2009243919A JP5249903B2 JP 5249903 B2 JP5249903 B2 JP 5249903B2 JP 2009243919 A JP2009243919 A JP 2009243919A JP 2009243919 A JP2009243919 A JP 2009243919A JP 5249903 B2 JP5249903 B2 JP 5249903B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- epoxy resin
- resin composition
- curing agent
- epoxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000011342 resin composition Substances 0.000 title claims description 83
- 229920000647 polyepoxide Polymers 0.000 claims description 138
- 239000003822 epoxy resin Substances 0.000 claims description 126
- 239000003795 chemical substances by application Substances 0.000 claims description 54
- 239000002245 particle Substances 0.000 claims description 50
- 229920005989 resin Polymers 0.000 claims description 44
- 239000011347 resin Substances 0.000 claims description 44
- 239000011256 inorganic filler Substances 0.000 claims description 38
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 38
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 20
- 229920006287 phenoxy resin Polymers 0.000 claims description 19
- 239000013034 phenoxy resin Substances 0.000 claims description 19
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 12
- 229920002554 vinyl polymer Polymers 0.000 claims description 12
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 11
- 239000011354 acetal resin Substances 0.000 claims description 11
- 125000003700 epoxy group Chemical group 0.000 claims description 11
- 229920006324 polyoxymethylene Polymers 0.000 claims description 11
- 239000004643 cyanate ester Substances 0.000 claims description 10
- 238000004381 surface treatment Methods 0.000 claims description 10
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 8
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 239000010410 layer Substances 0.000 description 85
- 238000001723 curing Methods 0.000 description 58
- 239000004593 Epoxy Substances 0.000 description 36
- -1 glycidyl ester Chemical class 0.000 description 36
- 239000004020 conductor Substances 0.000 description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 27
- 239000002313 adhesive film Substances 0.000 description 27
- 238000000034 method Methods 0.000 description 27
- 229920001971 elastomer Polymers 0.000 description 17
- 239000002966 varnish Substances 0.000 description 17
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 16
- 238000007788 roughening Methods 0.000 description 15
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 14
- 238000005259 measurement Methods 0.000 description 14
- 229920003986 novolac Polymers 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 239000005060 rubber Substances 0.000 description 14
- 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 13
- 239000003960 organic solvent Substances 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 12
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 12
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 12
- 239000000377 silicon dioxide Substances 0.000 description 12
- 239000000758 substrate Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 11
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 10
- 238000007747 plating Methods 0.000 description 10
- 238000010030 laminating Methods 0.000 description 9
- 229910052698 phosphorus Inorganic materials 0.000 description 9
- 239000011574 phosphorus Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 239000004305 biphenyl Substances 0.000 description 8
- 235000010290 biphenyl Nutrition 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 229920001187 thermosetting polymer Polymers 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 150000002430 hydrocarbons Chemical group 0.000 description 7
- 235000013824 polyphenols Nutrition 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 6
- 230000001681 protective effect Effects 0.000 description 6
- 230000003014 reinforcing effect Effects 0.000 description 6
- 229910000679 solder Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229920000459 Nitrile rubber Polymers 0.000 description 5
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 150000002902 organometallic compounds Chemical class 0.000 description 5
- 230000003746 surface roughness Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- WBODDOZXDKQEFS-UHFFFAOYSA-N 1,2,3,4-tetramethyl-5-phenylbenzene Chemical group CC1=C(C)C(C)=CC(C=2C=CC=CC=2)=C1C WBODDOZXDKQEFS-UHFFFAOYSA-N 0.000 description 3
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000012792 core layer Substances 0.000 description 3
- 239000011258 core-shell material Substances 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 238000005553 drilling Methods 0.000 description 3
- 238000007772 electroless plating Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 150000003018 phosphorus compounds Chemical class 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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 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
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 2
- JYLNVJYYQQXNEK-UHFFFAOYSA-N 3-amino-2-(4-chlorophenyl)-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(CN)C1=CC=C(Cl)C=C1 JYLNVJYYQQXNEK-UHFFFAOYSA-N 0.000 description 2
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 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
- 229930185605 Bisphenol Natural products 0.000 description 2
- 229920002799 BoPET Polymers 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-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
- 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
- 229920000800 acrylic rubber Polymers 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
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 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
- 230000001588 bifunctional effect Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000011362 coarse particle Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- AZDCYKCDXXPQIK-UHFFFAOYSA-N ethenoxymethylbenzene Chemical compound C=COCC1=CC=CC=C1 AZDCYKCDXXPQIK-UHFFFAOYSA-N 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- 239000012943 hotmelt Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000001477 organic nitrogen group Chemical group 0.000 description 2
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 2
- 150000003918 triazines Chemical class 0.000 description 2
- XXEYMOUSTWPDDB-OJMIUMIFSA-N (2r)-5-[(5s,7r,8s,9r)-8,9-dihydroxy-2,4-dioxo-7-(phosphonooxymethyl)-6-oxa-1,3-diazaspiro[4.4]nonan-3-yl]-2-[formyl(hydroxy)amino]pentanoic acid Chemical compound O[C@@H]1[C@H](O)[C@@H](COP(O)(O)=O)O[C@]11C(=O)N(CCC[C@@H](N(O)C=O)C(O)=O)C(=O)N1 XXEYMOUSTWPDDB-OJMIUMIFSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-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
- MEBONNVPKOBPEA-UHFFFAOYSA-N 1,1,2-trimethylcyclohexane Chemical group CC1CCCCC1(C)C MEBONNVPKOBPEA-UHFFFAOYSA-N 0.000 description 1
- CNNPULJFGORMOI-UHFFFAOYSA-N 1-[[[dimethyl(octyl)silyl]amino]-dimethylsilyl]octane Chemical compound CCCCCCCC[Si](C)(C)N[Si](C)(C)CCCCCCCC CNNPULJFGORMOI-UHFFFAOYSA-N 0.000 description 1
- XNVKQSYMDNUWNH-UHFFFAOYSA-N 1-[[[dimethyl(propyl)silyl]amino]-dimethylsilyl]propane Chemical compound CCC[Si](C)(C)N[Si](C)(C)CCC XNVKQSYMDNUWNH-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 1
- DJOYTAUERRJRAT-UHFFFAOYSA-N 2-(n-methyl-4-nitroanilino)acetonitrile Chemical compound N#CCN(C)C1=CC=C([N+]([O-])=O)C=C1 DJOYTAUERRJRAT-UHFFFAOYSA-N 0.000 description 1
- LMVLMHGTZULBRX-UHFFFAOYSA-N 2-[2,2,2-tris(2-hydroxyphenyl)ethyl]phenol Chemical compound OC1=CC=CC=C1CC(C=1C(=CC=CC=1)O)(C=1C(=CC=CC=1)O)C1=CC=CC=C1O LMVLMHGTZULBRX-UHFFFAOYSA-N 0.000 description 1
- UNRPFVWRKQHKMU-UHFFFAOYSA-N 2-[ditert-butyl-(tritert-butylsilylamino)silyl]-2-methylpropane Chemical compound CC(C)(C)[Si](C(C)(C)C)(C(C)(C)C)N[Si](C(C)(C)C)(C(C)(C)C)C(C)(C)C UNRPFVWRKQHKMU-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- 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 1
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 description 1
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 1
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、特定の、エポキシ樹脂、硬化剤、無機充填材を含有する樹脂組成物に関する。 The present invention relates to a specific resin composition containing an epoxy resin, a curing agent, and an inorganic filler.
多層プリント配線板の絶縁層の低熱膨張化を図る手段としては、シリカ等の無機充填材を各種カップリング剤により表面処理し、樹脂組成物中に添加する方法が知られている（特許文献１）。しかしながら、無機充填材の脱落による絶縁層表面粗度の不均一化や、絶縁層表面に形成される導体層のピール強度の低下、さらにはリフローテスト後に導体層の剥離が発生するなど不安定である。 As a means for reducing the thermal expansion of the insulating layer of the multilayer printed wiring board, a method is known in which an inorganic filler such as silica is surface-treated with various coupling agents and added to the resin composition (Patent Document 1). ). However, it is unstable such as non-uniformity of the surface roughness of the insulating layer due to falling off of the inorganic filler, reduction of the peel strength of the conductor layer formed on the surface of the insulating layer, and peeling of the conductor layer after the reflow test. is there.
本発明が解決しようとする課題は、低熱膨張率を維持しながら、硬化して得られる絶縁層表面の粗度が安定して低く、高いピール強度を有する導体層の形成を可能にし、半田耐熱性に優れた、回路基板の絶縁層形成に好適に使用することができる樹脂組成物及び絶縁樹脂シートを提供することにある。 The problem to be solved by the present invention is that the insulating layer surface obtained by curing has a stable and low roughness while maintaining a low coefficient of thermal expansion, enabling the formation of a conductor layer having high peel strength, and solder heat resistance. An object of the present invention is to provide a resin composition and an insulating resin sheet which are excellent in properties and can be suitably used for forming an insulating layer of a circuit board.
本発明者らは鋭意検討した結果、特定の、エポキシ樹脂、硬化剤、無機充填材を含有する樹脂組成物であることにより上記課題が解決できることを見出し、本発明を完成するに至った。 As a result of intensive studies, the present inventors have found that the above problems can be solved by using a specific resin composition containing an epoxy resin, a curing agent, and an inorganic filler, and have completed the present invention.
すなわち、本発明は以下の態様を含む。
[１]（Ａ１）１分子中に２以上のエポキシ基を有し、温度２０℃で液状の芳香族系エポキシ樹脂である第１のエポキシ樹脂と、（Ａ２）ビフェニルアラルキル型エポキシ樹脂及び／又は下記一般式（１）で表されるエポキシ樹脂である第２のエポキシ樹脂とを含む（Ａ）エポキシ樹脂、（Ｂ）フェノール系硬化剤、ナフトール系硬化剤、活性エステル系硬化剤、ベンゾオキサジン系硬化剤、シアネートエステル樹脂から選択される１種又は２種以上の硬化剤、（Ｃ）シラザン化合物で表面処理後、シランカップリング剤で表面処理された、その表面に結合しているカーボン量が単位面積当たり０．２５〜１．００ｍｇ／ｍ２の範囲にあり、平均粒子径が２μｍ以下かつ最大粒子径が５μｍ以下である無機充填材、及び（Ｄ）重量平均分子量が８，０００〜１５０，０００のフェノキシ樹脂及び／又はポリビニルアセタール樹脂、を含有する樹脂組成物であり、該樹脂組成物中の不揮発分１００質量％に対し、成分（Ｃ）の含有量が３０〜８５質量％であることを特徴とする樹脂組成物。
That is, the present invention includes the following aspects.
[1] (A1) a first epoxy resin which is an aromatic epoxy resin having two or more epoxy groups in one molecule and is liquid at a temperature of 20 ° C., and (A2) a biphenylaralkyl type epoxy resin and / or (A) an epoxy resin containing a second epoxy resin that is an epoxy resin represented by the following general formula (1), (B) a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, a benzoxazine-based One or two or more curing agents selected from a curing agent and a cyanate ester resin, (C) after surface treatment with a silazane compound, surface treatment with a silane coupling agent, and the amount of carbon bonded to the surface An inorganic filler having a mean particle size of 2 μm or less and a maximum particle size of 5 μm or less, and (D) a weight average molecular weight of 8 to 0.25 mg / m 2 per unit area; , 150,000 to 150,000 phenoxy resin and / or polyvinyl acetal resin, and the content of the component (C) is 30 to 85 with respect to 100% by mass of the nonvolatile content in the resin composition. A resin composition characterized by being a mass%.
（ｎは平均値として１〜６の数を示し、Ｘはグリシジル基又は炭素数１〜８の炭化水素基を示し、炭化水素基／グリシジル基の比率は０．０５〜２．０である。）
[２]無機充填材の表面に結合しているカーボン量が単位面積当たり０．２５〜０．７５ｍｇ／ｍ２である、上記[１]の樹脂組成物。
[３]無機充填材の表面に結合しているカーボン量が単位面積当たり０．２５〜０．７０ｍｇ／ｍ２である、上記[１]の樹脂組成物。
[４]樹脂組成物中に存在するエポキシ基と成分（Ｂ）の硬化剤の反応基の比率が質量比で１：０．４〜１：２となる範囲で成分（Ｂ）の硬化剤を含む、上記[１]〜［３］のいずれかの樹脂組成物。
[５]上記[１]〜[４]のいずれかの樹脂組成物を含有することを特徴とするシート状材料。
[６]上記[５]のシート状材料を含有することを特徴とする多層プリント配線板。
(N shows the number of 1-6 as an average value, X shows a glycidyl group or a C1-C8 hydrocarbon group, and the ratio of a hydrocarbon group / glycidyl group is 0.05-2.0. )
[2] The resin composition according to the above [1], wherein the amount of carbon bonded to the surface of the inorganic filler is 0.25 to 0.75 mg / m 2 per unit area.
[3] The resin composition according to the above [1], wherein the amount of carbon bonded to the surface of the inorganic filler is 0.25 to 0.70 mg / m 2 per unit area.
[4] The curing agent of component (B) is added in such a range that the ratio of epoxy groups present in the resin composition to the reactive group of the curing agent of component (B) is 1: 0.4 to 1: 2. A resin composition according to any one of the above [1] to [3].
[5] A sheet-like material comprising the resin composition according to any one of [1] to [4] above.
[6] A multilayer printed wiring board comprising the sheet-like material according to [5] above.
特定の、エポキシ樹脂、硬化剤、無機充填材を含有する樹脂組成物により、低熱膨張率を維持しながら、硬化して得られる絶縁層表面の粗度が安定して低く、高いピール強度を有する導体層の形成を可能にし、半田耐熱性に優れた、回路基板の絶縁層形成に好適に使用することができる樹脂組成物及び絶縁樹脂シートが提供できるようになった。 A specific resin composition containing an epoxy resin, a curing agent, and an inorganic filler, while maintaining a low coefficient of thermal expansion, the roughness of the surface of the insulating layer obtained by curing is stably low and has a high peel strength. It has become possible to provide a resin composition and an insulating resin sheet that can form a conductor layer and have excellent solder heat resistance and can be suitably used for forming an insulating layer of a circuit board.
以下、本発明をその好適な実施形態に即して説明する。
[（Ａ）エポキシ樹脂]
本発明の樹脂組成物において、（Ａ）エポキシ樹脂は、（Ａ１）１分子中に２以上のエポキシ基を有し、温度２０℃で液状の芳香族系エポキシ樹脂である第１のエポキシ樹脂と、（Ａ２）ビフェニルアラルキル型エポキシ樹脂及び／又は下記の一般式（１）で表されるエポキシ樹脂（以下、「一般式（１）のエポキシ樹脂」と略称する。）である第２のエポキシ樹脂とを含む。なお、一般式（１）のエポキシ樹脂における炭化水素基／グリシジル基の比率はモル比である。また、本発明において「芳香族系エポキシ樹脂」とは、１分子中に少なくとも１個の芳香環を有するエポキシ樹脂を意味する。
Hereinafter, the present invention will be described with reference to preferred embodiments thereof.
[(A) Epoxy resin]
In the resin composition of the present invention, (A) the epoxy resin is (A1) a first epoxy resin that is an aromatic epoxy resin that has two or more epoxy groups in one molecule and is liquid at a temperature of 20 ° C. (A2) a second epoxy resin which is a biphenyl aralkyl type epoxy resin and / or an epoxy resin represented by the following general formula (1) (hereinafter abbreviated as “epoxy resin of general formula (1)”) Including. In addition, the ratio of the hydrocarbon group / glycidyl group in the epoxy resin of the general formula (1) is a molar ratio. In the present invention, the “aromatic epoxy resin” means an epoxy resin having at least one aromatic ring in one molecule.
