JP4691401B2 - Adhesive composition for semiconductor device and adhesive sheet for semiconductor device - Google Patents
Adhesive composition for semiconductor device and adhesive sheet for semiconductor device Download PDFInfo
- Publication number
- JP4691401B2 JP4691401B2 JP2005181711A JP2005181711A JP4691401B2 JP 4691401 B2 JP4691401 B2 JP 4691401B2 JP 2005181711 A JP2005181711 A JP 2005181711A JP 2005181711 A JP2005181711 A JP 2005181711A JP 4691401 B2 JP4691401 B2 JP 4691401B2
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- Prior art keywords
- adhesive
- semiconductor device
- adhesive composition
- component
- mass
- Prior art date
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- 239000000853 adhesive Substances 0.000 title claims description 207
- 230000001070 adhesive effect Effects 0.000 title claims description 207
- 239000000203 mixture Substances 0.000 title claims description 91
- 239000004065 semiconductor Substances 0.000 title claims description 53
- 239000012790 adhesive layer Substances 0.000 claims description 64
- 239000003822 epoxy resin Substances 0.000 claims description 39
- 229920000647 polyepoxide Polymers 0.000 claims description 39
- -1 siloxane compound Chemical class 0.000 claims description 35
- 239000010410 layer Substances 0.000 claims description 30
- 239000007787 solid Substances 0.000 claims description 20
- 239000000178 monomer Substances 0.000 claims description 19
- 238000010521 absorption reaction Methods 0.000 claims description 17
- 125000000524 functional group Chemical group 0.000 claims description 16
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 12
- 239000005977 Ethylene Substances 0.000 claims description 12
- 238000005259 measurement Methods 0.000 claims description 12
- 229920006163 vinyl copolymer Polymers 0.000 claims description 12
- 239000005011 phenolic resin Substances 0.000 claims description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 150000008064 anhydrides Chemical group 0.000 claims description 3
- 238000004581 coalescence Methods 0.000 claims 1
- 239000000758 substrate Substances 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 26
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- 229920006267 polyester film Polymers 0.000 description 25
- 206010040844 Skin exfoliation Diseases 0.000 description 23
- 238000001035 drying Methods 0.000 description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 19
- 230000035882 stress Effects 0.000 description 19
- 239000004698 Polyethylene Substances 0.000 description 18
- 229920000573 polyethylene Polymers 0.000 description 18
- 238000005187 foaming Methods 0.000 description 17
- 238000011156 evaluation Methods 0.000 description 16
- 230000032798 delamination Effects 0.000 description 13
- 239000003973 paint Substances 0.000 description 13
- 239000004593 Epoxy Substances 0.000 description 12
- 239000011889 copper foil Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 230000006866 deterioration Effects 0.000 description 10
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- 230000008859 change Effects 0.000 description 8
- 239000008199 coating composition Substances 0.000 description 8
- 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 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
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- 239000000463 material Substances 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
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- 241000482268 Zea mays subsp. mays Species 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 5
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- 229910052802 copper Inorganic materials 0.000 description 5
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 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 description 4
- 239000007822 coupling agent Substances 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
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- 239000002356 single layer Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-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
- 239000004642 Polyimide Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
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- 238000012545 processing Methods 0.000 description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- DMMPEDIYXNEVTK-UHFFFAOYSA-N N[SiH](N)O[SiH3] Chemical compound N[SiH](N)O[SiH3] DMMPEDIYXNEVTK-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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920003987 resole Polymers 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
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- 238000000926 separation method Methods 0.000 description 2
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- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- SSUJUUNLZQVZMO-UHFFFAOYSA-N 1,2,3,4,8,9,10,10a-octahydropyrimido[1,2-a]azepine Chemical compound C1CCC=CN2CCCNC21 SSUJUUNLZQVZMO-UHFFFAOYSA-N 0.000 description 1
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OFEAOSSMQHGXMM-UHFFFAOYSA-N 12007-10-2 Chemical compound [W].[W]=[B] OFEAOSSMQHGXMM-UHFFFAOYSA-N 0.000 description 1
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
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- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- CXXSQMDHHYTRKY-UHFFFAOYSA-N 4-amino-2,3,5-tris(oxiran-2-ylmethyl)phenol Chemical compound C1=C(O)C(CC2OC2)=C(CC2OC2)C(N)=C1CC1CO1 CXXSQMDHHYTRKY-UHFFFAOYSA-N 0.000 description 1
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- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
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- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
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- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
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- UACSZOWTRIJIFU-UHFFFAOYSA-N hydroxymethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCO UACSZOWTRIJIFU-UHFFFAOYSA-N 0.000 description 1
- GJIDOLBZYSCZRX-UHFFFAOYSA-N hydroxymethyl prop-2-enoate Chemical compound OCOC(=O)C=C GJIDOLBZYSCZRX-UHFFFAOYSA-N 0.000 description 1
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
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- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
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- 229920001778 nylon Polymers 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- IGALFTFNPPBUDN-UHFFFAOYSA-N phenyl-[2,3,4,5-tetrakis(oxiran-2-ylmethyl)phenyl]methanediamine Chemical compound C=1C(CC2OC2)=C(CC2OC2)C(CC2OC2)=C(CC2OC2)C=1C(N)(N)C1=CC=CC=C1 IGALFTFNPPBUDN-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920003055 poly(ester-imide) Polymers 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Die Bonding (AREA)
Description
本発明は、各種の半導体を用いてなる半導体装置に好適に用いられる半導体装置用接着剤組成物および半導体装置用接着シートに関する。 The present invention relates to an adhesive composition for a semiconductor device and an adhesive sheet for a semiconductor device that are suitably used for a semiconductor device using various semiconductors.
携帯電話、ノートＰＣ等の電子機器の小型・軽量化、高速・高機能化に伴い、ＩＣチップも高集積・高速化し、実装技術もＱＦＰ（Ｑｕａｄ Ｆｌａｔ Ｐａｃｋａｇｅ；リードがパッケージの４辺に設けられたタイプ）から、ＢＧＡ（Ｂａｌｌ ＧｒｉｄＡｒｒａｙ）、ＣＳＰ（Ｃｈｉｐ Ｓｃａｌｅ Ｐａｃｋａｇｅ）、ＭＣＰ（Ｍｕｌｔｉ Ｃｈｉｐ Ｐａｃｋａｇｅ）等の新たな実装形態へと発展してきた。
それに伴い、ＩＣチップ等の半導体が搭載される側の基板についても、リードフレームからテープ基板、プリント基板と、微細化・高密度化が可能な構造に変化している。特に、配線を積層する方式であるビルトアップ基板の役割が重要になってきている。
これらの基板は、通常、支持体上に、配線と、該配線を電気的に絶縁する絶縁層とが設けられている。かかる絶縁層は電気的な絶縁性を保証することが重要であり、また、そのほかにも様々な特性が要求される。
As electronic devices such as mobile phones and notebook PCs become smaller, lighter, faster, and more functional, IC chips also become more integrated and faster, and the mounting technology is QFP (Quad Flat Package). Leads are provided on the four sides of the package. Type) to new mounting forms such as BGA (Ball Grid Array), CSP (Chip Scale Package), and MCP (Multi Chip Package).
Along with this, the substrate on which a semiconductor such as an IC chip is mounted has also changed from a lead frame to a tape substrate and a printed substrate, and a structure that can be miniaturized and densified. In particular, the role of a built-up substrate, which is a method of laminating wiring, has become important.
In these substrates, a wiring and an insulating layer that electrically insulates the wiring are usually provided on a support. It is important for such an insulating layer to ensure electrical insulation, and various other characteristics are required.
たとえば、一般的に用いられている基板の製造方法として、表面に配線回路が形成された支持体と、未硬化の接着剤を主成分とする接着剤層を有する接着シートとを、配線と接着剤層とが接するように貼り合わせ、接着剤層が配線間に埋め込み、該接着剤層を熱等により硬化させる方法がある。ここでは、硬化した接着剤層が絶縁層として機能する。このとき、接着剤層内に発泡が生じたり、配線との間に隙間が残ったりすると絶縁性が良くないため、接着剤層には、配線の埋め込み時に、発泡したり隙間を生じたりすることなく配線間に埋め込まれる埋め込み性が求められる。かかる埋め込み性は、配線が微細化・高密度化するほど重要になってくる。
上述のような接着剤層に用いられる接着剤としては、通常、ポリイミド樹脂、エポキシ樹脂、フェノ−ル樹脂、スチレン−ブタジエン−スチレンブロック共重合体等のジエンを有する重合体（ジオレフィン系樹脂）などの熱硬化性樹脂が用いられている。
For example, as a generally used substrate manufacturing method, a support having a wiring circuit formed on the surface and an adhesive sheet having an adhesive layer mainly composed of an uncured adhesive are bonded to the wiring. There is a method in which bonding is performed so that the adhesive layer is in contact, the adhesive layer is embedded between wirings, and the adhesive layer is cured by heat or the like. Here, the cured adhesive layer functions as an insulating layer. At this time, if foaming occurs in the adhesive layer or if there is a gap between the wiring, insulation is not good, so the adhesive layer may foam or create a gap when embedding the wiring. There is a need for embedding between the wirings. Such embeddability becomes more important as the wiring becomes finer and denser.
As an adhesive used for the adhesive layer as described above, a polymer having a diene such as a polyimide resin, an epoxy resin, a phenol resin, a styrene-butadiene-styrene block copolymer (diolefin resin) is usually used. Thermosetting resins such as are used.
接着剤には、さらに、耐熱性、耐熱温度サイクル性、応力変化に対する応力緩和性なども必要とされる。
たとえば、ＩＣパッケージは、駆動時には、ＩＣの発熱のため１００℃以上の温度になる。つまり、ＩＣパッケージは、室温〜高温（１００℃以上）の温度変化に曝されることとなる。したがって、ＩＣパッケージには、その場合に発生する高温に対する耐熱性、温度変化に対する耐熱温度サイクル性が求められている。
また、金属等の配線、該配線が形成された支持体、絶縁層など、熱膨張率の異なるもの同士が張り合わされるため、上述のような高温時や温度変化の際に、熱膨張率の違いによって生じる応力の変化に対応するために応力緩和性が求められる。特に近年、実装密度が上がり、金属等の配線が占める割合が増大するなか、応力緩和性の向上が重要となっている。
また、配線を積層するビルトアップ基板の場合、同時に、複数層の絶縁層を設けるため、接着剤の硬化のための加熱を積層枚数分行わなければならず、その時の耐熱性も必要となる。
The adhesive further requires heat resistance, heat temperature cycleability, stress relaxation against stress change, and the like.
For example, when the IC package is driven, the temperature becomes 100 ° C. or higher due to heat generated by the IC. That is, the IC package is exposed to a temperature change from room temperature to high temperature (100 ° C. or more). Therefore, the IC package is required to have heat resistance against high temperatures generated in that case and heat resistance temperature cycle resistance against temperature changes.
