JP6377094B2 - Thermosetting resin composition - Google Patents
Thermosetting resin composition Download PDFInfo
- Publication number
- JP6377094B2 JP6377094B2 JP2016070702A JP2016070702A JP6377094B2 JP 6377094 B2 JP6377094 B2 JP 6377094B2 JP 2016070702 A JP2016070702 A JP 2016070702A JP 2016070702 A JP2016070702 A JP 2016070702A JP 6377094 B2 JP6377094 B2 JP 6377094B2
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- resin
- thermosetting resin
- mass
- epoxy resin
- 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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- 229920001187 thermosetting polymer Polymers 0.000 title claims description 58
- 239000011342 resin composition Substances 0.000 title claims description 57
- 229920005989 resin Polymers 0.000 claims description 67
- 239000011347 resin Substances 0.000 claims description 67
- 239000003822 epoxy resin Substances 0.000 claims description 57
- 229920000647 polyepoxide Polymers 0.000 claims description 57
- -1 aromatic diamine compound Chemical class 0.000 claims description 54
- 239000007787 solid Substances 0.000 claims description 37
- 239000004962 Polyamide-imide Substances 0.000 claims description 29
- 229920002312 polyamide-imide Polymers 0.000 claims description 29
- 239000013034 phenoxy resin Substances 0.000 claims description 25
- 229920006287 phenoxy resin Polymers 0.000 claims description 25
- 239000000758 substrate Substances 0.000 claims description 25
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 claims description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 17
- 239000000853 adhesive Substances 0.000 claims description 16
- 230000001070 adhesive effect Effects 0.000 claims description 15
- 230000017525 heat dissipation Effects 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 12
- 239000000945 filler Substances 0.000 claims description 11
- 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 claims description 9
- 239000003063 flame retardant Substances 0.000 claims description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 9
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical group OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 150000003627 tricarboxylic acid derivatives Chemical class 0.000 claims description 5
- 229910052582 BN Inorganic materials 0.000 claims description 4
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 4
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 4
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 239000002966 varnish Substances 0.000 description 24
- 239000000047 product Substances 0.000 description 16
- 238000000576 coating method Methods 0.000 description 15
- 238000005530 etching Methods 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 14
- 239000011889 copper foil Substances 0.000 description 12
- 238000002844 melting Methods 0.000 description 11
- 230000008018 melting Effects 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000011888 foil Substances 0.000 description 9
- 239000004593 Epoxy Substances 0.000 description 8
- 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 8
- 229920001721 polyimide Polymers 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 238000001723 curing Methods 0.000 description 6
- 238000009413 insulation Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229920003986 novolac Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 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 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 239000010959 steel Substances 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
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- XSAOTYCWGCRGCP-UHFFFAOYSA-K aluminum;diethylphosphinate Chemical compound [Al+3].CCP([O-])(=O)CC.CCP([O-])(=O)CC.CCP([O-])(=O)CC XSAOTYCWGCRGCP-UHFFFAOYSA-K 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
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- FHBXQJDYHHJCIF-UHFFFAOYSA-N (2,3-diaminophenyl)-phenylmethanone Chemical compound NC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1N FHBXQJDYHHJCIF-UHFFFAOYSA-N 0.000 description 1
- SGXRTWRRYSEZLP-UHFFFAOYSA-N (2-hydroxyphenyl) diphenyl phosphate Chemical compound OC1=CC=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 SGXRTWRRYSEZLP-UHFFFAOYSA-N 0.000 description 1
- DAZHWGHCARQALS-UHFFFAOYSA-N (2-methylphenyl) (4-methylphenyl) phenyl phosphate Chemical compound C1=CC(C)=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1 DAZHWGHCARQALS-UHFFFAOYSA-N 0.000 description 1
- LPVHVQFTYXQKAP-YFKPBYRVSA-N (4r)-3-formyl-2,2-dimethyl-1,3-thiazolidine-4-carboxylic acid Chemical compound CC1(C)SC[C@@H](C(O)=O)N1C=O LPVHVQFTYXQKAP-YFKPBYRVSA-N 0.000 description 1
- 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
- LUYHWJKHJNFYGV-UHFFFAOYSA-N 1,2-diisocyanato-3-phenylbenzene Chemical compound O=C=NC1=CC=CC(C=2C=CC=CC=2)=C1N=C=O LUYHWJKHJNFYGV-UHFFFAOYSA-N 0.000 description 1
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-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
- RUFZNDNBXKOZQV-UHFFFAOYSA-N 2,3-dihydro-1h-pyrrolo[1,2-a]benzimidazole Chemical compound C1=CC=C2N(CCC3)C3=NC2=C1 RUFZNDNBXKOZQV-UHFFFAOYSA-N 0.000 description 1
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 description 1
- DUCHOMQDJBOBMI-UHFFFAOYSA-N 2-[4-[4-(2-aminophenoxy)phenyl]phenoxy]aniline Chemical group NC1=CC=CC=C1OC1=CC=C(C=2C=CC(OC=3C(=CC=CC=3)N)=CC=2)C=C1 DUCHOMQDJBOBMI-UHFFFAOYSA-N 0.000 description 1
- QFZKVFCEJRXRBD-UHFFFAOYSA-N 2-ethyl-4-[(2-ethyl-5-methyl-1h-imidazol-4-yl)methyl]-5-methyl-1h-imidazole Chemical compound N1C(CC)=NC(CC2=C(NC(CC)=N2)C)=C1C QFZKVFCEJRXRBD-UHFFFAOYSA-N 0.000 description 1
- LIAWCKFOFPPVGF-UHFFFAOYSA-N 2-ethyladamantane Chemical compound C1C(C2)CC3CC1C(CC)C2C3 LIAWCKFOFPPVGF-UHFFFAOYSA-N 0.000 description 1
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-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
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- RJIQELZAIWFNTQ-UHFFFAOYSA-N 2-phenyl-1h-imidazole;1,3,5-triazinane-2,4,6-trione Chemical compound O=C1NC(=O)NC(=O)N1.C1=CNC(C=2C=CC=CC=2)=N1 RJIQELZAIWFNTQ-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
- UIDDPPKZYZTEGS-UHFFFAOYSA-N 3-(2-ethyl-4-methylimidazol-1-yl)propanenitrile Chemical compound CCC1=NC(C)=CN1CCC#N UIDDPPKZYZTEGS-UHFFFAOYSA-N 0.000 description 1
- YGOFNNAZFZYNIX-UHFFFAOYSA-N 3-N-phenylbenzene-1,2,3-triamine Chemical compound NC=1C(=C(C=CC1)NC1=CC=CC=C1)N YGOFNNAZFZYNIX-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
- LJPCNSSTRWGCMZ-UHFFFAOYSA-N 3-methyloxolane Chemical compound CC1CCOC1 LJPCNSSTRWGCMZ-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- 229940086681 4-aminobenzoate Drugs 0.000 description 1
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-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
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- YIOOQBRBZWOGDH-UHFFFAOYSA-N C1(=CC=CC=C1)P(C1=CC=CC=C1)=O.C(C1CO1)OCC=C Chemical compound C1(=CC=CC=C1)P(C1=CC=CC=C1)=O.C(C1CO1)OCC=C YIOOQBRBZWOGDH-UHFFFAOYSA-N 0.000 description 1
- WUKNPIYSKBLCQI-UHFFFAOYSA-N CC(C=C1)=CC=C1C1=CC=C(C)C=C1.N=C=O.N=C=O Chemical compound CC(C=C1)=CC=C1C1=CC=C(C)C=C1.N=C=O.N=C=O WUKNPIYSKBLCQI-UHFFFAOYSA-N 0.000 description 1
- ANALBGQGSOHBHD-UHFFFAOYSA-K CC(CP([O-])=O)(C)C.[Al+3].CC(CP([O-])=O)(C)C.CC(CP([O-])=O)(C)C Chemical compound CC(CP([O-])=O)(C)C.[Al+3].CC(CP([O-])=O)(C)C.CC(CP([O-])=O)(C)C ANALBGQGSOHBHD-UHFFFAOYSA-K 0.000 description 1
- HQCBBXGPVVYLPW-UHFFFAOYSA-N CCC(C=C1)=CC=C1C1=CC=C(CC)C=C1.N=C=O.N=C=O Chemical compound CCC(C=C1)=CC=C1C1=CC=C(CC)C=C1.N=C=O.N=C=O HQCBBXGPVVYLPW-UHFFFAOYSA-N 0.000 description 1
- GASHPBNAWAEWCX-UHFFFAOYSA-N COC(C=C1)=CC=C1C(C=C1)=CC=C1OC.N=C=O.N=C=O Chemical compound COC(C=C1)=CC=C1C(C=C1)=CC=C1OC.N=C=O.N=C=O GASHPBNAWAEWCX-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- UUGLJVMIFJNVFH-UHFFFAOYSA-N Hexyl benzoate Chemical compound CCCCCCOC(=O)C1=CC=CC=C1 UUGLJVMIFJNVFH-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- CDROCTSEAIEUOM-UHFFFAOYSA-N [2-phenyl-3,4-di(propan-2-yl)phenyl] dihydrogen phosphate Chemical compound CC(C)C1=C(C(=C(C=C1)OP(=O)(O)O)C2=CC=CC=C2)C(C)C CDROCTSEAIEUOM-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
- HZSAGZAJGQNWSD-UHFFFAOYSA-J [Ti+4].[O-]P(=O)(c1ccccc1)c1ccccc1.[O-]P(=O)(c1ccccc1)c1ccccc1.[O-]P(=O)(c1ccccc1)c1ccccc1.[O-]P(=O)(c1ccccc1)c1ccccc1 Chemical compound [Ti+4].[O-]P(=O)(c1ccccc1)c1ccccc1.[O-]P(=O)(c1ccccc1)c1ccccc1.[O-]P(=O)(c1ccccc1)c1ccccc1.[O-]P(=O)(c1ccccc1)c1ccccc1 HZSAGZAJGQNWSD-UHFFFAOYSA-J 0.000 description 1
- BBUVVWFDWAGLPU-UHFFFAOYSA-L [Zn++].CC(C)(C)P([O-])=O.CC(C)(C)P([O-])=O Chemical compound [Zn++].CC(C)(C)P([O-])=O.CC(C)(C)P([O-])=O BBUVVWFDWAGLPU-UHFFFAOYSA-L 0.000 description 1
- CQCGPNRIAFVNBY-UHFFFAOYSA-N [ethenyl(phenyl)phosphoryl]benzene Chemical compound C=1C=CC=CC=1P(=O)(C=C)C1=CC=CC=C1 CQCGPNRIAFVNBY-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- QNNHFEIZWVGBTM-UHFFFAOYSA-K aluminum;diphenylphosphinate Chemical compound [Al+3].C=1C=CC=CC=1P(=O)([O-])C1=CC=CC=C1.C=1C=CC=CC=1P(=O)([O-])C1=CC=CC=C1.C=1C=CC=CC=1P(=O)([O-])C1=CC=CC=C1 QNNHFEIZWVGBTM-UHFFFAOYSA-K 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- HGZJAPYAZZMDTJ-UHFFFAOYSA-N bis(2-hydroxyethyl) 2-methylbutanedioate Chemical compound OCCOC(=O)C(C)CC(=O)OCCO HGZJAPYAZZMDTJ-UHFFFAOYSA-N 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229930003836 cresol Natural products 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
