JP2014009356A - Epoxy resin composition, insulating film made of the same, and multilayer printed board comprising the same - Google Patents
Epoxy resin composition, insulating film made of the same, and multilayer printed board comprising the same Download PDFInfo
- Publication number
- JP2014009356A JP2014009356A JP2012266697A JP2012266697A JP2014009356A JP 2014009356 A JP2014009356 A JP 2014009356A JP 2012266697 A JP2012266697 A JP 2012266697A JP 2012266697 A JP2012266697 A JP 2012266697A JP 2014009356 A JP2014009356 A JP 2014009356A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- resin composition
- start temperature
- curing
- curing agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 135
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 133
- 239000000203 mixture Substances 0.000 title claims abstract description 51
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 29
- 239000011256 inorganic filler Substances 0.000 claims abstract description 17
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 17
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000004593 Epoxy Substances 0.000 claims description 12
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 12
- 229920003986 novolac Polymers 0.000 claims description 8
- -1 tertiary amine compound Chemical class 0.000 claims description 8
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 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 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 150000008065 acid anhydrides Chemical class 0.000 claims description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- 229930003836 cresol Natural products 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 239000004843 novolac epoxy resin Substances 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 3
- 229910052582 BN Inorganic materials 0.000 claims description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 3
- 229910002113 barium titanate Inorganic materials 0.000 claims description 3
- 229910021523 barium zirconate Inorganic materials 0.000 claims description 3
- DQBAOWPVHRWLJC-UHFFFAOYSA-N barium(2+);dioxido(oxo)zirconium Chemical compound [Ba+2].[O-][Zr]([O-])=O DQBAOWPVHRWLJC-UHFFFAOYSA-N 0.000 claims description 3
- 229910002115 bismuth titanate Inorganic materials 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 3
- 229910052570 clay Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 3
- 239000001095 magnesium carbonate Substances 0.000 claims description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- VSWALKINGSNVAR-UHFFFAOYSA-N naphthalen-1-ol;phenol Chemical compound OC1=CC=CC=C1.C1=CC=C2C(O)=CC=CC2=C1 VSWALKINGSNVAR-UHFFFAOYSA-N 0.000 claims description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 3
- 229920000768 polyamine Polymers 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000000454 talc Substances 0.000 claims description 3
- 229910052623 talc Inorganic materials 0.000 claims description 3
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- 238000001723 curing Methods 0.000 description 54
- 239000010410 layer Substances 0.000 description 26
- 238000000034 method Methods 0.000 description 21
- 230000008569 process Effects 0.000 description 10
- 239000010949 copper Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 6
- 239000011810 insulating material Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 238000009713 electroplating Methods 0.000 description 5
- 239000011342 resin composition Substances 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 4
- 238000005191 phase separation Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229920005992 thermoplastic resin Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 229920002799 BoPET Polymers 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-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
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 230000000930 thermomechanical effect Effects 0.000 description 3
- QQOWHRYOXYEMTL-UHFFFAOYSA-N triazin-4-amine Chemical compound N=C1C=CN=NN1 QQOWHRYOXYEMTL-UHFFFAOYSA-N 0.000 description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 2
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000001029 thermal curing Methods 0.000 description 2
- RUEBPOOTFCZRBC-UHFFFAOYSA-N (5-methyl-2-phenyl-1h-imidazol-4-yl)methanol Chemical compound OCC1=C(C)NC(C=2C=CC=CC=2)=N1 RUEBPOOTFCZRBC-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- FQERLIOIVXPZKH-UHFFFAOYSA-N 1,2,4-trioxane Chemical compound C1COOCO1 FQERLIOIVXPZKH-UHFFFAOYSA-N 0.000 description 1
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 1
- XZKLXPPYISZJCV-UHFFFAOYSA-N 1-benzyl-2-phenylimidazole Chemical compound C1=CN=C(C=2C=CC=CC=2)N1CC1=CC=CC=C1 XZKLXPPYISZJCV-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-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
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 1
- BVYPJEBKDLFIDL-UHFFFAOYSA-N 3-(2-phenylimidazol-1-yl)propanenitrile Chemical compound N#CCCN1C=CN=C1C1=CC=CC=C1 BVYPJEBKDLFIDL-UHFFFAOYSA-N 0.000 description 1
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 1
- LYWVNPSVLAFTFX-UHFFFAOYSA-N 4-methylbenzenesulfonate;morpholin-4-ium Chemical compound C1COCCN1.CC1=CC=C(S(O)(=O)=O)C=C1 LYWVNPSVLAFTFX-UHFFFAOYSA-N 0.000 description 1
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- NVSXXGLICVTSNN-UHFFFAOYSA-N C(CCCCCCCCCCCCCCCC)C=1NC=CN1.C(C1=CC=CC=C1)N1C(=NC=C1)C Chemical compound C(CCCCCCCCCCCCCCCC)C=1NC=CN1.C(C1=CC=CC=C1)N1C(=NC=C1)C NVSXXGLICVTSNN-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- UUQQGGWZVKUCBD-UHFFFAOYSA-N [4-(hydroxymethyl)-2-phenyl-1h-imidazol-5-yl]methanol Chemical compound N1C(CO)=C(CO)N=C1C1=CC=CC=C1 UUQQGGWZVKUCBD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 1
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- ZJLMKPKYJBQJNH-UHFFFAOYSA-N propane-1,3-dithiol Chemical compound SCCCS ZJLMKPKYJBQJNH-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/05—Insulated conductive substrates, e.g. insulated metal substrate
- H05K1/056—Insulated conductive substrates, e.g. insulated metal substrate the metal substrate being covered by an organic insulating layer
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
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Abstract
Description
本発明は、エポキシ樹脂組成物、これから製造された絶縁フィルム、及びこれを備えた多層プリント基板に関する。 The present invention relates to an epoxy resin composition, an insulating film produced therefrom, and a multilayer printed board including the same.
プリント基板（ＰＣＢ）は、一般に、高分子複合素材を用いて、Ｃｕからなる内部回路同士を絶縁して多層を形成することを基本として作られる。基板が正常的に作動し且つ信頼性が確保されるために、絶縁層とＣｕ層の接着力が重要である。十分な接着力を確保するために、絶縁層にＣｕとの結合力が高い成分を含ませることはもとより、絶縁層の表面に適切な粗さを与えて界面の表面積を高める方法が一般に使われている。 A printed circuit board (PCB) is generally made on the basis of forming a multi-layer by insulating internal circuits made of Cu using a polymer composite material. In order for the substrate to operate normally and to ensure reliability, the adhesion between the insulating layer and the Cu layer is important. In order to ensure sufficient adhesion, not only the insulating layer contains a component that has high bonding strength with Cu, but also a method that increases the surface area of the interface by imparting appropriate roughness to the surface of the insulating layer is generally used. ing.