In addition, since wires with different coefficients of thermal expansion, such as wiring made of metal, a support on which the wiring is formed, and an insulating layer are bonded together, the coefficient of thermal expansion is Stress relaxation is required to cope with stress changes caused by differences. In particular, in recent years, as the mounting density has increased and the proportion of wiring such as metal has increased, it has become important to improve stress relaxation.
Further, in the case of a built-up substrate on which wirings are laminated, since a plurality of insulating layers are provided at the same time, heating for curing the adhesive must be performed for the number of laminated layers, and heat resistance at that time is also required.
しかしながら、上述したような従来の接着剤は、これらの特性を充分に満足するものではなかった。
具体的には、これらの接着剤層は、フロ−性が悪く、たとえば高密度に配された配線に接着剤層を埋め込む場合には、顕著な泡の巻き込みが発生する。そして、フロー性を高めるべく、接着剤層の粘度を下げると、上記張り合わせの際に、接着剤層のはみ出しが多くなりすぎて加工性が悪くなるなどの問題がある。
また、ＩＣチップ等の半導体装置とされた後においては、室温〜高温（１００℃以上）の温度変化が繰り返されて生じる応力によって、絶縁層とＩＣチップとの間、もしくは該基板の内部で、絶縁層に起因する層間剥離や基板の反りを引き起こすことがあった。このような問題は、特に、配線および絶縁層が複数積層されるビルトアップ基板等の積層基板において顕著である。そして、層間剥離や反りは、半導体装置の電気的信頼性を低下させてしまうため、その改善が求められる。
However, the conventional adhesives as described above do not sufficiently satisfy these characteristics.
Specifically, these adhesive layers have poor flow properties. For example, when the adhesive layer is embedded in wiring arranged at a high density, significant bubble entrainment occurs. If the viscosity of the adhesive layer is lowered in order to improve the flowability, there is a problem that the adhesive layer is excessively protruded and the workability is deteriorated during the pasting.
In addition, after a semiconductor device such as an IC chip, the stress generated by repeated temperature changes from room temperature to high temperature (100 ° C. or higher), between the insulating layer and the IC chip, or inside the substrate, In some cases, delamination caused by the insulating layer or warpage of the substrate may occur. Such a problem is particularly noticeable in a laminated substrate such as a built-up substrate in which a plurality of wirings and insulating layers are laminated. Further, delamination and warpage deteriorate the electrical reliability of the semiconductor device, and hence improvement is required.
さらに、上述のような積層型の高密度実装方法では、基板として、薄型にする目的で、絶縁フィルムに接着剤層を介して銅箔等の金属層を積層した、ＴＡＢ（Ｔａｐｅ Ａｕｔｏｍａｔｅｄ Ｂｏｎｄｉｎｇ）基板、フレキシブル基板（ＦＰＣ）等を使用する場合が多くなっており、絶縁フィルムとしては、ポリイミド樹脂等の樹脂フィルムが多く用いられている。
しかし、これまでの接着剤は、これらの絶縁フィルムや金属層に対する接着力が充分ではなかったり、その後の温度変化等により接着力が低下しやすい等の問題がある。特に、ポリイミドフィルムに対しては非常に接着しにくい。
この接着力には、支持体界面の状態が大きく影響するが、その他にも、接着剤の吸湿性なども影響し、たとえば吸湿性が低いほど接着力の変化が抑制される傾向があり、吸湿性の低い接着剤が望まれる。
Further, in the above-described laminated high-density mounting method, a TAB (Tape Automated Bonding) substrate in which a metal layer such as a copper foil is laminated on an insulating film via an adhesive layer for the purpose of thinning the substrate. In many cases, a flexible substrate (FPC) or the like is used, and a resin film such as a polyimide resin is often used as an insulating film.
However, conventional adhesives have problems such as insufficient adhesive strength to these insulating films and metal layers, and the adhesive strength tends to decrease due to subsequent temperature changes. In particular, it is very difficult to adhere to a polyimide film.
This adhesive force is greatly influenced by the state of the support interface, but also affects the hygroscopicity of the adhesive. For example, the lower the hygroscopicity, the more the change in adhesive force tends to be suppressed. An adhesive with low properties is desired.
さらに近年、鉛フリー化によりＩＲリフロー温度が高くなっている。そのため、接着剤層に含まれる水分がリフロー時に気化し、接着剤を押しのけて膨れ（ボイド）を生じるポップコーン現象が発生しやすくなっている。
現在、このポップコーン現象の原因となる水分を除去するため、リフロー前の半製品を防湿状態で管理することが行われている。
しかし、防湿状態での管理には多大な作業量とコストがかかるため、防湿状態の管理を必要とすることなくリフロー時のポップコーン現象の発生を抑制できる、耐リフロー性に優れた接着剤組成物が求められている。
Further, in recent years, the IR reflow temperature has increased due to the lead-free process. Therefore, the moisture contained in the adhesive layer is easily vaporized at the time of reflow, and the popcorn phenomenon that causes the adhesive to push away and swell (void) tends to occur.
Currently, in order to remove the water that causes the popcorn phenomenon, the semi-finished product before reflow is managed in a moisture-proof state.
However, since the management in the moisture-proof state requires a large amount of work and cost, the adhesive composition with excellent reflow resistance can suppress the occurrence of the popcorn phenomenon during reflow without requiring the management of the moisture-proof state. Is required.
また、接着剤は、配線に接触する材料であるため、過酷な環境下でも高い絶縁性が維持されるといった電気的な信頼性も重要であるが、従来、温度変化が繰り返されたり、長期間熱にさらされた場合に、絶縁性が低下し、電食等の不具合を生じやすいという問題もある。 In addition, since the adhesive is a material that comes into contact with the wiring, it is also important to have electrical reliability that maintains high insulation even in harsh environments. There is also a problem that when exposed to heat, the insulating properties are reduced and problems such as electrolytic corrosion are likely to occur.
このような要求に対して、本出願人は、たとえば特許文献１において、エポキシ化スチレン−ブタジエン−スチレンブロック共重合体を用いた接着剤組成物を提案している。
しかし、かかる接着剤組成物は、種々の優れた特性を有しているものの、上述したようなポリイミドフィルム等の絶縁フィルムや銅箔等の金属層に対する接着力は充分ではなかった。
また、温度変化が繰り返されたり、長期間熱にさらされた場合に、接着力等の特性が劣化する場合があり、耐熱劣化性が充分ではないという問題もある。
本発明は、上記事情に鑑みてなされたものであって、種々の優れた特性を有し、特に、接着力および耐熱劣化性に優れた半導体装置用接着剤組成物および半導体装置用接着シートを提供することを目的とする。
However, although such an adhesive composition has various excellent properties, the adhesive strength to an insulating film such as a polyimide film as described above and a metal layer such as a copper foil is not sufficient.
Further, when the temperature change is repeated or when exposed to heat for a long period of time, characteristics such as adhesive strength may be deteriorated, and there is a problem that the heat deterioration resistance is not sufficient.
The present invention has been made in view of the above circumstances, and has various excellent characteristics, in particular, an adhesive composition for semiconductor devices and an adhesive sheet for semiconductor devices, which are excellent in adhesive strength and heat deterioration resistance. The purpose is to provide.
上記課題を解決する本発明の第一の態様は、エポキシ樹脂（Ａ）と、フェノール樹脂（Ｂ）と、モノマー成分として、エチレンと、グリシジル基またはカルボキシル基（無水物基を含む）を有する不飽和カルボン酸またはその誘導体とを有するビニル共重合体（Ｃ）と、下記一般式（１）又は一般式（２）で示されるシロキサン化合物からなる群から選択される少なくとも１種のシロキサン化合物（Ｄ）と、を含有し、前記エポキシ樹脂（Ａ）の含有量が、全固形量の３〜４５質量％であり、前記フェノール樹脂（Ｂ）の含有量が、全固形量の２〜３０質量％であり、前記ビニル共重合体（Ｃ）の含有量が、全固形量の２０〜８０質量％であり、前記シロキサン化合物（Ｄ）の含有量が、全固形量の０．０５〜１０質量％であり、かつ硬化前の動的粘弾性測定における最低溶融粘度が４００〜５００００Ｐａ．ｓの範囲内であることを特徴とする半導体装置用接着剤組成物である。
上記課題を解決する本発明の第二の態様は、支持体の少なくとも一面に、第一の態様の半導体装置用接着剤組成物からなる接着剤層が積層してなることを特徴とする半導体装置用接着シートである。
本発明の第三の態様は、金属層の少なくとも一面に、第一の態様の半導体装置用接着剤組成物からなる接着剤層と、絶縁性フィルムまたは剥離性フィルムとが順次積層してなることを特徴とする半導体装置用接着シートである。
本発明の第四の態様は、絶縁性フィルムの両面に、第一の態様の半導体装置用接着剤組成物からなる接着剤層と、絶縁性フィルムまたは剥離性フィルムとが順次積層してなることを特徴とする半導体装置用接着シートである。
The first aspect of the present invention that solves the above problems is an epoxy resin (A), a phenol resin (B), and a monomer component having ethylene and a glycidyl group or carboxyl group (including an anhydride group). At least one siloxane compound (D) selected from the group consisting of a vinyl copolymer (C) having a saturated carboxylic acid or a derivative thereof and a siloxane compound represented by the following general formula (1) or general formula (2) And the content of the epoxy resin (A) is 3 to 45% by mass of the total solid amount, and the content of the phenol resin (B) is 2 to 30% by mass of the total solid amount. The content of the vinyl copolymer (C) is 20 to 80% by mass of the total solid amount, and the content of the siloxane compound (D) is 0.05 to 10% by mass of the total solid amount. , and the and before curing Minimum melt viscosity in a dynamic viscoelasticity measurement 400～50000Pa. It is the adhesive composition for semiconductor devices characterized by being in the range of s.
According to a second aspect of the present invention for solving the above-mentioned problems, a semiconductor device is characterized in that an adhesive layer made of the adhesive composition for a semiconductor device according to the first aspect is laminated on at least one surface of a support. It is an adhesive sheet for use.
In the third aspect of the present invention, an adhesive layer composed of the adhesive composition for a semiconductor device of the first aspect and an insulating film or a peelable film are sequentially laminated on at least one surface of the metal layer. It is the adhesive sheet for semiconductor devices characterized by these.
According to a fourth aspect of the present invention, an adhesive layer made of the adhesive composition for a semiconductor device of the first aspect and an insulating film or a peelable film are sequentially laminated on both surfaces of the insulating film. It is the adhesive sheet for semiconductor devices characterized by these.