（ｎは平均値として１〜６の数を示し、Ｘはグリシジル基又は炭素数１〜８の炭化水素基を示し、炭化水素基／グリシジル基の比率は０．０５〜２．０である。） (N shows the number of 1-6 as an average value, X shows a glycidyl group or a C1-C8 hydrocarbon group, and the ratio of a hydrocarbon group / glycidyl group is 0.05-2.0. )
（Ａ１）１分子中に２以上のエポキシ基を有し、温度２０℃で液状の芳香族系エポキシ樹脂である第１のエポキシ樹脂は、樹脂組成物の熱硬化前の可とう性、熱時流動性、密着性等を付与させることができる。第１のエポキシ樹脂は、特に限定されないが、ビスフェノールＡ型エポキシ樹脂、ナフタレン型エポキシ樹脂、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、フェノールノボラック型エポキシ樹脂、グリシジルエステル型エポキシ樹脂、グリシジルアミン型エポキシ樹脂並びにこれらのエポキシ樹脂のアルキル置換体、ハロゲン化物、リン変性物及び部分水素添加物等が挙げられる。また、融点以上で溶解させた後、室温にて液状となる結晶性エポキシ樹脂も、該第１のエポキシ樹脂と同様にして扱える。当該結晶性エポキシ樹脂は、具体的には、テトラメチルビフェニル型エポキシ樹脂、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、ナフタレン型エポキシ樹脂、ｔｅｒｔ-ブチル-カテコール型エポキシ樹脂等が挙げられる。 (A1) The first epoxy resin, which is an aromatic epoxy resin that has two or more epoxy groups in one molecule and is liquid at a temperature of 20 ° C., is flexible before heat curing of the resin composition. Fluidity, adhesion, etc. can be imparted. The first epoxy resin is not particularly limited, but bisphenol A type epoxy resin, naphthalene type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type Examples thereof include epoxy resins and alkyl-substituted products, halides, phosphorus-modified products and partially hydrogenated products of these epoxy resins. In addition, a crystalline epoxy resin that is dissolved at a melting point or higher and then becomes liquid at room temperature can be handled in the same manner as the first epoxy resin. Specific examples of the crystalline epoxy resin include tetramethylbiphenyl type epoxy resin, biphenyl type epoxy resin, anthracene type epoxy resin, naphthalene type epoxy resin, tert-butyl-catechol type epoxy resin, and the like.
第１のエポキシ樹脂は、中でも、耐熱性、絶縁信頼性、金属膜との密着性等に優れるという観点から、ビスフェノールＡ型エポキシ樹脂、ナフタレン型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、グリシジルエステル型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、テトラメチルビフェニル型エポキシ樹脂が好ましい。 The first epoxy resin is, among other things, bisphenol A type epoxy resin, naphthalene type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy from the viewpoint of excellent heat resistance, insulation reliability, adhesion to a metal film, and the like. Resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, and tetramethylbiphenyl type epoxy resins are preferred.
第１のエポキシ樹脂の好適な具体例は、液状ビスフェノールＡ型エポキシ樹脂（ジャパンエポキシレジン（株）製「ｊＥＲ８２８ＥＬ」（エポキシ当量：１８０）、「ＹＬ９８０」（エポキシ当量：１８５））、液状ナフタレン型２官能エポキシ樹脂（大日本インキ化学工業（株）製「ＨＰ４０３２」（エポキシ当量：１４４）、「ＨＰ４０３２Ｄ］（エポキシ当量：１４４））、液状ビスフェノールＦ型エポキシ樹脂（ジャパンエポキシレジン（株）製「ｊＥＲ８０６」（エポキシ当量：１６５）、「ＹＬ９８３Ｕ」（エポキシ当量：１７０））、液状フェノールノボラック型エポキシ樹脂（ＤＩＣ（株）製「Ｎ−７４０」（エポキシ当量：１８１）、「Ｎ−７３８−ＳＳ」（エポキシ当量：１８１））、グリシジルエステル型エポキシ樹脂（ジャパンエポキシレジン（株）製「ｊＥＲ８７１」（エポキシ当量：４２２））、グリシジルアミン型エポキシ樹脂（ジャパンエポキシレジン（株）製「ｊＥＲ６３０」（エポキシ当量：９６）、「ｊＥＲ６３０ＬＳＤ」（エポキシ当量：９６））等を挙げることができる。また、融点以上で溶解させた後、室温にて液状となる結晶性エポキシ樹脂としては、テトラメチルビフェニル型エポキシ樹脂（ジャパンエポキシレジン（株）製「ＹＸ４０００Ｈ」（エポキシ当量：１９２）、「ＹＸ８８００」（エポキシ当量：１７８））、ｔｅｒｔ-ブチル-カテコール型エポキシ樹脂（東都化成（株）製「ＹＤＣ１３１２」（エポキシ当量１７８）、「ＹＳＬＶ−８０ＸＹ」（エポキシ当量１９５）、「ＹＳＬＶ−１２０ＴＥ」（エポキシ当量２４５））などが挙げられる。 Suitable specific examples of the first epoxy resin include liquid bisphenol A type epoxy resin (“JER828EL” (epoxy equivalent: 180), “YL980” (epoxy equivalent: 185), manufactured by Japan Epoxy Resin Co., Ltd.)), liquid naphthalene type Bifunctional epoxy resin (“HP4032” (epoxy equivalent: 144), “HP4032D” (epoxy equivalent: 144), manufactured by Dainippon Ink and Chemicals, Inc.), liquid bisphenol F-type epoxy resin (manufactured by Japan Epoxy Resins, Inc. jER806 "(epoxy equivalent: 165)," YL983U "(epoxy equivalent: 170)), liquid phenol novolac type epoxy resin (" N-740 "(epoxy equivalent: 181) manufactured by DIC Corporation)," N-738-SS " (Epoxy equivalent: 181)), glycidyl ester type epoxy tree ("JER871" manufactured by Japan Epoxy Resin Co., Ltd. (epoxy equivalent: 422)), glycidylamine epoxy resin ("jER630" manufactured by Japan Epoxy Resin Co., Ltd. (epoxy equivalent: 96), "jER630LSD" (epoxy equivalent: 96) )) And the like. In addition, as a crystalline epoxy resin which is dissolved at a melting point or higher and becomes liquid at room temperature, tetramethylbiphenyl type epoxy resin (“YX4000H” (epoxy equivalent: 192), “YX8800” manufactured by Japan Epoxy Resin Co., Ltd.) (Epoxy equivalent: 178)), tert-butyl-catechol type epoxy resin (“YDC1312” (epoxy equivalent 178), “YSLV-80XY” (epoxy equivalent 195), “YSLV-120TE” (epoxy) manufactured by Tohto Kasei Co., Ltd. Equivalent 245)).
本明細書中、「エポキシ当量」とは１グラム当量のエポキシ基を含む樹脂のグラム数（g/eq）であり、ＪＩＳ Ｋ ７２３６に規定された方法に従って測定される。 In the present specification, the “epoxy equivalent” is the number of grams (g / eq) of a resin containing 1 gram equivalent of an epoxy group, and is measured according to a method defined in JIS K 7236.
（Ａ２）ビフェニルアラルキル型エポキシ樹脂及び／又は一般式（１）のエポキシ樹脂である第２のエポキシ樹脂は、デスミアでの銅めっき安定性を付与させる事ができる。 (A2) The 2nd epoxy resin which is a biphenyl aralkyl type epoxy resin and / or the epoxy resin of General formula (1) can provide copper plating stability in a desmear.
第２のエポキシ樹脂は、温度２０℃で固形状のものが好ましい。また、ビフェニルアラルキル型エポキシ樹脂と一般式（１）のエポキシ樹脂の両方を使用する場合、ビフェニルアラルキル型エポキシ樹脂と一般式（１）のエポキシ樹脂の使用量比は特に限定はされないが、好ましくは不揮発分の質量比で１：９〜９：１である。 The second epoxy resin is preferably solid at a temperature of 20 ° C. Moreover, when using both a biphenyl aralkyl type epoxy resin and the epoxy resin of General formula (1), the usage-amount ratio of a biphenyl aralkyl type epoxy resin and the epoxy resin of General formula (1) is not specifically limited, The mass ratio of the non-volatile content is 1: 9 to 9: 1.
第２のエポキシ樹脂の好適な具体例は、ビフェニルアラルキル型エポキシ樹脂として、日本化薬（株）製「ＮＣ３０００−ＦＨ」、「ＮＣ３０００−Ｈ」、「ＮＣ３０００」、「ＮＣ３０００−Ｌ」（エポキシ当量：２６５−３３０）、「ＮＣ３１００」（エポキシ当量：２５４）が挙げられる。また、一般式（１）のエポキシ樹脂として、東都化成（株）製ナフトール型エポキシ樹脂「ＥＳＮ−４７５Ｖ」（一般式（１）中のＸで表される炭素数１〜８の炭化水素基がメチル基、炭化水素基／グリシジル基の比率が約０．１、エポキシ当量：３３２）等が挙げられる。 Preferred specific examples of the second epoxy resin include “NC3000-FH”, “NC3000-H”, “NC3000”, “NC3000-L” (epoxy equivalent) manufactured by Nippon Kayaku Co., Ltd. as a biphenylaralkyl type epoxy resin. : 265-330), "NC3100" (epoxy equivalent: 254). In addition, as an epoxy resin of the general formula (1), a naphthol type epoxy resin “ESN-475V” manufactured by Toto Kasei Co., Ltd. (a hydrocarbon group having 1 to 8 carbon atoms represented by X in the general formula (1) Examples thereof include a methyl group, a hydrocarbon group / glycidyl group ratio of about 0.1, and an epoxy equivalent: 332).
本発明において、第１のエポキシ樹脂と第２のエポキシ樹脂の使用量比は不揮発分の質量比で５〜６０：９５〜４０が好ましく、１０〜５０：９０〜５０がより好ましい。かかる範囲を外れて第１のエポキシ樹脂の使用量が少なすぎると、樹脂組成物が脆くなる傾向にあり、第１のエポキシ樹脂の使用量が多すぎると、樹脂組成物に粘着性が出る傾向となり、いずれも取り扱い性に劣る傾向にある。 In the present invention, the amount ratio of the first epoxy resin to the second epoxy resin is preferably 5 to 60:95 to 40, more preferably 10 to 50:90 to 50 in terms of mass ratio of non-volatile content. If the amount of the first epoxy resin is too small outside this range, the resin composition tends to be brittle, and if the amount of the first epoxy resin is too large, the resin composition tends to be sticky. Both tend to be inferior in handleability.
本発明の樹脂組成物には、第１、第２のエポキシ樹脂以外の他のエポキシ樹脂を含有することもできる。例えば、クレゾールノボラック型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、ビスフェノールＡノボラック型エポキシ樹脂、ナフタレン型エポキシ樹脂、リン含有エポキシ樹脂、トリスフェノール型エポキシ樹脂、テトラキス（ヒドロキシフェニル）エタン型エポキシ樹脂、脂環式エポキシ樹脂、脂肪族鎖状エポキシ樹脂、シクロヘキサンジメタノール型エポキシ樹脂、ブタジエン構造を有するエポキシ樹脂、スピロ環含有エポキシ樹脂、ビスフェノールのジグリシジルエーテル化物、ナフタレンジオールのジグリシジルエーテル化物、フェノール類のグリシジルエーテル化物、及びアルコール類のジグリシジルエーテル化物、並びにこれらのエポキシ樹脂のアルキル置換体、ハロゲン化物及び水素添加物等が挙げられる。これらのうち、芳香族系エポキシ樹脂に属するものは、温度２０℃で固形状である。また、これらのエポキシ樹脂はいずれか１種または２種以上組み合わせて使用してもよい。 The resin composition of the present invention may contain an epoxy resin other than the first and second epoxy resins. For example, cresol novolac type epoxy resin, phenol novolak type epoxy resin, bisphenol A novolac type epoxy resin, naphthalene type epoxy resin, phosphorus-containing epoxy resin, trisphenol type epoxy resin, tetrakis (hydroxyphenyl) ethane type epoxy resin, alicyclic type Epoxy resin, aliphatic chain epoxy resin, cyclohexanedimethanol type epoxy resin, epoxy resin having butadiene structure, spiro ring-containing epoxy resin, diglycidyl etherified product of bisphenol, diglycidyl etherified product of naphthalenediol, glycidyl ether of phenols And diglycidyl etherified products of alcohols, and alkyl-substituted products, halides and hydrogenated products of these epoxy resins. Among these, those belonging to the aromatic epoxy resin are solid at a temperature of 20 ° C. These epoxy resins may be used alone or in combination of two or more.
他のエポキシ樹脂は反応性の観点から、エポキシ当量が９０〜５００のものが好適であり、具体的には、ナフタレン型４官能エポキシ樹脂（ＤＩＣ（株）製「ＨＰ４７００」、エポキシ当量：１６２）、トリスフェノール型エポキシ樹脂（日本化薬（株）製「ＥＰＰＮ−５０２Ｈ」、エポキシ当量：１６０）、リン含有エポキシ樹脂（東都化成（株）製「ＦＸ２８９」エポキシ当量：３００〜３５０、「ＦＸ３０５」エポキシ当量：５００〜５５０）等が挙げられる。 Other epoxy resins preferably have an epoxy equivalent of 90 to 500 from the viewpoint of reactivity. Specifically, naphthalene type tetrafunctional epoxy resin (“HP4700” manufactured by DIC Corporation, epoxy equivalent: 162) , Trisphenol-type epoxy resin (“EPPN-502H” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 160), phosphorus-containing epoxy resin (“FX289” manufactured by Toto Kasei Co., Ltd.) epoxy equivalent: 300 to 350, “FX305” Epoxy equivalent: 500-550) and the like.
他のエポキシ樹脂を使用する場合、その使用量（不揮発分）は第１のエポキシ樹脂と第２のエポキシ樹脂の合計量（不揮発分）に対し１００質量％以下である。 When other epoxy resins are used, the amount used (nonvolatile content) is 100% by mass or less based on the total amount (nonvolatile content) of the first epoxy resin and the second epoxy resin.
樹脂組成物中のエポキシ樹脂の含有量は、特に制限はないが、樹脂組成物中のエポキシ樹脂の含有量の上限値は、低熱膨張率化の観点から、樹脂組成物中の不揮発分１００質量％に対し、６０質量％が好ましく、５０質量％がより好ましい。一方、樹脂組成物中のエポキシ樹脂の含有量の下限値は、高耐熱性の観点から、樹脂組成物中の不揮発分１００質量％に対し、５質量％が好ましく、１０質量％がより好ましい。 The content of the epoxy resin in the resin composition is not particularly limited, but the upper limit of the content of the epoxy resin in the resin composition is 100% by mass from the viewpoint of reducing the coefficient of thermal expansion. 60 mass% is preferable with respect to%, and 50 mass% is more preferable. On the other hand, the lower limit of the content of the epoxy resin in the resin composition is preferably 5% by mass and more preferably 10% by mass with respect to 100% by mass of the nonvolatile content in the resin composition from the viewpoint of high heat resistance.