多層プリント基板を製造する方法としては、絶縁層のガラス繊維をエポキシ樹脂に含浸させ、これを硬化させて製造した数個のプリプレグシート（Ｐｒｅｐｒｅｇ ｓｈｅｅｔ）を用いて、プレス（ｐｒｅｓｓ）によって、銅箔（ｃｏｐｐｅｒ ｆｏｉｌ）回路が形成された内層回路基板上に積層し、層間接続を貫通孔（ｔｈｒｏｕｇｈ−Ｈｏｌｅ）によって実現する方法が公知になっている。ところが、このような方法は、大規模の設備により高いコストがかかり、積層プレスにより加熱加圧の下で成形させるには、長時間がかかるうえ、外層上で貫通孔をメッキすることにより、銅の厚さが増加して微細パターンの形成が難しいという問題がある。 As a method of manufacturing a multilayer printed board, copper foil is obtained by pressing a few prepreg sheets (prepreg sheets) manufactured by impregnating an epoxy resin with glass fibers of an insulating layer and curing the epoxy resin. A method of stacking on an inner circuit board on which a (copper foil) circuit is formed and realizing interlayer connection by a through-hole is known. However, such a method is costly due to large-scale equipment, and it takes a long time to form it under heat and pressure with a laminating press, and copper is plated by plating through holes on the outer layer. There is a problem in that it is difficult to form a fine pattern due to an increase in thickness of the substrate.
かかる問題を解決するための手段として、最近、ビルドアップ方式の多層プリント基板の製造のために、回路基板の導体層に有機絶縁層（又は絶縁フィルム）を交互に積層する製造技術の開発が行われている。 As a means for solving such a problem, recently, in order to manufacture a build-up type multilayer printed circuit board, a manufacturing technique in which organic insulating layers (or insulating films) are alternately laminated on a conductor layer of a circuit board has been developed. It has been broken.
一般に、ビルドアップ方式で多層プリント基板を製造する過程は、内層回路形成の後、ビルドアップフィルムをラミネートして絶縁層を形成する。その後、前硬化（ｐｒｏｃｕｒｅ）→ドリリング→デスミア（ｄｅｓｍｅａｒ）→無電解メッキ→電解メッキ→後硬化（ｐｏｓｔｃｕｒｅ）を経て、外層経路を形成する。この際、絶縁フィルムのスミア（ｓｍｅａｒ）を除去するために、酸溶液で溶出させるデスミア工程が必須的であるが、デスミア工程において化学的処理を介してフィルムの表面に粗さを与える。この場合、一部硬化した絶縁層の表面も一定量浸食されて粗さが与えられる。ここで、絶縁層との配線密着力は、前硬化におけるフィルムの硬化度に応じてデスミアで生成される粗さに影響されるが、接着力は、プリプレグと銅箔の熱圧着方式に比べて著しく低下する。 In general, in the process of manufacturing a multilayer printed board by a build-up method, after forming an inner layer circuit, a build-up film is laminated to form an insulating layer. Thereafter, an outer layer path is formed through pre-curing → drilling → desmear → electroless plating → electrolytic plating → post-curing. At this time, in order to remove smear of the insulating film, a desmear process eluted with an acid solution is essential. In the desmear process, roughness is given to the surface of the film through chemical treatment. In this case, the surface of the partially cured insulating layer is also eroded by a certain amount to give roughness. Here, the wiring adhesion strength with the insulating layer is affected by the roughness generated by desmear according to the degree of curing of the film in the pre-curing, but the adhesive strength is compared with the thermocompression bonding method of prepreg and copper foil. It drops significantly.
かかる問題点を解決するために、特許文献１では、エポキシ樹脂に熱可塑性樹脂を混合して相分離を誘導し、デスミアの後に粗さを与える方法を開示しているが、熱可塑性樹脂使用の際に耐熱性、耐化学性などの特性が弱化するという問題点がある。また、特許文献２では、トリアジン構造を含有するフェノール系硬化剤を多官能性エポキシ樹脂に対して使用し、これにゴム成分を加える場合、熱硬化によって当該表面に微細な凸凹部を簡単に形成させることができることを開示しているが、ゴム成分の添加により、絶縁フィルムの熱膨張係数（ＣＴＥ）が高くなって基材自体が変形する傾向がある。 In order to solve such a problem, Patent Document 1 discloses a method in which a thermoplastic resin is mixed with an epoxy resin to induce phase separation and give roughness after desmear. However, there is a problem that characteristics such as heat resistance and chemical resistance are weakened. Further, in Patent Document 2, when a phenolic curing agent containing a triazine structure is used for a polyfunctional epoxy resin and a rubber component is added thereto, a fine convex / concave portion is easily formed on the surface by thermal curing. However, the addition of the rubber component tends to increase the coefficient of thermal expansion (CTE) of the insulating film and cause the substrate itself to be deformed.
そこで、本発明者は、硬化反応性が高く且つ硬化開始温度（ａ℃）が低いエポキシ樹脂（Ａ）と、硬化反応性が低く且つ硬化開始温度（ｂ℃）が高いエポキシ樹脂（Ｂ）とを混合し、ａ℃〜ｂ℃の温度で前硬化（ｐｒｅｃｕｒｅ）を行い、硬化開始温度の低いエポキシ樹脂（Ａ）の硬化が行われるにつれて、硬化していないエポキシ樹脂（Ｂ）との相分離を用いて前硬化の後にデスミア工程を介して硬化していないエポキシ樹脂（Ｂ）が表面に溶出し、サイズ数百ｎｍ〜約１μｍの球状の微細な粗さ付与によって改善された剥離強度、及び基材自体の優れた熱膨張係数を得ることができることを見出し、これに基づいて本発明を完成した。 Therefore, the inventor has an epoxy resin (A) having a high curing reactivity and a low curing start temperature (a ° C.), and an epoxy resin (B) having a low curing reactivity and a high curing start temperature (b ° C.). Are mixed and precured at a temperature of a ° C to b ° C, and as the epoxy resin (A) having a low curing start temperature is cured, phase separation from the uncured epoxy resin (B) is performed. The epoxy resin (B) which has not been cured through a desmear process after pre-curing using a resin is eluted on the surface, and the peel strength is improved by imparting a spherical fine roughness having a size of several hundred nm to about 1 μm, and The inventors have found that an excellent thermal expansion coefficient of the substrate itself can be obtained, and based on this, the present invention has been completed.
よって、本発明の目的は、熱膨張係数が低く且つ剥離強度に優れたエポキシ樹脂組成物を提供する。 Therefore, an object of the present invention is to provide an epoxy resin composition having a low thermal expansion coefficient and excellent peel strength.
本発明の他の目的は、前記エポキシ樹脂組成物から製造されて微細回路パターンの形成が可能な絶縁フィルムを提供する。 Another object of the present invention is to provide an insulating film manufactured from the epoxy resin composition and capable of forming a fine circuit pattern.
本発明の別の目的は、前記絶縁フィルムを備える多層プリント基板を提供する。 Another object of the present invention is to provide a multilayer printed circuit board comprising the insulating film.