本発明によれば、埋め込み性、耐熱性、耐熱温度サイクル性、応力緩和性、電気的信頼性、接着性、耐リフロー性等に優れ、吸湿性が低いなど、種々の特性に優れ、特に接着性および耐熱劣化性に優れた接着剤組成物および接着シートを提供することができる。
そのため、本発明の接着剤組成物および接着シートによれば、たとえば温度変化が繰り返されることによる層間剥離や反り等の不良を解決することができる。したがって、本発明の接着剤組成物および接着シートによって、半導体装置の信頼性を向上させることができる。
また、耐湿性も高く、たとえば接着剤に含まれる水分がリフロー時に気化することによって発生するポップコーン現象を改善できるなど、耐リフロー性にも優れている。そのため、リフロー前の半製品を防湿状態で管理する手間が低減される。
さらに、本発明の接着シートは加工性にも優れており、工業的に提供することが容易である。
According to the present invention, it has excellent various characteristics such as excellent embedding property, heat resistance, heat resistance temperature cycle property, stress relaxation property, electrical reliability, adhesion property, reflow resistance property, etc. An adhesive composition and an adhesive sheet excellent in heat resistance and heat deterioration resistance can be provided.
Therefore, according to the adhesive composition and adhesive sheet of the present invention, defects such as delamination and warpage due to repeated temperature changes can be solved. Therefore, the reliability of the semiconductor device can be improved by the adhesive composition and the adhesive sheet of the present invention.
Also, the moisture resistance is high, and for example, the popcorn phenomenon generated when the moisture contained in the adhesive is vaporized at the time of reflow can be improved. Therefore, the trouble of managing the semi-finished product before reflow in a moisture-proof state is reduced.
Furthermore, the adhesive sheet of the present invention is excellent in processability and can be easily provided industrially.
以下、本発明を詳細に説明する。
＜半導体装置用接着剤組成物＞
本発明の第一の態様の半導体装置用接着剤組成物（以下、単に接着剤組成物ということがある。）は、エポキシ樹脂（Ａ）（以下、（Ａ）成分という）と、フェノール樹脂（Ｂ）（以下、（Ｂ）成分という）、モノマー成分として少なくとも特定の２種を含有するビニル共重合体（Ｃ）（以下、（Ｃ）成分という）とを必須成分として含有する、熱硬化型の接着剤組成物である。
Hereinafter, the present invention will be described in detail.
<Adhesive composition for semiconductor device>
The adhesive composition for a semiconductor device according to the first aspect of the present invention (hereinafter sometimes simply referred to as an adhesive composition) comprises an epoxy resin (A) (hereinafter referred to as component (A)) and a phenol resin ( B) (hereinafter referred to as component (B)), a vinyl copolymer (C) (hereinafter referred to as component (C)) containing at least two specific types as monomer components, and a thermosetting type It is an adhesive composition.
また、本発明の接着剤組成物は、硬化前の動的粘弾性測定における最低溶融粘度が４００Ｐａ．ｓ〜５００００Ｐａ．ｓである必要がある。
硬化前の動的粘弾性測定における最低溶融粘度が４００Ｐａ．ｓ以上であると、加工時の樹脂流れが小さく、また、５００００Ｐａ．ｓ以下であると、配線が埋まり込みやすく、貼り合わせ面の凹凸に左右されにくい。つまり、最低溶融粘度が４００〜５００００Ｐａ．ｓの範囲であることにより、本発明の接着剤組成物は、配線、特に高密度に配された配線への埋め込み性が良好なものとなる。また、加工も非常にし易いものとなる。
上記最低溶融粘度は、（Ａ）成分、（Ｂ）成分、（Ｃ）成分等の種類や配合量等を調整する等によって調整できる。たとえば、後述するように、組成物中の（Ｃ）成分の配合量を全固形分の２０〜８０質量％の範囲内で調整する等により、該最低溶融粘度を調整できる。
Further, the adhesive composition of the present invention has a minimum melt viscosity of 400 Pa.s in dynamic viscoelasticity measurement before curing. s to 50000 Pa. It must be s.
The minimum melt viscosity in the measurement of dynamic viscoelasticity before curing is 400 Pa. s or more, the resin flow during processing is small, and 50000 Pa. If it is s or less, the wiring is easily buried and hardly affected by the unevenness of the bonding surface. That is, the minimum melt viscosity is 400 to 50000 Pa. By being in the range of s, the adhesive composition of the present invention has good embeddability in wiring, particularly wiring arranged at high density. In addition, processing becomes very easy.
The minimum melt viscosity can be adjusted by adjusting the type and blending amount of the component (A), the component (B) and the component (C). For example, as will be described later, the minimum melt viscosity can be adjusted by adjusting the blending amount of the component (C) in the composition within a range of 20 to 80% by mass of the total solid content.
なお、本発明において、硬化前の動的粘弾性測定における最低溶融粘度は、次の条件にて粘度変化を測定した際の粘度の最低値である。
［最低溶融粘度の測定条件］
・装置：剪断弾性率測定装置（ＨＡＡＫＥ社製Ｒｈｅｏ Ｓｔｒｅｓｓ ＲＳ７５（製品名））
・測定温度範囲：−１０℃〜３００℃
・昇温速度：３℃／ｍｉｎ
・測定周波数：１Ｈｚ
・加重：１５Ｎ
・歪み率：０．０１％±０．００２５％
In addition, in this invention, the minimum melt viscosity in the dynamic viscoelasticity measurement before hardening is the minimum value of the viscosity at the time of measuring a viscosity change on the following conditions.
[Minimum melt viscosity measurement conditions]
・ Apparatus: Shear modulus measuring device (Rheo Stress RS75 (product name) manufactured by HAAKE)
Measurement temperature range: -10 ° C to 300 ° C
・ Rise rate: 3 ° C / min
・ Measurement frequency: 1Hz
・ Weight: 15N
-Strain rate: 0.01% ± 0.0025%
また、本発明の接着剤組成物は、硬化後の２００〜２８０℃における動的弾性率が５００Ｐａ〜２００Ｍｐａの範囲内であることが好ましく、１ＭＰａ〜１００Ｍｐａの範囲内であることがより好ましい。
すなわち、本発明の接着剤組成物を用いて支持体上に接着剤層を形成して得られる接着シートは、被着体に貼付（仮接着）した後、加熱し、接着剤組成物を硬化させることにより被着体と接着される。そして、硬化した接着剤組成物は、ＢＧＡ、積層基板などをメイン基板に、ハンダボールを介して実装させる際のリフロー工程（ハンダ付けの工程）時に、２００〜２８０℃に加熱される。したがって、硬化後の２００〜２８０℃における動的弾性率が５００Ｐａ〜２００Ｍｐａの範囲内であると、リフロー工程時のボイドの発生が抑制され、耐リフロー性が向上する。また、応力緩和性にも優れたものとなる。
なお、上記動的弾性率は、剥離性フィルム上に、当該接着剤組成物を用いて硬化後の厚さが１００μｍである接着剤層を設けた接着シートについて、接着剤組成物を硬化させた後、剥離性フィルムを取り除き、オリエンテック社製のレオバイブロンＤＤＶ−ＩＩを用いて、周波数１１Ｈｚ、昇温速度３℃／分で測定した値である。
The adhesive composition of the present invention preferably has a dynamic elastic modulus at 200 to 280 ° C. after curing in the range of 500 Pa to 200 Mpa, and more preferably in the range of 1 MPa to 100 Mpa.
That is, an adhesive sheet obtained by forming an adhesive layer on a support using the adhesive composition of the present invention is applied (temporary adhesion) to an adherend and then heated to cure the adhesive composition. To adhere to the adherend. The cured adhesive composition is heated to 200 to 280 ° C. during a reflow process (soldering process) when mounting a BGA, a laminated substrate or the like on a main substrate via solder balls. Therefore, when the dynamic elastic modulus at 200 to 280 ° C. after curing is in the range of 500 Pa to 200 Mpa, the generation of voids during the reflow process is suppressed, and the reflow resistance is improved. In addition, the stress relaxation property is excellent.
In addition, the said dynamic elastic modulus hardened the adhesive composition about the adhesive sheet which provided the adhesive layer whose thickness after hardening is 100 micrometers using the said adhesive composition on a peelable film. Thereafter, the peelable film was removed, and a value measured at a frequency of 11 Hz and a heating rate of 3 ° C./min using Leovibron DDV-II manufactured by Orientech.
本発明の接着剤組成物は、リフロー工程等においてボイドが発生し、ポップコーン現象を引き起こす主原因が水分であることから、耐リフロー性の向上のためには、硬化後の吸湿率が１％以下であることが好ましい。
吸湿率の下限としては特に制限はなく、吸湿率が小さいほど、上記効果に優れ、好ましい。
上記吸湿率は、（Ａ）成分、（Ｂ）成分、（Ｃ）成分等の種類や配合量を調整する等によって調整できる。たとえば、後述するように、組成物中の（Ｃ）成分の配合量を全固形分の２０〜８０質量％の範囲内で調整する、（Ａ）成分と（Ｂ）成分との比率を官能基当量比で１：０．６〜１：１．４の範囲内で調整する等により、吸湿率を調整できる。
In the adhesive composition of the present invention, voids are generated in the reflow process and the like, and moisture is the main cause of the popcorn phenomenon. Therefore, in order to improve the reflow resistance, the moisture absorption after curing is 1% or less. It is preferable that
There is no restriction | limiting in particular as a minimum of a moisture absorption rate, and the said effect is excellent and preferable, so that a moisture absorption rate is small.
The moisture absorption rate can be adjusted by adjusting the type and amount of the component (A), the component (B), the component (C), and the like. For example, as will be described later, the ratio of the component (A) to the component (B) is adjusted so that the amount of the component (C) in the composition is adjusted within the range of 20 to 80% by mass of the total solid content. The moisture absorption rate can be adjusted by adjusting the equivalent ratio within the range of 1: 0.6 to 1: 1.4.
本発明の接着剤組成物は、硬化後の引っ張り伸び率が３０％以上であることが好ましい。引っ張り伸び率が３０％以上であれば、応力緩和性が向上し、たとえば異種材料の貼り合わせた場合に、高温時や温度変化時における各材料間の熱膨張の差が緩和され、熱膨張の差による基板の反りや層間剥離を抑制できる。
上記引っ張り伸び率は、（Ａ）成分、（Ｂ）成分、（Ｃ）成分等の種類や配合量等を調整する等によって調整できる。たとえば、後述するように、組成物中の（Ｃ）成分の配合量を全固形分の２０〜８０質量％の範囲内で調整する、（Ａ）成分と（Ｂ）成分との比率を官能基当量比で１：０．６〜１：１．４の範囲内で調整する、（Ｃ）成分中の不飽和カルボン酸またはその誘導体の割合を０．１〜４０質量％の範囲内で調整する、（Ｃ）成分の官能基当量を１００〜２５００の範囲内で調整する等により、引っ張り伸び率を調整できる。
The adhesive composition of the present invention preferably has a tensile elongation after curing of 30% or more. If the tensile elongation is 30% or more, the stress relaxation property is improved. For example, when different materials are bonded together, the difference in thermal expansion between the materials at high temperature or temperature change is alleviated, and thermal expansion is reduced. Substrate warpage and delamination due to the difference can be suppressed.