[（Ｂ）硬化剤］
本発明において使用される（Ｂ）硬化剤は、樹脂組成物の高耐熱性、高耐水性、低熱膨張率等を付与させることができる。（Ｂ）硬化剤は、エポキシ樹脂を硬化する機能を有するものであれば特に限定されないが、フェノール系硬化剤、ナフトール系硬化剤、活性エステル系硬化剤、ベンゾオキサジン系硬化剤、シアネートエステル樹脂等が好ましい。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。
[(B) Curing agent]
The (B) curing agent used in the present invention can impart high heat resistance, high water resistance, a low coefficient of thermal expansion and the like of the resin composition. (B) The curing agent is not particularly limited as long as it has a function of curing the epoxy resin, but a phenolic curing agent, a naphthol curing agent, an active ester curing agent, a benzoxazine curing agent, a cyanate ester resin, and the like. Is preferred. You may use these 1 type or in combination of 2 or more types.
フェノール系硬化剤、ナフトール系硬化剤としては、耐熱性、耐水性に優れるという観点から、ノボラック構造を有するフェノール系硬化剤やノボラック構造を有するナフトール系硬化剤が好ましい。市販品のフェノール系硬化剤としては、ＭＥＨ−７７００、ＭＥＨ−７８１０、ＭＥＨ７８５１−４Ｈ（明和化成（株）製）、ＧＰＨ（日本化薬（株）製）、ＴＤ２０９３−６０Ｍ、ＴＤ−２０９０−６０Ｍ、ＬＦ−７９１１、ＬＦ−６１６１、ＬＦ−４８７１、ＬＡ−７０５２、ＬＡ−７０５４、ＬＡ７７５１、ＬＡ−１３５６、ＬＡ３０１８−５０Ｐ（ＤＩＣ（株）製）等が挙げられる。市販品のナフトール系硬化剤としては、ＮＨＮ、ＣＢＮ（日本化薬（株）製）、ＳＮ１７０、ＳＮ１８０、ＳＮ１９０、ＳＮ４７５、ＳＮ４８５、ＳＮ４９５、ＳＮ３７５、ＳＮ３９５（東都化成（株）製）等が挙げられる。活性エステル系硬化剤としては、ＥＸＢ−９４６０Ｓ（ＤＩＣ（株）製）、ＤＣ８０８、ＹＬＨ１０３０（ジャパンエポキシレジン（株）製）等が挙げられる。ベンゾオキサジン系硬化剤としては、ＨＦＢ２００６Ｍ（昭和高分子（株）製）、Ｐ−ｄ、Ｆ−ａ（四国化成工業（株）製）などが挙げられる。シアネートエステル樹脂としては、具体的には、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。市販されているシアネートエステル樹脂としては、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「ＰＴ３０」、シアネート当量１２４）やビスフェノールＡジシアネートの一部また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「ＢＡ２３０」、シアネート当量２３２）、ジシクロペンタジエン型シアネートエステル樹脂（ロンザジャパン（株）製「ＤＴ−４０００」、シアネート当量１４４）等が挙げられる。 As a phenol type hardening | curing agent and a naphthol type hardening | curing agent, the viewpoint of being excellent in heat resistance and water resistance, the phenol type hardening | curing agent which has a novolak structure, and the naphthol type hardening | curing agent which has a novolak structure are preferable. Commercially available phenolic curing agents include MEH-7700, MEH-7810, MEH7851-4H (Maywa Kasei Co., Ltd.), GPH (Nippon Kayaku Co., Ltd.), TD2093-60M, TD-2090-60M. LF-7911, LF-6161, LF-4871, LA-7052, LA-7054, LA7751, LA-1356, LA3018-50P (manufactured by DIC Corporation) and the like. Examples of commercially available naphthol-based curing agents include NHN, CBN (manufactured by Nippon Kayaku Co., Ltd.), SN170, SN180, SN190, SN475, SN485, SN495, SN375, SN395 (manufactured by Tohto Kasei Co., Ltd.) and the like. . Examples of the active ester curing agent include EXB-9460S (manufactured by DIC Corporation), DC808, YLH1030 (manufactured by Japan Epoxy Resin Corporation), and the like. Examples of the benzoxazine-based curing agent include HFB2006M (manufactured by Showa Polymer Co., Ltd.), Pd, Fa (manufactured by Shikoku Kasei Kogyo Co., Ltd.), and the like. Specific examples of the cyanate ester resin include bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate), 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- Bifunctional cyanate resins such as dimethylphenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, bis (4-cyanatephenyl) ether, phenol Novolac and Cresor Examples include polyfunctional cyanate resins derived from novolak, etc., prepolymers in which these cyanate resins are partially triazines, etc. Examples of commercially available cyanate ester resins include phenol novolac type polyfunctional cyanate ester resins (Lonza Japan Ltd.). ) "PT30", cyanate equivalent 124) and a prepolymer in which a part or all of bisphenol A dicyanate is triazine-modified into a trimer ("BA230", cyanate equivalent 232 from Lonza Japan Co., Ltd.), dicyclopentadiene Type cyanate ester resin (Lonza Japan Co., Ltd. "DT-4000", cyanate equivalent 144) etc. are mentioned.
樹脂組成物中の硬化剤の含有量は、特に制限はないが、樹脂組成物中の硬化剤の含有量の上限値は、十分な硬化を行うという観点から、樹脂組成物中の不揮発分１００質量％に対し、６０質量％が好ましく、５０質量％がより好ましく、４０質量％が更に好ましい。一方、樹脂組成物中の硬化剤の含有量の下限値も、十分な硬化を行うという観点から、樹脂組成物中の不揮発分１００質量％に対し、５質量％が好ましく、１０質量％がより好ましく、２０質量％が更に好ましい。 Although there is no restriction | limiting in particular in content of the hardening | curing agent in a resin composition, the upper limit of content of the hardening | curing agent in a resin composition is 100% of the non volatile matter in a resin composition from a viewpoint of performing sufficient hardening. 60 mass% is preferable with respect to mass%, 50 mass% is more preferable, and 40 mass% is still more preferable. On the other hand, the lower limit of the content of the curing agent in the resin composition is also preferably 5% by mass and more preferably 10% by mass with respect to 100% by mass of the nonvolatile content in the resin composition from the viewpoint of sufficient curing. 20% by mass is more preferable.
またさらに、（Ａ）エポキシ樹脂と（Ｂ）硬化剤とを、樹脂組成物中に存在するエポキシ樹脂のエポキシ基の合計数と硬化剤の反応基の合計数の比（エポキシ基の合計数：硬化剤の反応基の合計数）が１：０．４〜２．０、さらには１：０．５〜１．５となる量で使用するのが好ましい。なお、樹脂組成物中に存在するエポキシ樹脂のエポキシ基の合計数とは、各エポキシ樹脂の固形分質量をエポキシ当量で除した値をすべてのエポキシ樹脂について合計した値であり、硬化剤の反応基（活性水酸基、活性エステル基等）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。 Furthermore, (A) the epoxy resin and (B) the curing agent, the ratio of the total number of epoxy groups of the epoxy resin present in the resin composition and the total number of reactive groups of the curing agent (total number of epoxy groups: The total number of reactive groups in the curing agent is preferably 1: 0.4 to 2.0, more preferably 1: 0.5 to 1.5. The total number of epoxy groups in the epoxy resin present in the resin composition is a value obtained by dividing the solid mass of each epoxy resin by the epoxy equivalent for all epoxy resins, and the reaction of the curing agent. The total number of groups (active hydroxyl group, active ester group, etc.) is a value obtained by totaling the values obtained by dividing the solid content mass of each curing agent by the reactive group equivalent for all curing agents.
[（Ｃ）シラザン化合物で表面処理後、シランカップリング剤で表面処理された無機充填材]
本発明において使用される（Ｃ）シラザン化合物で表面処理後、シランカップリング剤で表面処理された無機充填材は、樹脂組成物から形成される絶縁層の熱膨張率を低下させる目的で配合されるが、その表面に結合している単位面積当たりのカーボン量の上限値は１.００ｍｇ／ｍ２が好ましく、０.７５ｍｇ／ｍ２がより好ましく、０．７０ｍｇ／ｍ２が更に好ましく、０．６５ｍｇ／ｍ２が更に一層好ましく、０．６０ｍｇ／ｍ２が殊更好ましく、０．５５ｍｇ／ｍ２が特に好ましい。一方、その表面に結合している単位面積当たりのカーボン量の下限値は、０．２５ｍｇ／ｍ２が好ましく、０．３０ｍｇ／ｍ２がより好ましく、０．３４ｍｇ／ｍ２がさらに好ましく、０．３８ｍｇ／ｍ２が更に一層好ましく、０．４２ｍｇ／ｍ２が殊更好ましく、０．４６ｍｇ／ｍ２が特に好ましい。これにより、得られる絶縁層は表面の粗度が安定で、かつ高いピール強度の導体層を安定的に形成できるものとなる。すなわち、得られる絶縁層は、粗化処理によって、表面粗さが比較的低く抑えられながら、高ピール強度で、耐熱剥離性に優れる導体層を形成し得る粗化面を形成できるものとなる。
[(C) Inorganic filler surface-treated with silazane compound and then surface-treated with silane coupling agent]
The inorganic filler surface-treated with the silazane compound (C) used in the present invention and then surface-treated with the silane coupling agent is blended for the purpose of reducing the thermal expansion coefficient of the insulating layer formed from the resin composition. that is, the upper limit of the amount of carbon per unit area attached to its surface is preferably 1.00 mg / m 2, more preferably 0.75 mg / m 2, more preferably 0.70 mg / m 2, 0 .65 mg / m 2 is even more preferred, 0.60 mg / m 2 is even more preferred, and 0.55 mg / m 2 is particularly preferred. On the other hand, the lower limit of the carbon content per unit area is then attached to that surface, preferably 0.25 mg / m 2, more preferably 0.30 mg / m 2, more preferably 0.34 mg / m 2, 0 .38 mg / m 2 is even more preferred, 0.42 mg / m 2 is even more preferred, and 0.46 mg / m 2 is particularly preferred. Accordingly, the obtained insulating layer has a stable surface roughness and can stably form a conductor layer having a high peel strength. That is, the obtained insulating layer can form a roughened surface capable of forming a conductor layer having high peel strength and excellent heat-resistant peelability, while the surface roughness is kept relatively low by the roughening treatment.
表面処理が施される無機充填材としては、シリカ、アルミナ、硫酸バリウム、タルク、クレー、雲母粉、水酸化アルミニウム、水酸化マグネシウム、炭酸カルシウム、炭酸マグネシウム、酸化マグネシウム、窒化ホウ素、ホウ酸アルミニウム、チタン酸バリウム、チタン酸ストロンチウム、チタン酸カルシウム、チタン酸マグネシウム、チタン酸ビスマス、酸化チタン、ジルコン酸バリウム、ジルコン酸カルシウムなどが挙げられる。なかでも、シリカが好ましく、球状シリカ、無定形シリカ、溶融シリカ、結晶シリカ、合成シリカがより好ましく、球状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。 Examples of inorganic fillers to be surface-treated include silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, Examples include barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate. Among these, silica is preferable, spherical silica, amorphous silica, fused silica, crystalline silica, and synthetic silica are more preferable, and spherical silica is still more preferable. You may use these 1 type or in combination of 2 or more types.
表面処理が施される無機充填材の平均粒子径は２μｍ以下であるのが好ましく、１μｍ以下がより好ましい。当該無機充填材の平均粒子径が２μｍを超える場合、樹脂組成物から形成された絶縁層上にメッキにより導体層を形成したときの導体層のピール強度が低下する傾向となる。なお、無機充填材の平均粒子径が小さくなりすぎると、樹脂組成物を樹脂ワニスとした場合に、ワニスの粘度が上昇し、取り扱い性が低下する傾向となることから、平均粒子径は０．０１μｍ以上であるのが好ましく、０．０５μｍがより好ましい。また、無機充填材の平均粒子径が２μｍ以下であっても粗大な粒子を多く含むと、粗化処理時に粗大な粒子由来の凹凸が生じ、メッキによる導体層形成時にその凹凸にメッキ銅が浸透し、微細化された導体間が短絡化しやすくなる。従って、無機充填材は最大粒子径が５μｍ以下であるのが好ましい。 The average particle diameter of the inorganic filler subjected to the surface treatment is preferably 2 μm or less, and more preferably 1 μm or less. When the average particle diameter of the inorganic filler exceeds 2 μm, the peel strength of the conductor layer tends to decrease when the conductor layer is formed by plating on the insulating layer formed from the resin composition. If the average particle size of the inorganic filler is too small, the viscosity of the varnish tends to increase and the handleability tends to decrease when the resin composition is a resin varnish. It is preferably 01 μm or more, more preferably 0.05 μm. Even if the average particle size of the inorganic filler is 2 μm or less, if it contains a large amount of coarse particles, irregularities derived from coarse particles are produced during the roughening treatment, and plated copper penetrates into the irregularities when forming a conductor layer by plating. However, it becomes easy to short-circuit between the miniaturized conductors. Therefore, the inorganic filler preferably has a maximum particle size of 5 μm or less.
ここでいう表面処理が施される無機充填材の平均粒子径及び最大粒子径はミー（Mie）散乱理論に基づくレーザー回折・散乱法により測定することができる。具体的にはレーザー回折式粒度分布測定装置により、無機充填材の粒度分布を体積基準で作成し、そのメディアン径（５０％値）を平均粒子径とし、５％値を最大粒子径とすることで測定される。測定サンプルは、無機充填材を超音波により水中に分散させたものを好ましく使用することができる。レーザー回折式粒度分布測定装置としては、（株）堀場製作所製ＬＡ−５００等を使用することができる。 The average particle diameter and the maximum particle diameter of the inorganic filler to be subjected to the surface treatment here can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is created on a volume basis with a laser diffraction particle size distribution measuring device, the median diameter (50% value) is the average particle diameter, and the 5% value is the maximum particle diameter. Measured in As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As a laser diffraction type particle size distribution measuring apparatus, LA-500 manufactured by Horiba, Ltd. or the like can be used.
表面処理に使用されるシラザン化合物としては、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、オクタメチルトリシラザン、ヘキサ（ｔｅｒｔ−ブチル）ジシラザン、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、ヘキサフェニルジシラザン、ジメチルアミノトリメチルシラザン、トリシラザン、シクロトリシラザン、１，１，３，３，５，５−ヘキサメチルシクロトリシラザン等を挙げることができ、特にヘキサメチルジシラザンが好ましい。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。 Examples of the silazane compound used for the surface treatment include hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, octamethyltrisilazane, hexa (tert-butyl) disilazane, hexabutyl. Disilazane, hexaoctyldisilazane, 1,3-diethyltetramethyldisilazane, 1,3-di-n-octyltetramethyldisilazane, 1,3-diphenyltetramethyldisilazane, 1,3-dimethyltetraphenyldi Silazane, 1,3-diethyltetramethyldisilazane, 1,1,3,3-tetraphenyl-1,3-dimethyldisilazane, 1,3-dipropyltetramethyldisilazane, hexamethylcyclotrisilazane, hexaphenyl Disilazane, dimethylaminotrimethylsilazane, trisilazane, cyclo Rishirazan, 1,1,3,3,5,5 hexamethylcyclotrisilazane, etc. can be mentioned, particularly preferably hexamethyldisilazane. You may use these 1 type or in combination of 2 or more types.