上記目的を達成するために、本発明のある観点によれば、硬化開始温度が７５〜１１０℃の温度範囲である熱硬化性第１エポキシ樹脂（Ａ）と、硬化開始温度が１１０〜１５０℃の温度範囲である熱硬化性第２エポキシ樹脂（Ｂ）と、硬化剤（Ｃ）と、無機充填剤（Ｄ）とを含んでなり、前記第１エポキシ樹脂（Ａ）の硬化開始温度が第２エポキシ樹脂の硬化開始温度より低いことを特徴とするエポキシ樹脂組成物を提供する。 In order to achieve the above object, according to one aspect of the present invention, a thermosetting first epoxy resin (A) having a curing start temperature in a temperature range of 75 to 110 ° C. and a curing start temperature of 110 to 150 ° C. A thermosetting second epoxy resin (B), a curing agent (C), and an inorganic filler (D), wherein the first epoxy resin (A) has a curing start temperature of (2) An epoxy resin composition characterized by being lower than the curing start temperature of the epoxy resin is provided.
本発明のエポキシ樹脂組成物において、前記エポキシ樹脂組成物は、第１エポキシ樹脂（Ａ）５〜１５重量％、第２エポキシ樹脂（Ｂ）５〜１５重量％、硬化剤（Ｃ）１０〜２０重量％、及び無機充填剤（Ｄ）５０〜８０重量％を含んでなることを特徴とする。 In the epoxy resin composition of the present invention, the epoxy resin composition comprises 5 to 15% by weight of the first epoxy resin (A), 5 to 15% by weight of the second epoxy resin (B), and 10 to 20 of the curing agent (C). It is characterized by comprising 50% by weight and 50-80% by weight of inorganic filler (D).
本発明のエポキシ樹脂組成物において、前記第１エポキシ樹脂（Ａ）の硬化開始温度は、８０〜１００℃の温度範囲であり、前記第２エポキシ樹脂（Ｂ）の硬化開始温度は、１２０〜１５０℃の温度範囲であることを特徴とする。 In the epoxy resin composition of the present invention, the curing start temperature of the first epoxy resin (A) is in a temperature range of 80 to 100 ° C., and the curing start temperature of the second epoxy resin (B) is 120 to 150. It is characterized by a temperature range of ° C.
本発明のエポキシ樹脂組成物において、前記第１エポキシ樹脂（Ａ）は、エポキシ当量が１００〜２００当量であり、前記第２エポキシ樹脂（Ｂ）は、エポキシ当量が２００〜１０００当量であることを特徴とする。 In the epoxy resin composition of the present invention, the first epoxy resin (A) has an epoxy equivalent of 100 to 200 equivalents, and the second epoxy resin (B) has an epoxy equivalent of 200 to 1000 equivalents. Features.
本発明のエポキシ樹脂組成物において、前記第１エポキシ樹脂（Ａ）は、ナフタレン系エポキシ樹脂、ナフトール−フェノール系エポキシ樹脂、及びオレフィン系エポキシ樹脂から１種以上選択され、前記第２エポキシ樹脂（Ｂ）は、クレゾールノボラックエポキシ樹脂、ビスフェノールＡエポキシ樹脂、及びゴム変性エポキシ樹脂から１種以上選択されることを特徴とする。 In the epoxy resin composition of the present invention, the first epoxy resin (A) is at least one selected from a naphthalene epoxy resin, a naphthol-phenol epoxy resin, and an olefin epoxy resin, and the second epoxy resin (B ) Is one or more selected from cresol novolac epoxy resin, bisphenol A epoxy resin, and rubber-modified epoxy resin.
本発明のエポキシ樹脂組成物において、前記第１エポキシ樹脂（Ａ）と第２エポキシ樹脂（Ｂ）の硬化開始温度の差が、１０℃以上であることを特徴とする。 In the epoxy resin composition of the present invention, the difference in curing start temperature between the first epoxy resin (A) and the second epoxy resin (B) is 10 ° C. or more.
本発明のエポキシ樹脂組成物において、前記第１エポキシ樹脂（Ａ）と第２エポキシ樹脂（Ｂ）の硬化開始温度の差が、２０℃以上であることを特徴とする。 The epoxy resin composition of the present invention is characterized in that a difference in curing start temperature between the first epoxy resin (A) and the second epoxy resin (B) is 20 ° C. or more.
本発明のエポキシ樹脂組成物において、前記第１エポキシ樹脂（Ａ）と第２エポキシ樹脂（Ｂ）の硬化開始温度の差が、３０℃以上であることを特徴とする。 In the epoxy resin composition of the present invention, the difference in curing start temperature between the first epoxy resin (A) and the second epoxy resin (B) is 30 ° C. or more.
本発明のエポキシ樹脂組成物において、前記硬化剤は、ポリアミン系硬化剤、酸無水物硬化剤、フェノールノボラック型硬化剤、ポリメルカプタン硬化剤、第３アミン化合物、及びイミダゾール化合物から１種以上選択されることを特徴とする。 In the epoxy resin composition of the present invention, the curing agent is selected from one or more of a polyamine curing agent, an acid anhydride curing agent, a phenol novolac curing agent, a polymercaptan curing agent, a tertiary amine compound, and an imidazole compound. It is characterized by that.
本発明のエポキシ樹脂組成物において、前記無機充填剤は、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、及びジルコン酸カルシウムから１種以上選択されることを特徴とする。 In the epoxy resin composition of the present invention, the inorganic filler includes silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, boron. One or more kinds selected from aluminum oxide, barium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate are characterized.
本発明の他の観点によれば、前記エポキシ樹脂組成物から製造された絶縁フィルムを提供する。 According to another aspect of the present invention, there is provided an insulating film manufactured from the epoxy resin composition.
本発明の別の観点によれば、前記絶縁フィルムを備えた多層プリント基板を提供する。 According to another viewpoint of this invention, the multilayer printed circuit board provided with the said insulating film is provided.
本発明に係るエポキシ樹脂組成物から製造されたビルドアップ方式の多層プリント基板用絶縁フィルムは、絶縁フィルムにサイズ数百ｎｍ〜約１μｍの球状の微細な粗さを与えることができるため、接着強度（剥離強度（ｐｅｅｌ ｓｔｒｅｎｇｔｈ））が改善されて微細回路の形成が可能であるうえ、絶縁フィルム自体の熱膨張係数が低いため、フィルムの変形がないという効果を得ることができる。 The build-up type multilayer printed circuit board insulating film manufactured from the epoxy resin composition according to the present invention can give the insulating film a spherical fine roughness having a size of several hundred nm to about 1 μm. (Peel strength) can be improved and a fine circuit can be formed, and since the thermal expansion coefficient of the insulating film itself is low, an effect that the film is not deformed can be obtained.