The tensile elongation can be adjusted by adjusting the type and blending amount of the component (A), the component (B), the component (C), and the like. For example, as will be described later, the ratio of the component (A) to the component (B) is adjusted so that the amount of the component (C) in the composition is adjusted within the range of 20 to 80% by mass of the total solid content. The ratio of the unsaturated carboxylic acid or its derivative in the component (C) is adjusted within the range of 0.1 to 40% by mass, adjusted in an equivalent ratio within the range of 1: 0.6 to 1: 1.4. The tensile elongation can be adjusted by adjusting the functional group equivalent of the component (C) within the range of 100 to 2500.
さらに、本発明の接着剤組成物は、硬化後、さらに１５０℃の環境に２４時間放置した後の２００℃〜２８０℃における動的弾性率が５００Ｐａ〜５００ＭＰａの範囲内であることが好ましく、３ＭＰａ〜２００ＭＰａの範囲内であることがより好ましい。
たとえば、ビルトアップ工法により基板が製造される場合は、複数の接着剤層を積層するため、接着剤を硬化させるために、積層枚数分の硬化温度を掛けなければならない。その為、その時繰り返し曝される硬化温度に対する耐熱劣化性も重要となる。したがって、硬化後に１５０℃の２４時間放置する加速試験を行った後にも、２００℃〜２８０℃における動的弾性率が５００Ｐａ〜５００ＭＰａの範囲であると、耐熱劣化性が非常に優れている。
ここで、動的弾性率の測定は、接着剤組成物を硬化させた後、さらに１５０℃の環境に２４時間放置する以外は、前記硬化後の２００〜２８０℃における動的弾性率と同様にして測定できる。
上記動的弾性率は、（Ａ）成分、（Ｂ）成分、（Ｃ）成分等の種類や配合量等を調整する等によって調整できる。たとえば、後述するように、（Ｃ）成分の官能基当量を１００〜２５００の範囲内で調整する等により、該動的弾性率を調整できる。
Furthermore, the adhesive composition of the present invention preferably has a dynamic elastic modulus at 200 ° C. to 280 ° C. after being allowed to stand in an environment of 150 ° C. for 24 hours after curing, within a range of 500 Pa to 500 MPa. More preferably, it is in the range of -200 MPa.
For example, when a substrate is manufactured by a built-up method, a plurality of adhesive layers are stacked, and thus a curing temperature corresponding to the number of stacked layers must be applied in order to cure the adhesive. For this reason, the heat deterioration resistance with respect to the curing temperature repeatedly exposed at that time is also important. Accordingly, even after an accelerated test that is allowed to stand at 150 ° C. for 24 hours after curing, if the dynamic elastic modulus at 200 ° C. to 280 ° C. is in the range of 500 Pa to 500 MPa, the heat deterioration resistance is very excellent.
Here, the dynamic elastic modulus is measured in the same manner as the dynamic elastic modulus at 200 to 280 ° C. after curing, except that the adhesive composition is cured and then left in an environment of 150 ° C. for 24 hours. Can be measured.
The dynamic elastic modulus can be adjusted by adjusting the type and blending amount of the component (A), the component (B), the component (C), and the like. For example, as described later, the dynamic elastic modulus can be adjusted by adjusting the functional group equivalent of the component (C) within the range of 100 to 2500.
さらに、本発明の接着剤組成物は、硬化後の、ポリイミドフィルム（商品名：ユーピレックス５０Ｓ，宇部興産社製）との間の接着力が、１８０°方向に引き剥がした場合において４．５Ｎ／ｃｍ以上であり、かつ硬化後、温度１２１℃、湿度１００％の環境に３００時間放置した後の前記ポリイミドフィルムとの間の接着力が、１８０°方向に引き剥がした場合において２Ｎ／ｃｍ以上であることが好ましい。これにより、応力緩和性、耐熱温度サイクル性、接着力等が向上し、吸湿性も低減できる。そのため、物理的衝撃、特にリフロー工程時の物理的衝撃等に対する耐性が向上し、また、ＢＧＡ、積層基板などの基板を製造する際に水分等によるボイドの発生等に対する耐性が向上する。 Furthermore, the adhesive composition of the present invention is 4.5 N / in the case where the adhesive strength between the cured polyimide film (trade name: Upilex 50S, manufactured by Ube Industries) is peeled in the 180 ° direction. When the adhesive strength with the polyimide film after being cured for 300 hours in an environment of temperature 121 ° C. and humidity 100% after peeling is 180 N ° or more, it is 2 N / cm or more. Preferably there is. Thereby, stress relaxation property, heat-resistant temperature cycle property, adhesive force, etc. improve, and hygroscopicity can also be reduced. For this reason, resistance to physical impact, particularly physical impact during the reflow process is improved, and resistance to generation of voids due to moisture and the like is improved when manufacturing a substrate such as a BGA or a laminated substrate.
以下、本発明の接着剤組成物の組成についてより詳細に説明する。
本発明の接着剤組成物において、（Ａ）成分は、加熱により（Ｂ）成分および／または（Ｃ）成分と反応して３次元網状構造を形成する。そして、これらの成分と上記最低溶融粘度との組み合わせにより、本発明の効果が得られる。（Ａ）成分および（Ｂ）成分は、特に、耐熱温度サイクル性、電気的信頼性、銅やポリイミドフィルム等に対する接着力、耐リフロー性等に対する寄与が大きい。また、（Ｃ）成分は、特に、応力緩和性、耐熱温度サイクル性、電気的信頼性、銅やポリイミドフィルム等に対する接着力、耐湿性等に対する寄与が大きい。
Hereinafter, the composition of the adhesive composition of the present invention will be described in more detail.
In the adhesive composition of the present invention, the component (A) reacts with the component (B) and / or the component (C) by heating to form a three-dimensional network structure. And the effect of this invention is acquired by the combination of these components and the said minimum melt viscosity. In particular, the component (A) and the component (B) greatly contribute to heat-resistant temperature cycle performance, electrical reliability, adhesion to copper, polyimide film, etc., reflow resistance, and the like. In addition, the component (C) has a large contribution to stress relaxation, heat-resistant temperature cycle performance, electrical reliability, adhesion to copper, polyimide film, etc., moisture resistance, and the like.
［（Ａ）成分］
エポキシ樹脂は、分子内に２個以上のエポキシ基を有している樹脂である。
[(A) component]
The epoxy resin is a resin having two or more epoxy groups in the molecule.
（Ａ）成分としては、例えば、グリシジルエーテル、グリシジルエステル、グリシジルアミン、線状脂肪族エポキサイト、脂環族エポキサイトなどいずれの構造のものも用いることができる。これらは単独で用いてもよく、２種以上を併用することもできる。
具体的には、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、ナフタレン型エポキシ樹脂などの二官能エポキシ樹脂、トリグリシジルイソシアヌレート型エポキシ樹脂、トリグリシジル−ｐ−アミノフェノ−ル型エポキシ樹脂、テトラグリシジルジアミノジフェニルメタン型エポキシ樹脂、テトラグリシジルメタキシレンジアミン型エポキシ樹脂、テトラグリシジル−１，３−ビスアミノメチルシクロフェキサン型エポキシ樹脂などの多官能グリシジルアミン型エポキシ樹脂、テトラフェニルグリシジルエーテルエタン型エポキシ樹脂、トリフェニルグリシジルエーテルメタン型エポキシ樹脂などの多官能グリシジルエーテル型エポキシ樹脂、フェノール型エポキシ樹脂、アルキルフェノール型エポキシ樹脂などの多官能レゾール型エポキシ樹脂、シクロペンタジエン型エポキシ樹脂、ビフェニル型エポキシ樹脂、フェノール型エポキシ樹脂、クレゾール型エポキシ樹脂などの多官能ノボラック型エポキシ樹脂などが挙げられる。
これらの中でも、ビスフェノール型エポキシ樹脂は、安価であるため本発明において好適に用いられる。また、多官能エポキシ樹脂は、絶縁性および耐熱性に優れるため本発明において好適に用いられる。
As the component (A), for example, any structure such as glycidyl ether, glycidyl ester, glycidyl amine, linear aliphatic epoxide, alicyclic epoxide can be used. These may be used alone or in combination of two or more.
Specifically, bifunctional epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, naphthalene type epoxy resin, triglycidyl isocyanurate type epoxy resin, triglycidyl-p-aminophenol Type epoxy resin, tetraglycidyldiaminodiphenylmethane type epoxy resin, tetraglycidylmetaxylenediamine type epoxy resin, tetraglycidyl-1,3-bisaminomethylcyclophene type epoxy resin, etc., polyfunctional glycidylamine type epoxy resin, tetraphenylglycidyl Polyfunctional glycidyl ether type epoxy resin such as ether ethane type epoxy resin, triphenyl glycidyl ether methane type epoxy resin, phenol type epoxy resin, alkylphenol Multifunctional resol type epoxy resins such as Nord type epoxy resin, cyclopentadiene type epoxy resin, biphenyl type epoxy resin, phenol epoxy resins, such as a polyfunctional novolak epoxy resins and cresol type epoxy resins.
Among these, bisphenol type epoxy resins are preferably used in the present invention because they are inexpensive. In addition, the polyfunctional epoxy resin is suitably used in the present invention because of its excellent insulation and heat resistance.
本発明に好適に用いられる（Ａ）成分として、具体的には、油化シェルエポキシ社製の、商品名：エピコート８０６、８２８、８３４、１００１等のビスフェノール型、商品名：ＹＸ−４０００、ＹＸ−４０００Ｈ等のビフェニル型などの２官能エポキシ樹脂；油化シェルエポキシ社製の、商品名：エピコート１５２、１５４、１８０Ｓ６５、１０３２Ｈ６０、１５７Ｓ７０等の多官能ノボラック型、商品名：６０４等のテトラグリシジルジフェニルメタン型、商品名：ＨＰ−７２００、ＨＰ−７２００Ｈ等のジシクロ型などの多官能エポキシ樹脂；日本化薬社製の、商品名：ＥＯＣＮＩ０２Ｓ、１０３Ｓ、１０４Ｓ、１０２０等のｏ−クレゾールノボラック型、商品名：ＥＰＰＮ５０１Ｈ、５０２Ｈ等のトリフェニルメタン型などの多官能エポキシ樹脂等を挙げることができる。 As the component (A) suitably used in the present invention, specifically, bisphenol types such as Epicoat 806, 828, 834, and 1001 manufactured by Yuka Shell Epoxy Co., Ltd., trade names: YX-4000, YX Bifunctional epoxy resin such as biphenyl type such as -4000H; Trade name: Epicoat 152, 154, 180S65, 1032H60, 157S70, etc., polyfunctional novolac type, trade name: 604 etc. tetraglycidyl diphenylmethane manufactured by Yuka Shell Epoxy Co., Ltd. Type, product name: polyfunctional epoxy resin such as dicyclo type such as HP-7200, HP-7200H, etc .; product name: o-cresol novolak type such as EOCNI02S, 103S, 104S, 1020 manufactured by Nippon Kayaku Co., Ltd., product name : Multifunctional such as triphenylmethane type such as EPPN501H and 502H Epoxy resins and the like.