また、表面処理に使用されるシランカップリング剤としては、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（ジメトキシ）メチルシランおよび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などのエポキシ系シランカップリング剤；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及び１１−メルカプトウンデシルトリメトキシシランなどのメルカプト系シランカップリング剤；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−アミノプロピルジメ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および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などのアミノ系シランカップリング剤；３−ウレイドプロピルトリエトキシシランなどのウレイド系シランカップリング剤、ビニルトリメトキシシラン、ビニルトリエトキシシランおよびビニルメチルジエトキシシランなどのビニル系シランカップリング剤；ｐ−スチリルトリメトキシシランなどのスチリル系シランカップリング剤；３−アクリルオキシプロピルトリメトキシシランおよび３−メタクリルオキシプロピルトリメトキシシランなどのアクリレート系シランカップリング剤；３−イソシアネートプロピルトリメトキシシランなどのイソシアネート系シランカップリング剤、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）テトラスルフィドなどのスルフィド系シランカップリング剤；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、トリアジンシラン等を挙げることができる。中でも、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、イミダゾールシランが好ましい。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。 Examples of the silane coupling agent used for the surface treatment include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyl (dimethoxy) methylsilane, and 2- (3,4- Epoxy cyclohexyl) Epoxy silane coupling agents such as ethyltrimethoxysilane; 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane and 11-mercaptoundecyltrimethoxysilane Mercapto silane coupling agent; 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, N-phenyl-3-a Nopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropyldimethoxymethylsilane Amino silane coupling agents; ureido silane coupling agents such as 3-ureidopropyltriethoxysilane, vinyl silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane and vinylmethyldiethoxysilane; p-styryl Styryl silane coupling agents such as trimethoxysilane; acrylate silane coupling agents such as 3-acryloxypropyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane; 3-isocyanate Isocyanate-based silane coupling agents such as propyltrimethoxysilane, sulfide-based silane coupling agents such as bis (triethoxysilylpropyl) disulfide and bis (triethoxysilylpropyl) tetrasulfide; methyltrimethoxysilane, octadecyltrimethoxysilane , Phenyltrimethoxysilane, methacryloxypropyltrimethoxysilane, imidazolesilane, triazinesilane and the like. Of these, aminosilane coupling agents, epoxysilane coupling agents, and imidazolesilane are preferable. You may use these 1 type or in combination of 2 or more types.
無機充填材の表面処理は、例えば、未処理の無機充填材を混合機で常温にて攪拌分散させながら、シラザン化合物を添加噴霧して５〜１５分間攪拌し、続いて、シランカップリング剤を添加噴霧して５〜１５分間攪拌する。なお、市販品のシラザン化合物で表面処理した無機充填材（シラザン化合物処理付無機充填材）を使用することができ、この場合は、市販品のシラザン化合物で表面処理した無機充填材を常温にて攪拌分散させながら、シランカップリング剤を添加噴霧して５〜１５分間攪拌することによって行えばよい。なお、シラザン化合物及び／又はシランカップリング剤を無機充填材に強固に被着させ、本発明のカーボン量を実現させるために、上記の操作後、混合機から無機充填材を取り出して７日以上放置させるのが好ましい。また、シラザン化合物を添加噴霧した後の攪拌操作後、及び／又は、シランカップリング剤を添加噴霧した後の攪拌操作後に、軽微な加熱処理を行なうのも好ましい。また、シラザン化合物及び／又はシランカップリング剤を無機充填材に均一に被着させるために、シラザン化合物の添加噴霧後、及び／又は、シランカップリング剤の添加噴霧後に、有機溶媒を添加し混合してもよい。混合機としては、公知の混合機を使用することができ、Ｖブレンダー、リボンブレンダー及びバブルコーンブレンダー等のブレンダー、ヘンシェルミキサー及びコンクリートミキサー等のミキサー、ボールミル等が挙げられ、ミキサーが好ましく使用される。 For example, the surface treatment of the inorganic filler may be performed by adding and spraying a silazane compound and stirring for 5 to 15 minutes while stirring and dispersing the untreated inorganic filler at room temperature with a mixer, followed by adding a silane coupling agent. Add spray and stir for 5-15 minutes. In addition, an inorganic filler surface-treated with a commercially available silazane compound (inorganic filler with silazane compound treatment) can be used. In this case, the inorganic filler surface-treated with a commercially available silazane compound is used at room temperature. What is necessary is just to carry out by adding and spraying a silane coupling agent and stirring for 5 to 15 minutes while stirring and dispersing. In order to firmly adhere the silazane compound and / or silane coupling agent to the inorganic filler and to realize the carbon amount of the present invention, the inorganic filler is taken out from the mixer after the above operation for 7 days or more. It is preferable to let it stand. Further, it is also preferable to perform a slight heat treatment after the stirring operation after adding and spraying the silazane compound and / or after the stirring operation after adding and spraying the silane coupling agent. In order to uniformly deposit the silazane compound and / or silane coupling agent on the inorganic filler, an organic solvent is added and mixed after the addition spray of the silazane compound and / or after the addition spray of the silane coupling agent. May be. As the mixer, a known mixer can be used, and blenders such as a V blender, a ribbon blender and a bubble cone blender, mixers such as a Henschel mixer and a concrete mixer, a ball mill and the like can be mentioned, and a mixer is preferably used. .
シラザン化合物の処理量は無機充填材１００質量部当たり０．０１〜１．０質量部程度が好ましい。また、シランカップリング剤の処理量は無機充填材１００質量部当たり０．５〜２質量部程度が好ましい。なお、市販品のシラザン化合物処理付無機充填材を使用する場合、シランカップリング剤の処理量はシラザン化合物処理付無機充填材１００質量部当たり０．５〜２質量部程度が好ましい。 The treatment amount of the silazane compound is preferably about 0.01 to 1.0 part by mass per 100 parts by mass of the inorganic filler. Moreover, the processing amount of the silane coupling agent is preferably about 0.5 to 2 parts by mass per 100 parts by mass of the inorganic filler. In addition, when using the inorganic filler with silazane compound processing of a commercial item, the processing amount of a silane coupling agent has about 0.5-2 mass parts per 100 mass parts of inorganic fillers with silazane compound treatment.
無機充填材の含有量の上限値は、硬化物が脆くなることや、ピール強度が低下することを防止するという観点から、樹脂組成物中の不揮発分１００質量％に対し、８５質量％が好ましく、７０質量％がより好ましく、６０質量％が更に好ましい。一方、無機充填材の含有量の下限値は、無機充填材を配合することの効果を十分得るという観点から、樹脂組成物中の不揮発分１００質量％に対し、３０質量％が好ましく、４０質量％がより好ましく、５０質量％が更に好ましい。 The upper limit of the content of the inorganic filler is preferably 85% by mass with respect to 100% by mass of the non-volatile content in the resin composition from the viewpoint of preventing the cured product from becoming brittle and reducing the peel strength. 70 mass% is more preferable, and 60 mass% is still more preferable. On the other hand, the lower limit of the content of the inorganic filler is preferably 30% by mass and 40% by mass with respect to 100% by mass of the nonvolatile content in the resin composition from the viewpoint of sufficiently obtaining the effect of blending the inorganic filler. % Is more preferable, and 50 mass% is still more preferable.
[（Ｄ）フェノキシ樹脂、ポリビニルアセタール樹脂]
本発明の樹脂組成物には、硬化物の機械的特性向上という観点から、フェノキシ樹脂及び／又はポリビニルアセタール樹脂をさらに含有させることができる。
[(D) Phenoxy resin, polyvinyl acetal resin]
The resin composition of the present invention may further contain a phenoxy resin and / or a polyvinyl acetal resin from the viewpoint of improving the mechanical properties of the cured product.
なお、フェノキシ樹脂及びポリビニルアセタール樹脂はいずれか一方を単独で使用しても、両者を混合して使用してもよいが、エポキシ樹脂組成物中における相溶性や絶縁層上に形成される導体層のピール強度の点から少なくともフェノキシ樹脂を使用するのが好ましい。これらはそれぞれ１種または２種以上組み合わせて使用してもよい。 The phenoxy resin and the polyvinyl acetal resin may be used either alone or in combination, but the compatibility in the epoxy resin composition and the conductor layer formed on the insulating layer From the viewpoint of the peel strength, it is preferable to use at least a phenoxy resin. These may be used alone or in combination of two or more.
フェノキシ樹脂としては、特に限定されないが、具体的にはビスフェノールＡ骨格、ビスフェノールＦ骨格、ビスフェノールＳ骨格、ビスフェノールアセトフェノン骨格、ノボラック骨格、ビフェニル骨格、フルオレン骨格、ジシクロペンタジエン骨格、ノルボルネン骨格、ナフタレン骨格、アントラセン骨格、アダマンタン骨格、テルペン骨格、トリメチルシクロヘキサン骨格から選択される１種以上の骨格を有するものが挙げられる。フェノキシ樹脂の末端はフェノール性水酸基、エポキシ基等のいずれの官能基でもよい。フェノキシ樹脂の市販品としては、ジャパンエポキシレジン（株）製１２５６、４２５０（ビスフェノールＡ骨格含有フェノキシ樹脂）、ジャパンエポキシレジン（株）製ＹＸ８１００（ビスフェノールＳ骨格含有フェノキシ樹脂）、ジャパンエポキシレジン（株）製ＹＸ６９５４（ビスフェノールアセトフェノン骨格含有フェノキシ樹脂）や、その他東都化成（株）製ＦＸ２８０、ＦＸ２９３、ジャパンエポキシレジン（株）製ＹＬ７５５３ＢＨ３０、ＹＬ６７９４、ＹＬ７２１３、ＹＬ７２９０、ＹＬ７４８２等が挙げられる。 The phenoxy resin is not particularly limited, and specifically, bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, Examples thereof include those having one or more skeletons selected from an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. Commercially available phenoxy resins include 1256, 4250 (bisphenol A skeleton-containing phenoxy resin) manufactured by Japan Epoxy Resin Co., Ltd., YX8100 (bisphenol S skeleton-containing phenoxy resin) manufactured by Japan Epoxy Resin Co., Ltd., Japan Epoxy Resin Co., Ltd. YX6954 manufactured by bisphenolacetophenone skeleton-containing phenoxy resin, FX280, FX293 manufactured by Toto Kasei Co., Ltd., YL7553BH30, YL6794, YL7213, YL7290, YL7482 manufactured by Japan Epoxy Resins Co., Ltd. and the like can be mentioned.
ポリビニルアセタール樹脂は、特に限定されないが、具体的にはポリビニルブチラール樹脂が好ましい。ポリビニルアセタール樹脂としては、具体的に、電気化学工業(株)製、電化ブチラール４０００−２、５０００−Ａ、６０００−Ｃ、６０００−ＥＰ、積水化学工業（株）製エスレックＢＨシリーズ、ＢＸシリーズ、ＫＳシリーズ、ＢＬシリーズ、ＢＭシリーズ等が挙げられる。 The polyvinyl acetal resin is not particularly limited, but specifically, a polyvinyl butyral resin is preferable. Specific examples of the polyvinyl acetal resin include Denki Butyral 4000-2, 5000-A, 6000-C, and 6000-EP manufactured by Denki Kagaku Kogyo Co., Ltd., S-Rec BH Series and BX Series manufactured by Sekisui Chemical Co., Ltd. KS series, BL series, BM series, etc. are mentioned.
フェノキシ樹脂及び／又はポリビニルアセタール樹脂は、絶縁層の熱膨張率上昇や粗化処理後の絶縁層表面の粗度上昇を防止するという観点から、その重量平均分子量の上限値は１５０，０００が好ましく、９０，０００がより好ましく、６０，０００が更に好ましい。一方、絶縁層上の導体層のピール強度低下を防止するという観点から、その重量平均分子量の下限値は８，０００が好ましく、１０，０００がより好ましく、２０，０００が更に好ましい。 The upper limit of the weight average molecular weight of the phenoxy resin and / or polyvinyl acetal resin is preferably 150,000 from the viewpoint of preventing the thermal expansion coefficient of the insulating layer from increasing and the roughness of the insulating layer surface after the roughening treatment from increasing. 90,000 is more preferable, and 60,000 is still more preferable. On the other hand, from the viewpoint of preventing a decrease in peel strength of the conductor layer on the insulating layer, the lower limit of the weight average molecular weight is preferably 8,000, more preferably 10,000, and still more preferably 20,000.
ここでいう「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）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。 The “weight average molecular weight” here is measured by 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. 804 L 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おけるフェノキシ樹脂及び／又はポリビニルアセタール樹脂の含有量は、特に制限されない。フェノキシ樹脂及び／又はポリビニルアセタール樹脂の含有量の上限値は、当該樹脂組成物の粘度が高くなりすぎてラミネート性が低下したり、導体パターン上の埋め込み性低下を防止するという観点から、樹脂組成物中の不揮発分１００質量％に対し、２０質量％が好ましく、１５質量％がより好ましい。一方、フェノキシ樹脂及び／又はポリビニルアセタール樹脂の含有量の下限値は、無機充填材の高充填化及び絶縁層上の導体層の高ピール強度化という所期の効果が十分に得られにくいという観点から、樹脂組成物中の不揮発分１００質量％に対し、１質量％が好ましく、２質量％がより好ましい。 The content of the phenoxy resin and / or the polyvinyl acetal resin in the resin composition of the present invention is not particularly limited. The upper limit of the content of the phenoxy resin and / or the polyvinyl acetal resin is the resin composition from the viewpoint of preventing the laminate property from being deteriorated due to the viscosity of the resin composition being too high, and the deterioration of the embedding property on the conductor pattern. 20 mass% is preferable with respect to 100 mass% of non volatile matter in a thing, and 15 mass% is more preferable. On the other hand, the lower limit of the content of the phenoxy resin and / or the polyvinyl acetal resin is a viewpoint that it is difficult to sufficiently obtain the desired effect of increasing the filling of the inorganic filler and increasing the peel strength of the conductor layer on the insulating layer. Therefore, 1% by mass is preferable and 2% by mass is more preferable with respect to 100% by mass of the nonvolatile content in the resin composition.
[硬化促進剤]
本発明の樹脂組成物には、十分な硬化を行うという観点から、本発明の効果を阻害しない範囲で、硬化促進剤をさらに配合することができる。硬化促進剤としては、特に限定されないが、具体的には有機ホスフィン化合物、有機ホスホニウム塩化合物、イミダゾール化合物、アミンアダクト化合物、３級アミン化合物などが挙げられる。有機ホスフィン化合物及び有機ホスホニウム塩化合物の具体例としては、ＴＰＰ、ＴＰＰ−Ｋ、ＴＰＰ−Ｓ、ＴＰＴＰ−Ｓ、ＴＢＰ−ＤＡ、ＴＰＰ−ＳＣＮ、ＴＰＴＰ−ＳＣＮ（北興化学工業（株）商品名）などが挙げられる。イミダゾール化合物の具体例としては、キュアゾール２ＭＺ、２Ｅ４ＭＺ、Ｃ１１Ｚ、Ｃ１１Ｚ-ＣＮ、Ｃ１１Ｚ-ＣＮＳ、Ｃ１１Ｚ-Ａ、２ＭＺ-ＯＫ、２ＭＡ-ＯＫ、２ＰＨＺ（四国化成工業（株）商品名）などが挙げられる。アミンアダクト化合物の具体例としては、ノバキュア（旭化成工業（株）商品名）、フジキュア（富士化成工業（株）商品名）などが挙げられる。３級アミン化合物の具体例としては、ＤＢＵ（１，８−ジアザビシクロ［５，４，０］ウンデカ−７−エン）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。
[Curing accelerator]
From the viewpoint of sufficient curing, the resin composition of the present invention can be further blended with a curing accelerator as long as the effects of the present invention are not impaired. Although it does not specifically limit as a hardening accelerator, Specifically, an organic phosphine compound, an organic phosphonium salt compound, an imidazole compound, an amine adduct compound, a tertiary amine compound, etc. are mentioned. Specific examples of organic phosphine compounds and organic phosphonium salt compounds include TPP, TPP-K, TPP-S, TPTP-S, TBP-DA, TPP-SCN, TPTP-SCN (trade name of Hokuko Chemical Co., Ltd.), etc. Is mentioned. Specific examples of the imidazole compound include Curazole 2MZ, 2E4MZ, C11Z, C11Z-CN, C11Z-CNS, C11Z-A, 2MZ-OK, 2MA-OK, 2PHZ (trade names of Shikoku Kasei Kogyo Co., Ltd.). . Specific examples of the amine adduct compound include Novacure (trade name of Asahi Kasei Kogyo Co., Ltd.) and Fuji Cure (trade name of Fuji Kasei Kogyo Co., Ltd.). Specific examples of the tertiary amine compound include DBU (1,8-diazabicyclo [5,4,0] undec-7-ene). You may use these 1 type or in combination of 2 or more types.