本発明の目的、特定の長所及び新規の特徴は、添付図面に係る以下の詳細な説明及び好ましい実施例によってさらに明らかになるであろう。本明細書において、各図面の構成要素に参照番号を付け加えるに際し、同一の構成要素に限っては、たとえ異なる図面に示されても、できるだけ同一の番号を付けるようにしていることに留意しなければならない。また、「一面」、「他面」、「第１」、「第２」などの用語は、一つの構成要素を他の構成要素から区別するために用いられるものであり、構成要素が前記用語によって限定されるものではない。以下、本発明を説明するにあたり、本発明の要旨を不明瞭にする可能性がある係る公知技術についての詳細な説明は省略する。 Objects, specific advantages and novel features of the present invention will become more apparent from the following detailed description and preferred embodiments with reference to the accompanying drawings. In this specification, it should be noted that when adding reference numerals to the components of each drawing, the same components are given the same number as much as possible even if they are shown in different drawings. I must. The terms “one side”, “other side”, “first”, “second” and the like are used to distinguish one component from another component, and the component is the term It is not limited by. Hereinafter, in describing the present invention, detailed descriptions of known techniques that may obscure the subject matter of the present invention are omitted.
以下、添付図面を参照して本発明の好ましい実施例を詳細に説明する。 Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.
前述したように、本発明は、導体回路層と絶縁層を交互に積層してなるビルドアップ（ｂｕｉｌｄ−ｕｐ）方式の多層プリント基板において、硬化開始温度の差に応じて熱硬化により表面に粗さを与えることが可能な層間絶縁用エポキシ樹脂組成物、前記組成物から製造された絶縁フィルム、及びこれを絶縁層として、銅で形成された内部回路を絶縁して多層を形成する多層プリント基板に関する。 As described above, according to the present invention, a build-up multilayer printed circuit board in which conductor circuit layers and insulating layers are alternately laminated is roughened on the surface by thermal curing according to a difference in curing start temperature. Epoxy resin composition for interlayer insulation capable of providing thickness, insulating film manufactured from the composition, and multilayer printed circuit board using this as an insulating layer to insulate an internal circuit formed of copper to form a multilayer About.
前述したように、本発明では、硬化開始温度の異なる２つのエポキシを混合して硬化開始温度の間で前硬化を行ったとき、低い硬化開始温度を有するエポキシは一部硬化し、高い硬化開始温度を有するエポキシは未硬化状態であるから、これらの間の相分離が起こる。これを用いて適切な表面粗さを与えることができる。既存の相分離現象のためにゴム変性エポキシを使用し或いは熱可塑性樹脂を使用する場合、ビルドアップフィルムの主要特性である熱膨張係数が上昇する傾向がある。 As described above, in the present invention, when two epoxies having different curing start temperatures are mixed and precured between the cure start temperatures, the epoxy having a low cure start temperature is partially cured and a high cure start is performed. Since the epoxy with temperature is in an uncured state, phase separation occurs between them. This can be used to provide an appropriate surface roughness. When using a rubber-modified epoxy or a thermoplastic resin due to an existing phase separation phenomenon, the thermal expansion coefficient, which is a main characteristic of the build-up film, tends to increase.
本発明において、相分離が行われた構造は、２つのエポキシの混合比と、硬化開始温度の異なる追加エポキシ樹脂、添加剤または無機充填剤（Ｉｎｏｒｇａｎｉｃ Ｆｉｌｌｅｒ）の混合有無及びそれぞれの比率によって海島（Ｓｅａ−Ｉｓｌａｎｄ）構造、二重連続（ｂｉ−ｃｏｔｉｎｕｏｕｓ）構造、逆海島（Ｉｎｖｅｒｓｅ Ｓｅａ−Ｉｓｌａｎｄ）構造などと異なりうる。これにより、前硬化の後、デスミア工程を介して、硬化開始温度の高い硬化していないエポキシ樹脂（Ｂ）が表面に溶出して、サイズ数百ｎｍ〜約１μｍの球状の微細な粗さが与えられることにより、以後、メッキで形成された銅（Ｃｕ）層との密着力が良くなって剥離強度が改善される。しかも、ゴム成分或いは熱可塑性樹脂を含むエポキシ樹脂組成物より熱膨張係数に優れるから、基材（絶縁フィルム）自体の変形が殆どないという効果がある。 In the present invention, the phase-separated structure is formed by sea islands depending on the mixing ratio of two epoxies, the presence or absence of additional epoxy resin, additive or inorganic filler (Inorganic Filler) having different curing start temperatures, and the ratio of each. It may be different from a Sea-Island structure, a bi-continuous structure, an Inverse Sea-Island structure, and the like. Thereby, after pre-curing, an uncured epoxy resin (B) having a high curing start temperature is eluted on the surface through a desmear process, and spherical fine roughness having a size of several hundred nm to about 1 μm is obtained. Then, the adhesion with the copper (Cu) layer formed by plating is improved, and the peel strength is improved. Moreover, since the thermal expansion coefficient is superior to that of an epoxy resin composition containing a rubber component or a thermoplastic resin, there is an effect that the base material (insulating film) itself is hardly deformed.
本発明のエポキシ樹脂組成物は、硬化開始温度が７５〜１１０℃の温度範囲である熱硬化性第１エポキシ樹脂（Ａ）と、硬化開始温度が１１０〜１５０℃の温度範囲である熱硬化性第２エポキシ樹脂（Ｂ）と、硬化剤（Ｃ）と、無機充填剤（Ｄ）とを含む。この際、前記第１エポキシ樹脂（Ａ）の硬化開始温度が、第２エポキシ樹脂（Ｂ）の硬化開始温度より低いことが所望の粗さを得ることができるため好ましい。また、前記エポキシ樹脂組成物は、その他の添加剤をさらに含むことができる。 The epoxy resin composition of the present invention has a thermosetting first epoxy resin (A) having a curing start temperature of 75 to 110 ° C. and a thermosetting having a curing start temperature of 110 to 150 ° C. A 2nd epoxy resin (B), a hardening | curing agent (C), and an inorganic filler (D) are included. At this time, it is preferable that the curing start temperature of the first epoxy resin (A) is lower than the curing start temperature of the second epoxy resin (B) because a desired roughness can be obtained. The epoxy resin composition may further include other additives.
前記第１エポキシ樹脂（Ａ）は、エポキシ当量が１００〜２００当量を有することが好ましく、前記第２エポキシ樹脂（Ｂ）は、エポキシ当量が、２００〜１０００当量であることが好ましく、３００当量以上であることがより好ましく、５００当量以上であることがさらに好ましい。 The first epoxy resin (A) preferably has an epoxy equivalent of 100 to 200 equivalents, and the second epoxy resin (B) preferably has an epoxy equivalent of 200 to 1000 equivalents, more than 300 equivalents. It is more preferable that it is 500 equivalents or more.
前記第１エポキシ樹脂（Ａ）は、低い硬化開始温度を有するエポキシ樹脂であって、これらの硬化開始温度は、７５〜１１０℃であり、好ましくは８０〜１００℃である。具体的に、ナフタレン系エポキシ樹脂、ナフトール−フェノール系エポキシ樹脂、及びオレフィン系エポキシ樹脂から１種以上選択できる。 Said 1st epoxy resin (A) is an epoxy resin which has a low hardening start temperature, Comprising: These hardening start temperatures are 75-110 degreeC, Preferably it is 80-100 degreeC. Specifically, one or more kinds can be selected from a naphthalene epoxy resin, a naphthol-phenol epoxy resin, and an olefin epoxy resin.