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical class CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- YAFOVCNAQTZDQB-UHFFFAOYSA-N octyl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OCCCCCCCC)OC1=CC=CC=C1 YAFOVCNAQTZDQB-UHFFFAOYSA-N 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 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
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 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 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- JEJAMASKDTUEBZ-UHFFFAOYSA-N tris(1,1,3-tribromo-2,2-dimethylpropyl) phosphate Chemical class BrCC(C)(C)C(Br)(Br)OP(=O)(OC(Br)(Br)C(C)(C)CBr)OC(Br)(Br)C(C)(C)CBr JEJAMASKDTUEBZ-UHFFFAOYSA-N 0.000 description 1
- VRRIVXLVXXAHJA-UHFFFAOYSA-N tris(2,3,4-tribromophenyl) phosphate Chemical compound BrC1=C(Br)C(Br)=CC=C1OP(=O)(OC=1C(=C(Br)C(Br)=CC=1)Br)OC1=CC=C(Br)C(Br)=C1Br VRRIVXLVXXAHJA-UHFFFAOYSA-N 0.000 description 1
- MHEGXVLDEDJADA-UHFFFAOYSA-N tris(2,3,4-trimethylphenyl) phosphate Chemical compound CC1=C(C)C(C)=CC=C1OP(=O)(OC=1C(=C(C)C(C)=CC=1)C)OC1=CC=C(C)C(C)=C1C MHEGXVLDEDJADA-UHFFFAOYSA-N 0.000 description 1
- LRSNDFOWYYKLHB-UHFFFAOYSA-N tris(2,3-dibromophenyl) phosphate Chemical compound BrC1=CC=CC(OP(=O)(OC=2C(=C(Br)C=CC=2)Br)OC=2C(=C(Br)C=CC=2)Br)=C1Br LRSNDFOWYYKLHB-UHFFFAOYSA-N 0.000 description 1
- JZZBTMVTLBHJHL-UHFFFAOYSA-N tris(2,3-dichloropropyl) phosphate Chemical compound ClCC(Cl)COP(=O)(OCC(Cl)CCl)OCC(Cl)CCl JZZBTMVTLBHJHL-UHFFFAOYSA-N 0.000 description 1
- KOWVWXQNQNCRRS-UHFFFAOYSA-N tris(2,4-dimethylphenyl) phosphate Chemical compound CC1=CC(C)=CC=C1OP(=O)(OC=1C(=CC(C)=CC=1)C)OC1=CC=C(C)C=C1C KOWVWXQNQNCRRS-UHFFFAOYSA-N 0.000 description 1
- WTLBZVNBAKMVDP-UHFFFAOYSA-N tris(2-butoxyethyl) phosphate Chemical compound CCCCOCCOP(=O)(OCCOCCCC)OCCOCCCC WTLBZVNBAKMVDP-UHFFFAOYSA-N 0.000 description 1
- HQUQLFOMPYWACS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCCl HQUQLFOMPYWACS-UHFFFAOYSA-N 0.000 description 1
- GTRSAMFYSUBAGN-UHFFFAOYSA-N tris(2-chloropropyl) phosphate Chemical compound CC(Cl)COP(=O)(OCC(C)Cl)OCC(C)Cl GTRSAMFYSUBAGN-UHFFFAOYSA-N 0.000 description 1
- LIPMRGQQBZJCTM-UHFFFAOYSA-N tris(2-propan-2-ylphenyl) phosphate Chemical compound CC(C)C1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C(C)C)OC1=CC=CC=C1C(C)C LIPMRGQQBZJCTM-UHFFFAOYSA-N 0.000 description 1
- SPUXJWDKFVXXBI-UHFFFAOYSA-N tris(2-tert-butylphenyl) phosphate Chemical compound CC(C)(C)C1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C(C)(C)C)OC1=CC=CC=C1C(C)(C)C SPUXJWDKFVXXBI-UHFFFAOYSA-N 0.000 description 1
- GNFABDZKXNKQKN-UHFFFAOYSA-N tris(prop-2-enyl)phosphane Chemical compound C=CCP(CC=C)CC=C GNFABDZKXNKQKN-UHFFFAOYSA-N 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
- PJEUXMXPJGWZOZ-UHFFFAOYSA-L zinc;diphenylphosphinate Chemical compound [Zn+2].C=1C=CC=CC=1P(=O)([O-])C1=CC=CC=C1.C=1C=CC=CC=1P(=O)([O-])C1=CC=CC=C1 PJEUXMXPJGWZOZ-UHFFFAOYSA-L 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は、熱硬化性樹脂組成物、例えば、放熱基板等の接着剤やプリプレグに用いることができる、塗工性に優れた熱硬化性樹脂組成物に関するものである。 The present invention relates to a thermosetting resin composition excellent in coating property, which can be used for a thermosetting resin composition, for example, an adhesive such as a heat dissipation substrate or a prepreg.
近年、電子機器の薄型化と小型化に伴い、これらの機器に使用されるプリント配線板やモジュール基板に、樹脂製基板に回路パターンを形成したフレキシブルプリント配線板が使用されることがある。フレキシブルプリント配線板に、例えば、プリプレグを形成する熱硬化性樹脂組成物は、その硬化物が、耐折性（柔軟性）、耐熱性、接続信頼性、絶縁信頼性等に優れることが要求されている。また、プリント配線板やモジュール基板に搭載される電子部品は、近年、高機能化等により発熱量が増大しているので、プリント配線板やモジュール基板には、放熱特性が要求される場合がある。 In recent years, as electronic devices have become thinner and smaller, flexible printed wiring boards having a circuit pattern formed on a resin substrate may be used for printed wiring boards and module boards used in these devices. For example, a thermosetting resin composition that forms a prepreg on a flexible printed wiring board is required to have excellent resistance to bending (flexibility), heat resistance, connection reliability, insulation reliability, and the like. ing. In addition, since electronic components mounted on printed wiring boards and module boards have recently increased in heat generation due to high functionality, the printed wiring boards and module boards may be required to have heat dissipation characteristics. .
さらに、フレキシブルプリント配線板上に、熱硬化性樹脂組成物を塗工し、塗工した熱硬化性樹脂組成物を半硬化状態（Ｂステージ）にすることで、フレキシブルプリント配線板上に接着剤を設け、該接着剤を用いて、銅、アルミニウム等の金属製材料（金属製の基板材料）をフレキシブルプリント配線板上に接着して、積層板を形成することがある。この場合、熱硬化性樹脂組成物の硬化物には、さらに、接着性や密着性も要求される。 Furthermore, an adhesive is applied on the flexible printed wiring board by applying the thermosetting resin composition on the flexible printed wiring board and making the applied thermosetting resin composition in a semi-cured state (B stage). And using the adhesive, a metal material (metal substrate material) such as copper or aluminum is adhered onto the flexible printed wiring board to form a laminated board. In this case, the cured product of the thermosetting resin composition is further required to have adhesiveness and adhesion.
そこで、耐折性、耐熱性、絶縁信頼性、接着性等に優れた樹脂組成物として、エポキシ樹脂（ａ）、硬化剤（ｂ）、フェノール性水酸基を有するポリアミド−ポリ（ブタジエン−アクリロニトリル）共重合体（ｃ）、イオン捕捉剤（ｄ）及び難燃性付与剤（ｅ）を含有するエポキシ樹脂組成物が提案されている（特許文献１）。 Therefore, epoxy resin (a), curing agent (b), and polyamide-poly (butadiene-acrylonitrile) having a phenolic hydroxyl group are used as resin compositions having excellent folding resistance, heat resistance, insulation reliability, adhesiveness, and the like. An epoxy resin composition containing a polymer (c), an ion scavenger (d), and a flame retardant agent (e) has been proposed (Patent Document 1).
しかし、特許文献１のエポキシ樹脂組成物は、揮発性溶剤との相溶性が十分とはいえず、揮発性溶剤に溶解しているエポキシ樹脂組成物の固形分を増大させることができないので、塗工性（例えば、厚い硬化膜を形成する場合の塗工性）が十分ではないという問題があった。また、特許文献１のエポキシ樹脂組成物の硬化物は、積層板を形成するにあたり、レーザー加工性やデスミアエッチング性も十分ではないという問題があった。 However, the epoxy resin composition of Patent Document 1 is not sufficiently compatible with the volatile solvent, and the solid content of the epoxy resin composition dissolved in the volatile solvent cannot be increased. There existed a problem that workability (for example, the coating property in the case of forming a thick cured film) was not enough. Moreover, the hardened | cured material of the epoxy resin composition of patent document 1 had the problem that laser workability and desmear etching property were not enough in forming a laminated board.
上記事情に鑑み、本発明の目的は、耐折性、耐熱性、接着性、接続信頼性、絶縁信頼性等の基本特性を有しつつ、レーザー加工性、デスミアエッチング性及び塗工性に優れた熱硬化性樹脂組成物を提供することにある。 In view of the above circumstances, the object of the present invention is excellent in laser workability, desmear etching property and coating property while having basic characteristics such as folding resistance, heat resistance, adhesiveness, connection reliability, insulation reliability and the like. Another object of the present invention is to provide a thermosetting resin composition.
本発明の態様は、（Ａ）液状エポキシ樹脂と、（Ｂ）軟化点１２５℃以下の固形エポキシ樹脂と、（Ｃ）ベンゾアート基および主鎖にポリメチレン基を有する芳香族ジアミン化合物と、（Ｄ）Ｔｇが１３０℃以上のフェノキシ樹脂と、（Ｅ）Ｔｇが２００℃以上、質量平均分子量が５００００以下である溶剤可溶性ポリアミドイミド樹脂と、を含むことを特徴とする熱硬化性樹脂組成物である。 Embodiments of the present invention include (A) a liquid epoxy resin, (B) a solid epoxy resin having a softening point of 125 ° C. or lower, (C) an aromatic diamine compound having a benzoate group and a polymethylene group in the main chain, and (D And (E) a solvent-soluble polyamideimide resin having a Tg of 200 ° C. or more and a weight average molecular weight of 50,000 or less. .
本明細書中、液状エポキシ樹脂の「液状」、固形エポキシ樹脂の「固形」は、それぞれ、常温常圧（２５℃、１ａｔｍ）にて、液相、固相であることを意味する。また、「溶剤可溶性」とは、本発明の熱硬化性樹脂組成物の製造に使用する溶剤に可溶性であることを意味する。 In this specification, “liquid” of the liquid epoxy resin and “solid” of the solid epoxy resin mean a liquid phase and a solid phase at normal temperature and normal pressure (25 ° C., 1 atm), respectively. The term “solvent soluble” means that the solvent is soluble in the solvent used for producing the thermosetting resin composition of the present invention.
本発明の態様は、前記（Ａ）液状エポキシ樹脂と前記（Ｂ）固形エポキシ樹脂と前記（Ｃ）芳香族ジアミン化合物との合計量１００質量部に対し、前記（Ｄ）フェノキシ樹脂と前記（Ｅ）溶剤可溶性ポリアミドイミド樹脂との合計量が、１０質量部以上５０質量部以下であることを特徴とする熱硬化性樹脂組成物である。 The aspect of the present invention is the above (D) phenoxy resin and (E) with respect to 100 parts by mass of the total amount of the (A) liquid epoxy resin, the (B) solid epoxy resin, and the (C) aromatic diamine compound. ) The total amount of the solvent-soluble polyamideimide resin is 10 parts by mass or more and 50 parts by mass or less.
本発明の態様は、酸化アルミニウム、窒化アルミニウム、窒化ホウ素、窒化ケイ素及び水酸化アルミニウムからなる群から選択された少なくとも１種の（Ｆ）フィラーを、さらに含むことを特徴とする熱硬化性樹脂組成物である。 The aspect of the present invention further includes at least one (F) filler selected from the group consisting of aluminum oxide, aluminum nitride, boron nitride, silicon nitride, and aluminum hydroxide, and a thermosetting resin composition It is a thing.
本発明の態様は、さらに、（Ｇ）難燃剤を含むことを特徴とする熱硬化性樹脂組成物である。 An aspect of the present invention is a thermosetting resin composition further including (G) a flame retardant.