本発明の樹脂組成物において、硬化促進剤の含有量は、樹脂組成物中に含まれるエポキシ樹脂と硬化剤の不揮発分の総量に対し、０．１〜５質量％の範囲で使用するのが好ましい。 In the resin composition of the present invention, the content of the curing accelerator is used in the range of 0.1 to 5% by mass with respect to the total nonvolatile content of the epoxy resin and the curing agent contained in the resin composition. preferable.
なお、硬化剤としてシアネートエステル樹脂を使用する場合は、硬化時間を短縮する目的で、従来からエポキシ樹脂とシアネート化合物とを併用した系で硬化触媒として用いられている有機金属化合物を添加してもよい。有機金属化合物としては、銅（ＩＩ）アセチルアセトナート等の有機銅化合物、亜鉛（ＩＩ）アセチルアセトナート等の有機亜鉛化合物、コバルト（ＩＩ）アセチルアセトナート、コバルト（ＩＩＩ）アセチルアセトナート等の有機コバルト化合物などが挙げられる。有機金属化合物の添加量は、シアネートエステル樹脂に対し、金属換算で１０〜５００ｐｐｍが好ましく、２５〜２００ｐｐｍがより好ましい。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。また、かかるシアネートエステル樹脂と有機金属化合物を使用する系では、有機金属化合物と上記任意の硬化促進剤１種または２種以上と併用してもよい。 In addition, when using a cyanate ester resin as a curing agent, an organometallic compound that has been used as a curing catalyst in a system in which an epoxy resin and a cyanate compound are used together can be added for the purpose of shortening the curing time. Good. Examples of organometallic compounds include organic copper compounds such as copper (II) acetylacetonate, organic zinc compounds such as zinc (II) acetylacetonate, and organic such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate. A cobalt compound etc. are mentioned. The amount of the organometallic compound added is preferably 10 to 500 ppm, more preferably 25 to 200 ppm in terms of metal, relative to the cyanate ester resin. You may use these 1 type or in combination of 2 or more types. In a system using such a cyanate ester resin and an organometallic compound, the organometallic compound may be used in combination with one or more of the above-mentioned optional accelerators.
[ゴム粒子]
本発明の樹脂組成物には、硬化物の機械強度の向上や応力緩和等の目的から、本発明の効果を阻害しない範囲で、更にゴム粒子を含有させることができる。当該ゴム粒子は、特に限定はされないが、樹脂組成物を調製する際の有機溶媒にも溶解せず、エポキシ樹脂等の樹脂組成物中の成分とも相溶せず、樹脂組成物のワニス中では分散状態で存在するものが好ましい。このようなゴム粒子は、一般には、ゴム成分の分子量を有機溶剤や樹脂に溶解しないレベルまで大きくし、粒子状とすることで調製することができ、具体的には、コアシェル型ゴム粒子、架橋アクリルニトリルブタジエンゴム粒子、架橋スチレンブタジエンゴム粒子、アクリルゴム粒子等が挙げられる。コアシェル型ゴム粒子は、粒子がコア層とシェル層を有するゴム粒子であり、例えば、外層のシェル層がガラス状ポリマー、内層のコア層がゴム状ポリマーで構成される２層構造、または外層のシェル層がガラス状ポリマー、中間層がゴム状ポリマー、コア層がガラス状ポリマーで構成される３層構造のものなどが挙げられる。ガラス層は例えば、メタクリル酸メチルの重合物などで構成され、ゴム状ポリマー層は例えば、ブチルアクリレート重合物（ブチルゴム）などで構成される。コアシェル型ゴム粒子の具体例としては、スタフィロイドＡＣ３８３２、ＡＣ３８１６Ｎ、（ガンツ化成（株）商品名）、メタブレンＫＷ-４４２６（三菱レイヨン（株）商品名）が挙げられる。アクリロニトリルブタジエンゴム（ＮＢＲ）粒子の具体例としては、ＸＥＲ-９１（平均粒子径０．５μｍ、ＪＳＲ（株）製）などが挙げられる。スチレンブタジエンゴム（ＳＢＲ）粒子の具体例としては、ＸＳＫ-５００（平均粒子径０．５μｍ、ＪＳＲ（株）製）などが挙げられる。アクリルゴム粒子の具体例としては、メタブレンＷ３００Ａ（平均粒子径０．１μｍ）、Ｗ４５０Ａ（平均粒子径０．５μｍ）（三菱レイヨン（株）製）を挙げることができる。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。
[Rubber particles]
The resin composition of the present invention may further contain rubber particles within a range that does not impair the effects of the present invention for the purpose of improving the mechanical strength of the cured product and relaxing the stress. The rubber particles are not particularly limited, but are not dissolved in an organic solvent when preparing the resin composition, are not compatible with components in the resin composition such as an epoxy resin, and are not compatible with the varnish of the resin composition. Those present in a dispersed state are preferred. Such rubber particles can generally be prepared by increasing the molecular weight of the rubber component to a level that does not dissolve in an organic solvent or resin and making it into particles. Specifically, core-shell type rubber particles, Examples thereof include acrylonitrile butadiene rubber particles, crosslinked styrene butadiene rubber particles, and acrylic rubber particles. The core-shell type rubber particles are rubber particles having a core layer and a shell layer. For example, the outer shell layer is a glassy polymer and the inner core layer is a rubbery polymer. Examples include a three-layer structure in which the shell layer is a glassy polymer, the intermediate layer is a rubbery polymer, and the core layer is a glassy polymer. The glass layer is made of, for example, a polymer of methyl methacrylate, and the rubbery polymer layer is made of, for example, a butyl acrylate polymer (butyl rubber). Specific examples of the core-shell type rubber particles include Staphyloid AC3832, AC3816N, (Ganz Kasei Co., Ltd. trade name), and Metabrene KW-4426 (Mitsubishi Rayon Co., Ltd. trade name). Specific examples of acrylonitrile butadiene rubber (NBR) particles include XER-91 (average particle size 0.5 μm, manufactured by JSR Corporation). Specific examples of styrene butadiene rubber (SBR) particles include XSK-500 (average particle size 0.5 μm, manufactured by JSR Corporation). Specific examples of the acrylic rubber particles include methabrene W300A (average particle size 0.1 μm), W450A (average particle size 0.5 μm) (manufactured by Mitsubishi Rayon Co., Ltd.). You may use these 1 type or in combination of 2 or more types.
ゴム粒子の平均粒子径は０．００５〜１μｍの範囲が好ましく、０．２〜０．６μｍの範囲がより好ましい。かかるゴム粒子の平均粒子径は、動的光散乱法を用いて測定することが出来る。例えば、適当な有機溶剤にゴム粒子を超音波などにより均一に分散させ、ＦＰＲＡ-１０００（大塚電子（株）製）を用いて、ゴム粒子の粒度分布を質量基準で作成し、そのメディアン径を平均粒子径とすることで測定される。 The average particle diameter of the rubber particles is preferably in the range of 0.005 to 1 μm, and more preferably in the range of 0.2 to 0.6 μm. The average particle diameter of such rubber particles can be measured using a dynamic light scattering method. For example, rubber particles are uniformly dispersed in a suitable organic solvent by ultrasonic waves, etc., and using FPRA-1000 (manufactured by Otsuka Electronics Co., Ltd.), the particle size distribution of the rubber particles is created on a mass basis, and the median diameter is determined. The average particle diameter is measured.
ゴム粒子を配合する場合の含有量は、樹脂組成物中の不揮発分１００質量％に対し、１〜１０質量％の範囲であるのが好ましく、２〜５質量％の範囲であるのがより好ましい。 When the rubber particles are blended, the content is preferably in the range of 1 to 10% by mass and more preferably in the range of 2 to 5% by mass with respect to 100% by mass of the nonvolatile content in the resin composition. .
[熱硬化性樹脂（エポキシ樹脂を除く）]
本発明の樹脂組成物は、本発明の効果を阻害しない程度に、熱硬化性樹脂（エポキシ樹脂を除く）を含有させることができる。当該熱硬化性樹脂は、特に限定はされないが、具体的にはマレイミド化合物、ビスアリルナジイミド化合物、ビニルベンジル樹脂、ビニルベンジルエーテル樹脂などが挙げられる。マレイミド樹脂としてはＢＭＩ１０００、ＢＭＩ２０００、ＢＭＩ３０００、ＢＭＩ４０００、ＢＭＩ５１００（大和化成工業（株）製）、ＢＭＩ、ＢＭＩ−７０、ＢＭＩ−８０（ケイ・アイ化成（株）製）、ＡＮＩＬＩＸ−ＭＩ（三井化学ファイン（株）製）、ビスアリルナジイミド化合物としてはＢＡＮＩ−Ｍ、ＢＡＮＩ−Ｘ（丸善石油化学工業（株）製）ビニルベンジル樹脂としてはＶ５０００（昭和高分子（株）製）、ビニルベンジルエーテル樹脂としてはＶ１０００Ｘ、Ｖ１１００Ｘ（昭和高分子（株）製）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。
[Thermosetting resin (excluding epoxy resin)]
The resin composition of the present invention can contain a thermosetting resin (excluding an epoxy resin) to the extent that the effects of the present invention are not impaired. The thermosetting resin is not particularly limited, and specific examples include a maleimide compound, a bisallyl nadiimide compound, a vinyl benzyl resin, and a vinyl benzyl ether resin. As maleimide resins, BMI1000, BMI2000, BMI3000, BMI4000, BMI5100 (manufactured by Daiwa Kasei Kogyo Co., Ltd.), BMI, BMI-70, BMI-80 (manufactured by KEI Kasei Co., Ltd.), ANILIX-MI (Mitsui Chemical Fine) BANI-M, BANI-X (manufactured by Maruzen Petrochemical Co., Ltd.) as a vinyl benzyl resin, V5000 (manufactured by Showa Polymer Co., Ltd.), vinyl benzyl ether resin V1000X, V1100X (manufactured by Showa Polymer Co., Ltd.). You may use these 1 type or in combination of 2 or more types.
[難燃剤]
本発明の樹脂組成物は、本発明の効果を阻害しない程度に、難燃剤を含有させることができる。難燃剤は、特に限定はされないが、具体的には有機リン系難燃剤、有機系窒素含有リン化合物、窒素化合物、シリコーン系難燃剤、金属水酸化物等が挙げられる。有機リン系難燃剤としては、三光（株）製のＨＣＡ、ＨＣＡ−ＨＱ、ＨＣＡ−ＮＱ等のフェナントレン型リン化合物、昭和高分子（株）製のＨＦＢ−２００６Ｍ等のリン含有ベンゾオキサジン化合物、味の素ファインテクノ（株）製のレオフォス３０、５０、６５、９０、１１０、ＴＰＰ、ＲＰＤ、ＢＡＰＰ、ＣＰＤ、ＴＣＰ、ＴＸＰ、ＴＢＰ、ＴＯＰ、ＫＰ１４０、ＴＩＢＰ、北興化学工業（株）製のＰＰＱ、クラリアント（株）製のＯＰ９３０、大八化学（株）製のＰＸ２００等のリン酸エステル化合物、東都化成（株）製のＦＸ２８９、ＦＸ３０５、ＴＸ−０７１２等のリン含有エポキシ樹脂、東都化成（株）製のＥＲＦ００１等のリン含有フェノキシ樹脂等が挙げられる。有機系窒素含有リン化合物としては、四国化成工業（株）製のＳＰ６７０、ＳＰ７０３等のリン酸エステルミド化合物、大塚化学（株）製のＳＰＢ１００、ＳＰＥ１００、（株）伏見製作所製ＦＰ−ｓｅｒｉｅｓ等のホスファゼン化合物等が挙げられる。金属水酸化物としては、宇部マテリアルズ（株）製のＵＤ６５、ＵＤ６５０、ＵＤ６５３等の水酸化マグネシウム、巴工業（株）製のＢ−３０、Ｂ−３２５、Ｂ−３１５、Ｂ−３０８、Ｂ−３０３、ＵＦＨ−２０等の水酸化アルミニウム等が挙げられる。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。
[Flame retardants]
The resin composition of this invention can contain a flame retardant to such an extent that the effect of this invention is not inhibited. The flame retardant is not particularly limited, and specific examples include organic phosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicone flame retardants, metal hydroxides, and the like. Examples of organic phosphorus flame retardants include phenanthrene-type phosphorus compounds such as HCA, HCA-HQ, and HCA-NQ manufactured by Sanko Co., Ltd., phosphorus-containing benzoxazine compounds such as HFB-2006M manufactured by Showa Polymer Co., Ltd., and Ajinomoto Co., Inc. Reefos 30, 50, 65, 90, 110, Fine Techno Co., TPP, RPD, BAPP, CPD, TCP, TXP, TBP, TOP, KP140, TIBP, PPQ, Clariant (made by Hokuko Chemical Co., Ltd.) Phosphoric acid ester compounds such as OP930 made by Daihachi Chemical Co., Ltd., PX200 made by Daihachi Chemical Co., Ltd., Phosphorus-containing epoxy resins such as FX289, FX305 and TX-0712 made by Toto Kasei Co., Ltd., manufactured by Toto Kasei Co., Ltd. Examples thereof include phosphorus-containing phenoxy resins such as ERF001. Examples of organic nitrogen-containing phosphorus compounds include phosphate ester compounds such as SP670 and SP703 manufactured by Shikoku Kasei Kogyo Co., Ltd., phosphazenes such as SPB100 and SPE100 manufactured by Otsuka Chemical Co., Ltd., and FP-series manufactured by Fushimi Seisakusho Co., Ltd. Compounds and the like. As the metal hydroxide, magnesium hydroxide such as UD65, UD650, UD653 manufactured by Ube Materials Co., Ltd., B-30, B-325, B-315, B-308, B manufactured by Sakai Kogyo Co., Ltd. And aluminum hydroxide such as -303 and UFH-20. You may use these 1 type or in combination of 2 or more types.
本発明の樹脂組成物は、本発明の効果を阻害しない程度に、樹脂組成物に配合しうる添加剤を使用することができる。具体的には、シリコンパウダー、ナイロンパウダー、フッ素パウダー等の有機充填剤、オルベン、ベントン等の増粘剤、シリコーン系、フッ素系、高分子系の消泡剤又はレベリング剤、シランカップリング剤、トリアゾール化合物、チアゾール化合物、トリアジン化合物、ポルフィリン化合物等の密着性付与剤、フタロシアニン・ブルー、フタロシアニン・グリーン、アイオジン・グリーン、ジスアゾイエロー、カーボンブラック等の着色剤等を挙げることができる。 The resin composition of this invention can use the additive which can be mix | blended with a resin composition to such an extent that the effect of this invention is not inhibited. Specifically, organic fillers such as silicon powder, nylon powder, fluorine powder, thickeners such as olven, benton, silicone-based, fluorine-based, polymer-based antifoaming or leveling agents, silane coupling agents, Examples thereof include adhesion imparting agents such as triazole compounds, thiazole compounds, triazine compounds and porphyrin compounds, and colorants such as phthalocyanine / blue, phthalocyanine / green, iodin / green, disazo yellow and carbon black.