前記第２エポキシ樹脂（Ｂ）は、高い硬化開始温度を有するエポキシ樹脂であって、これらの硬化開始温度は、１１０〜１５０℃であり、好ましくは１２０〜１５０℃である。具体的には、クレゾールノボラックエポキシ樹脂、ビスフェノールＡエポキシ樹脂（例えば、ＤＥＧＥＢＡ）、及びゴム変性エポキシ樹脂から１種以上選択できる。 Said 2nd epoxy resin (B) is an epoxy resin which has high hardening start temperature, Comprising: These hardening start temperatures are 110-150 degreeC, Preferably it is 120-150 degreeC. Specifically, one or more types can be selected from a cresol novolac epoxy resin, a bisphenol A epoxy resin (for example, DEGABA), and a rubber-modified epoxy resin.
本発明において、前記第１エポキシ樹脂（Ａ）と第２エポキシ樹脂（Ｂ）は、前記２つの樹脂の硬化開始温度の差が少なくとも１０℃以上であれば、特に限定されずに選択することができるが、高い接着強度を得るために、前記２つの樹脂の硬化開始温度の差が、好ましくは２０℃以上、さらに好ましくは３０℃以上である。一方、前硬化反応の経済性及び反応安定性などを考慮した好適な温度範囲は、８０〜１１０℃である。よって、前記第１エポキシ樹脂（Ａ）の硬化開始温度は、１１０℃以下であることが好ましく、前記第２エポキシ樹脂（Ｂ）の硬化開始温度は、１１０℃以上であることが好ましい。 In the present invention, the first epoxy resin (A) and the second epoxy resin (B) may be selected without particular limitation as long as the difference in the curing start temperature between the two resins is at least 10 ° C. or more. However, in order to obtain high adhesive strength, the difference between the curing start temperatures of the two resins is preferably 20 ° C or higher, more preferably 30 ° C or higher. On the other hand, a suitable temperature range in consideration of the economy and reaction stability of the precuring reaction is 80 to 110 ° C. Therefore, the curing start temperature of the first epoxy resin (A) is preferably 110 ° C. or lower, and the curing start temperature of the second epoxy resin (B) is preferably 110 ° C. or higher.
前記第１エポキシ樹脂（Ａ）と第２エポキシ樹脂（Ｂ）の使用量は、それぞれ５〜１５重量％であることが好ましいが、前記第１エポキシ樹脂（Ａ）の使用量が５重量％未満であれば、粗さは大きくなるが、微細パターンの形成が難しくなり、前記第１エポキシ樹脂（Ａ）の使用量が１５重量％超過であれば、粗さ形成が難しく、金属回路の接着力が低下する傾向がある。よって、前記第２エポキシ樹脂（Ｂ）は、第１エポキシ樹脂（Ａ）の添加効果とは反対の現象が現れる。しかも、全体的なエポキシ樹脂の使用量が増えると、相対的に無機充填剤の使用量が減少して、熱膨張係数が高くなる傾向がある。 The usage amount of the first epoxy resin (A) and the second epoxy resin (B) is preferably 5 to 15% by weight, respectively, but the usage amount of the first epoxy resin (A) is less than 5% by weight. If the amount of the first epoxy resin (A) is more than 15% by weight, the formation of the roughness is difficult and the adhesion of the metal circuit is increased. Tends to decrease. Therefore, the second epoxy resin (B) exhibits a phenomenon opposite to the effect of adding the first epoxy resin (A). In addition, as the overall amount of epoxy resin used increases, the amount of inorganic filler used decreases relatively and the thermal expansion coefficient tends to increase.
一方、本発明に使用される硬化剤は、通常、エポキシ樹脂を熱硬化するために使用することが可能なものであればいずれも使用可能であり、特に限定されない。具体的には、ジエチレントリアミン、トリエチレンテトラアミン、Ｎ−アミノエチルピペラジン、ジアミノジフェニルメタン、アジピン酸ジヒドラジドなどのポリアミン系硬化剤；ピロメタル酸無水物、ベンゾフェノンテトラカルボン酸無水物、エチレングリコールビストリメタル酸無水物、グリセロールトリストリメタル酸無水物、マレイン酸メチルシクロヘキセンテトラカルボン酸無水物などの酸無水物硬化剤；フェノールノボラック型硬化剤；トリオキサントリメチレンメルカプタンなどのポリメルカプタン硬化剤；ベンジルジメチルアミン、２，４，６−トリス（ジメチルアミノメチル）フェノールなどの第３アミン化合物；２−エチル−４−メチルイミダゾール、２−メチルイミダゾール、１−ベンジル−２−メチルイミダゾール、２−ヘプタデシルイミダゾール、２−ウンデシルイミダゾール、２−フェニル−４−メチル−５−ヒドロキシメチルイミダゾール、２−フェニルイミダゾール、２−フェニル−４−メチルイミダゾール、１−ベンジル−２−フェニルイミダゾール、１，２−ジメチルイミダゾール、１−シアノエチル−２−フェニルイミダゾール、２−フェニル−４，５−ジヒドロキシメチルイミダゾールなどのイミダゾール化合物を挙げることができ、粉末状の包接化合物を形成し易いとの観点から、２−エチル−４−メチルイミダゾール、２−メチルイミダゾールが好ましく、１液安定性の観点からは２−エチル−４−メチルイミダゾールであることが特に好ましい。 On the other hand, the curing agent used in the present invention is not particularly limited, and any curing agent that can be used for thermosetting an epoxy resin can be used. Specifically, polyamine curing agents such as diethylenetriamine, triethylenetetraamine, N-aminoethylpiperazine, diaminodiphenylmethane, adipic acid dihydrazide; pyrometal acid anhydride, benzophenone tetracarboxylic acid anhydride, ethylene glycol bistrimetal acid anhydride , Acid anhydride curing agents such as glycerol tristrimetal acid anhydride and methylcyclohexene maleate tetracarboxylic acid anhydride; phenol novolac type curing agents; polymercaptan curing agents such as trioxane trimethylene mercaptan; benzyldimethylamine, 2, 4 Tertiary amine compounds such as 1,6-tris (dimethylaminomethyl) phenol; 2-ethyl-4-methylimidazole, 2-methylimidazole, 1-benzyl-2-methylimidazole 2-heptadecylimidazole, 2-undecylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1 , 2-dimethylimidazole, 1-cyanoethyl-2-phenylimidazole, imidazole compounds such as 2-phenyl-4,5-dihydroxymethylimidazole, etc., from the viewpoint of easy formation of a powdery inclusion compound 2-ethyl-4-methylimidazole and 2-methylimidazole are preferable, and 2-ethyl-4-methylimidazole is particularly preferable from the viewpoint of stability of one liquid.