本発明の態様は、放熱基板の接着剤用であることを特徴とする熱硬化性樹脂組成物である。 An aspect of the present invention is a thermosetting resin composition that is used for an adhesive for a heat dissipation substrate.
本発明の態様は、前記放熱基板が、樹脂基板、銅製基板材料及び／またはアルミニウム製基板材料を備えることを特徴とする熱硬化性樹脂組成物である。 An aspect of the present invention is a thermosetting resin composition, wherein the heat dissipation substrate includes a resin substrate, a copper substrate material, and / or an aluminum substrate material.
本発明の態様は、上記熱硬化性樹脂組成物を含むことを特徴とする接着剤である。 An aspect of the present invention is an adhesive comprising the thermosetting resin composition.
本発明の態様は、放熱基板に用いることを特徴とする接着剤である。 An aspect of the present invention is an adhesive that is used for a heat dissipation substrate.
本発明の態様は、上記熱硬化性樹脂組成物を用いたことを特徴とするプリプレグである。 An aspect of the present invention is a prepreg using the thermosetting resin composition.
本発明の特徴は、上記接着剤を備えたことを特徴とする放熱基板である。 A feature of the present invention is a heat dissipation board provided with the above adhesive.
本発明の特徴は、上記プリプレグを用いて積層形成した積層板である。 A feature of the present invention is a laminated plate formed by using the prepreg.
本発明の態様によれば、（Ｃ）ベンゾアート基および主鎖にポリメチレン基を有する芳香族ジアミン化合物と（Ｅ）Ｔｇが２００℃以上、質量平均分子量が５００００以下である溶剤可溶性ポリアミドイミド樹脂とを含むことにより、接着性を向上させつつ、さらに、レーザー加工性、デスミアエッチング性及び塗工性に優れた熱硬化性樹脂組成物を得ることができる。 According to an aspect of the present invention, (C) an aromatic diamine compound having a benzoate group and a polymethylene group in the main chain, and (E) a solvent-soluble polyamideimide resin having a Tg of 200 ° C. or more and a mass average molecular weight of 50,000 or less By including, the thermosetting resin composition excellent in laser workability, desmear etching property, and coating property can be obtained while improving adhesiveness.
本発明の態様によれば、（Ａ）液状エポキシ樹脂と（Ｂ）固形エポキシ樹脂と（Ｃ）芳香族ジアミン化合物との合計量１００質量部に対し、（Ｄ）フェノキシ樹脂と（Ｅ）溶剤可溶性ポリアミドイミド樹脂との合計量が、１０質量部以上５０質量部以下であることにより、耐折性、耐熱性及び接着性と、接続信頼性、レーザー加工性、デスミアエッチング性及び塗工性とを、バランスよく向上させることができる According to an aspect of the present invention, (D) a phenoxy resin and (E) a solvent soluble with respect to a total amount of 100 parts by mass of (A) a liquid epoxy resin, (B) a solid epoxy resin, and (C) an aromatic diamine compound. When the total amount with the polyamide-imide resin is 10 parts by mass or more and 50 parts by mass or less, folding resistance, heat resistance and adhesiveness, connection reliability, laser workability, desmear etching property and coating property are obtained. Can improve in a well-balanced manner
本発明の態様によれば、酸化アルミニウム、窒化アルミニウム、窒化ホウ素、シリカ及び水酸化アルミニウムからなる群から選択された（Ｆ）フィラーを含むことにより、例えば、放熱基板の接着剤として用いた場合に、熱伝導率が向上し、優れた放熱特性を得ることができる。 According to an aspect of the present invention, by including (F) filler selected from the group consisting of aluminum oxide, aluminum nitride, boron nitride, silica and aluminum hydroxide, for example, when used as an adhesive for a heat dissipation substrate Thermal conductivity is improved, and excellent heat dissipation characteristics can be obtained.
次に、本発明の熱硬化性樹脂組成物について、以下に説明する。本発明の熱硬化性樹脂組成物は、（Ａ）液状エポキシ樹脂と、（Ｂ）軟化点１２５℃以下の固形エポキシ樹脂と、（Ｃ）ベンゾアート基および主鎖にポリメチレン基を有する芳香族ジアミン化合物と、（Ｄ）Ｔｇが１３０℃以上のフェノキシ樹脂と、（Ｅ）Ｔｇが２００℃以上、質量平均分子量が５００００以下である溶剤可溶性ポリアミドイミド樹脂と、を含む。 Next, the thermosetting resin composition of the present invention will be described below. The thermosetting resin composition of the present invention comprises (A) a liquid epoxy resin, (B) a solid epoxy resin having a softening point of 125 ° C. or less, (C) an aromatic diamine having a benzoate group and a polymethylene group in the main chain. A compound, (D) a phenoxy resin having a Tg of 130 ° C. or higher, and (E) a solvent-soluble polyamideimide resin having a Tg of 200 ° C. or higher and a mass average molecular weight of 50,000 or lower.
（Ａ）液状エポキシ樹脂
熱硬化性樹脂組成物の硬化物の特性を、プリント配線板の材料として多用されるＦＲ−４基板に近づけるには、固形エポキシ樹脂を使用するのが好ましいところ、エポキシ樹脂として、固形のもののみを配合するのでは、硬化工程の際に熱硬化性樹脂組成物全体を均一な溶融状態とするのが難しい。そこで、液状エポキシ樹脂と固形エポキシ樹脂を併用する、すなわち、常温にて液状であるエポキシ樹脂も配合することにより、硬化工程の際の溶融を連続的に生じさせ、熱硬化性樹脂組成物全体を均一な溶融状態にする。
(A) Liquid epoxy resin In order to bring the properties of the cured product of the thermosetting resin composition closer to the FR-4 substrate that is frequently used as a material for printed wiring boards, it is preferable to use a solid epoxy resin. As a result, it is difficult to make the entire thermosetting resin composition into a uniform molten state during the curing step if only solid components are blended. Therefore, by using a liquid epoxy resin and a solid epoxy resin together, that is, by blending an epoxy resin that is liquid at room temperature, the melting during the curing process is continuously generated, and the entire thermosetting resin composition is obtained. Make a uniform molten state.
上記液状エポキシ樹脂は、常温常圧（２５℃、１ａｔｍ）にて液状であるエポキシ樹脂であれば、特に限定されず、例えば、ビフェニル型エポキシ樹脂、ナフタレン型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、ε−カプロラクトン変性エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＡＤ型等のフェノールノボラック型エポキシ樹脂、о−クレゾールノボラック型等のクレゾ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、環状脂肪族多官能エポキシ樹脂、グリシジルエステル型多官能エポキシ樹脂、グリシジルアミン型多官能エポキシ樹脂、複素環式多官能エポキシ樹脂、ビスフェノール変性ノボラック型エポキシ樹脂、多官能変性ノボラック型エポキシ樹脂、フェノール類とフェノール性水酸基を有する芳香族アルデヒドとの縮合物型エポキシ樹脂等を挙げることができる。 The liquid epoxy resin is not particularly limited as long as it is an epoxy resin that is liquid at normal temperature and normal pressure (25 ° C., 1 atm). For example, biphenyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, ε-caprolactone modified epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin such as bisphenol AD type, о-cresol novolac type cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin, Cycloaliphatic polyfunctional epoxy resin, glycidyl ester polyfunctional epoxy resin, glycidylamine polyfunctional epoxy resin, heterocyclic polyfunctional epoxy resin, bisphenol-modified novolac epoxy resin, polyfunctional modified novolak And a condensate type epoxy resin of a phenol and an aromatic aldehyde having a phenolic hydroxyl group.
これらのうち、熱硬化性樹脂組成物の硬化物における耐折性の点から、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂が好ましく、また、耐熱性の点から、１分子中に２個以上のグリシジル基を持つエポキシ樹脂が好ましい。これらの液状エポキシ樹脂は、単独で使用してもよく、また２種以上を混合して使用してもよい。 Among these, bisphenol A type epoxy resin, bisphenol F type epoxy resin, and phenol novolac type epoxy resin are preferable from the viewpoint of folding resistance in the cured product of the thermosetting resin composition, and from the viewpoint of heat resistance, 1 Epoxy resins having two or more glycidyl groups in the molecule are preferred. These liquid epoxy resins may be used alone or in combination of two or more.
液状エボキシ樹脂の粘度は、特に限定されないが、２５℃で、１．０〜１２０Ｐａ・ｓが好ましく、１．２〜１００Ｐａ・ｓが特に好ましい。なお、上記粘度は、Ｅ型粘度計を用いて測定した値である。 The viscosity of the liquid epoxy resin is not particularly limited, but is preferably 1.0 to 120 Pa · s, particularly preferably 1.2 to 100 Pa · s at 25 ° C. The viscosity is a value measured using an E-type viscometer.
（Ｂ）軟化点１２５℃以下の固形エポキシ樹脂
軟化点が１２５℃以下であって、常温常圧（２５℃、１ａｔｍ）にて固形であるエポキシ樹脂であれば、特に限定されず、例えば、上記した各種エポキシ樹脂を挙げることができる。
(B) Solid epoxy resin having a softening point of 125 ° C. or lower There is no particular limitation as long as the epoxy resin has a softening point of 125 ° C. or lower and is solid at room temperature and normal pressure (25 ° C., 1 atm). And various epoxy resins.
これらのうち、ジシクロペンタジエン型エポキシ樹脂が好ましく、また、耐熱性の点から、１分子中に２個以上のグリシジル基を持つエポキシ樹脂が好ましい。これらの固形エポキシ樹脂は、単独で使用してもよく、また２種以上を混合して使用してもよい。 Among these, a dicyclopentadiene type epoxy resin is preferable, and an epoxy resin having two or more glycidyl groups in one molecule is preferable from the viewpoint of heat resistance. These solid epoxy resins may be used alone or in combination of two or more.
固形エポキシ樹脂の軟化点を１２５℃以下とするのは、変性材として用いる（Ｄ）成分であるフェノキシ樹脂のＴｇを１３０℃以上と限定していることによる。つまり、熱硬化性樹脂組成物が硬化する際に、（Ｂ）成分である固形エポキシ樹脂が（Ｄ）成分であるフェノキシ樹脂の溶融前に溶融していることにより、熱硬化性樹脂組成物の硬化物の均一化を図るためである。 The reason why the softening point of the solid epoxy resin is set to 125 ° C. or lower is that the Tg of the phenoxy resin, which is the component (D) used as the modifier, is limited to 130 ° C. or higher. That is, when the thermosetting resin composition is cured, the solid epoxy resin as the component (B) is melted before the phenoxy resin as the component (D) is melted. This is to make the cured product uniform.
固形エポキシ樹脂の軟化点は１２５℃以下であれば、特に限定されないが、例えば、その上限値は、（Ｄ）成分であるフェノキシ樹脂の溶融前に確実に溶融させる点から１００℃が好ましい。また、上記軟化点の下限値は、特に限定されないが、例えば、熱硬化性樹脂組成物全体を確実に均一な溶融状態とする点から、５０℃が好ましい。 The softening point of the solid epoxy resin is not particularly limited as long as it is 125 ° C. or lower. For example, the upper limit is preferably 100 ° C. from the viewpoint of reliably melting the phenoxy resin as the component (D). Moreover, the lower limit value of the softening point is not particularly limited. For example, 50 ° C. is preferable from the viewpoint of ensuring that the entire thermosetting resin composition is in a uniform molten state.