本発明の樹脂組成物は、接着フィルム、プリプレグ等のシート状材料として使用することができる。 The resin composition of the present invention can be used as a sheet-like material such as an adhesive film or a prepreg.
[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にて作製することができる。有機溶剤に樹脂組成物を溶解した樹脂ワニスを調製し、この樹脂ワニスを、ダイコーターなどを用いて、支持体に塗布し、更に加熱、あるいは熱風吹きつけ等により有機溶剤を乾燥させて樹脂組成物層を形成させることにより製造することが挙げられる。
[Adhesive film]
The adhesive film of the present invention can be produced by methods known to those skilled in the art. A resin varnish in which a resin composition is dissolved in an organic solvent is prepared, and this resin varnish is applied to a support using a die coater or the like, and further dried by heating or hot air blowing, etc. It can be produced by forming a physical layer.
有機溶剤としては、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。 Examples of organic solvents include ketones such as acetone, methyl ethyl ketone, and cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, acetate esters such as carbitol acetate, and carbitols such as cellosolve and butyl carbitol. Aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like can be mentioned. You may use these 1 type or in combination of 2 or more types.
乾燥条件は特に限定されないが、乾燥後の樹脂組成物層への有機溶剤の含有量は１０質量％以下が好ましく、５質量％以下がより好ましい。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、３０〜６０質量％の有機溶剤を含むワニスを５０〜１５０℃で３〜１０分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。当業者であれば、簡単な実験により適宜、好適な乾燥条件を設定することができる。 Although drying conditions are not specifically limited, 10 mass% or less is preferable and, as for content of the organic solvent to the resin composition layer after drying, 5 mass% or less is more preferable. Depending on the amount of organic solvent in the varnish and the boiling point of the organic solvent, a resin composition layer is formed by drying a varnish containing 30 to 60% by mass of an organic solvent at 50 to 150 ° C. for 3 to 10 minutes. Can do. Those skilled in the art can appropriately set suitable drying conditions through simple experiments.
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ことが好ましい。回路基板が有する導体層の厚さが５〜７０μｍである場合には、樹脂組成物層は１０〜１００μｍの厚さを有するのが好ましい。 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. When the thickness of the conductor layer included in the circuit board is 5 to 70 μm, the resin composition layer preferably has a thickness of 10 to 100 μm.
支持体としては、ポリエチレン、ポリプロピレン、ポリ塩化ビニル等のポリオレフィンのフィルム、ポリエチレンテレフタレート（以下「ＰＥＴ」と略称することがある。）、ポリエチレンナフタレート等のポリエステルのフィルム、ポリカーボネートフィルム、ポリイミドフィルムなどの各種プラスチックフィルムが挙げられる。また離型紙や銅箔、アルミニウム箔等の金属箔などを使用してもよい。支持体及び後述する保護フィルムには、マッド処理、コロナ処理等の表面処理が施してあってもよい。また、シリコーン樹脂系離型剤、アルキッド樹脂系離型剤、フッ素樹脂系離型剤等の離型剤で離型処理が施してあってもよい。 Examples of the support include polyolefin films such as polyethylene, polypropylene, and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyester films such as polyethylene naphthalate, polycarbonate films, and polyimide films. Various plastic films are listed. Moreover, you may use release foil, metal foil, such as copper foil and aluminum foil. The support and a protective film described later may be subjected to surface treatment such as mud treatment or corona treatment. The release treatment may be performed with a release agent such as a silicone resin release agent, an alkyd resin release agent, or a fluororesin release agent.
支持体の厚さは特に限定されないが、１０〜１５０μｍが好ましく、２５〜５０μｍがより好ましい。 Although the thickness of a support body is not specifically limited, 10-150 micrometers is preferable and 25-50 micrometers is more preferable.
樹脂組成物層の支持体が密着していない面には、支持体に準じた保護フィルムをさらに積層することができる。保護フィルムの厚みは、特に限定されるものではないが、１〜４０μｍが好ましく、１０〜３０μｍがより好ましい。保護フィルムを積層することにより、樹脂組成物層の表面へのゴミ等の付着やキズを防止することができる。接着フィルムは、ロール状に巻きとって貯蔵することもできる。 A protective film according to the support can be further laminated on the surface of the resin composition layer on which the support is not in close contact. Although the thickness of a protective film is not specifically limited, 1-40 micrometers is preferable and 10-30 micrometers is more preferable. By laminating the protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches. The adhesive film can also be stored in a roll.
[プリプレグ］
本発明のプリプレグは、本発明の樹脂組成物を繊維からなるシート状補強基材にホットメルト法又はソルベント法により含浸させ、加熱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繊維からなるシート状補強基材に含浸した状態となるプリプレグとすることができる。繊維からなるシート状補強基材としては、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。
[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 made of fibers by a hot melt method or a solvent method, and heating and semi-curing. That is, it can be set as the prepreg which will be in the state which the resin composition of this invention impregnated the sheet-like reinforcement base material which consists of fibers. As the sheet-like reinforcing substrate made of fibers, those made of fibers commonly used as prepreg fibers such as glass cloth and aramid fibers can be used.
ホットメルト法は、樹脂を、有機溶剤に溶解することなく、該樹脂との剥離性の良い塗工紙に一旦コーティングし、それをシート状補強基材にラミネートする、あるいは樹脂を、有機溶剤に溶解することなく、ダイコーターによりシート状補強基材に直接塗工するなどして、プリプレグを製造する方法である。またソルベント法は、接着フィルムと同様にして樹脂を有機溶剤に溶解して樹脂ワニスを調製し、このワニスにシート状補強基材を浸漬し、樹脂ワニスをシート状補強基材に含浸させ、その後乾燥させる方法である。 In the hot melt method, the resin is once coated on a coated paper having good releasability from the resin without dissolving it in an organic solvent, and then laminated on a sheet-like reinforcing substrate, or the resin is used in an organic solvent. This is a method for producing a prepreg by directly coating a sheet-like reinforcing substrate with a die coater without dissolving it. In the solvent method, a resin varnish is prepared by dissolving a resin in an organic solvent in the same manner as the adhesive film, and a sheet-like reinforcing base material is immersed in the varnish, and then the resin-like varnish is impregnated into the sheet-like reinforcing base material. It is a method of drying.
[多層プリント配線板］
本発明の樹脂組成物は、多層プリント配線板の製造において絶縁層を形成するために好適に使用することができる。本発明の樹脂組成物は、ワニス状態で回路基板に塗布して絶縁層を形成することもできるが、工業的には、接着フィルム、プリプレグ等のシート状材料を積層する形態で用いるのが好ましい。樹脂組成物の軟化点は、シート状材料のラミネート性の観点から４０〜１５０℃が好ましい。
[Multilayer printed wiring board]
The resin composition of the present invention can be suitably used for forming an insulating layer in the production of a multilayer printed wiring board. The resin composition of the present invention can be applied to a circuit board in a varnish state to form an insulating layer, but industrially, it is preferably used in a form in which a sheet-like material such as an adhesive film or a prepreg is laminated. . The softening point of the resin composition is preferably 40 to 150 ° C. from the viewpoint of the laminate property of the sheet-like material.
まずは、上記のようにして製造した接着フィルム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。 First, an example of a method for producing a multilayer printed wiring board using the adhesive film produced as described above will be described.
まず、接着フィルムを、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する。回路基板に用いられる基板としては、ガラスエポキシ基板、金属基板、ポリエステル基板、ポリイミド基板、ＢＴレジン基板、熱硬化型ポリフェニレンエーテル基板等が挙げられる。なお、ここで回路基板とは、上記のような基板の片面又は両面にパターン加工された導体層（回路）が形成されたものをいう。また導体層と絶縁層とを交互に積層してなる多層プリント配線板において、該多層プリント配線板の最外層の片面又は両面がパターン加工された導体層（回路）となっているものも、ここでいう回路基板に含まれる。なお導体層表面には、黒化処理、銅エッチング等により予め粗化処理が施されていてもよい。 First, an adhesive film is laminated on one side or both sides of a circuit board using a vacuum laminator. Examples of the substrate used for the circuit substrate include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. In addition, a circuit board means here that the conductor layer (circuit) patterned was formed in the one or both surfaces of the above boards. Also, in a multilayer printed wiring board in which conductor layers and insulating layers are alternately laminated, one of the outermost layers of the multilayer printed wiring board is a conductor layer (circuit) in which one or both sides are patterned. It is included in the circuit board. The surface of the conductor layer may be previously roughened by blackening, copper etching, or the like.
上記ラミネートにおいて、接着フィルム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、必要に応じて接着フィルム及び回路基板をプレヒートし、接着フィルムを加圧及び加熱しながら回路基板に圧着する。本発明の接着フィルムにおいては、真空ラミネート法により減圧下で回路基板にラミネートする方法が好適に用いられる。ラミネートの条件は、特に限定されるものではないが、圧着温度（ラミネート温度）を好ましくは７０〜１４０℃、圧着圧力を好ましくは１〜１１ｋｇｆ／ｃｍ２（９．８×１０４〜１０７．９×１０４Ｎ／ｍ２）とし、空気圧２０ｍｍＨｇ（２６．７ｈＰａ）以下の減圧下でラミネートするのが好ましい。また、ラミネートの方法は、バッチ式であってもロールでの連続式であってもよい。 In the above laminate, when the adhesive film has a protective film, after removing the protective film, the adhesive film and the circuit board are preheated as necessary, and the adhesive film is pressed and heated to the circuit board. Crimp. In the adhesive film of the present invention, a method of laminating on a circuit board under reduced pressure by a vacuum laminating method is preferably used. Lamination conditions are not particularly limited, but the pressure bonding temperature (laminating temperature) is preferably 70 to 140 ° C., and the pressure bonding pressure is preferably 1 to 11 kgf / cm 2 (9.8 × 10 4 to 107.9). × 10 4 N / m 2 ) and laminating 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.
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、ニチゴー・モートン（株）製バキュームアップリケーター、（株）名機製作所製真空加圧式ラミネーター、（株）日立インダストリイズ製ロール式ドライコータ、日立エーアイーシー（株）製真空ラミネーター等を挙げることができる。 The vacuum lamination can be performed using a commercially available vacuum laminator. Commercially available vacuum laminators include Nichigo Morton's vacuum applicator, Maki Seisakusho's vacuum pressurizing laminator, Hitachi Industries' roll-type dry coater, Hitachi AIC Co., Ltd. A vacuum laminator etc. can be mentioned.
接着フィルムを回路基板にラミネートした後、室温付近に冷却してから、支持体を剥離する場合は剥離し、熱硬化することにより回路基板に絶縁層を形成することができる。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く、硬化温度は１５０℃〜２２０℃が好ましく、１６０℃〜２００℃がより好ましい。硬化時間は２０分〜１８０分が好ましく、３０〜１２０分がより好ましい。 After laminating the adhesive film on the circuit board, it is cooled to around room temperature, and when the support is peeled off, the insulating film can be formed on the circuit board by peeling and thermosetting. The thermosetting conditions may be appropriately selected according to the type and content of the resin component in the resin composition, and the curing temperature is preferably 150 ° C to 220 ° C, more preferably 160 ° C to 200 ° C. The curing time is preferably 20 minutes to 180 minutes, more preferably 30 to 120 minutes.
絶縁層を形成した後、硬化前に支持体を剥離しなかった場合は、ここで剥離する。次いで必要により、回路基板上に形成された絶縁層に穴開けを行ってビアホール、スルーホールを形成する。穴あけは、ドリル、レーザー、プラズマ等の公知の方法により、また必要によりこれらの方法を組み合わせて行うことができる。なかでも、炭酸ガスレーザー、ＹＡＧレーザー等のレーザーによる穴あけが好ましい。 If the support is not peeled off after the insulating layer is formed, it is peeled off here. Next, if necessary, holes are formed in the insulating layer formed on the circuit board to form via holes and through holes. Drilling can be performed by a known method such as drilling, laser, plasma, or a combination of these methods if necessary. Of these, drilling with a laser such as a carbon dioxide laser or a YAG laser is preferred.
次いで、絶縁層表面に粗化処理を行う。本発明における粗化処理は、酸化剤を使用した湿式粗化方法で行うのが好ましい。酸化剤としては、過マンガン酸塩（過マンガン酸カリウム、過マンガン酸ナトリウム等）、重クロム酸塩、オゾン、過酸化水素／硫酸、硝酸等が挙げられる。ビルトアップ工法による多層プリント配線板の製造における絶縁層の粗化に汎用されている酸化剤である、アルカリ性過マンガン酸溶液（過マンガン酸カリウム、過マンガン酸ナトリウムの水酸化ナトリウム水溶液等）を用いて粗化を行うのが好ましい。 Next, a roughening process is performed on the surface of the insulating layer. The roughening treatment in the present invention is preferably performed by a wet roughening method using an oxidizing agent. Examples of the oxidizing agent include permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid and the like. Using alkaline permanganate solution (potassium permanganate, sodium hydroxide aqueous solution of sodium permanganate, etc.), which is an oxidizer widely used for roughening the insulation layer in the production of multilayer printed wiring boards by built-up method It is preferable to perform roughening.
絶縁層表面を粗化処理した粗化面の粗さは、微細配線を形成する上で、算術平均粗さ（Ｒａ値）で５０〜６５０ｎｍであるのが好ましい。なお、ここで、算術平均粗さ（Ｒａ値）とは、表面粗さを表す数値の一種であり、具体的には測定領域内で変化する高さの絶対値を平均ラインである表面から測定して算術平均したものである。ビーコインスツルメンツ社製 ＷＹＫＯ ＮＴ３３００を用いて、ＶＳＩコンタクトモード、５０倍レンズにより測定範囲を１２１μｍ×９２μｍとして得られる数値により求めることができる。 The roughness of the roughened surface obtained by roughening the surface of the insulating layer is preferably 50 to 650 nm in terms of arithmetic average roughness (Ra value) in forming fine wiring. Here, the arithmetic average roughness (Ra value) is a kind of numerical value representing the surface roughness. Specifically, the absolute value of the height changing in the measurement region is measured from the surface which is the average line. The arithmetic average. Using WYKO NT3300 manufactured by BEIKO INSTRUMENTS Co., Ltd., it can be obtained from a numerical value obtained by setting the measurement range to 121 μm × 92 μm with a VSI contact mode and a 50 × lens.
次に、粗化された絶縁層表面に、無電解メッキと電解メッキを組み合わせた方法で導体層を形成する。また導体層とは逆パターンのメッキレジストを形成し、無電解メッキのみで導体層を形成することもできる。なお導体層形成後、１５０〜２００℃で２０〜９０分アニール（anneal）処理することにより、導体層のピール強度をさらに向上、安定化させることができる。導体層のピール強度は、０．６ｋｇｆ／ｃｍ以上であるのが好ましい。 Next, a conductor layer is formed on the roughened insulating layer surface by a method combining electroless plating and electrolytic plating. Alternatively, a plating resist having a pattern opposite to that of the conductor layer can be formed, and the conductor layer can be formed only by electroless plating. In addition, after forming the conductor layer, the peel strength of the conductor layer can be further improved and stabilized by annealing at 150 to 200 ° C. for 20 to 90 minutes. The peel strength of the conductor layer is preferably 0.6 kgf / cm or more.
また、導体層をパターン加工し回路形成する方法としては、例えば当業者に公知のサブトラクティブ法、セミアディディブ法などを用いることができる。 Moreover, as a method of patterning the conductor layer to form a circuit, for example, a subtractive method or a semi-additive method known to those skilled in the art can be used.