前記硬化剤Ｃの使用量は、１０〜２０重量％が好ましく、１０重量％未満であれば、硬化速度が低下し、２０重量％超過であれば、未反応硬化剤が存在して絶縁フィルムの吸湿率が高くなって、電気的特性が低下する傾向がある。 The amount of the curing agent C used is preferably 10 to 20% by weight, and if it is less than 10% by weight, the curing rate decreases, and if it exceeds 20% by weight, an unreacted curing agent is present and the insulating film There is a tendency for the moisture absorption rate to increase and the electrical characteristics to decrease.
本発明に係るエポキシ樹脂組成物は、エポキシ樹脂の熱膨張係数（ＣＴＥ）を低めるために、無機充填剤を含む。前記無機充填剤Ｄは、熱膨張係数を低めるもので、樹脂組成物に対する含有比率は、樹脂組成物の用途などを考慮して要求される特性によって異なるが、樹脂組成物中の５０〜８０重量％であることが好ましい。５０重量％未満であれば、熱膨張率が高くなり、８０重量％超過であれば、接着強度が低下する傾向がある。さらに好ましくは、無機充填剤の含量が全体樹脂組成物の固形分に対して６０重量％以上である。 The epoxy resin composition according to the present invention contains an inorganic filler in order to reduce the coefficient of thermal expansion (CTE) of the epoxy resin. The inorganic filler D lowers the thermal expansion coefficient, and the content ratio with respect to the resin composition varies depending on the properties required in consideration of the use of the resin composition, but is 50 to 80 weight in the resin composition. % Is preferred. If it is less than 50% by weight, the coefficient of thermal expansion increases, and if it exceeds 80% by weight, the adhesive strength tends to decrease. More preferably, the content of the inorganic filler is 60% by weight or more based on the solid content of the entire resin composition.
本発明に使用される無機充填剤の具体的な例としては、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を単独で又は２種以上混合して使用する。特に、シリカが好ましい。 Specific examples of the inorganic filler used in the present invention include silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride. Aluminum borate, barium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate and the like are used alone or in combination. In particular, silica is preferable.
しかも、無機充填剤は、平均粒径が５μｍ超過であれば、導体層に回路パターンを形成するときに微細パターンを安定的に形成することが困難であるから、平均直径５μｍ以下のものが好ましい。また、無機充填剤は、耐湿性を向上させるために、シランカップリング剤などの表面処理剤で表面処理されていることが好ましい。 In addition, if the average particle diameter exceeds 5 μm, it is difficult to stably form a fine pattern when forming a circuit pattern on the conductor layer, so that the inorganic filler preferably has an average diameter of 5 μm or less. . The inorganic filler is preferably surface-treated with a surface treatment agent such as a silane coupling agent in order to improve moisture resistance.
一方、本発明に係るエポキシ樹脂組成物は、上記の必須成分以外にも、通常用いられるその他の添加剤をさらに含有することができる。その他の添加剤の例としては、増粘剤（例えば、石綿、オルベン又はベントン）、シリコン系、フッ素系または高分子系消泡剤及び／または均染剤及び接着増進剤（例えば、イミダゾール、チアゾール、トリアゾール又はシランカップリング剤）がある。必要に応じて、フタロシアニンブルー、フタロシアニングリーン、ヨードグリーン、ジスアゾイエロー、酸化チタン又はカーボンブラックなどの公知かつ常用の着色剤も使用することができる。 On the other hand, the epoxy resin composition according to the present invention can further contain other commonly used additives in addition to the above essential components. Examples of other additives include thickeners (eg asbestos, olben or benton), silicon-based, fluorine-based or polymeric antifoams and / or leveling agents and adhesion promoters (eg imidazole, thiazole) , Triazole or silane coupling agents). If necessary, known and commonly used colorants such as phthalocyanine blue, phthalocyanine green, iodogreen, disazo yellow, titanium oxide, or carbon black can also be used.
本発明に係るエポキシ樹脂組成物は、有機溶媒存在の下で混合される。有機溶媒としては、本発明に使用される樹脂及びその他の添加剤の溶解性及び混和性を考慮し、２−メトキシエタノール、アセトン、メチルエチルケトン、シクロヘキサノン、エチルアセテート、ブチルアセテート、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、エチレングリコールモノブチルエーテルアセテート、セロソルブ、ブチルセロソルブ、カルビトール、ブチルカルビトール、キシレン、ジメチルホルムアミド及びジメチルアセトアミドが使用できるが、特にこれに限定されない。 The epoxy resin composition according to the present invention is mixed in the presence of an organic solvent. As the organic solvent, in consideration of the solubility and miscibility of the resin and other additives used in the present invention, 2-methoxyethanol, acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl Ether acetate, ethylene glycol monobutyl ether acetate, cellosolve, butyl cellosolve, carbitol, butyl carbitol, xylene, dimethylformamide and dimethylacetamide can be used, but are not particularly limited thereto.
本発明のエポキシ樹脂組成物は、当該技術分野における公知のある一般な方法で半固状のドライフィルムに製造できる。例えば、ロールコーター（ｒｏｌｌ ｃｏａｔｅｒ）又はカーテンコーター（ｃｕｒｔａｉｎ ｃｏａｔｅｒ）などを用いてフィルム状に製造して乾燥させた後、これを基板上に適用して、ビルドアップ方式による多層プリント基板製造の際に、絶縁層（又は絶縁フィルム）として使用する。 The epoxy resin composition of the present invention can be produced into a semisolid dry film by a general method known in the art. For example, after manufacturing in a film form using a roll coater or curtain coater and drying it, it is applied to the substrate, and a multilayer printed circuit board is manufactured by a build-up method. Used as an insulating layer (or insulating film).
このように、本発明のエポキシ樹脂組成物から製造された絶縁フィルムを、多層プリント基板製造の際に内層として使用されるＣＣＬ（ｃｏｐｐｅｒ ｃｌａｄ ｌａｍｉｎａｔｅ）上にラミネートして、プリント基板の製造に使用する。例えば、前記エポキシ樹脂組成物から製造された絶縁フィルムを、パターン加工させた内層回路基板上にラミネートした後、８０〜１１０℃の温度で２０〜３０分間硬化させ、デスミア工程を行った後、回路層を電気メッキ工程によって形成して多層プリント基板を製造することができる。 As described above, the insulating film produced from the epoxy resin composition of the present invention is laminated on a CCL (copper clad laminate) used as an inner layer in the production of a multilayer printed circuit board and used for the production of a printed circuit board. . For example, after laminating an insulating film manufactured from the epoxy resin composition on a patterned inner layer circuit board, it is cured at a temperature of 80 to 110 ° C. for 20 to 30 minutes, and a desmear process is performed. The layers can be formed by an electroplating process to produce a multilayer printed circuit board.
以下、実施例及び比較例によって本発明をより具体的に説明する。本発明の範疇はこれらの実施例に限定されない。 Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. The scope of the present invention is not limited to these examples.