液状エポキシ樹脂と軟化点１２５℃以下の固形エポキシ樹脂との配合割合は、特に限定されず、硬化物の特性と硬化工程時の溶融制御の点から、適宜選択可能である。例えば、液状エポキシ樹脂１００質量部に対して、耐熱性の点から軟化点１２５℃以下の固形エポキシ樹脂を１００〜４００質量部配合するのが好ましく、接続信頼性の点から軟化点１２５℃以下の固形エポキシ樹脂を１３０〜２００質量部配合するのが特に好ましい。 The blending ratio of the liquid epoxy resin and the solid epoxy resin having a softening point of 125 ° C. or lower is not particularly limited, and can be appropriately selected from the characteristics of the cured product and the melting control during the curing step. For example, it is preferable to mix 100 to 400 parts by mass of a solid epoxy resin having a softening point of 125 ° C. or less from the viewpoint of heat resistance with respect to 100 parts by mass of the liquid epoxy resin, and a softening point of 125 ° C. or less from the viewpoint of connection reliability. It is particularly preferable to blend 130 to 200 parts by mass of the solid epoxy resin.
（Ｃ）ベンゾアート基および主鎖にポリメチレン基を有する芳香族ジアミン化合物
（Ｃ）成分である芳香族ジアミン化合物は、ポリイミドフィルム等の樹脂製基板やアルミニウム、酸化アルミニウム等の金属材料（例えば、基板に用いる材料）に対する接着性の向上と、耐熱性と耐折性の向上に寄与する。
(C) An aromatic diamine compound having a benzoate group and a polymethylene group in the main chain (C) The aromatic diamine compound is a resin substrate such as a polyimide film or a metal material such as aluminum or aluminum oxide (for example, a substrate It contributes to the improvement of the adhesion to the material used for the heat treatment and the heat resistance and folding resistance.
上記ポリメチレン基が有するメチレン基の個数は、特に限定されないが、その下限値は、耐折性をより向上させる点から３個が好ましく、４個が特に好ましい。一方で、その上限値は、耐熱性の低下を防止する点から１６個が好ましく、１０個が特に好ましい。 The number of methylene groups contained in the polymethylene group is not particularly limited, but the lower limit is preferably 3 from the viewpoint of further improving folding resistance, and 4 is particularly preferred. On the other hand, the upper limit value is preferably 16 from the viewpoint of preventing a decrease in heat resistance, and 10 is particularly preferable.
（Ｃ）成分である芳香族ジアミン化合物としては、例えば、トリメチレン-ビス(４-アミノベンゾアート)（融点１２２℃）、ポリ(テトラ／３-メチルテトラメチレンエーテル)グリコールビス(４-アミノベンゾアート)（液状）、ポリテトラメチレンオキシド-ジ-p-アミノベンゾアート（融点１５〜６０℃）等が挙げられる。これらの芳香族ジアミン化合物は、単独で使用してもよく、また２種以上を混合して使用してもよい。 Examples of the aromatic diamine compound as component (C) include trimethylene-bis (4-aminobenzoate) (melting point 122 ° C.), poly (tetra / 3-methyltetramethylene ether) glycol bis (4-aminobenzoate). ) (Liquid), polytetramethylene oxide-di-p-aminobenzoate (melting point: 15 to 60 ° C.), and the like. These aromatic diamine compounds may be used alone or in combination of two or more.
（Ｃ）成分である芳香族ジアミン化合物は、固形である場合、その融点は特に限定されないが、上記した固形エポキシ樹脂の軟化点と同じ理由から、上限値は、１２５℃が好ましく、１００℃が特に好ましい。一方で、融点の下限値は、５０℃が好ましい。 When the aromatic diamine compound as component (C) is solid, its melting point is not particularly limited, but for the same reason as the softening point of the solid epoxy resin described above, the upper limit is preferably 125 ° C., and 100 ° C. Particularly preferred. On the other hand, the lower limit of the melting point is preferably 50 ° C.
（Ｃ）成分である芳香族ジアミン化合物の配合量は、特に限定されないが、耐熱性の点から、（Ａ）液状エポキシ樹脂のエポキシ当量数と（Ｂ）軟化点１２５℃以下の固形エポキシ樹脂のエポキシ当量数との合計値１．０に対して、（Ｃ）成分である芳香族ジアミン化合物の活性水素当量数０．９５〜１．５となる配合量が好ましい。 (C) Although the compounding quantity of the aromatic diamine compound which is a component is not specifically limited, From the point of heat resistance, (A) Epoxy equivalent number of liquid epoxy resin, and (B) Solid epoxy resin of softening point of 125 degrees C or less The compounding quantity which becomes 0.95-1.5 active hydrogen equivalent number of the aromatic diamine compound which is (C) component with respect to 1.0 total with epoxy equivalent number is preferable.
なお、各エポキシ樹脂のエポキシ当量数は、以下のものである。各エポキシ樹脂の各エポキシ当量数＝（組成物中の各エポキシ樹脂の固形分質量）／（各エポキシ樹脂の各エポキシ当量）。また、（Ｃ）成分である芳香族ジアミン化合物の活性水素当量数は、以下のものである。芳香族ジアミン化合物の活性水素当量数＝（組成物中の芳香族ジアミン化合物の質量）／（芳香族ジアミン化合物の活性水素当量）。 In addition, the epoxy equivalent number of each epoxy resin is as follows. Each epoxy equivalent number of each epoxy resin = (solid content mass of each epoxy resin in the composition) / (each epoxy equivalent of each epoxy resin). Moreover, the active hydrogen equivalent number of the aromatic diamine compound which is (C) component is as follows. Number of active hydrogen equivalents of aromatic diamine compound = (mass of aromatic diamine compound in composition) / (active hydrogen equivalent of aromatic diamine compound).
（Ｄ）Ｔｇが１３０℃以上のフェノキシ樹脂
Ｔｇが１３０℃以上のフェノキシ樹脂は、特に、接続信頼性の向上に寄与し、例えば、ＦＲ−４基板と同等程度の接続信頼性を得ることができる。接続信頼性は、１２５℃と６５℃との間の冷熱サイクル試験により判断されることが多く、接続信頼性を左右する要素の一つである熱膨張率はＴｇの前後で大きく変化することから、フェノキシ樹脂のＴｇは１３０℃以上が必要となる。なお、本明細書において、Ｔｇ(ガラス転移温度)は、ＤＳＣ法で測定した値である。また、Ｔｇが１３０℃以上のフェノキシ樹脂は、さらに、レーザー加工性とデスミアエッチング性に寄与する。
(D) Phenoxy resin having a Tg of 130 ° C. or higher A phenoxy resin having a Tg of 130 ° C. or higher contributes particularly to improvement in connection reliability, and can obtain connection reliability comparable to that of an FR-4 substrate, for example. . The connection reliability is often judged by a thermal cycle test between 125 ° C. and 65 ° C., and the coefficient of thermal expansion, which is one of the factors affecting the connection reliability, greatly changes before and after Tg. The Tg of the phenoxy resin needs to be 130 ° C. or higher. In the present specification, Tg (glass transition temperature) is a value measured by DSC method. A phenoxy resin having a Tg of 130 ° C. or higher further contributes to laser processability and desmear etching property.
Ｔｇが１３０℃以上のフェノキシ樹脂の種類は特に限定されず、例えば、ＢＰＡ/ＢＰＳ型、ＢＰ/ＢＰＳ型、ＢＰ型、ＢＰＳ型等を挙げることができ、このうち、耐熱骨格を有するものが好ましい。これらは、単独で使用してもよく、また２種以上を混合して使用してもよい。また、Ｔｇが１３０℃以上のフェノキシ樹脂の質量平均分子量は、特に限定されないが、上記硬化物の耐折性の点から１００００〜２０００００が好ましく、２００００〜１０００００が特に好ましい。 The type of phenoxy resin having a Tg of 130 ° C. or higher is not particularly limited, and examples thereof include BPA / BPS type, BP / BPS type, BP type, and BPS type. Among these, those having a heat-resistant skeleton are preferable. . These may be used singly or in combination of two or more. Moreover, although the mass mean molecular weight of phenoxy resin whose Tg is 130 degreeC or more is not specifically limited, 10000-200000 are preferable from the point of the bending resistance of the said hardened | cured material, and 20000-100,000 are especially preferable.
Ｔｇが１３０℃以上のフェノキシ樹脂のＴｇの上限値は、特に限定されないが、均一溶融の点から、本発明の熱硬化性樹脂組成物の熱硬化処理温度以下が好ましい。なお、本発明の熱硬化性樹脂組成物は、エポキシ樹脂を含有する組成物なので、通常、熱硬化処理温度は１８０℃以下である。従って、Ｔｇが１３０℃以上のフェノキシ樹脂のＴｇの上限値は、例えば、１８０℃以下である。 The upper limit of Tg of the phenoxy resin having a Tg of 130 ° C. or higher is not particularly limited, but is preferably equal to or lower than the thermosetting temperature of the thermosetting resin composition of the present invention from the viewpoint of uniform melting. In addition, since the thermosetting resin composition of this invention is a composition containing an epoxy resin, the thermosetting temperature is usually 180 degrees C or less. Therefore, the upper limit of Tg of a phenoxy resin having a Tg of 130 ° C. or higher is, for example, 180 ° C. or lower.
上市されている，Ｔｇが１３０℃以上のフェノキシ樹脂としては、例えば、ＹＬ６９５４ＢＨ３０(ＪＥＲ社製、Ｔｇ１３０℃)、ＥＲＦ−００１Ｍ３０(新日鐵化学社製、Ｔｇ１４６℃)、ＹＸ８１００ＢＨ３０(ＪＥＲ社製、Ｔｇ１５０℃)等が挙げられる。 Examples of commercially available phenoxy resins having a Tg of 130 ° C. or higher include YL6954BH30 (manufactured by JER, Tg 130 ° C.), ERF-001M30 (manufactured by Nippon Steel Chemical Co., Tg 146 ° C.), YX8100BH30 (manufactured by JER, Tg150 ° C) and the like.
（Ｅ）Ｔｇが２００℃以上、質量平均分子量が５００００以下である溶剤可溶性ポリアミドイミド樹脂
Ｔｇが２００℃以上、質量平均分子量が５００００以下である溶剤可溶性ポリアミドイミド樹脂（以下、「溶剤可溶性ポリアミドイミド樹脂」ということがある。）は、（Ｃ）成分である芳香族ジアミン化合物と相まって、接着性の向上に寄与しつつ、優れたレーザー加工性、デスミアエッチング性及び塗工性の付与に寄与する。上記の通り、通常の熱硬化処理温度は最大１８０℃程度なので、耐熱性の点から、溶剤可溶性ポリアミドイミド樹脂のＴｇは２００℃以上が必要である。また、樹脂ワニス相溶性（ひいては、例えば、厚い硬化膜を形成する場合等、における優れた塗工性）を得る点から、質量平均分子量が５００００以下であることが必要である。
(E) Solvent-soluble polyamideimide resin having a Tg of 200 ° C. or more and a mass average molecular weight of 50000 or less. Solvent-soluble polyamideimide resin having a Tg of 200 ° C. or more and a mass average molecular weight of 50000 or less (hereinafter “solvent-soluble polyamideimide resin”). ”, In combination with the aromatic diamine compound as component (C), contributes to the improvement of adhesiveness, and contributes to imparting excellent laser processability, desmear etching property and coating property. As described above, the normal thermosetting temperature is about 180 ° C. at the maximum, so that the Tg of the solvent-soluble polyamideimide resin needs to be 200 ° C. or more from the viewpoint of heat resistance. In addition, the mass average molecular weight is required to be 50000 or less from the viewpoint of obtaining resin varnish compatibility (and, for example, excellent coating properties when, for example, a thick cured film is formed).