本発明のプリプレグを用いた多層プリント配線板等の回路基板の製造は例えば次のようにして行うことができる。内層回路基板に本発明のプリプレグを１枚あるいは必要により数枚重ね、離型フィルムを介して金属プレートを挟み加圧・加熱条件下でプレス積層する。圧力は好ましくは５〜４０ｋｇｆ／ｃｍ２（４９×１０４〜３９２×１０４Ｎ／ｍ２）、温度は好ましくは１２０〜２００℃で２０〜１００分の範囲で成型するのが好ましい。また、接着フィルムと同様に真空ラミネート法により内層回路基板にラミネートした後、加熱硬化することによっても製造可能である。その後、前述の方法と同様、酸化剤により硬化したプリプレグ表面を粗化した後、導体層をメッキにより形成することで、多層プリント配線板等の回路基板を製造することができる。 Production of a circuit board such as a multilayer printed wiring board using the prepreg of the present invention can be performed as follows, for example. One or several prepregs of the present invention are stacked on the inner layer circuit board, and a metal plate is sandwiched through a release film, and press laminated under pressure and heating conditions. The pressure is preferably 5 to 40 kgf / cm 2 (49 × 10 4 to 392 × 10 4 N / m 2 ), and the temperature is preferably 120 to 200 ° C. for 20 to 100 minutes. Moreover, it can also be manufactured by laminating to an inner layer circuit board by a vacuum laminating method as in the case of the adhesive film, followed by heat curing. Thereafter, in the same manner as described above, the surface of the prepreg cured with an oxidizing agent is roughened, and then the conductor layer is formed by plating, whereby a circuit board such as a multilayer printed wiring board can be manufactured.
本発明のシート状材料（接着フィルム、プリプレグ等）は、その硬化物（すなわち、本発明の樹脂組成物の硬化物）の２５℃から１５０℃までの平均線熱膨張率が好ましくは２０〜５０ｐｐｍであり、より好ましくは２０〜４５ｐｐｍである。かかる平均線熱膨張率を有することによって、回路基板の熱膨張率低減に有効に作用する。 The sheet-like material (adhesive film, prepreg, etc.) of the present invention preferably has an average linear thermal expansion coefficient of 25 to 150 ° C. of the cured product (that is, the cured product of the resin composition of the present invention) of 20 to 50 ppm. More preferably, it is 20 to 45 ppm. By having such an average linear thermal expansion coefficient, it effectively acts to reduce the thermal expansion coefficient of the circuit board.
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〕
まずは各種測定方法・評価方法について説明する。
[Measurement and evaluation methods]
First, various measurement methods and evaluation methods will be described.
＜単位面積当たりのカーボン量の測定＞
表面処理された無機充填材の５ｇを試料として用いた。試料と２４ｇのＩＰＡ（イソプロピルアルコール）とを遠心分離機の遠心管に入れ、撹拌し固形分を懸濁させて、５００Ｗの超音波を５分間照射した。その後、遠心分離により固液分離し、上澄液を除去した。さらに、２４ｇのＩＰＡを足し、撹拌して固形分を懸濁させて、５００Ｗの超音波を５分間照射した。その後、遠心分離により固液分離し、上澄液を除去した。さらに、２４ｇのＩＰＡを足し、撹拌して固形分を懸濁させて、５００Ｗの超音波を５分間照射した。固形分をデシケータ内にて室温で９６時間乾燥させた。この乾燥試料０．２ｇを測定用坩堝に正確に量りとり、さらに測定用坩堝に助燃剤（タングステン３．０ｇ，スズ０．３ｇ）を入れた。測定用坩堝をカーボン分析計にセットし、カーボン量を測定した。ここで、カーボン量はカーボン分析計を使用して測定することができる。カーボン分析計は、堀場製作所製ＥＭＩＡ−３２０Ｖ等を使用することができる。カーボン量を比表面積で割った値を単位面積当たりのカーボン量とした。
<Measurement of carbon amount per unit area>
5 g of the surface-treated inorganic filler was used as a sample. The sample and 24 g of IPA (isopropyl alcohol) were placed in a centrifuge tube, stirred to suspend solids, and irradiated with 500 W ultrasonic waves for 5 minutes. Thereafter, solid-liquid separation was performed by centrifugation, and the supernatant was removed. Furthermore, 24 g of IPA was added, the solid content was suspended by stirring, and 500 W ultrasonic waves were irradiated for 5 minutes. Thereafter, solid-liquid separation was performed by centrifugation, and the supernatant was removed. Furthermore, 24 g of IPA was added, the solid content was suspended by stirring, and 500 W ultrasonic waves were irradiated for 5 minutes. The solid content was dried for 96 hours at room temperature in a desiccator. 0.2 g of this dried sample was accurately weighed into a measuring crucible, and a combustion aid (3.0 g of tungsten, 0.3 g of tin) was further placed in the measuring crucible. The measurement crucible was set in a carbon analyzer and the amount of carbon was measured. Here, the amount of carbon can be measured using a carbon analyzer. As the carbon analyzer, EMIA-320V manufactured by Horiba, Ltd. can be used. A value obtained by dividing the carbon amount by the specific surface area was defined as the carbon amount per unit area.
＜メッキピール強度の測定＞
（１）内層回路基板の下地処理
内層回路を形成したガラス布基材エポキシ樹脂両面銅張積層板（銅箔の厚さ１８μｍ、基板厚み０．３ｍｍ、松下電工（株）製Ｒ５７１５ＥＳ）の両面をメック（株）製ＣＺ８１００（アゾール類の銅錯体、有機酸を含む表面処理剤）に浸漬して銅表面の粗化処理をおこなった。
（２）接着フィルムのラミネート
実施例及び比較例で作製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、内層回路基板の両面にラミネートした。ラミネートは、３０秒間減圧して気圧を１３ｈＰａ以下とし、その後３０秒間、１００℃、圧力０．７４ＭＰａでプレスすることにより行った。
（３）樹脂組成物の硬化
（３−１）実施例１及び比較例１
ラミネートされた接着フィルムからＰＥＴフィルムを剥離し、１８０℃、３０分の硬化条件で樹脂組成物を硬化して絶縁層を形成した。
（３−２）実施例２、３及び比較例２、３
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、１００℃、３０分、さらに１８０℃、３０分の硬化条件で樹脂組成物を硬化して絶縁層を形成した。
（４）粗化処理
積層板を、膨潤液である、アトテックジャパン（株）のジエチレングリコールモノブチルエーテル含有のスエリングディップ・セキュリガンドＰに浸漬し、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）に浸漬、最後に中和液として、アトテックジャパン（株）のリダクションショリューシン・セキュリガントＰに４０℃で５分間浸漬した（粗化条件：膨潤液に６０℃で５分間浸漬、粗化液に８０℃で２０分間浸漬）。
（５）セミアディティブ工法によるメッキ
絶縁層表面に回路を形成するために、内層回路基板を、ＰｄＣｌ２を含む無電解メッキ用溶液に浸漬し、次に無電解銅メッキ液に浸漬した。１５０℃にて３０分間加熱してアニール処理を行った後に、エッチングレジストを形成し、エッチングによるパターン形成の後に、硫酸銅電解メッキを行い、３０±５μｍの厚さで導体層を形成した。次に、アニール処理を１８０℃にて６０分間行った。
（６）メッキ導体層の引き剥がし強さ（ピール強度） 上記（５）で得られた回路基板の導体層に、幅１０ｍｍ、長さ１００ｍｍの部分の切込みをいれ、この一端を剥がしてつかみ具で掴み、インストロン万能試験機を用いて、室温中にて、５０ｍｍ／分の速度で垂直方向に３５ｍｍを引き剥がした時の荷重をＪＩＳ Ｃ６４８１に準拠して測定し、ピール強度（ｋｇｆ／ｃｍ）とした。
<Measurement of plating peel strength>
(1) Underlayer treatment of inner layer circuit board Both sides of a glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.3 mm, Matsushita Electric Works R5715ES) on which an inner layer circuit is formed The copper surface was roughened by immersing in CZ8100 (a surface treatment agent containing an azoles copper complex and an organic acid) manufactured by MEC Co., Ltd.
(2) Lamination of adhesive film The adhesive films produced in the examples and comparative examples are laminated on both sides of the inner circuit board using a batch type vacuum pressure laminator MVLP-500 (trade name, manufactured by Meiki Seisakusho Co., Ltd.). did. Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressing at 100 ° C. and a pressure of 0.74 MPa for 30 seconds.
(3) Curing of resin composition (3-1) Example 1 and Comparative Example 1
The PET film was peeled off from the laminated adhesive film, and the resin composition was cured under curing conditions at 180 ° C. for 30 minutes to form an insulating layer.
(3-2) Examples 2 and 3 and Comparative Examples 2 and 3
The PET film was peeled from the laminated adhesive film, and the resin composition was cured under curing conditions at 100 ° C. for 30 minutes, and further at 180 ° C. for 30 minutes to form an insulating layer.
(4) Roughening treatment The laminate was immersed in a swelling dip secu-ligand P containing diethylene glycol monobutyl ether of Atotech Japan Co., Ltd., which is a swelling liquid, and then the outlet of Atotech Japan Co., Ltd. as a roughening liquid. Immerse in rate compact P (KMnO 4 : 60 g / L, NaOH: 40 g / L aqueous solution) and finally neutralize it with Atotech Japan Co., Ltd. Reduction Sholyshin Securigant P at 40 ° C. for 5 minutes. Immersion (roughening conditions: immersion in swelling liquid at 60 ° C. for 5 minutes, immersion in roughening liquid at 80 ° C. for 20 minutes).
(5) Plating by semi-additive method In order to form a circuit on the surface of the insulating layer, the inner layer circuit board was immersed in an electroless plating solution containing PdCl 2 and then immersed in an electroless copper plating solution. After annealing at 150 ° C. for 30 minutes, an etching resist was formed, and after pattern formation by etching, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 30 ± 5 μm. Next, annealing was performed at 180 ° C. for 60 minutes.
(6) Peeling strength of peeled conductor layer (peel strength) The conductor layer of the circuit board obtained in the above (5) is cut into a 10 mm width and 100 mm length portion, and one end is peeled off to grasp Then, using an Instron universal testing machine, the load when peeling off 35 mm in the vertical direction at a speed of 50 mm / min at room temperature was measured according to JIS C6481, and peel strength (kgf / cm ).
＜粗化後の算術平均粗さ（Ｒａ値）の測定＞
上記の粗化処理後の積層板について、 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算術平均粗さ（Ｒａ値）を求めた。なお、Ｒａ値は全測定範囲の１０点の平均値とした。
<Measurement of arithmetic average roughness (Ra value) after roughening>
About the laminated plate after the above roughening treatment, using a non-contact type surface roughness meter (WYKO NT3300 manufactured by BEIKO INSTRUMENTS Co., Ltd.), VSI contact mode, arithmetically by numerical values obtained with a measurement range of 121 μm × 92 μm by a 50 × lens The average roughness (Ra value) was determined. In addition, Ra value was made into the average value of 10 points | pieces of the whole measurement range.
＜メッキ導体層の半田耐熱性の評価＞
ピール強度測定後のサンプルを、２６０℃の半田浴に３分間浸漬し、導体層の剥離の有無を目視確認した。評価として、剥離が見られなかった場合を○とし、一部でも剥離した場合は×とした。
<Evaluation of solder heat resistance of plated conductor layer>
The sample after the peel strength measurement was immersed in a 260 ° C. solder bath for 3 minutes, and the presence or absence of peeling of the conductor layer was visually confirmed. As evaluation, the case where peeling was not seen was set as (circle), and when even one part peeled, it was set as x.
＜ガラス転移温度（Ｔｇ）及び線熱膨張率の測定＞
実施例および比較例で得られた接着フィルムを１９０℃で９０分間加熱して樹脂組成物層を熱硬化させた。その硬化物を、幅約５ｍｍ、長さ約１５ｍｍの試験片に切断し、（株）リガク製熱機械分析装置（Ｔｈｅｒｍｏ Ｐｌｕｓ ＴＭＡ８３１０）を使用して、引張加重法で熱機械分析を行った。試験片を前記装置に装着後、荷重１ｇ、昇温速度５℃／分の測定条件にて連続して２回測定した。２回目の測定においてガラス転移温度と、２５℃から１５０℃までの平均線熱膨張率（ｐｐｍ）を算出した。また２回目の測定における寸法変化シグナルの傾きが変化する点からガラス転移温度（℃）を算出した。
<Measurement of glass transition temperature (Tg) and linear thermal expansion coefficient>
The adhesive films obtained in Examples and Comparative Examples were heated at 190 ° C. for 90 minutes to thermally cure the resin composition layer. The cured product was cut into a test piece having a width of about 5 mm and a length of about 15 mm, and thermomechanical analysis was performed by a tensile load method using a thermomechanical analyzer manufactured by Rigaku Corporation (Thermo Plus TMA8310). After mounting the test piece on the apparatus, the test piece was measured twice continuously under the measurement conditions of a load of 1 g and a heating rate of 5 ° C./min. In the second measurement, the glass transition temperature and the average linear thermal expansion coefficient (ppm) from 25 ° C. to 150 ° C. were calculated. The glass transition temperature (° C.) was calculated from the point at which the slope of the dimensional change signal in the second measurement changed.