また、（Ａ）成分として、ハロゲン化エポキシ樹脂、特に臭素化エポキシ樹脂を用いると、接着剤組成物に難燃性を付与するのに有効であるため好ましい。臭素化エポキシ樹脂の具体例としては、油化シェルエポキシ社製の、商品名：エピコート５０４５、５０４６、５０５０；日本化薬社製の、商品名：ＢＲＥＮ−Ｓ、ＢＲＥＮ−１０５、ＢＲＥＮ−３０１などが挙げられる。また、ハロゲン化エポキシ樹脂に代えて、リン化エポキシ樹脂等を使用しても何ら問題はない。 Moreover, it is preferable to use a halogenated epoxy resin, particularly a brominated epoxy resin, as the component (A) because it is effective for imparting flame retardancy to the adhesive composition. Specific examples of brominated epoxy resins include trade names: Epicoat 5045, 5046, 5050 manufactured by Yuka Shell Epoxy Co., Ltd., trade names: BREN-S, BREN-105, BREN-301 manufactured by Nippon Kayaku Co., Ltd. Is mentioned. Further, there is no problem even if a phosphide epoxy resin or the like is used instead of the halogenated epoxy resin.
（Ａ）成分は、エポキシ当量（エポキシ基１個あたりの分子量）が１００〜４０００であることが好ましく、１００〜２０００がより好ましく、１００〜１０００が特に好ましい。エポキシ当量が１００以上であると、硬化させたときに、未硬化の（Ａ）成分が残りにくく、そのため発泡しにくくなる。エポキシ当量が４０００以下であると、溶媒に溶けやすく、他の樹脂との相溶性が良好である。 The component (A) preferably has an epoxy equivalent (molecular weight per epoxy group) of 100 to 4000, more preferably 100 to 2000, and particularly preferably 100 to 1000. When the epoxy equivalent is 100 or more, when cured, the uncured (A) component is unlikely to remain, and therefore it is difficult to foam. When the epoxy equivalent is 4000 or less, the resin is easily soluble in a solvent and has good compatibility with other resins.
本発明の接着剤組成物中、（Ａ）成分の含有量は、当該接着剤組成物の全固形量の３〜４５質量％が好ましく、５〜２５質量％がより好ましい。 In the adhesive composition of the present invention, the content of the component (A) is preferably 3 to 45% by mass, more preferably 5 to 25% by mass, based on the total solid content of the adhesive composition.
［（Ｂ）成分］
フェノール樹脂は、フェノール類とアルデヒドとの付加・縮合で得られる樹脂である。
（Ｂ）成分として、具体的には、レゾールフェノール樹脂、フェノールノボラック樹脂、クレゾールノボラック樹脂、レゾールシノール樹脂、キシレン樹脂などのフェノール誘導体が挙げられる。中でもフェノールノボラック樹脂は、反応性に優れ、半導体装置用途において、優れた耐湿性および耐熱性を有するため好ましい。
（Ｂ）成分は、ヒドロキシル当量（ヒドロキシル基１個あたりの分子量）が５０〜４０００であることが好ましく、１００〜２０００がより好ましく、１００〜１０００が特に好ましい。ヒドロキシル当量が５０未満の場合は硬化後の接着剤が脆くなりやすく、４０００を越えた場合は有機溶剤に溶けにくいため製造上問題となりやすい。
[Component (B)]
The phenol resin is a resin obtained by addition / condensation of phenols and aldehydes.
Specific examples of the component (B) include phenol derivatives such as a resole phenol resin, a phenol novolac resin, a cresol novolac resin, a resorcinol resin, and a xylene resin. Among these, phenol novolac resins are preferable because they are excellent in reactivity and have excellent moisture resistance and heat resistance in semiconductor device applications.
The component (B) preferably has a hydroxyl equivalent (molecular weight per hydroxyl group) of 50 to 4000, more preferably 100 to 2000, and particularly preferably 100 to 1000. When the hydroxyl equivalent is less than 50, the adhesive after curing tends to be brittle, and when it exceeds 4000, it is difficult to dissolve in an organic solvent, which tends to cause a problem in production.
本発明の接着剤組成物中、（Ｂ）成分の含有量は、当該接着剤組成物の全固形量の２〜３０質量％が好ましく、５〜２５質量％がより好ましい。 In the adhesive composition of the present invention, the content of the component (B) is preferably 2 to 30% by mass and more preferably 5 to 25% by mass with respect to the total solid content of the adhesive composition.
また、本発明の接着剤組成物中、（Ａ）成分と（Ｂ）成分との比率は、官能基当量比で、１：０．６〜１：１．４の範囲内であることが好ましく、１：０．７〜１：１．１の範囲内であることがより好ましい。すなわち、（Ａ）成分を１とした場合の（Ｂ）成分の含有量が０．６以上であると、硬化後の接着剤組成物が、脆さのない、強度に優れたものとなり、応力緩和性が良好である。また、（Ａ）成分を１とした場合の（Ｂ）成分の含有量が１．４以下であると、接着力の劣化が抑制され、たとえば高温に曝された後の接着力の低下が抑制される。
また、（Ａ）成分と（Ｂ）成分との比率が上記範囲内であることにより、硬化後の接着剤組成物の引っ張り伸び率も向上する。また、硬化後、さらに１５０℃の環境に２４時間放置した後の２００℃〜２８０℃における動的弾性率も、半導体装置用として好適な範囲となる。
ここで、（Ａ）成分と（Ｂ）成分との官能基当量比とは、（Ａ）成分中のエポキシ基（（Ａ）成分の官能基）の数と、（Ｂ）成分中の水酸基（（Ｂ）成分の官能基）の数との比である。
Further, in the adhesive composition of the present invention, the ratio of the component (A) to the component (B) is preferably a functional group equivalent ratio in the range of 1: 0.6 to 1: 1.4. More preferably, the ratio is in the range of 1: 0.7 to 1: 1.1. That is, when the content of the component (B) when the component (A) is 1 is 0.6 or more, the cured adhesive composition has no brittleness and excellent strength, and stress Good relaxation. Further, when the content of the component (B) is 1 or less when the component (A) is 1, the deterioration of the adhesive strength is suppressed, for example, the decrease in the adhesive strength after being exposed to a high temperature is suppressed. Is done.
Moreover, the tensile elongation rate of the adhesive composition after hardening also improves because the ratio of (A) component and (B) component exists in the said range. In addition, the dynamic elastic modulus at 200 ° C. to 280 ° C. after being allowed to stand in an environment of 150 ° C. for 24 hours after curing is also a suitable range for a semiconductor device.
Here, the functional group equivalent ratio of the component (A) and the component (B) is the number of epoxy groups in the component (A) (the functional group of the component (A)) and the hydroxyl group in the component (B) ( (B) the ratio to the number of functional groups).
［（Ｃ）成分］
（Ｃ）成分は、モノマー成分として、少なくとも、エチレンと、前記（Ａ）成分と反応し得る官能基を有する不飽和カルボン酸またはその誘導体（以下、単に不飽和カルボン酸またはその誘導体ということがある）とを含有するビニル共重合体である。かかる（Ｃ）成分を含有することにより、本発明の接着剤組成物に可撓性が付与され、応力緩和性が向上する。また、耐湿性も向上する。さらに、上述したように、（Ａ）成分および（Ｂ）成分との組み合わせにより、耐熱温度サイクル性、電気的信頼性、銅やポリイミドフィルム等に対する接着力も向上する。
ここで、「モノマー成分」とは、重合反応により重合して重合体を生成した際に、該重合体の繰り返し単位を形成する化合物を意味する。たとえばモノマー成分としてエチレンを含有する重合体は、エチレンの二重結合が開裂して形成される式−［ＣＨ２−ＣＨ２］−で表される繰り返し単位を含有する。
[Component (C)]
Component (C) is an unsaturated carboxylic acid having at least ethylene and a functional group capable of reacting with component (A) or a derivative thereof (hereinafter simply referred to as an unsaturated carboxylic acid or a derivative thereof) as a monomer component. And a vinyl copolymer. By containing the component (C), flexibility is imparted to the adhesive composition of the present invention, and stress relaxation properties are improved. Also, moisture resistance is improved. Further, as described above, the combination with the component (A) and the component (B) improves the heat resistance temperature cycle property, the electrical reliability, and the adhesive force to copper, polyimide film, and the like.
Here, the “monomer component” means a compound that forms a repeating unit of a polymer when the polymer is produced by polymerization reaction. For example, a polymer containing ethylene as a monomer component contains a repeating unit represented by the formula — [CH 2 —CH 2 ] — formed by cleavage of a double bond of ethylene.
（Ｃ）成分中、エチレンおよび不飽和カルボン酸またはその誘導体の合計量は、全モノマー成分の合計に対し、４０〜９８質量％であることが好ましい。
（Ｃ）成分中、エチレンの割合は、全モノマー成分の合計に対し、４０質量％以上であることが好ましく、５０〜９８質量％がより好ましい。
(C) In component, it is preferable that the total amount of ethylene and unsaturated carboxylic acid or its derivative (s) is 40-98 mass% with respect to the sum total of all the monomer components.
(C) It is preferable that the ratio of ethylene in a component is 40 mass% or more with respect to the sum total of all the monomer components, and 50-98 mass% is more preferable.
不飽和カルボン酸またはその誘導体の有する、前記（Ａ）成分と反応し得る官能基としては、アミノ基、イソシアネート基、グリシジル基、カルボキシル基（無水物基を含む）、シラノール基、水酸基、ビニル基、メチロール基、メルカプト基、エステル基等が挙げられる。中でもアミノ基、カルボキシル基、グリシジル基、水酸基は、反応性に富むため好ましい。特に好ましい官能基はグリシジル基及びカルボキシル基である。
これらの基を有する不飽和カルボン酸またはその誘導体の具体例としては、例えば次のものが例示される。カルボキシル基を有するものとしては、アクリル酸、メタクリル酸、（無水）マレイン酸、カルボキシル基を有するプロピレン等のオレフィン類が挙げられる。グリシジル基を有するものとしては、グリシジルアクリレート、グリシジルメタクリレート等が挙げられる。水酸基を含むものとしては、ヒドロキシメチルアクリレート、ヒドロキシメチルメタクリレート、ヒドロキシエチルアクリレート、ヒドロキシエチルメタクリレート等が挙げられる。
The functional group that can react with the component (A) of the unsaturated carboxylic acid or derivative thereof includes amino group, isocyanate group, glycidyl group, carboxyl group (including anhydride group), silanol group, hydroxyl group, vinyl group , Methylol group, mercapto group, ester group and the like. Of these, amino groups, carboxyl groups, glycidyl groups, and hydroxyl groups are preferred because of their high reactivity. Particularly preferred functional groups are glycidyl and carboxyl groups.
Specific examples of the unsaturated carboxylic acid or derivative thereof having these groups include the following. Examples of those having a carboxyl group include olefins such as acrylic acid, methacrylic acid, (anhydrous) maleic acid, and propylene having a carboxyl group. Examples of those having a glycidyl group include glycidyl acrylate and glycidyl methacrylate. Examples of those containing a hydroxyl group include hydroxymethyl acrylate, hydroxymethyl methacrylate, hydroxyethyl acrylate, and hydroxyethyl methacrylate.