溶剤可溶性ポリアミドイミド樹脂は、Ｔｇが２００℃以上なので、１８０℃程度の熱硬化処理工程において、溶剤可溶性ポリアミドイミド樹脂自体は軟化が起こらず他成分との相溶が不均一になる。しかし、（Ｃ）成分である芳香族ジアミン化合物が配合されていることにより、熱硬化性樹脂組成物は、全体としては概ね軟化し、溶剤可溶性ポリイミド樹脂を含む全ての構成成分が擬似相溶状態にて熱硬化できる。これにより、熱硬化後の硬化物性が均一化される。 Since the solvent-soluble polyamide-imide resin has a Tg of 200 ° C. or higher, the solvent-soluble polyamide-imide resin itself is not softened in the thermosetting process at about 180 ° C. and becomes incompatible with other components. However, since the aromatic diamine compound as component (C) is blended, the thermosetting resin composition is generally softened as a whole, and all the components including the solvent-soluble polyimide resin are in a pseudo-compatible state. Can be cured by heating. Thereby, the cured physical properties after thermosetting are made uniform.
また、均一化された硬化物性は、硬化物の加工特性の向上にも寄与する。すなわち、レーザー加工性やデスミアエッチング性が向上して、デスミアエッチング後におけるスミアの残渣を低減できる。 Moreover, the uniform cured material property also contributes to the improvement of the processing characteristics of the cured product. That is, laser processability and desmear etching property are improved, and smear residues after desmear etching can be reduced.
溶剤可溶性ポリアミドイミド樹脂の種類は特に限定されず、例えば、トリカルボン酸無水物とジイソシアネート化合物とをイミド化反応させた反応生成物、トリカルボン酸無水物のクロリドとジアミン化合物とをイミド化反応させた反応生成物を挙げることができる。 The type of the solvent-soluble polyamideimide resin is not particularly limited. For example, a reaction product obtained by imidizing a tricarboxylic acid anhydride and a diisocyanate compound, a reaction obtained by imidizing a chloride of a tricarboxylic acid anhydride and a diamine compound. Mention may be made of the products.
トリカルボン酸無水物としては、例えば、トリメリット酸無水物を挙げることができる。 Examples of the tricarboxylic acid anhydride include trimellitic acid anhydride.
ジイソシアネート化合物としては、例えば、芳香族ジイソシアネートを挙げることができ、例えば、ビフェニルジイソシアネート、ジメチルビフェニルジイソシアネート、ジエチルビフェニルジイソシアネート、ジメトキシビフェニルジイソシアネート等を挙げることができる。 Examples of the diisocyanate compound include aromatic diisocyanates, and examples include biphenyl diisocyanate, dimethylbiphenyl diisocyanate, diethylbiphenyl diisocyanate, and dimethoxybiphenyl diisocyanate.
ジアミン化合物としては、芳香族ジアミン化合物を挙げることができ、例えば、ジアミノベンゾフェノン、フェニレンジアミン、ジアミノジフェニル、ジアミノジフェニルエーテル、ジアミノジフェニルアミド、ジアミノジフェニルメタン、ビス（アミノフェノキシ）ビフェニル等を挙げることができる。 Examples of the diamine compound include aromatic diamine compounds, such as diaminobenzophenone, phenylenediamine, diaminodiphenyl, diaminodiphenyl ether, diaminodiphenylamide, diaminodiphenylmethane, and bis (aminophenoxy) biphenyl.
これらの溶剤可溶性ポリアミドイミド樹脂は、単独で使用してもよく、また２種以上を混合して使用してもよい。 These solvent-soluble polyamideimide resins may be used alone or in admixture of two or more.
溶剤可溶性ポリアミドイミド樹脂の質量平均分子量は、５００００以下であれば特に限定されないが、確実に樹脂ワニス相溶性を得る点から３５０００以下が好ましく、樹脂ワニス相溶性をより向上させる点から３００００以下が特に好ましい。一方で、溶剤可溶性ポリアミドイミド樹脂の質量平均分子量の下限値は、特に限定されないが、耐熱性の点から２００００が好ましく、上記硬化物の耐折性の点から２５０００が特に好ましい。 The mass average molecular weight of the solvent-soluble polyamideimide resin is not particularly limited as long as it is 50000 or less, but is preferably 35000 or less from the viewpoint of surely obtaining resin varnish compatibility, and particularly 30000 or less from the viewpoint of further improving resin varnish compatibility. preferable. On the other hand, the lower limit of the mass average molecular weight of the solvent-soluble polyamideimide resin is not particularly limited, but is preferably 20000 from the viewpoint of heat resistance, and particularly preferably 25000 from the viewpoint of folding resistance of the cured product.
また、溶剤可溶性ポリアミドイミド樹脂のＴｇは、２００℃以上であれば、特に限定されないが、耐熱性をより向上させる点から２５０℃以上が好ましい。一方で、溶剤可溶性ポリアミドイミド樹脂のＴｇの上限値は、特に限定されないが、樹脂ワニス相溶性の低下を確実に防止する点から３５０℃が好ましい。 The Tg of the solvent-soluble polyamideimide resin is not particularly limited as long as it is 200 ° C. or higher, but is preferably 250 ° C. or higher from the viewpoint of further improving heat resistance. On the other hand, the upper limit value of Tg of the solvent-soluble polyamideimide resin is not particularly limited, but 350 ° C. is preferable from the viewpoint of reliably preventing the resin varnish compatibility from being lowered.
（Ａ）液状エポキシ樹脂と（Ｂ）成分の固形エポキシ樹脂と（Ｃ）成分の芳香族ジアミン化合物との合計量１００質量部に対する、（Ｄ）成分のフェノキシ樹脂と（Ｅ）溶剤可溶性ポリアミドイミド樹脂との合計の配合量は、特に限定されないが、その下限値は、接続信頼性と接着性をより向上させつつ、より優れたレーザー加工性、デスミアエッチング性及び塗工性を付与する点から１０質量部が好ましく、上記硬化物の耐折性の点から２０質量部が特に好ましい。一方で、上記配合量の上限値は、本発明の熱硬化性樹脂組成物の硬化物において、優れた機械的強度を得る点から５０質量部が好ましく、４０質量部が特に好ましい。 (D) Component phenoxy resin and (E) solvent-soluble polyamideimide resin with respect to 100 parts by mass of (A) liquid epoxy resin, (B) component solid epoxy resin and (C) component aromatic diamine compound The total blending amount is not particularly limited, but the lower limit is 10 from the viewpoint of imparting better laser workability, desmear etching property and coating property while further improving connection reliability and adhesiveness. Mass parts are preferred, and 20 parts by mass is particularly preferred from the viewpoint of folding resistance of the cured product. On the other hand, the upper limit of the blending amount is preferably 50 parts by weight, particularly preferably 40 parts by weight, from the viewpoint of obtaining excellent mechanical strength in the cured product of the thermosetting resin composition of the present invention.
また、（Ｄ）成分のフェノキシ樹脂と（Ｅ）溶剤可溶性ポリアミドイミド樹脂との配合割合は、特に限定されないが、（Ｅ）溶剤可溶性ポリアミドイミド樹脂の質量：（Ｄ）成分のフェノキシ樹脂の質量は、上記擬似相溶状態での熱硬化による硬化物性の均一化と上記溶剤可溶性ポリアミドイミド樹脂の作用とのバランスの点から、１．０：１．５〜１．０：１９が好ましく、より優れた擬似相溶状態を得る点から、１．０：３．０〜１．０：７．０が特に好ましい。 Moreover, the blending ratio of the phenoxy resin of the component (D) and the solvent-soluble polyamideimide resin (E) is not particularly limited, but the mass of the solvent-soluble polyamideimide resin (E): the mass of the phenoxy resin of the component (D) is From the viewpoint of the balance between the homogenization of cured properties by heat curing in the pseudo-compatible state and the action of the solvent-soluble polyamideimide resin, 1.0: 1.5 to 1.0: 19 is preferable and more excellent From the point of obtaining a quasi-compatible state, 1.0: 3.0 to 1.0: 7.0 is particularly preferable.
本発明の熱硬化性樹脂組成物では、上記（Ａ）成分〜（Ｅ）成分に加えて、必要に応じて、さらに、（Ｆ）フィラーや（Ｇ）難燃剤を配合してもよい。 In the thermosetting resin composition of the present invention, in addition to the components (A) to (E), a (F) filler and a (G) flame retardant may be further blended as necessary.
（Ｆ）フィラー
本発明の熱硬化性樹脂組成物では、フィラーを配合することで、例えば、本発明の熱硬化性樹脂組成物を、放熱基板の接着剤として用いる際に、該接着剤の熱伝導率を向上させることができ、また、熱硬化性樹脂組成物の硬化物の機械的強度を向上させることができる。優れた熱伝導率を付与しつつ、機械的強度を向上させるフィラーとしては、例えば、酸化アルミニウム（熱伝導率３２Ｗ／ｍＫ）、窒化アルミニウム（熱伝導率１５０Ｗ／ｍＫ）、窒化ホウ素（熱伝導率３３〜５５Ｗ／ｍＫ）、窒化ケイ素（熱伝導率２０Ｗ／ｍＫ）、水酸化アルミニウム（熱伝導率７．０Ｗ／ｍＫ）等を挙げることができる。これらは、単独で使用してもよく、また２種以上を混合して使用してもよい。
(F) Filler In the thermosetting resin composition of the present invention, when the filler is blended, for example, when the thermosetting resin composition of the present invention is used as an adhesive for a heat dissipation substrate, the heat of the adhesive is used. The conductivity can be improved, and the mechanical strength of the cured product of the thermosetting resin composition can be improved. Examples of fillers that improve mechanical strength while imparting excellent thermal conductivity include aluminum oxide (thermal conductivity 32 W / mK), aluminum nitride (thermal conductivity 150 W / mK), boron nitride (thermal conductivity) 33-55 W / mK), silicon nitride (thermal conductivity 20 W / mK), aluminum hydroxide (thermal conductivity 7.0 W / mK), and the like. These may be used singly or in combination of two or more.
フィラーの配合量は、特に限定されないが、例えば、その下限値は、上記（Ａ）成分〜（Ｅ）成分の合計量１００質量部に対し、熱伝導率と機械的強度とを確実に向上させる点から３０質量部が好ましく、４０質量部がより好ましく、より優れた放熱特性を得る点から５０質量部が特に好ましい。一方で、その上限値は、上記（Ａ）成分〜（Ｅ）成分の合計量１００質量部に対し、優れたレーザー加工性、デスミアエッチング性及び塗工性を維持する点から３００質量部が好ましく、２５０質量部がより好ましく、２００質量部が特に好ましい。 Although the compounding quantity of a filler is not specifically limited, For example, the lower limit reliably improves thermal conductivity and mechanical strength with respect to 100 parts by mass of the total amount of the components (A) to (E). 30 parts by mass is preferable from the point, 40 parts by mass is more preferable, and 50 parts by mass is particularly preferable from the viewpoint of obtaining more excellent heat dissipation characteristics. On the other hand, the upper limit is preferably 300 parts by mass from the viewpoint of maintaining excellent laser processability, desmear etching property and coating property with respect to 100 parts by mass of the total amount of the components (A) to (E). 250 parts by mass is more preferable, and 200 parts by mass is particularly preferable.