（実施例１）
液状ビスフェノールＡ型エポキシ樹脂（ジャパンエポキシレジン（株）製「ｊＥＲ８２８ＥＬ」、エポキシ当量１８０）３０部と、ビフェニルアラルキル型エポキシ樹脂（日本化薬（株）製「ＮＣ３０００−Ｈ」、エポキシ当量２９１）２５部、ナフタレン型４官能エポキシ樹脂（ＤＩＣ（株）製「ＨＰ−４７００」、エポキシ当量１６２、２０℃で固形状）６部、フェノキシ樹脂（重量平均分子量３８０００、ジャパンエポキシレジン（株）製「ＹＸ６９５４」のメチルエチルケトン（以下「ＭＥＫ」と略称する。）とシクロヘキサノンの１：１（質量比）の混合溶媒を使用した不揮発分３０質量％の溶液）３０部とを、ＭＥＫ１５部及びシクロヘキサノン１５部の混合溶媒に撹拌しながら加熱溶解させた。そこへ、フェノールノボラック系硬化剤（ＤＩＣ（株）製「ＬＡ−７０５４」の固形分６０％のＭＥＫ溶液、フェノール性水酸基当量１２４）３５部、硬化触媒（四国化成工業（株）製、「２Ｅ４ＭＺ−ＣＮ」）０．１部、球形シリカ（アドマテックス（株）製「ＳＯＣ４」、平均粒径１μｍ、５μｍ上限カット、ヘキサメチルジシラザン処理後、Ｎ−フェニル−３−アミノプロピルトリメトキシシランをシリカに対して１質量％で処理し、室温で２０日経過させた。表面に結合する単位面積当たりのカーボン量０．４０ｍｇ／ｍ２）６０部、さらにフェナントレン型リン化合物（三光（株）製「ＨＣＡ−ＨＱ」平均粒径２μｍ）５部を混合し、高速回転ミキサーで均一に分散して、樹脂ワニスを作製した。次に、かかる樹脂ワニスをポリエチレンテレフタレート（厚さ３８μｍ、以下「ＰＥＴ」と略称する。）上に、乾燥後の樹脂厚みが４０μｍとなるようにダイコーターにて塗布し、８０〜１２０℃（平均１００℃）で６分間乾燥した（残留溶媒量約２質量％）。次いで樹脂組成物の表面に厚さ１５μｍのポリプロピレンフィルムを貼り合わせながらロール状に巻き取った。ロール状の接着フィルムを幅５０７ｍｍにスリットし、これより５０７×３３６ｍｍサイズのシート状の接着フィルムを得た。
Example 1
30 parts of liquid bisphenol A type epoxy resin (Japan Epoxy Resin Co., Ltd. “jER828EL”, epoxy equivalent 180) and biphenyl aralkyl type epoxy resin (Nippon Kayaku Co., Ltd. “NC3000-H”, epoxy equivalent 291) 25 Parts, naphthalene-type tetrafunctional epoxy resin (“HP-4700” manufactured by DIC Corporation, epoxy equivalent 162, solid at 20 ° C.) 6 parts, phenoxy resin (weight average molecular weight 38000, manufactured by Japan Epoxy Resins Co., Ltd. “YX6954” Of methyl ethyl ketone (hereinafter abbreviated as “MEK”) and cyclohexanone in a 1: 1 (mass ratio) mixed solvent of 30 parts by mass (a non-volatile content of 30% by mass) are mixed with 15 parts of MEK and 15 parts of cyclohexanone. The mixture was dissolved in a solvent with stirring. Thereto, 35 parts of a phenol novolac-based curing agent (MEK solution having a solid content of 60%, “LA-7054” manufactured by DIC Corporation, phenolic hydroxyl group equivalent 124), a curing catalyst (manufactured by Shikoku Kasei Kogyo Co., Ltd., “2E4MZ”) -CN ") 0.1 part, spherical silica (" SOC4 "manufactured by Admatechs Co., Ltd.), average particle size 1 µm, 5 µm upper limit cut, hexamethyldisilazane treatment, N-phenyl-3-aminopropyltrimethoxysilane Treated at 1% by mass with respect to silica and allowed to stand for 20 days at room temperature, 60 parts of carbon per unit area bound to the surface, 0.40 mg / m 2 , and phenanthrene-type phosphorus compound (manufactured by Sanko) 5 parts of “HCA-HQ” (average particle diameter 2 μm) were mixed and dispersed uniformly with a high-speed rotary mixer to prepare a resin varnish. Next, the resin varnish was applied onto polyethylene terephthalate (thickness 38 μm, hereinafter abbreviated as “PET”) with a die coater so that the resin thickness after drying was 40 μm, and 80 to 120 ° C. (average (100 ° C.) for 6 minutes (residual solvent amount: about 2% by mass). Subsequently, it wound up in roll shape, bonding a 15-micrometer-thick polypropylene film on the surface of a resin composition. The roll-like adhesive film was slit to a width of 507 mm, and a sheet-like adhesive film having a size of 507 × 336 mm was obtained therefrom.
（実施例２）
液状ビスフェノールＡ型エポキシ樹脂（ジャパンエポキシレジン（株）製「ＹＬ９８０」、エポキシ当量１８５）２５部と、ビフェニルアラルキル型エポキシ樹脂（日本化薬（株）製「ＮＣ３０００−Ｌ」、エポキシ当量２６９）２０部、ナフタレン型多官能エポキシ樹脂（ＤＩＣ（株）製「ＥＸＡ−４７１０」、エポキシ当量１７０、２０℃で固形状）６部、フェノキシ樹脂（重量平均分子量３８０００、ジャパンエポキシレジン（株）製「ＹＸ６９５４」のＭＥＫとシクロヘキサノンの１：１（質量比）の混合溶媒を使用した不揮発分３０質量％の溶液）１０部とを、ＭＥＫ１５部とシクロヘキサノン１５部の混合溶媒に撹拌しながら加熱溶解させた。そこへ、フェノールノボラック系硬化剤（ＤＩＣ（株）製「ＬＡ−７０５４」の固形分６０％のＭＥＫ溶液、フェノール性水酸基当量１２４）２０部、ナフトール系硬化剤（東都化成（株）製「ＳＮ−４８５」の固形分６０％のＭＥＫ溶液、フェノール性水酸基当量２１５）２０部、ポリビニルアセトアセタール樹脂（積水化学工業（株）製「ＫＳ−１」のＭＥＫとシクロヘキサノンの１：１（質量比）の混合溶媒を使用した固形分１５質量％の溶液）１０部、硬化触媒（四国化成工業（株）製、「２Ｅ４ＭＺ−ＣＮ」）０．１部、球形シリカ（アドマテックス（株）製「ＳＯＣ２」、平均粒径０．５μｍ、５μｍ上限カット、ヘキサメチルジシラザン処理後、Ｎ−フェニル−３−アミノプロピルトリメトキシシランをシリカに対して０．６質量％で処理し、４０℃で７日経過させた。単位面積当たりのカーボン量０．４７ｍｇ／ｍ２）１２０部、さらにフェナントレン型リン化合物（三光（株）製「ＨＣＡ−ＨＱ」平均粒径２μｍ）５部を混合し、高速回転ミキサーで均一に分散して、樹脂ワニスを作製した。かかる樹脂ワニスを使用し、実施例１と全く同様にして接着フィルムを得た。
(Example 2)
25 parts of liquid bisphenol A type epoxy resin (Japan Epoxy Resin Co., Ltd. “YL980”, epoxy equivalent 185) and biphenyl aralkyl type epoxy resin (Nippon Kayaku Co., Ltd. “NC3000-L”, epoxy equivalent 269) 20 Parts, naphthalene-type polyfunctional epoxy resin (DIC Corporation “EXA-4710”, epoxy equivalent 170, solid at 20 ° C.) 6 parts, phenoxy resin (weight average molecular weight 38000, Japan Epoxy Resins Co., Ltd. “YX6954” 10 parts of a mixed solvent of MEK and cyclohexanone in a 1: 1 (mass ratio) mixture having a nonvolatile content of 30% by mass was dissolved in a mixed solvent of 15 parts of MEK and 15 parts of cyclohexanone with stirring. Thereto, 20 parts of a phenol novolac-based curing agent (“LA-7054” manufactured by DIC Corporation, 60% solid MEK solution, phenolic hydroxyl group equivalent 124), naphthol-based curing agent (“SN” manufactured by Toto Kasei Co., Ltd.) -485 "solid content 60% MEK solution, phenolic hydroxyl group equivalent 215), polyvinyl acetoacetal resin (Sekisui Chemical Co., Ltd." KS-1 "MEK and cyclohexanone 1: 1 (mass ratio) 10 parts of solid solution using a mixed solvent of 10%, a curing catalyst (manufactured by Shikoku Kasei Kogyo Co., Ltd., “2E4MZ-CN”) 0.1 part, spherical silica (manufactured by Admatechs Co., Ltd. “SOC2”) ”, Average particle size 0.5 μm, 5 μm upper limit cut, after hexamethyldisilazane treatment, N-phenyl-3-aminopropyltrimethoxysilane is 0.6 quality relative to silica The amount of carbon was treated for 7 days at 40 ° C. 120 parts of carbon per unit area 0.47 mg / m 2 , and phenanthrene-type phosphorus compound (“HCA-HQ” average particle diameter manufactured by Sanko Co., Ltd.) 2 μm) 5 parts were mixed and dispersed uniformly with a high-speed rotary mixer to prepare a resin varnish. Using this resin varnish, an adhesive film was obtained in exactly the same manner as in Example 1.
（比較例１）
実施例１において、球形シリカを（アドマテックス（株）製「ＳＯＣ４」、平均粒径１μｍ、５μｍ上限カット、ヘキサメチルジシラザン処理、Ｎ−フェニル−３−アミノプロピルトリメトキシシラン処理と同じ処理を行い、室温で１日経過させた。単位面積当たりのカーボン量０．２０ｍｇ／ｍ２）６０部に変更した熱硬化性樹脂組成物のワニスを使用する以外は実施例１と全く同様にして接着フィルムを得た。
(Comparative Example 1)
In Example 1, spherical silica (“SOC4” manufactured by Admatechs Co., Ltd., average particle size 1 μm, 5 μm upper limit cut, hexamethyldisilazane treatment, N-phenyl-3-aminopropyltrimethoxysilane treatment) performed, in the same manner as in example 1 except that using a varnish of carbon amount 0.20 mg / m 2) thermosetting resin composition was changed to 60 parts per. unit area aged 1 day at room temperature adhesion A film was obtained.
（比較例２）
実施例２において、球形シリカを（アドマテックス（株）製「ＳＯＣ２」、平均粒径０．５μｍ、３μｍ上限カット、ヘキサメチルジシラザン処理、Ｎ−フェニル−３−アミノプロピルトリメトキシシラン処理と同じ処理を行い、室温で１日経過させた。単位面積当たりのカーボン量０．１５ｍｇ／ｍ２）１２０部に変更した熱硬化性樹脂組成物のワニスを使用する以外は実施例２と全く同様にして接着フィルムを得た。
(Comparative Example 2)
In Example 2, spherical silica (“SOC2” manufactured by Admatechs Co., Ltd., average particle size 0.5 μm, 3 μm upper limit cut, hexamethyldisilazane treatment, N-phenyl-3-aminopropyltrimethoxysilane treatment is the same. The amount of carbon per unit area was 0.15 mg / m 2 ) Except that a varnish of a thermosetting resin composition changed to 120 parts was used, exactly the same as in Example 2. To obtain an adhesive film.
表１の結果から、本発明の実施例１〜２で得られた接着フィルムを構成する樹脂組成物は、シリカの充填量に応じた熱膨張性を有し、絶縁層上にメッキピール強度が０．６ｋｇｆ／ｃｍ以上という高ピール強度の導体層を形成できている。一方、比較例１〜２の接着フィルムは表面処理剤の反応量が十分でないために、粗度が高く、かつ低メッキピール強度であって、かつ半田浸漬により導体層一部に剥離が見られる結果であった。 From the result of Table 1, the resin composition which comprises the adhesive film obtained in Examples 1-2 of this invention has thermal expansibility according to the filling amount of silica, and plating peel strength is on an insulating layer. A conductor layer having a high peel strength of 0.6 kgf / cm or more can be formed. On the other hand, the adhesive films of Comparative Examples 1 and 2 have a high degree of roughness and low plating peel strength because the amount of reaction of the surface treating agent is not sufficient, and peeling of the conductor layer is observed due to solder immersion. It was a result.
特定の多官能エポキシ樹脂、硬化剤、無機充填材を含有する樹脂組成物により、低熱膨張率を維持しながら、硬化して得られる絶縁層表面の粗度が低く、高いピール強度を有する導体層の形成を可能にし、半田耐熱性に優れた、回路基板の絶縁層形成に好適に使用することができる樹脂組成物及び絶縁樹脂シートが提供できるようになったことは意義深い。 Conductive layer having low peel coefficient and high peel strength, while maintaining a low coefficient of thermal expansion with a resin composition containing a specific polyfunctional epoxy resin, curing agent and inorganic filler. It is significant that a resin composition and an insulating resin sheet that can be suitably used for forming an insulating layer of a circuit board and have excellent solder heat resistance can be provided.
Claims (4)
A multilayer printed wiring board comprising the sheet-like material according to claim 3.
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| JP5768529B2 (en) * | 2011-06-24 | 2015-08-26 | 三菱化学株式会社 | Interlayer filler composition for three-dimensional stacked semiconductor device and coating solution thereof |
| TWI602873B (en) * | 2012-06-11 | 2017-10-21 | 味之素股份有限公司 | Resin composition |
| KR102078522B1 (en) * | 2012-06-12 | 2020-02-18 | 아지노모토 가부시키가이샤 | Resin composition |
| JP6123177B2 (en) * | 2012-07-04 | 2017-05-10 | 味の素株式会社 | Resin composition |
| JP6011079B2 (en) * | 2012-07-05 | 2016-10-19 | 味の素株式会社 | Resin sheet with support |
| JP2014028880A (en) * | 2012-07-31 | 2014-02-13 | Ajinomoto Co Inc | Resin composition |
| JP6217895B2 (en) * | 2013-02-14 | 2017-10-25 | 味の素株式会社 | Curable resin composition |
| JP6183583B2 (en) * | 2013-02-14 | 2017-08-23 | 味の素株式会社 | Curable resin composition |
| JP6308344B2 (en) * | 2013-04-08 | 2018-04-11 | 味の素株式会社 | Curable resin composition |
| KR102228718B1 (en) * | 2013-07-04 | 2021-03-18 | 아지노모토 가부시키가이샤 | Photosensitive resin composition |
| CN105542127B (en) | 2014-10-22 | 2020-04-10 | 味之素株式会社 | Resin composition |
| CN107207705B (en) * | 2015-02-03 | 2019-11-01 | 日立化成株式会社 | Composition epoxy resin, membranaceous composition epoxy resin, solidfied material and electronic device |
| JP6511840B2 (en) * | 2015-02-03 | 2019-05-15 | 日立化成株式会社 | Epoxy resin composition, film-like epoxy resin composition and electronic component device |
| JP6670293B2 (en) * | 2015-03-04 | 2020-03-18 | エア・ウォーター株式会社 | A thermosetting resin composition, an insulating material containing the thermosetting resin composition, a sealing agent and a conductive paste, a cured product obtained by curing the thermosetting resin composition, and the thermosetting resin composition. A substrate material, a prepreg obtained by impregnating a substrate with the thermosetting resin composition, a member obtained by curing the thermosetting resin composition of the prepreg, a method of adjusting a coefficient of thermal expansion, and a method of manufacturing using the adjusting method. Material |
| JP7102682B2 (en) * | 2016-07-20 | 2022-07-20 | 昭和電工マテリアルズ株式会社 | Resin composition, support with resin layer, prepreg, laminated board, multilayer printed wiring board and printed wiring board for millimeter wave radar |
| CN109963921B (en) * | 2016-11-18 | 2021-09-24 | 住友电气工业株式会社 | Adhesive composition and printed wiring board |
| JP6534986B2 (en) * | 2016-11-29 | 2019-06-26 | 味の素株式会社 | Resin composition |
| JP7240085B2 (en) * | 2017-03-31 | 2023-03-15 | 住友ベークライト株式会社 | Thermosetting resin composition, resin film with carrier, prepreg, printed wiring board and semiconductor device |
| CN110506066B (en) * | 2017-04-10 | 2021-11-19 | 三菱瓦斯化学株式会社 | Resin composition, prepreg, metal foil-clad laminate, resin sheet, and printed wiring board |
| JP2021073328A (en) * | 2020-12-25 | 2021-05-13 | 住友ベークライト株式会社 | Thermosetting resin composition, resin film with carrier, prepreg, printed wiring board, and semiconductor device |
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Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| DE10145162A1 (en) * | 2001-09-13 | 2003-04-10 | Wacker Chemie Gmbh | Silylated silica with low levels of silicon-bonded hydroxy groups useful in toners, developers, charge control agents and flow improvers for powder systems and in crosslinkable polymer and resin compositions |
| JP4279521B2 (en) * | 2002-07-30 | 2009-06-17 | トヨタ自動車株式会社 | Metal oxide powder for epoxy resin composition for semiconductor encapsulation, its production method, and epoxy resin composition for semiconductor encapsulation |
| JP5032328B2 (en) * | 2004-10-20 | 2012-09-26 | キャボット コーポレイション | Production of direct hydrophobic silica from aqueous colloidal silica dispersions |
| WO2009028493A1 (en) * | 2007-08-28 | 2009-03-05 | Sumitomo Bakelite Company, Ltd. | Insulating resin composition for multilayer printed wiring board, insulating resin sheet with base material, multilayer printed wiring board, and semiconductor device |
| JP5195454B2 (en) * | 2009-01-22 | 2013-05-08 | 味の素株式会社 | Resin composition |
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