（実施例１）
ナフタレンエポキシ樹脂（ＳＥ−８０）５０ｇ、クレゾールノボラックエポキシ樹脂（ＫＵＫＤＯ化学、ＹＤＣＮ−００−０１Ｐ）５０ｇ、２−メトキシエタノールを溶媒として、６６．７重量％の濃度を有するアミノトリアジン系ノボラック硬化剤（ＧＵＮ ＥＩ ＣＨＥＭＩＣＡＬ ＩＮＤＵＳＴＲＹ Ｃｏ．，ＬＴＤ、ＰＳ−６３１３）３８．２０ｇ、２−メトキシエタノールを溶媒として、６６．７重量％の濃度を有するビスフェノールＡノボラック硬化剤（ＫＢＮ−１３６）５１．６２ｇを添加した後、この混合物を９０℃で１時間、３００ｒｐｍにて攪拌した。次いで、０．１〜１．２μｍのサイズ分布を有する球状のシリカを２９６．９７ｇ添加した後、４００ｒｐｍで３時間攪拌した。温度を常温に低めた後、２−エチル−４−メチルイミダゾール１．２５ｇを添加し、約３０分間攪拌して絶縁材料組成物を製造した。
Example 1
50 g of naphthalene epoxy resin (SE-80), 50 g of cresol novolac epoxy resin (KUKDO Chemical, YDCN-00-01P), aminotriazine novolak curing agent having a concentration of 66.7% by weight using 2-methoxyethanol as a solvent ( GUN EI CHEMICAL INDUSTRY Co., LTD, PS-6313) 38.20 g, 2-methoxyethanol as a solvent, and 51.62 g of bisphenol A novolac curing agent (KBN-136) having a concentration of 66.7 wt% were added. The mixture was then stirred at 90 ° C. for 1 hour at 300 rpm. Next, 296.97 g of spherical silica having a size distribution of 0.1 to 1.2 μm was added, and then stirred at 400 rpm for 3 hours. After the temperature was lowered to room temperature, 1.25 g of 2-ethyl-4-methylimidazole was added and stirred for about 30 minutes to produce an insulating material composition.
前記絶縁材料組成物を、ＰＥＴフィルムにフィルムキャスティング（ｆｉｌｍ ｃａｓｔｉｎｇ）して４０５ｍｍ×５１０ｍｍのサイズに切り、１００℃でラミネートを行った。ラミネートの後、１１０℃で３０分間硬化させ、通常の方法でデスミアして粗さを与えた。その結果を、電子顕微鏡（ＳＥＭ）で撮影して図１に示した。その後、電気メッキ工程によって厚さ約２５μｍの回路層を形成した。 The insulating material composition was film casted on a PET film, cut into a size of 405 mm × 510 mm, and laminated at 100 ° C. After laminating, it was cured at 110 ° C. for 30 minutes and desmeared by a usual method to give roughness. The results were taken with an electron microscope (SEM) and shown in FIG. Thereafter, a circuit layer having a thickness of about 25 μm was formed by an electroplating process.
（実施例２）
ナフタレンエポキシ樹脂（ＳＥ−８０）４０ｇ、クレゾールノボラックエポキシ樹脂（ＫＵＫＤＯ化学、ＹＤＣＮ−５００−０１Ｐ）４０ｇ、ゴム変性エポキシ樹脂（ＳＴＲＵＫＴＯＬ、Ｐｏｌｙｄｉｓ３６１６）２０ｇ、２−メトキシエタノールを溶媒として、６６．７重量％の濃度を有するアミノトリアジン系ノボラック硬化剤（ＧＵＮ ＥＩ ＣＨＥＭＩＣＡＬ ＩＮＤＵＳＴＲＹ Ｃｏ．，ＬＴＤ、ＰＳ−６３１３）７１．６０ｇを添加した後、この混合物を約９０℃で約１時間、３００ｒｐｍにて攪拌した。次いで、０．１〜１．２μｍのサイズ分布を有する球状のシリカを２９６．９７ｇ添加した後、４００ｒｐｍで３時間攪拌した。温度を常温に低めた後、２−エチル−４−メチルイミダゾール１．２５ｇを添加し、３０分間攪拌して絶縁材料組成物を製造した。
(Example 2)
40 g of naphthalene epoxy resin (SE-80), 40 g of cresol novolac epoxy resin (KUKDO Chemical, YDCN-500-01P), 20 g of rubber-modified epoxy resin (STRUKTOL, Polydis 3616), 66.7% by weight using 2-methoxyethanol as a solvent. After adding 71.60 g of aminotriazine novolak curing agent (GUN EI CHEMICAL INDUSTRY Co., LTD, PS-6313) having a concentration of: The mixture was stirred at about 90 ° C. for about 1 hour at 300 rpm. Next, 296.97 g of spherical silica having a size distribution of 0.1 to 1.2 μm was added, and then stirred at 400 rpm for 3 hours. After lowering the temperature to room temperature, 1.25 g of 2-ethyl-4-methylimidazole was added and stirred for 30 minutes to produce an insulating material composition.
前記絶縁材料組成物を、ＰＥＴフィルムにフィルムキャスティングして４０５ｍｍ×５１０ｍｍのサイズに切り、約１００℃でラミネートを行った。ラミネートの後、約１１０℃で３０分間硬化させ、デスミアして粗さを与えた。その結果を、電子顕微鏡（ＳＥＭ）で撮影して図２に示した。その後、電気メッキ工程によって厚さ約２５μｍの回路層を形成した。 The insulating material composition was film-cast on a PET film, cut into a size of 405 mm × 510 mm, and laminated at about 100 ° C. After lamination, it was cured at about 110 ° C. for 30 minutes and desmeared to give roughness. The results were taken with an electron microscope (SEM) and shown in FIG. Thereafter, a circuit layer having a thickness of about 25 μm was formed by an electroplating process.
（比較例）
ナフタレンエポキシ樹脂（ＳＥ−８０）４０ｇ、クレゾールノボラック樹脂（ＫＵＫＤＯ化学、ＹＤＣＮ−５００−０１Ｐ）４０ｇ、ゴム変性エポキシ樹脂（ＳＴＲＵＫＴＯＬ、Ｐｏｌｙｄｉｓ ３６１６）２０ｇ、２−メトキシエタノールを溶媒として、６６．７重量％の濃度を有するアミノトリアジン系ノボラック硬化剤（ＧＵＮ ＥＩ ＣＨＥＭＩＣＡＬ ＩＮＤＵＳＴＲＹ Ｃｏ．，ＬＴＤ、ＰＳ−６３１３）７１．６０ｇ、熱可塑性樹脂（フェノキシ）３６．９４ｇを添加した後、この混合物を約９０℃で約１時間、３００ｒｐｍにて攪拌した。次いで、０．１〜１．２μｍのサイズ分布を有する球状のシリカを２９６．９７ｇ添加した後、４００ｒｐｍで３時間攪拌した。温度を常温に低めた後、２−エチル−４−メチルイミダゾール１．２５ｇを添加し、３０分間攪拌して絶縁材料組成物を製造した。
(Comparative example)
40 g of naphthalene epoxy resin (SE-80), 40 g of cresol novolak resin (KUKDO Chemical, YDCN-500-01P), 20 g of rubber-modified epoxy resin (STRUKTOL, Polydis 3616), 66.7% by weight using 2-methoxyethanol as a solvent. After adding 71.60 g of aminotriazine novolak curing agent (GUN EI CHEMICAL INDUSTRY Co., LTD, PS-6313) and 36.94 g of thermoplastic resin (phenoxy) having a concentration of Stir at 300 rpm for 1 hour. Next, 296.97 g of spherical silica having a size distribution of 0.1 to 1.2 μm was added, and then stirred at 400 rpm for 3 hours. After lowering the temperature to room temperature, 1.25 g of 2-ethyl-4-methylimidazole was added and stirred for 30 minutes to produce an insulating material composition.