（Ｃ）成分中、不飽和カルボン酸またはその誘導体の割合は、全モノマー成分の合計に対し、０．１〜４０質量％であることが好ましく、０．８〜２０質量％がより好ましい。（Ｃ）成分中の不飽和カルボン酸またはその誘導体の割合が０．１質量％以上であると、（Ａ）成分との反応性が高く、硬化後の引っ張り伸び率や、硬化後の基材との間の接着力が向上する。また、有機溶剤への溶解度も高く、塗料としやすい。また、該割合が４０質量％以下であると、塗料状態での安定性が良好である。 (C) It is preferable that the ratio of unsaturated carboxylic acid or its derivative (s) in a component is 0.1-40 mass% with respect to the sum total of all the monomer components, and 0.8-20 mass% is more preferable. When the proportion of the unsaturated carboxylic acid or derivative thereof in component (C) is 0.1% by mass or more, the reactivity with component (A) is high, the tensile elongation after curing, and the substrate after curing. Adhesive strength between the two is improved. In addition, it has high solubility in organic solvents and is easy to use as a paint. Further, when the ratio is 40% by mass or less, the stability in the paint state is good.
（Ｃ）成分は、本発明の効果を損なわない範囲で、モノマー成分として、エチレンおよび不飽和カルボン酸またはその誘導体以外の他のモノマーを含有してもよい。
他のモノマーとしては、上記エチレン及び不飽和カルボン酸またはその誘導体と共重合可能なものであればよく、たとえばアクリル酸メチル、アクリル酸エチル、メタクリル酸メチル、メタクリル酸エチル等の（メタ）アクリル酸のアルキルエステル又はアリールエステル、酢酸ビニル等が挙げられる。
（Ｃ）成分が上記他のモノマーを含有する場合、その含有量は、全モノマー成分の合計に対し、４０質量％以下であることが好ましく、３０質量％以下がより好ましい。
(C) A component may contain other monomers other than ethylene and unsaturated carboxylic acid or its derivative (s) as a monomer component in the range which does not impair the effect of this invention.
Other monomers may be any monomers that can be copolymerized with the above-mentioned ethylene and unsaturated carboxylic acid or derivatives thereof. For example, (meth) acrylic acid such as methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate Alkyl ester or aryl ester, vinyl acetate and the like.
(C) When a component contains the said other monomer, it is preferable that the content is 40 mass% or less with respect to the sum total of all the monomer components, and 30 mass% or less is more preferable.
本発明において、（Ｃ）成分としては、特に、モノマー成分としてエチレンおよび（メタ）アクリル酸エステルを含有するビニル共重合体が好ましい。かかるビニル共重合体は、主鎖にジエン結合を含まないため、高温放置時の熱劣化（弾性が無くなってしまう）が殆ど無く、長期にわたって応力緩和性を保持できる。また、エステル結合を側鎖に有しているため、比較的有機溶剤への溶解性が高く、かつ、加水分解しにくいため高温高湿環境下において接着剤組成物に接着させた電極の腐食が抑えられ、電気的信頼性が高い。
モノマー成分としてエチレンおよび（メタ）アクリル酸エステルを含有するビニル共重合体として、具体的には、エチレン−（メタ）アクリル酸エステル−無水マレイン酸共重合体、エチレン−（メタ）アクリル酸アルキルエステル−グリシジル（メタ）アクリレート共重合体、エチレン−グリシジル（メタ）アクリレート共重合体、エチレン−（メタ）アクリル酸共重合体、エチレン−グリシジル（メタ）アクリレート−酢酸ビニル共重合体が挙げられる。中でも、エチレン−（メタ）アクリル酸アルキルエステル−無水マレイン酸共重合体、エチレン−（メタ）アクリル酸アルキルエステル−グリシジル（メタ）アクリレート共重合体、エチレン−グリシジル（メタ）アクリレート共重合体が挙げられる。
これらのビニル共重合体は、いずれかを単独で用いてもよく、２種以上を併用しても良い。本発明の接着剤組成物においては、上記ビニル共重合体を２種以上併用して用いることも好ましい。
モノマー成分としてエチレンおよび（メタ）アクリル酸エステルを含有する共重合体中のアクリル酸エステルの比率は、全モノマー成分の合計に対し、５〜４０モル％が好ましい。５モル％以上であると有機溶剤への溶解度が良好で、塗工用溶液（塗料）としやすい。また４０モル％以下であると、加水分解による電気特性の低下を抑制する効果が高い。
In the present invention, the (C) component is particularly preferably a vinyl copolymer containing ethylene and (meth) acrylic acid ester as monomer components. Since such a vinyl copolymer does not contain a diene bond in the main chain, there is almost no thermal deterioration (no elasticity) when left at high temperatures, and stress relaxation can be maintained over a long period of time. In addition, since it has an ester bond in the side chain, it has relatively high solubility in organic solvents and is difficult to hydrolyze, so corrosion of the electrode bonded to the adhesive composition in a high temperature and high humidity environment It is suppressed and has high electrical reliability.
As a vinyl copolymer containing ethylene and (meth) acrylic acid ester as monomer components, specifically, ethylene- (meth) acrylic acid ester-maleic anhydride copolymer, ethylene- (meth) acrylic acid alkyl ester -Glycidyl (meth) acrylate copolymer, ethylene-glycidyl (meth) acrylate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene-glycidyl (meth) acrylate-vinyl acetate copolymer are mentioned. Among them, ethylene- (meth) acrylic acid alkyl ester-maleic anhydride copolymer, ethylene- (meth) acrylic acid alkyl ester-glycidyl (meth) acrylate copolymer, ethylene-glycidyl (meth) acrylate copolymer are mentioned. It is done.
Any of these vinyl copolymers may be used alone or in combination of two or more. In the adhesive composition of the present invention, it is also preferable to use two or more of the above vinyl copolymers in combination.
The ratio of the acrylic acid ester in the copolymer containing ethylene and (meth) acrylic acid ester as the monomer component is preferably 5 to 40 mol% with respect to the total of all the monomer components. If it is 5 mol% or more, the solubility in an organic solvent is good, and it is easy to obtain a coating solution (paint). Moreover, the effect which suppresses the fall of the electrical property by hydrolysis as it is 40 mol% or less is high.
（Ｃ）成分の質量平均分子量は、１０００〜２００００００の範囲内であることが好ましく、１０００００〜１００００００がより好ましい。なお、質量平均分子量は、ゲルパーミエーションクロマトグラフィ（ＧＰＣ）にて、スチレンを標準として測定した値である。
特に、（Ｃ）成分の官能基当量（官能基１個あたりの分子量（質量平均分子量を官能基の数で割った値））が１００〜２５００の範囲内であると、硬化後の引っ張り伸び率や、硬化後の基材との間の接着力が良好である。
ここで、（Ｃ）成分の官能基とは、前記不飽和カルボン酸またはその誘導体が有する、前記（Ａ）成分と反応し得る官能基を意味する。
The mass average molecular weight of the component (C) is preferably in the range of 1,000 to 2,000,000, more preferably 100,000 to 1,000,000. The mass average molecular weight is a value measured by gel permeation chromatography (GPC) using styrene as a standard.
Particularly, when the functional group equivalent of the component (C) (molecular weight per functional group (value obtained by dividing the mass average molecular weight by the number of functional groups)) is in the range of 100 to 2500, the tensile elongation after curing Moreover, the adhesive force between the base material after curing is good.
Here, the functional group of (C) component means the functional group which the said unsaturated carboxylic acid or its derivative has and can react with the said (A) component.
本発明において、（Ｃ）成分の含有量は、当該接着剤組成物の全固形量の２０〜８０質量％であることが好ましく、３０〜７０質量％がより好ましい。（Ｃ）成分の含有量が上記範囲内であると、本発明の効果に優れ、特に応力緩和性、耐熱温度サイクル性、銅やポリイミドフィルム等との間の接着性、耐湿性等が良好である。
また、（Ｃ）成分の含有量は、（Ａ）成分１００質量部に対して、２０〜２００質量部の範囲内であることが好ましく、５０〜１５０質量部がより好ましい。含有量が２００質量部以下であると接着剤層の成膜性が良好であり、２０質量部以上であると、接着剤層の強度が高い。
In this invention, it is preferable that content of (C) component is 20-80 mass% of the total solid of the said adhesive composition, and 30-70 mass% is more preferable. When the content of the component (C) is within the above range, the effect of the present invention is excellent, and particularly stress relaxation, heat-resistant temperature cycle property, adhesion between copper and polyimide films, moisture resistance, etc. are good. is there.
Moreover, it is preferable that content of (C) component exists in the range of 20-200 mass parts with respect to 100 mass parts of (A) component, and 50-150 mass parts is more preferable. When the content is 200 parts by mass or less, the film formability of the adhesive layer is good, and when it is 20 parts by mass or more, the strength of the adhesive layer is high.
［シロキサン化合物（Ｄ）］
本発明の接着剤組成物は、さらに、シロキサン化合物（Ｄ）（以下、（Ｄ）成分という）を含有することが好ましい。これにより、上記（Ａ）〜（Ｃ）成分を有機溶剤に溶解して塗料とした際の各成分の相溶性が向上する。また、硬化後の吸湿率を低減できる等の利点がある。
（Ｄ）成分としては、エポキシ基に対する反応性を有する反応基を有しているものが好ましい。かかる反応基としては、水酸基、アルコキシ基、アミノ基、メタクリル基、エポキシ基等が挙げられる。
[Siloxane compound (D)]
The adhesive composition of the present invention preferably further contains a siloxane compound (D) (hereinafter referred to as component (D)). Thereby, the compatibility of each component at the time of melt | dissolving the said (A)-(C) component in an organic solvent and using it as a coating material improves. Further, there is an advantage that the moisture absorption after curing can be reduced.
(D) As a component, what has the reactive group which has the reactivity with respect to an epoxy group is preferable. Examples of such a reactive group include a hydroxyl group, an alkoxy group, an amino group, a methacryl group, and an epoxy group.
（Ｄ）成分としては、両末端にアミノ基を有するシロキサン化合物が好ましく、特に、下記一般式（１）又は一般式（２）で示されるシロキサン化合物からなる群から選択される少なくとも１種であることが好ましい。 The component (D) is preferably a siloxane compound having an amino group at both ends, and is particularly at least one selected from the group consisting of siloxane compounds represented by the following general formula (1) or general formula (2). It is preferable.
式（１）中、Ｒ１のアルキレン基としては、直鎖状でも分岐状でもよく、特に、炭素数２〜５の直鎖状のアルキレン基が好ましい。
ｍとしては、３〜８の整数が好ましい。
ｎとしては、０〜８の整数が好ましい。
In formula (1), the alkylene group for R 1 may be linear or branched, and is particularly preferably a linear alkylene group having 2 to 5 carbon atoms.
As m, the integer of 3-8 is preferable.
n is preferably an integer of 0 to 8.