（Ｇ）難燃剤
難燃剤を配合することで、本発明の熱硬化性樹脂組成物に難燃性を付与することができる。難燃剤は特に限定されず、公知のものを使用できる。難燃剤としては、例えば、有機リン酸塩等のリン元素含有化合物等を挙げることができる。リン元素含有化合物の具体例としては、トリス（クロロエチル）ホスフェート、トリス（２，３−ジクロロプロピル）ホスフェート、トリス（２−クロロプロピル）ホスフェート、トリス（２，３−ブロモプロピル）ホスフェート、トリス（ブロモクロロプロピル）ホスフェート、２，３−ジブロモプロピル−２，３−クロロプロピルホスフェート、トリス（トリブロモフェニル）ホスフェート、トリス（ジブロモフェニル）ホスフェート、トリス（トリブロモネオペンチル）ホスフェートなどの含ハロゲン系リン酸エステル；トリメチルホスフェート、トリエチルホスフェート、トリブチルホスフェート、トリオクチルホスフェート、トリブトキシエチルホスフェート等のノンハロゲン系脂肪族リン酸エステル；トリフェニルホスフェート、クレジルジフェニルホスフェート、ジクレジルフェニルホスフェート、トリクレジルホスフェート、トリキシレニルホスフェート、キシレニルジフェニルホスフェート、トリス（イソプロピルフェニル）ホスフェート、イソプロピルフェニルジフェニルホスフェート、ジイソプロピルフェニルフェニルホスフェート、トリス（トリメチルフェニル）ホスフェート、トリス（ｔ−ブチルフェニル）ホスフェート、ヒドロキシフェニルジフェニルホスフェート、オクチルジフェニルホスフェート、３−グリシジルオキシプロピレンジフェニルホスフィンオキシド、３−グリシジルオキシジフェニルホスフィンオキシド、ジフェニルビニルホスフィンオキシド、１０−(２，５−ジヒドロキシフェニル）−１０H−９−オキサ−１０−ホスファフェナントレン−１０−オキシド、２−（９，１０−ジヒドロ−９−オキサ−１０−オキサイド−１０−ホスファフェナントレン−１０−イル）メチルコハク酸ビス−（２−ヒドロキシエチル）−エステル重合物などのノンハロゲン系芳香族リン酸エステル；トリスジエチルホスフィン酸アルミニウム、ジエチルホスフィン酸アルミニウム、トリスメチルエチルホスフィン酸アルミニウム、トリスジフェニルホスフィン酸アルミニウム、ビスジエチルホスフィン酸亜鉛、ビスメチルエチルホスフィン酸亜鉛、ビスジフェニルホスフィン酸亜鉛、ビスジエチルホスフィン酸チタニル、テトラキスジエチルホスフィン酸チタン、ビスメチルエチルホスフィン酸チタニル、テトラキスメチルエチルホスフィン酸チタン、ビスジフェニルホスフィン酸チタニル、テトラキスジフェニルホスフィン酸チタンなどのホスフィン酸の金属塩、環状フェノキシホスファゼン、環状シアノフェノキシホスファゼンなどの、置換若しくは非置換のフェノキシ基または置換若しくは非置換のナフトキシ基を有する環状若しくは鎖状のホスファゼン系化合物等のホスファゼン類、トリアリルホスフィン等が挙げられる。これらは、単独で使用してもよく、また２種以上を混合して使用してもよい。
(G) Flame retardant A flame retardance can be provided to the thermosetting resin composition of this invention by mix | blending a flame retardant. A flame retardant is not specifically limited, A well-known thing can be used. Examples of the flame retardant include phosphorus element-containing compounds such as organic phosphates. Specific examples of the phosphorus element-containing compound include tris (chloroethyl) phosphate, tris (2,3-dichloropropyl) phosphate, tris (2-chloropropyl) phosphate, tris (2,3-bromopropyl) phosphate, tris (bromo). Halogenated phosphoric acid such as chloropropyl) phosphate, 2,3-dibromopropyl-2,3-chloropropyl phosphate, tris (tribromophenyl) phosphate, tris (dibromophenyl) phosphate, tris (tribromoneopentyl) phosphate Esters; non-halogen aliphatic phosphate esters such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate; triphenyl phosphate Cresyl diphenyl phosphate, dicresyl phenyl phosphate, tricresyl phosphate, trixylenyl phosphate, xylenyl diphenyl phosphate, tris (isopropylphenyl) phosphate, isopropylphenyl diphenyl phosphate, diisopropylphenylphenyl phosphate, tris (trimethylphenyl) phosphate, Tris (t-butylphenyl) phosphate, hydroxyphenyl diphenyl phosphate, octyl diphenyl phosphate, 3-glycidyloxypropylene diphenylphosphine oxide, 3-glycidyloxydiphenylphosphine oxide, diphenylvinylphosphine oxide, 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphafena Non-halogens such as entolen-10-oxide, 2- (9,10-dihydro-9-oxa-10-oxide-10-phosphaphenanthrene-10-yl) methylsuccinic acid bis- (2-hydroxyethyl) -ester polymer Aromatic phosphoric acid ester; aluminum trisdiethylphosphinate, aluminum diethylphosphinate, aluminum trismethylethylphosphinate, aluminum trisdiphenylphosphinate, zinc bisdiethylphosphinate, zinc bismethylethylphosphinate, zinc bisdiphenylphosphinate, Bisdiethylphosphinate titanyl, tetrakisdiethylphosphinate titanium, bismethylethylphosphinate titanyl, tetrakismethylethylphosphinate titanium, bisdiphenylphosphinate titani Cyclic or chain phosphazene compounds having a substituted or unsubstituted phenoxy group or a substituted or unsubstituted naphthoxy group, such as metal salts of phosphinic acids such as titanium tetrakisdiphenylphosphinate, cyclic phenoxyphosphazenes, and cyclic cyanophenoxyphosphazenes And phosphazenes such as triallylphosphine. These may be used singly or in combination of two or more.
難燃剤の配合量は、特に限定されず、例えば、上記（Ａ）成分〜（Ｅ）成分の合計量１００質量部に対し、１．０〜２０質量部が好ましく、２．０〜１０質量部が特に好ましい。 The blending amount of the flame retardant is not particularly limited, and is preferably 1.0 to 20 parts by mass, for example, 2.0 to 10 parts by mass with respect to 100 parts by mass of the total amount of the components (A) to (E). Is particularly preferred.
本発明の熱硬化性樹脂組成物では、上記（Ａ）成分〜（Ｅ）成分に加えて、必要に応じて、さらに、硬化促進剤をすることができる。硬化促進剤としては、例えば、イミダゾール類等を挙げることができ、主に、反応速度、ポットライフの観点から選択することができる。 In the thermosetting resin composition of the present invention, in addition to the components (A) to (E), a curing accelerator can be further used as necessary. Examples of the curing accelerator include imidazoles, and can be selected mainly from the viewpoint of reaction rate and pot life.
イミダゾール類としては、例えば、２-メチルイミダゾール、２-ウンデシルイミダゾール、２-ヘプタデシルイミダゾール、２-エチル-４-メチルイミダゾール、２-フェニルイミダゾール、２-フェニル-４-メチルイミダゾール、１-ベンジル-２-メチルイミダゾール、１-ベンジル-２-フェニルイミダゾール、１,２-ジメチルイミダゾール、１-シアノエチル-２-エチル-４-メチルイミダゾール、１-シアノエチル-２-ウンデシルイミダゾリウムトリメリテイト、１-シアノエチル-２-フェニルイミダゾリウムトリメリテイト、２,４-ジアミノ-６-[２’-メチルイミダゾリル-(１’)]-エチル-ｓ-トリアジン、２,４-ジアミノ-６-[２’-ウンデシルイミダゾリル-(１’)]-エチル-s-トリアジン、２,４-ジアミノ-６-[２’-メチルイミダゾリル-(１’)]-エチル-s-トリアジンイソシアヌル酸付加物、２-フェニルイミダゾールイソシアヌル酸付加物、２-フェニル-４,５-ジヒドロキシメチルイミダゾール、２-フェニル-４-メチル-５-ヒドロキシメチルイミダゾール、２,３-ジヒドロ-１H-ピロロ[１,２-a]ベンズイミダゾール、４,４’-メチレンビス(２-エチル-５-メチルイミダゾール)やＴＰＰなどがある。 Examples of imidazoles include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 1-benzyl. -2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1 -Cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2' -Undecylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine Soocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [ 1,2-a] benzimidazole, 4,4′-methylenebis (2-ethyl-5-methylimidazole), TPP, and the like.
本発明の熱硬化性樹脂組成物に使用可能な溶剤は、特に限定されず、例えば、ＮＭＰ（Ｎ−メチルピロリドン）やγ-ブチロラクトン等の高沸点（沸点１８０〜２５０℃）有機溶剤とシクロヘキサノンやＭＥＫ（メチルエチルケトン）等の中、低沸点（沸点６０〜１５０℃）有機溶剤を組み合わせることが好ましい。また、他の溶剤としては、ＤＭＦ（ジメチルホルムアミド）、ＤＭＡＣ（ジメチルアセトアミド）等を挙げることができる。 The solvent that can be used in the thermosetting resin composition of the present invention is not particularly limited. For example, organic solvents such as NMP (N-methylpyrrolidone) and γ-butyrolactone (boiling point 180 to 250 ° C.) and cyclohexanone can be used. Among MEK (methyl ethyl ketone) and the like, it is preferable to combine an organic solvent having a low boiling point (boiling point: 60 to 150 ° C.). Examples of other solvents include DMF (dimethylformamide) and DMAC (dimethylacetamide).
本発明の熱硬化性樹脂組成物をＢステージ（半硬化の状態）化することにより、樹脂フィルムを得ることができる。すなわち、本発明の樹脂組成物を有機溶剤で希釈することでワニスとし、これを必要に応じて離型処理した樹脂フィルム（例えば、ポリエチレンテレフタレートフィルム（ＰＥＴフィルム））上にダイコーター等の公知の塗工方法で塗布し、乾燥することにより、半硬化状態の熱硬化性樹脂フィルムを得ることができる。 A resin film can be obtained by converting the thermosetting resin composition of the present invention into a B-stage (semi-cured state). That is, the resin composition of the present invention is diluted with an organic solvent to form a varnish, and a resin film (for example, a polyethylene terephthalate film (PET film)) that has been subjected to a mold release treatment as necessary is known as a die coater. By applying and drying by a coating method, a semi-cured thermosetting resin film can be obtained.
また、本発明の熱硬化性樹脂組成物を金属箔に塗工することにより、接着剤付き金属箔を得ることができる。この金属箔としては、例えば、表面粗化した銅箔、アルミニウム箔等を挙げることができ、熱伝導性と導電性の点から銅箔が特に好ましい。なお、上記金属箔は、例えば、放熱基板等の基板に用いる材料として使用することができる。 Moreover, metal foil with an adhesive agent can be obtained by applying the thermosetting resin composition of the present invention to metal foil. Examples of the metal foil include a roughened copper foil and an aluminum foil, and a copper foil is particularly preferable from the viewpoint of thermal conductivity and conductivity. In addition, the said metal foil can be used as a material used for board | substrates, such as a thermal radiation board | substrate, for example.
また、上記樹脂フィルム及び樹脂付き銅箔（ＲＣＣ）は、リジッドコア又はフレキシブル配線板（ＦＰＣ）コアを有するビルドアップ基板の高密度配線（ＨＤＩ）材料として、レーザービアなどの非貫通ビアホールを持つプリント配線板にも使用することができる。 In addition, the resin film and the copper foil with resin (RCC) are printed with a non-through via hole such as a laser via as a high density wiring (HDI) material of a build-up board having a rigid core or a flexible wiring board (FPC) core. It can also be used for wiring boards.
次に、本発明の実施例を説明するが、本発明はその趣旨を超えない限り、これらの例に限定されるものではない。 Next, examples of the present invention will be described. However, the present invention is not limited to these examples as long as the gist thereof is not exceeded.
実施例１〜５、比較例１〜７
下記表１に示す各成分を下記表１に示す配合割合にて配合し、３本ロールを用いて室温にて混合分散させて、実施例１〜５、比較例１〜７にて使用する熱硬化性樹脂組成物（樹脂ワニス）を調製した。そして、調製した上記樹脂ワニスを以下のように塗工して試験片を作製した。下記表１中の数字は質量部を示す。また、下記表１中の空欄は配合なしを意味する。
Examples 1-5, Comparative Examples 1-7
Heats used in Examples 1 to 5 and Comparative Examples 1 to 7 by blending the components shown in Table 1 below at the blending ratios shown in Table 1 and mixing and dispersing at room temperature using three rolls. A curable resin composition (resin varnish) was prepared. And the prepared said resin varnish was apply | coated as follows and the test piece was produced. The numbers in Table 1 below indicate parts by mass. Moreover, the blank in Table 1 below means no blending.