前記絶縁材料組成物を、ＰＥＴフィルムにフィルムキャスティングして４０５ｍｍ×５１０ｍｍのサイズに切り、約１００℃でラミネートを行った。ラミネートの後、約１１０℃で３０分間硬化させた後、デスミアして粗さを与えた。その結果を、電子顕微鏡（ＳＥＭ）で撮影して図３に示した。その後、電気メッキ工程によって厚さ約２５μｍの回路層を形成した。 The insulating material composition was film-cast on a PET film, cut into a size of 405 mm × 510 mm, and laminated at about 100 ° C. After lamination, the film was cured at about 110 ° C. for 30 minutes and then desmeared to give roughness. The results were taken with an electron microscope (SEM) and shown in FIG. Thereafter, a circuit layer having a thickness of about 25 μm was formed by an electroplating process.
熱膨張率（ＣＴＥ）の測定及び評価は、樹脂組成物フィルムを１９０℃で２時間熱硬化させて支持体を剥離することにより、シート状の硬化物を収得し、硬化物を幅約４ｍｍ、長さ約２４ｍｍの試験片に切断し、熱機械分析装置（ＴＭＡ、Ｔｈｅｒｍｏ Ｍｅｃｈａｎｉｃａｌ Ａｎａｌｙｓｉｓ）を用いて、引張加重法で熱機械分析を行った。試験片を前記装置に取り付けた後、昇温速度５℃／分の測定条件で連続して２回測定した。２回目の測定における熱膨張係数（α１、Ｔｇ以下）から、５０℃〜１００℃の平均線熱膨張率（ｐｐｍ）を算出した。 The coefficient of thermal expansion (CTE) was measured and evaluated by thermally curing the resin composition film at 190 ° C. for 2 hours and peeling off the support to obtain a sheet-like cured product. The cured product had a width of about 4 mm, A test piece having a length of about 24 mm was cut, and thermomechanical analysis was performed by a tensile load method using a thermomechanical analyzer (TMA, Thermo Mechanical Analysis). After the test piece was attached to the apparatus, it was measured twice continuously under the measurement condition of a temperature rising rate of 5 ° C./min. From the coefficient of thermal expansion (α1, Tg or less) in the second measurement, an average linear thermal expansion coefficient (ppm) of 50 ° C. to 100 ° C. was calculated.
前記粗さ（Ｒａ）の測定及び評価は、非接触微細表面分析器（Ｓｕｒｆａｃｅ Ｐｒｏｆｉｌｅｒ）（ＮＶＭ−５１６１Ｐ：Ｎａｎｏ Ｖｉｅｗ Ｍａｃｈｉｎｅ）を用いて、コア基板にフィルムがラミネートされた状態で表面粗さを測定し、これを算術平均して粗さ（Ｒａ）を測定した。 The roughness (Ra) is measured and evaluated by using a non-contact surface profiler (NVM-5161P: Nano View Machine) to measure the surface roughness with the film laminated on the core substrate. This was arithmetically averaged to measure roughness (Ra).
以上、本発明を具体的な実施例に基づいて詳細に説明したが、これは本発明を具体的に説明するためのものであり、本発明はこれに限定されず、当該分野における通常の知識を有する者であれば、本発明の技術的思想内にての変形や改良が可能であることは明白であろう。 The present invention has been described in detail on the basis of specific embodiments. However, the present invention is intended to specifically describe the present invention, and the present invention is not limited thereto. It will be apparent to those skilled in the art that modifications and improvements within the technical idea of the present invention are possible.
本発明の単純な変形乃至変更はいずれも本発明の領域に属するものであり、本発明の具体的な保護範囲は添付の特許請求の範囲により明確になるであろう。 All simple variations and modifications of the present invention belong to the scope of the present invention, and the specific scope of protection of the present invention will be apparent from the appended claims.
本発明は、エポキシ樹脂組成物、これから製造された絶縁フィルム、及びこれを備えた多層プリント基板に適用可能である。 The present invention can be applied to an epoxy resin composition, an insulating film produced therefrom, and a multilayer printed board including the same.
Claims (12)
硬化開始温度が１１０〜１５０℃の温度範囲である熱硬化性第２エポキシ樹脂（Ｂ）と、
硬化剤（Ｃ）と、
無機充填剤（Ｄ）とを含んでなり、
前記第１エポキシ樹脂（Ａ）の硬化開始温度が第２エポキシ樹脂の硬化開始温度より低いことを特徴とするエポキシ樹脂組成物。 A thermosetting first epoxy resin (A) having a curing start temperature of 75 to 110 ° C., and
A thermosetting second epoxy resin (B) having a curing start temperature in the temperature range of 110 to 150 ° C .;
A curing agent (C);
An inorganic filler (D),
An epoxy resin composition, wherein the curing start temperature of the first epoxy resin (A) is lower than the curing start temperature of the second epoxy resin.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005336426A (en) * | 2004-05-31 | 2005-12-08 | Asahi Denka Kogyo Kk | Epoxy resin composition |
| JP2007204670A (en) * | 2006-02-03 | 2007-08-16 | Asahi Kasei Chemicals Corp | Curing agent for highly water-containing solvent-containing epoxy resin and epoxy resin composition |
| JP2010085769A (en) * | 2008-09-30 | 2010-04-15 | Dainippon Printing Co Ltd | Red curable resin composition, color filter, and display device |
| JP2012102315A (en) * | 2010-11-05 | 2012-05-31 | Samsung Electro-Mechanics Co Ltd | Flame retardant resin composition for multilayer wiring board, and multilayer wiring board comprising the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005336426A (en) * | 2004-05-31 | 2005-12-08 | Asahi Denka Kogyo Kk | Epoxy resin composition |
| JP2007204670A (en) * | 2006-02-03 | 2007-08-16 | Asahi Kasei Chemicals Corp | Curing agent for highly water-containing solvent-containing epoxy resin and epoxy resin composition |
| JP2010085769A (en) * | 2008-09-30 | 2010-04-15 | Dainippon Printing Co Ltd | Red curable resin composition, color filter, and display device |
| JP2012102315A (en) * | 2010-11-05 | 2012-05-31 | Samsung Electro-Mechanics Co Ltd | Flame retardant resin composition for multilayer wiring board, and multilayer wiring board comprising the same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2023033292A (en) * | 2019-07-30 | 2023-03-10 | 味の素株式会社 | resin composition |
| JP7521573B2 (en) | 2019-07-30 | 2024-07-24 | 味の素株式会社 | Resin composition |
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