上記一般式（１）又は（２）で示される、両末端にアミノ基を有するシロキサン化合物としては、東芝シリコ−ン社製の商品名：ＴＳＬ９３０６（ジアミノジシロキサン）、商品名：ＴＳＬ９８８６（ジアミノポリシロキサン）、商品名：ＴＳＦ４７０６（ジアミノジシロキサン）、商品名：ＸＦ４２−Ａ２６４５（ジアミノポリシロキサン）等を挙げることができる。 As a siloxane compound having an amino group at both ends represented by the above general formula (1) or (2), product names: TSL9306 (diaminodisiloxane) manufactured by Toshiba Silicone Co., Ltd., product names: TSL9886 (diaminopoly) Siloxane), trade name: TSF4706 (diaminodisiloxane), trade name: XF42-A2645 (diaminopolysiloxane), and the like.
本発明の接着剤組成物中、（Ｄ）成分の含有量は、当該接着剤組成物の全固形量の０．０５〜１０質量％が好ましく、０．３〜５質量％がより好ましい。０．０５質量％以上であると、本発明の接着剤組成物を塗料とした際の（Ａ）〜（Ｃ）成分の相溶性が良好であり、また、硬化後の吸湿率も低い。１０質量％以下であると、接着力の低下が抑制される。 In the adhesive composition of the present invention, the content of the component (D) is preferably 0.05 to 10% by mass, more preferably 0.3 to 5% by mass, based on the total solid content of the adhesive composition. When the content is 0.05% by mass or more, the compatibility of the components (A) to (C) when the adhesive composition of the present invention is used as a paint is good, and the moisture absorption after curing is also low. The fall of adhesive force is suppressed as it is 10 mass% or less.
［その他の任意成分］
また、本発明の接着剤組成物には、被着体との密着性を向上させるために、カップリング剤を添加することが好ましい。
カップリング剤としては、シランカップリング剤、チタンカップリング剤及びアルミニウムカップリング剤が好ましく使用される。
[Other optional ingredients]
Moreover, in order to improve adhesiveness with a to-be-adhered body, it is preferable to add a coupling agent to the adhesive composition of this invention.
As the coupling agent, a silane coupling agent, a titanium coupling agent and an aluminum coupling agent are preferably used.
本発明の接着剤組成物は、上記（Ａ）成分とともに、エポキシ硬化剤を含有することが好ましい。これにより、本発明の接着剤組成物の硬化反応が促進され、耐熱性が向上する。
エポキシ硬化剤としては、一般的に用いられているものが使用でき、具体的には、イミダゾール類、１，８−ジアザビシクロ（５，４，０）ウンデセン等のアミン系触媒、トリフェニルホスフィン等のリン系触媒等が例示できる。
本発明の接着剤組成物中、エポキシ硬化剤の含有量は、当該接着剤組成物の全固形量の０．１〜１０質量％が好ましく、０．１〜３質量％がより好ましい。
The adhesive composition of the present invention preferably contains an epoxy curing agent together with the component (A). Thereby, the curing reaction of the adhesive composition of the present invention is promoted, and the heat resistance is improved.
As the epoxy curing agent, commonly used ones can be used. Specifically, amine catalysts such as imidazoles, 1,8-diazabicyclo (5,4,0) undecene, triphenylphosphine and the like can be used. A phosphorus catalyst etc. can be illustrated.
In the adhesive composition of the present invention, the content of the epoxy curing agent is preferably from 0.1 to 10 mass%, more preferably from 0.1 to 3 mass%, based on the total solid content of the adhesive composition.
本発明の接着剤組成物には、熱膨張係数、熱伝導率の調整或いは作業性の制御等の目的で、無機フィラー、有機フィラー等のフィラーを含有させることが好ましい。
無機フィラーとしては、シリカ、アルミナ、酸化チタン、酸化ベリリウム、酸化マグネシウム、炭酸カルシウム、窒化チタン、窒化珪素、窒化硼素、硼化チタン、硼化タングステン、炭化珪素、炭化チタン、炭化ジルコニウム、炭化モリブデン、マイカ、クレイ、酸化亜鉛、カーボンブラック、水酸化アルミニウム、水酸化カルシウム、水酸化マグネシウム、三酸化アンチモン又はこれ等の表面をトリメチルシロキシル基等で処理したもの等があげられる。
有機フィラーとしては、ポリイミド、ポリアミドイミド、ポリエーテルエーテルケトン、ポリエーテルイミド、ポリエステルイミド、ナイロン、シリコーン等があげられる。
本発明の接着剤組成物中、フィラーの含有量は、前記（Ａ）成分、（Ｂ）成分および（Ｃ）成分、並びに任意成分である（Ｄ）成分の総和１００質量部に対して、２〜９５質量部の範囲内であることが好ましく、５〜５０質量部がより好ましい。
The adhesive composition of the present invention preferably contains a filler such as an inorganic filler or an organic filler for the purpose of adjusting the thermal expansion coefficient, thermal conductivity, or controlling workability.
Examples of inorganic fillers include silica, alumina, titanium oxide, beryllium oxide, magnesium oxide, calcium carbonate, titanium nitride, silicon nitride, boron nitride, titanium boride, tungsten boride, silicon carbide, titanium carbide, zirconium carbide, molybdenum carbide, Examples thereof include mica, clay, zinc oxide, carbon black, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, antimony trioxide, and those whose surfaces are treated with a trimethylsiloxyl group.
Examples of the organic filler include polyimide, polyamideimide, polyetheretherketone, polyetherimide, polyesterimide, nylon, and silicone.
In the adhesive composition of the present invention, the filler content is 2 with respect to 100 parts by mass of the total of the component (A), the component (B), the component (C), and the component (D), which is an optional component. It is preferable to be within the range of -95 parts by mass, and more preferably 5-50 parts by mass.
本発明の接着剤組成物は、必須成分である上記（Ａ）〜（Ｃ）成分を有機溶剤に溶解させ、任意に（Ｄ）成分等を添加した塗料として接着剤層の形成に用いることができる。
好ましく使用される有機溶剤としては、Ｎ−メチル−２−ピロリドン、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジメチルホルムアミド、ピリジン、メチルエチルケトン、メチルイソブチルケトン、トルエン、キシレン、１，４−ジオキサン、テトラヒドロフラン、エタノール、メタノール、メチルセロソルブ等いくつかの種類と量を適宜選択して使用することができる。
塗料は、固形分濃度が５質量％以上となるよう調製されることが好ましく、１０〜５０質量％がより好ましい。固形分濃度が５質量％以上であると、接着剤層の厚さが均一な接着シートを容易に作製できる。
The adhesive composition of the present invention can be used for forming an adhesive layer as a paint in which the components (A) to (C), which are essential components, are dissolved in an organic solvent and the component (D) is optionally added. it can.
Preferred organic solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, pyridine, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, 1,4-dioxane, tetrahydrofuran Several types and amounts such as ethanol, methanol, methyl cellosolve and the like can be appropriately selected and used.
The paint is preferably prepared so that the solid content concentration is 5% by mass or more, and more preferably 10 to 50% by mass. When the solid content concentration is 5% by mass or more, an adhesive sheet having a uniform adhesive layer thickness can be easily produced.
＜半導体装置用接着シート＞
本発明の第二の態様の半導体装置用接着シート（以下、接着シート（２）ということがある。）は、支持体の少なくとも一面に、前記本発明の接着剤組成物からなる接着剤層が積層してなることを特徴とする。
<Semiconductor device adhesive sheet>
The adhesive sheet for a semiconductor device according to the second aspect of the present invention (hereinafter sometimes referred to as an adhesive sheet (2)) has an adhesive layer made of the adhesive composition of the present invention on at least one surface of a support. It is characterized by being laminated.
接着シート（２）において、支持体としては、銅やアルミニウム等の金属からなる金属層、剥離性フィルム、絶縁性フィルム、剥離紙等が使用でき、特に、金属層、剥離性フィルム及び絶縁性フィルムからなる群から選択される少なくとも１種が好ましい。
絶縁性フィルムとしては、ポリエチレンテレフタレート（以下、ＰＥＴと略す。）等のポリエステル類、ポリエチレン等のポリオレフィン類、ポリイミド、ポリアミド、ポリエーテルサルフォン、ポリフェニレンサルファイド、ポリエーテルケトン、トリアセチルセルロース等が好ましいものとして挙げられ、さらに好ましくは、ポリエステル類、ポリオレフィン類及びポリイミド等の材質のフィルムが挙げられる。
剥離性フィルムとしては、上記絶縁性フィルムとして挙げたものと同様の材質のフィルムに、シリコーン等の離型剤で剥離処理を施したものが好ましく使用される。
In the adhesive sheet (2), as the support, a metal layer made of a metal such as copper or aluminum, a peelable film, an insulating film, a release paper, etc. can be used, and in particular, the metal layer, the peelable film and the insulating film. At least one selected from the group consisting of
Preferred insulating films include polyesters such as polyethylene terephthalate (hereinafter abbreviated as PET), polyolefins such as polyethylene, polyimide, polyamide, polyethersulfone, polyphenylene sulfide, polyetherketone, and triacetylcellulose. More preferably, films made of materials such as polyesters, polyolefins, and polyimide are used.
As the peelable film, a film made of the same material as that mentioned as the insulating film and subjected to a release treatment with a release agent such as silicone is preferably used.
本発明の接着シート（２）は、たとえば、支持体の少なくとも一面に、上記接着剤組成物を含有する塗料を塗布し、乾燥する等により接着剤層を形成することによって製造できる。
該接着剤層は、加熱処理を行い、半硬化状態とすることが好ましい。特に、加工使用条件、例えば硬化時間の短縮、導体パターンの埋め込み等でフロー性や発泡を押さえる為、半硬化状態を適宜コントロールする。半硬化状態のコントロール方法は限定しないが、エージング等でコントロールすることが好ましい。
接着剤層の乾燥後の厚さは、３〜４００μｍの範囲内であることが好ましく、５〜１００μｍであることがより好ましい。
The adhesive sheet (2) of the present invention can be produced, for example, by forming an adhesive layer by applying a coating containing the adhesive composition on at least one surface of a support and drying.
The adhesive layer is preferably heat-treated to be in a semi-cured state. In particular, the semi-cured state is appropriately controlled in order to suppress flowability and foaming by processing and use conditions such as shortening of the curing time and embedding of the conductor pattern. The method for controlling the semi-cured state is not limited, but is preferably controlled by aging or the like.
The thickness of the adhesive layer after drying is preferably in the range of 3 to 400 μm, and more preferably 5 to 100 μm.
支持体の少なくとも一面に接着剤層を形成してなる本発明の接着シート（２）は、保管時において、該接着剤層上にさらに剥離性フィルムを貼着しておくと、接着剤層が汚染されないため好ましい。かかる接着シートは、使用時に、その剥離性フィルムを剥離して用いることができる。
また、接着剤層のみを半導体装置に用いる場合は、支持体についても剥離性フィルムとし、使用時において、接着剤層の両側の剥離性フィルムを剥がして用いることもできる。
In the adhesive sheet (2) of the present invention formed by forming an adhesive layer on at least one surface of the support, when the peelable film is further adhered on the adhesive layer during storage, the adhesive layer It is preferable because it is not contaminated. Such an adhesive sheet can be used by peeling the peelable film at the time of use.