なお、表１中の各成分についての詳細は以下の通りである。 The details of each component in Table 1 are as follows.
（Ａ）液状エポキシ樹脂
・エピクロン８５０−Ｓ：ＤＩＣ社製、エポキシ当量１８８
(A) Liquid epoxy resin / Epicron 850-S: manufactured by DIC Corporation, epoxy equivalent 188
（Ｂ）軟化点１２５℃以下の固形エポキシ樹脂
・ＨＰ−７２００Ｈ：ＤＩＣ社製、エポキシ当量２８３、軟化点８３℃
・Ｎ−６９５：ＤＩＣ社製、エポキシ当量２０９〜２１９、軟化点９０〜１００℃
(B) Solid epoxy resin having a softening point of 125 ° C. or lower. HP-7200H: manufactured by DIC, epoxy equivalent 283, softening point 83 ° C.
N-695: manufactured by DIC, epoxy equivalents 209 to 219, softening point 90 to 100 ° C.
（Ｃ）ベンゾアート基および主鎖にポリメチレン基を有する芳香族ジアミン化合物
・エラストマー２５０Ｐ：イハラケミカル社製、融点６０℃
・ＣＵＡ−４：イハラケミカル社製、融点１２２℃
(C) Aromatic diamine compound / elastomer 250P having a benzoate group and a polymethylene group in the main chain: Ihara Chemical Co., Ltd., melting point 60 ° C.
-CUA-4: Ihara Chemical Co., Ltd., melting point 122 ° C
（Ｄ）Ｔｇが１３０℃以上のフェノキシ樹脂
・ＥＲＦ-００１Ｍ３０：新日鐵化学社製、Ｔｇ１４６℃、樹脂固形分３０質量％
・ＹＸ８１００ＢＨ３０：三菱化学社製、Ｔｇ１５０℃、樹脂固形分３０重量%
(D) Phenoxy resin with Tg of 130 ° C. or higher. ERF-001M30: manufactured by Nippon Steel Chemical Co., Ltd., Tg 146 ° C., resin solid content: 30% by mass
YX8100BH30: manufactured by Mitsubishi Chemical Corporation, Tg 150 ° C., resin solid content 30% by weight
（Ｅ）Ｔｇが２００℃以上、質量平均分子量が５００００以下である溶剤可溶性ポリアミドイミド樹脂
・バイロマックスＨＲ−１２Ｎ２：東洋紡社製、Ｔｇ２５５℃、質量平均分子量１１０００、樹脂固形分３０質量％
・ＨＰＣ−５０２０−３０：日立化成社製、Ｔｇ２５６℃、質量平均分子量３００００、樹脂固形分３０質量％
(E) Solvent-soluble polyamideimide resin / Vilomax HR-12N2 having a Tg of 200 ° C. or higher and a mass average molecular weight of 50,000 or less: manufactured by Toyobo Co., Ltd., Tg 255 ° C., mass average molecular weight 11000, resin solid content 30% by mass
-HPC-5020-30: manufactured by Hitachi Chemical Co., Ltd., Tg 256 ° C, mass average molecular weight 30000, resin solid content 30% by mass
（Ｆ）フィラー
・ハイジライトＨ−４２Ｍ：昭和電工社製
（Ｇ）難燃剤
・ラビトルＦＰ−１１０：伏見製薬所社製
(F) Filler Heidilite H-42M: Showa Denko Co., Ltd. (G) Flame retardant, Rabitol FP-110: Fushimi Pharmaceutical Co., Ltd.
その他の成分
・ＢＡＰＰ：セイカ社製、融点１２８℃
・ＬＡ−７０５４：ＤＩＣ社製、水酸基価１２５、樹脂固形分６０質量%
・ＹＰ−５５：新日鐵住金化学社製、Ｔｇ８４℃
・リカコートＳＮ−２０：新日本理化社製、Ｔｇ３００℃、質量平均分子量１３００００、樹脂固形分２０質量％
Other ingredients BAPP: Seika, melting point 128 ° C
LA-7054: DIC Corporation, hydroxyl value 125, resin solid content 60% by mass
YP-55: manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., Tg 84 ° C.
-Rika Coat SN-20: Shin Nippon Rika Co., Ltd., Tg 300 ° C., mass average molecular weight 130000, resin solid content 20% by mass
試験片作製工程
それぞれの樹脂ワニスについて、固形分４５質量％となるように溶剤（ＮＭＰ）で調整した。樹脂ワニスを３８μｍポリエチレンテレフタレートフィルム(ＰＥＴフィルム)上にダイコーターで塗布し１２０℃の温度で乾燥して厚さ５１μｍのＢ状態の熱硬化性樹脂組成物を有するフィルム(a)を製造した。また、揮発分は０．５質量％に調整した。保護フィルムとしてポリエチレンフィルム(ＰＥフィルム)をＢ状態の熱硬化性樹脂組成物上にラミネートした。その後、ポリエチレンフィルム（ラミネート）を剥離し、Ｂ状態の熱硬化性樹脂組成物上に１８μｍの表面処理なし銅箔を重ね合わせ、１７０℃×３分、１ＭＰａにてクイックプレスをした。その後、ポリエチレンテレフタレートフィルムを剥離してから、真空プレスに仕込み（真空度５torr）、１８０℃×１２０分、１ＭＰａにて、完全に硬化させて成形し、成形物（１）を得た。
Test piece preparation process About each resin varnish, it adjusted with the solvent (NMP) so that it might become 45 mass% of solid content. The resin varnish was coated on a 38 μm polyethylene terephthalate film (PET film) with a die coater and dried at a temperature of 120 ° C. to produce a film (a) having a 51 μm thick B state thermosetting resin composition. The volatile content was adjusted to 0.5% by mass. A polyethylene film (PE film) was laminated as a protective film on the thermosetting resin composition in the B state. Thereafter, the polyethylene film (laminate) was peeled off, and a copper foil without surface treatment of 18 μm was superimposed on the thermosetting resin composition in the B state, and a quick press was performed at 170 ° C. × 3 minutes and 1 MPa. Thereafter, the polyethylene terephthalate film was peeled off, then charged into a vacuum press (vacuum degree 5 torr), completely cured at 180 ° C. for 120 minutes at 1 MPa, and molded to obtain a molded product (1).
表面処理なし銅箔に代えて、処理足付きの銅箔を用いた以外は、上記成形物（１）の製法と同様にして、成形物（２）を得た。 A molded product (2) was obtained in the same manner as the molded product (1) except that a copper foil with treated feet was used instead of the copper foil without surface treatment.
厚さ２５μｍのオールポリイミド銅張板（銅箔１８μｍ）に、回路及びスルーホールを形成し、回路を黒色酸化銅処理してから、保護フィルムの剥離された上記フィルム（a）のＢ状態の熱硬化性樹脂組成物が塗工された側を、銅張板と重ね合わせることで、銅張板の両面を上記フィルム（a）でラミネートした。次に、１７０℃×３分、１ＭＰａにてクイックプレスをし、上記フィルム（a）のポリエチレンテレフタレートフィルムを剥離した。次に、両面に銅箔を重ね合わせ、真空プレスに仕込み（真空度１torr）、１８０℃×９０分、１ＭＰａにて、完全に硬化させて成形した。冷却後に真空プレスから取り出し、コンフォーマルマスク法で、銅箔をエッチングし、該エッチング部位からＣＯ２レーザーを照射し、熱硬化した熱硬化性樹脂組成物に所定孔径のブラインドビアを形成した。その後、過マンガン酸デスミア溶液でブラインドビアの表面粗化を行い、ブラインドビア内底部の残存物も溶解除去した。これに無電解銅メッキ０．５μｍ、電解銅メッキ２０μｍを付け、１８０℃×３０分のアフターベーキングを行った。これに回路を形成し、ビルドアップ層が片側１層の４層ビルドアップ多層プリント配線板(ＰＷＢ（Ｉ））を作製した。 A circuit and through-holes are formed on an all-polyimide copper-clad plate (copper foil 18 μm) having a thickness of 25 μm, the circuit is treated with black copper oxide, and then the heat in the B state of the film (a) from which the protective film has been peeled off The both sides of the copper-clad plate were laminated with the film (a) by overlapping the side coated with the curable resin composition with the copper-clad plate. Next, quick pressing was performed at 170 ° C. for 3 minutes at 1 MPa, and the polyethylene terephthalate film of the film (a) was peeled off. Next, copper foils were superposed on both sides, charged in a vacuum press (vacuum degree: 1 torr), 180 ° C. × 90 minutes, completely cured at 1 MPa, and molded. After cooling, it was taken out from the vacuum press, the copper foil was etched by a conformal mask method, and a CO 2 laser was irradiated from the etched portion to form a blind via having a predetermined hole diameter in the thermosetting resin composition. Thereafter, the surface of the blind via was roughened with a permanganate desmear solution, and the residue at the bottom of the blind via was dissolved and removed. Electroless copper plating 0.5 μm and electrolytic copper plating 20 μm were applied thereto, and after baking was performed at 180 ° C. for 30 minutes. A circuit was formed thereon, and a four-layer build-up multilayer printed wiring board (PWB (I)) having one build-up layer on one side was produced.
ＪＰＣＡ−ＨＤ０１のテストパターン基板を用いた以外は、上記ＰＷＢ（Ｉ）の作製方法に準拠して、多層プリント配線板(ＰＷＢ（ＩＩ））を作製した。 A multilayer printed wiring board (PWB (II)) was produced in accordance with the production method of PWB (I) except that a test pattern substrate of JPCA-HD01 was used.
なお、表２中、＊１）は、上記成形物（２）の銅箔の代わりに、酸化アルミニウム箔（ＡＬ１０６０）を使用したものである。また、＊２）は、上記成形物（２）の銅箔の代わりに、ポリイミドフィルムを使用したものである。 In Table 2, * 1) indicates that an aluminum oxide foil (AL1060) is used instead of the copper foil of the molded product (2). * 2) uses a polyimide film instead of the copper foil of the molded product (2).
評価方法を以下に示す。
（１）耐折性
ＭＩＴ試験：ＪＩＳ Ｐ ８１１５ 折り曲げ角度１３５°
（２）Ｔｇ
ＴＭＡ法 ＩＰＣ ＴＭ−６５０ ２．４．２４Ｃ
（３）ＣＴＥ（熱膨張率）
ＩＰＣ ＴＭ−６５０ ２．４．２４Ｃ
The evaluation method is shown below.
(1) Folding resistance MIT test: JIS P 8115 Bending angle 135 °
(2) Tg
TMA method IPC TM-650 2.4.24C
(3) CTE (thermal expansion coefficient)
IPC TM-650 2.4.24C
（４）ピール強度
ＩＰＣ ＴＭ−６５０ ２．４．８
（５）接続信頼性
ＪＰＣＡ−ＢＵ０１による（１２５℃×３０ｍｉｎ←→−６５℃×３０ｍｉｎ(１ｃｙｃｌｅ）
（６）絶縁信頼性
高温高湿バイアス試験 ８５℃×８５％ＲＨ、ＤＣ＝３０Ｖ (ただし槽内測定)
(4) Peel strength IPC TM-650 2.4.8
(5) Connection reliability According to JPCA-BU01 (125 ° C. × 30 min ← → −65 ° C. × 30 min (1 cycle)
(6) Insulation reliability High-temperature and high-humidity bias test 85 ° C x 85% RH, DC = 30 V (however, measured in the tank)
（７）レーザー加工性
ＣＯ２レーザー加工後のブラインドビア（トップ径１００μｍ）の樹脂ワニスの残渣を顕微鏡（×２００）にて観察した。
○：ブラインドビアの底部の１割以下の領域に樹脂ワニスの残渣あり
△：ブラインドビアの底部の１割超半分以下の領域に樹脂ワニスの残渣あり
×：ブラインドビアの底部の半分超の領域に樹脂ワニスの残渣あり
（８）デスミアエッチング性
過マンガン酸デスミア溶液処理後のブラインドビア（トップ径１００μｍ）について、樹脂ワニスの残渣を顕微鏡（×２００）にて観察した。
○：ブラインドビアの底部の１割以下の領域に樹脂ワニスの残渣あり
△：ブラインドビアの底部の１割超半分以下の領域に樹脂ワニスの残渣あり
×：ブラインドビアの底部の半分超の領域に樹脂ワニスの残渣あり
（９）樹脂ワニス相溶性
樹脂組成物の固形分を４５質量％に調整した樹脂ワニス（溶剤はＮＭＰ）を２５℃にて７日間放置して、ＮＭＰに対する樹脂ワニスの相溶性（樹脂ワニスの析出状態）を目視にて観察した。
○：析出なし
△：析出若干あり
×：析出あり
（１０）熱伝導率（Ｗ／ｍｋ）
レーザーフラッシュ法を用いて測定した。
(7) Laser processability The residue of the resin varnish of the blind via (top diameter 100 μm) after the CO 2 laser processing was observed with a microscope (× 200).
○: Resin varnish residue is present in the area of 10% or less of the bottom of the blind via △: Resin varnish residue is present in the area of more than 10% of the bottom of the blind via ×: In the area of more than half of the bottom of the blind via Resin varnish residue present (8) Desmear etchability Resin varnish residue was observed with a microscope (× 200) for blind vias (top diameter 100 μm) after permanganate desmear solution treatment.
○: Resin varnish residue is present in the area of 10% or less of the bottom of the blind via △: Resin varnish residue is present in the area of more than 10% of the bottom of the blind via ×: In the area of more than half of the bottom of the blind via Resin varnish residue present (9) Resin varnish compatibility Resin varnish with a solid content of the resin composition adjusted to 45% by mass (solvent is NMP) is allowed to stand at 25 ° C. for 7 days, and the resin varnish is compatible with NMP. (Precipitation state of resin varnish) was visually observed.
○: No precipitation Δ: Some precipitation ×: Precipitation (10) Thermal conductivity (W / mk)
Measurement was performed using a laser flash method.
評価結果を下記表２に示す。 The evaluation results are shown in Table 2 below.
表２に示すように、（Ａ）液状エポキシ樹脂と、（Ｂ）軟化点１２５℃以下の固形エポキシ樹脂と、（Ｃ）ベンゾアート基および主鎖にポリメチレン基を有する芳香族ジアミン化合物と、（Ｄ）Ｔｇが１３０℃以上のフェノキシ樹脂と、（Ｅ）Ｔｇが２００℃以上、質量平均分子量が５００００以下である溶剤可溶性ポリアミドイミド樹脂と、を含む実施例１〜５では、ピール強度、接続信頼性及び絶縁信頼性を向上させつつ、さらに、レーザー加工性、デスミアエッチング性及び樹脂ワニス相溶性に優れた熱硬化性樹脂組成物を得ることができた。実施例１〜５では、樹脂ワニス相溶性に優れるので、優れた塗工性（例えば、厚い硬化膜を形成する場合の塗工性）が得られることが判明した。また、実施例１〜５では、良好な熱伝導率を得ることができた。 As shown in Table 2, (A) a liquid epoxy resin, (B) a solid epoxy resin having a softening point of 125 ° C. or lower, (C) an aromatic diamine compound having a benzoate group and a polymethylene group in the main chain, In Examples 1 to 5 including D) a phenoxy resin having a Tg of 130 ° C. or more and (E) a solvent-soluble polyamideimide resin having a Tg of 200 ° C. or more and a mass average molecular weight of 50,000 or less, peel strength and connection reliability Furthermore, the thermosetting resin composition excellent in laser processability, desmear etching property, and resin varnish compatibility could be obtained while improving the property and insulation reliability. In Examples 1-5, since it was excellent in resin varnish compatibility, it turned out that the outstanding coating property (For example, coating property in the case of forming a thick cured film) is obtained. Moreover, in Examples 1-5, favorable thermal conductivity was able to be obtained.
さらにフィラーとして水酸化アルミニウムを配合した実施例５では、熱伝導率がさらに向上した。また、上記フィラーを配合しなかった実施例１〜４では、さらに、優れた耐折性が得られた。さらに、実施例では、Ｔｇが１２９℃以上と、良好な耐熱性が得られた。 Furthermore, in Example 5 which mix | blended aluminum hydroxide as a filler, thermal conductivity improved further. Moreover, in Examples 1-4 which did not mix | blend the said filler, the outstanding folding resistance was obtained further. Further, in the examples, Tg was 129 ° C. or higher and good heat resistance was obtained.
一方で、（Ｃ）成分ではない芳香族ジアミン化合物を配合した比較例１、芳香族ジアミン化合物を配合しなかった比較例２では、酸化アルミニウム箔とポリイミドフィルムに対するピール強度が低下した。また、液状エポキシ樹脂を配合しなかった比較例３、軟化点１２５℃以下の固形エポキシ樹脂を配合しなかった比較例４では、レーザー加工性、デスミアエッチング性が得られなかった。Ｔｇが１３０℃以上のフェノキシ樹脂に代えて、Ｔｇが１３０℃未満のフェノキシ樹脂を配合した比較例５では、酸化アルミニウム箔に対するピール強度と接続信頼性が低下し、レーザー加工性、デスミアエッチング性も得られなかった。 On the other hand, in Comparative Example 1 in which an aromatic diamine compound that is not the component (C) was blended and in Comparative Example 2 in which an aromatic diamine compound was not blended, the peel strength with respect to the aluminum oxide foil and the polyimide film was lowered. In Comparative Example 3 in which no liquid epoxy resin was blended and in Comparative Example 4 in which a solid epoxy resin having a softening point of 125 ° C. or lower was not blended, laser processability and desmear etching property were not obtained. In Comparative Example 5 in which a phenoxy resin having a Tg of less than 130 ° C. was blended instead of a phenoxy resin having a Tg of 130 ° C. or higher, the peel strength and connection reliability with respect to the aluminum oxide foil were lowered, and laser processability and desmear etching properties were also improved. It was not obtained.
Ｔｇが２００℃以上、質量平均分子量が５００００以下である溶剤可溶性ポリアミドイミド樹脂を配合しなかった比較例６では、銅箔、酸化アルミニウム箔、ポリイミドフィルムに対するピール強度、接続信頼性及び絶縁信頼性が、いずれも低下し、レーザー加工性、デスミアエッチング性も得られなかった。また、上記ポリアミドイミド樹脂に代えて、溶剤可溶性ポリイミド樹脂を配合した比較例７では、樹脂ワニス相溶性が得られなかったので、塗工性（例えば、厚い硬化膜を形成する場合の塗工性）が得られないことが判明した。 In Comparative Example 6 in which a solvent-soluble polyamideimide resin having a Tg of 200 ° C. or higher and a mass average molecular weight of 50,000 or less was not blended, the peel strength, connection reliability, and insulation reliability for copper foil, aluminum oxide foil, and polyimide film were , Both were lowered and neither laser processability nor desmear etching property was obtained. Further, in Comparative Example 7 in which a solvent-soluble polyimide resin was blended in place of the polyamide-imide resin, the resin varnish compatibility was not obtained, so that the coating property (for example, the coating property when forming a thick cured film) ) Was not obtained.
本発明は、接着性を向上させつつ、さらに、レーザー加工性、デスミアエッチング性及び塗工性に優れた熱硬化性樹脂組成物を得ることができ、また良好な熱伝導性を有するので、例えば、フレキシブルビルドアッププリント配線板用や放熱基板用として使用することができる。 The present invention can improve the adhesiveness, and further can obtain a thermosetting resin composition excellent in laser processability, desmear etching property and coating property, and has good thermal conductivity, for example, It can be used for flexible build-up printed wiring boards and heat dissipation boards.
Claims (10)
前記（Ｅ）溶剤可溶性ポリアミドイミド樹脂の質量：前記（Ｄ）成分のフェノキシ樹脂の質量が、１．０：３．０〜１．０：７．０であり、
前記（Ａ）液状エポキシ樹脂と前記（Ｂ）固形エポキシ樹脂と前記（Ｃ）芳香族ジアミン化合物との合計量１００質量部に対し、前記（Ｄ）フェノキシ樹脂と前記（Ｅ）溶剤可溶性ポリアミドイミド樹脂との合計量が、１０質量部以上４０質量部以下であり、
前記（Ｅ）溶剤可溶性ポリアミドイミド樹脂が、トリカルボン酸無水物とジイソシアネート化合物とをイミド化反応させた反応生成物及び／またはトリカルボン酸無水物のクロリドとジアミン化合物とをイミド化反応させた反応生成物を含むことを特徴とする熱硬化性樹脂組成物。 (A) a liquid epoxy resin, (B) a solid epoxy resin having a softening point of 125 ° C. or lower, (C) an aromatic diamine compound having a benzoate group and a polymethylene group in the main chain, and (D) Tg of 130 ° C. or higher. and phenoxy resin, a (E) Tg is 200 ° C. or higher, by weight and a solvent-soluble polyamide-imide resin average molecular weight of 50,000 or less, the including thermosetting resin composition,
The mass of the (E) solvent-soluble polyamideimide resin: the mass of the phenoxy resin of the component (D) is 1.0: 3.0 to 1.0: 7.0,
The (D) phenoxy resin and the (E) solvent-soluble polyamideimide resin with respect to 100 parts by mass of the total amount of the (A) liquid epoxy resin, the (B) solid epoxy resin, and the (C) aromatic diamine compound. And the total amount is 10 parts by mass or more and 40 parts by mass or less,
The (E) solvent-soluble polyamideimide resin is a reaction product obtained by imidizing a tricarboxylic acid anhydride and a diisocyanate compound and / or a reaction product obtained by imidizing a chloride of a tricarboxylic acid anhydride and a diamine compound. The thermosetting resin composition characterized by including .
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| KR102760652B1 (en) * | 2022-12-08 | 2025-02-03 | 국도화학 주식회사 | Solvent-soluble highly heat-resistant polyimide-based adhesive resin |
| WO2025115640A1 (en) * | 2023-11-27 | 2025-06-05 | 株式会社トクヤマ | Resin composition |
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| JP5245338B2 (en) * | 2006-10-11 | 2013-07-24 | 日立化成株式会社 | Polyamideimide, method for producing polyamideimide, and resin composition and resin varnish containing polyamideimide |
| JP5398087B2 (en) * | 2011-08-03 | 2014-01-29 | 株式会社タムラ製作所 | Adhesive for heat dissipation substrate and heat dissipation substrate |
| JP2013203950A (en) * | 2012-03-29 | 2013-10-07 | Tamura Seisakusho Co Ltd | Thermosetting resin composition, resin film, copper-clad sheet and flexible printed wiring board |
| JP2014058592A (en) * | 2012-09-14 | 2014-04-03 | Tamura Seisakusho Co Ltd | Thermosetting resin composition, resin film in b-stage, metal foil, copper-clad plate, and multilayer buildup substrate |
| JP6328414B2 (en) * | 2013-12-04 | 2018-05-23 | 株式会社タムラ製作所 | Flame retardant resin composition, B-staged resin film, metal foil with resin, and coverlay film |
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