Moreover, when using only an adhesive bond layer for a semiconductor device, it can also use as a peelable film also about a support body, and can peel and use the peelable film of both sides of an adhesive bond layer at the time of use.
次に、本発明の第三の態様の半導体装置用接着シート（以下、接着シート（３）ということがある。）は、金属層の少なくとも一面に、上記本発明の半導体装置用接着剤組成物からなる接着剤層と、絶縁性フィルムまたは剥離性フィルムとが順次積層してなることを特徴とする。
金属層、接着剤層、絶縁性フィルムおよび剥離性フィルムの説明については、上記接着シート（２）において、支持体として例示した金属層、接着剤層、絶縁性フィルムおよび剥離性フィルムの説明と同様である。
接着シート（３）は、かかる構成を有することにより、そのまま配線基板とすることができる。
Next, the adhesive sheet for a semiconductor device according to the third aspect of the present invention (hereinafter sometimes referred to as an adhesive sheet (3)) is formed on at least one surface of the metal layer. It is characterized in that an adhesive layer made of and an insulating film or a peelable film are sequentially laminated.
About description of a metal layer, an adhesive bond layer, an insulating film, and a peelable film, in the said adhesive sheet (2), it is the same as description of the metal layer illustrated as a support body, an adhesive bond layer, an insulating film, and a peelable film. It is.
By having such a configuration, the adhesive sheet (3) can be used as a wiring board as it is.
次に、本発明の第四の態様の半導体装置用接着シート（以下、接着シート（４）ということがある。）は、絶縁性フィルムの両面に、上記本発明の半導体装置用接着剤組成物からなる接着剤層と、絶縁性フィルムまたは剥離性フィルムとが順次積層してなることを特徴とする。
接着剤層、絶縁性フィルムおよび剥離性フィルムの説明については、上記接着シート（２）における接着剤層、絶縁性フィルムおよび剥離性フィルムの説明と同様である。
接着シート（４）は、かかる構成を有することにより、優れた電気信頼性を有する。
Next, the adhesive sheet for a semiconductor device according to the fourth aspect of the present invention (hereinafter sometimes referred to as an adhesive sheet (4)) is formed on both sides of the insulating film. It is characterized in that an adhesive layer made of and an insulating film or a peelable film are sequentially laminated.
About description of an adhesive bond layer, an insulating film, and a peelable film, it is the same as that of description of the adhesive bond layer in the said adhesive sheet (2), an insulating film, and a peelable film.
The adhesive sheet (4) has excellent electrical reliability due to such a configuration.
本発明の接着剤組成物および接着シートは、種々の半導体装置において適用でき、特に、絶縁体層および導体回路を具備して構成されるＩＣ用基板の回路面またはその裏面にＩＣチップを積層した半導体装置に特に好適である。かかる半導体装置として、具体的には、ＴＡＢ技術を利用したＴ−ＢＧＡ、ＦＰＣやガラスエポキシ基板を用いたビルドアップ基板または面実装型のＣＳＰ半導体などが挙げられる。
本発明の接着剤組成物および接着シートのより具体的な用途としては、上記半導体装置において、そのＩＣチップとＩＣ用基板の絶縁体層および／または導体回路とを接着もしくは回路を形成する接着剤、回路基板同士の接着そしてそれを保護する保護フィルムとの接着剤として好適である。
The adhesive composition and adhesive sheet of the present invention can be applied to various semiconductor devices, and in particular, an IC chip is laminated on the circuit surface or the back surface of an IC substrate comprising an insulator layer and a conductor circuit. It is particularly suitable for a semiconductor device. Specific examples of such a semiconductor device include T-BGA using TAB technology, a build-up substrate using a FPC or a glass epoxy substrate, or a surface-mount type CSP semiconductor.
As a more specific application of the adhesive composition and adhesive sheet of the present invention, in the semiconductor device described above, an adhesive that bonds or forms a circuit between the IC chip and the insulator layer and / or conductor circuit of the IC substrate. It is suitable as an adhesive for bonding between circuit boards and a protective film for protecting the circuit boards.
以下、本発明を実施例に基づいてより詳細に説明するが、本発明はこれらに限定されるものではない。
実施例１〜１５，比較例１〜６
［接着剤組成物の塗料の調製］
表１に略号で示した（Ａ）成分、（Ｂ）成分、（Ｃ）成分、（Ｄ）成分、シランカップリング剤、エポキシ硬化剤、フィラー、及びジエンを有する共重合体を、それぞれ、表１に示す配合量（全固形分に対する質量％）となるように、常温〜８０℃程度でトルエンに溶解して、接着剤組成物を含有する塗料（固形分濃度３５質量％）を得た。
なお、フィラーの含有量は、（Ａ）成分、（Ｂ）成分、（Ｃ）成分及び（Ｄ）成分の総和１００質量部に対する部数（質量部）である。
また、実施例１〜１５及び比較例１〜６において用いた各成分の種類を示す表１中の略号の意味は表２に示した。
EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to these.
Examples 1-15, Comparative Examples 1-6
[Preparation of paint for adhesive composition]
Copolymers having (A) component, (B) component, (C) component, (D) component, silane coupling agent, epoxy curing agent, filler, and diene shown in abbreviations in Table 1, respectively, 1 was dissolved in toluene at about room temperature to about 80 ° C. so that the blending amount shown in FIG. 1 (mass% relative to the total solid content) was obtained to obtain a paint (solid content concentration 35 mass%) containing the adhesive composition.
In addition, content of a filler is the number of parts (mass part) with respect to 100 mass parts of sum total of (A) component, (B) component, (C) component, and (D) component.
Moreover, the meaning of the symbol in Table 1 which shows the kind of each component used in Examples 1-15 and Comparative Examples 1-6 was shown in Table 2.
次に、得られた塗料を用いて下記の評価を行った。
（１）硬化前評価
［最低溶融粘度］
得られた接着剤組成物の塗料を用いて、下記の手順で、硬化前の動的粘弾性測定における最低溶融粘度を測定した。その結果を表３に示した。
上記実施例１〜１５および比較例１〜６の接着剤組成物の塗料を、乾燥後の厚さが２５μｍとなるように、剥離処理を施した厚さ３８μｍのポリエステルフィルム上に塗布し、熱風循環型乾燥機中にて１３０℃で５分間乾燥して接着剤層を形成した。次に、得られた接着剤層を、ポリエステルフィルムから剥離して単層とし、この単層の接着剤層を複数重ねた後、この積層体の両面に、ポリエステルフィルム上の接着剤層を更に重ね、全体の接着剤層の厚さが０．８ｍｍとなるようにしてラミネーターで貼り合わせた。ラミネーター温度は、ポリイミドフィルム（商品名：ユーピレックス５０Ｓ、宇部興産社製）に貼り合わせた場合に、反対から観て濡れて色が変わる温度＋３℃〜＋１３℃以内とした。貼り合わせ速度１ｍ／ｍｉｎとした。次に、両面のポリエステルフィルムを剥離して、接着剤層が複数積層された未硬化フィルムを得た。
得られた未硬化フィルムについて、動的測定機（ＨＡＡＫＥ社製ＲＳ７５）を用いて最低溶融粘度を測定した。
表３から明らかなように、実施例１〜１５に基づく未硬化フィルムは、４００Ｐａ・ｓ〜５００００Ｐａ・ｓの範囲に入り適正な最低溶融粘度を有していた。一方、比較例１，３，５，６に基づく未硬化フィルムは、最低溶融粘度が４００〜５００００Ｐａ・ｓの範囲外であった。
Next, the following evaluation was performed using the obtained paint.
(1) Evaluation before curing [minimum melt viscosity]
The minimum melt viscosity in the measurement of dynamic viscoelasticity before curing was measured by the following procedure using the obtained paint of the adhesive composition. The results are shown in Table 3.
The coating compositions of the adhesive compositions of Examples 1 to 15 and Comparative Examples 1 to 6 were applied onto a polyester film having a thickness of 38 μm subjected to a peeling treatment so that the thickness after drying was 25 μm. It dried for 5 minutes at 130 degreeC in the circulation type dryer, and formed the adhesive bond layer. Next, the obtained adhesive layer is peeled from the polyester film to form a single layer, and a plurality of the single-layer adhesive layers are stacked, and then an adhesive layer on the polyester film is further formed on both sides of the laminate. The laminate was laminated with a laminator so that the thickness of the entire adhesive layer was 0.8 mm. The laminator temperature was set to a temperature within + 3 ° C. to + 13 ° C. when the film was bonded to a polyimide film (trade name: Upilex 50S, manufactured by Ube Industries Co., Ltd.). The bonding speed was 1 m / min. Next, the polyester films on both sides were peeled to obtain an uncured film in which a plurality of adhesive layers were laminated.
About the obtained uncured film, the minimum melt viscosity was measured using the dynamic measuring machine (RS75 by HAAKE).
As is clear from Table 3, the uncured films based on Examples 1 to 15 entered the range of 400 Pa · s to 50000 Pa · s and had an appropriate minimum melt viscosity. On the other hand, the uncured film based on Comparative Examples 1, 3, 5, and 6 had a minimum melt viscosity outside the range of 400 to 50000 Pa · s.
［相容性］
上記実施例１〜１５および比較例１〜６の接着剤組成物の塗料を、乾燥後の厚さが２５μｍとなるように、剥離処理を施した厚さ３８μｍのポリエステルフィルム上に塗布し、熱風循環型乾燥機中にて１３０℃で５分間乾燥した後、剥離処理を施した厚さ５０μｍのポリエチレンフィルムを貼り合わせた。その後、乾燥した接着剤層を顕微鏡により観察して（Ａ）成分、（Ｂ）成分及び（Ｃ）成分の相容状態を確認した。その結果、班模様や縞模様等の分離が見られなかったものについては相容性が良好と判断し、班模様や縞模様等の分離が見られたものは相容性が悪いと判断した。その結果を、相容性が良好なものを○、悪いものを×として表３に示した。
表３から明らかなように、実施例１〜１５に基づく本発明の接着剤組成物では相容状態が良好であった。これに対して、比較例４，６のものは相容状態が悪かった。
[Compatibility]
The coating compositions of the adhesive compositions of Examples 1 to 15 and Comparative Examples 1 to 6 were applied onto a polyester film having a thickness of 38 μm subjected to a peeling treatment so that the thickness after drying was 25 μm. After drying for 5 minutes at 130 ° C. in a circulation dryer, a polyethylene film having a thickness of 50 μm subjected to a peeling treatment was bonded. Thereafter, the dried adhesive layer was observed with a microscope, and the compatibility state of the component (A), the component (B) and the component (C) was confirmed. As a result, it was judged that compatibility was good for those in which no separation such as a group pattern or a striped pattern was found, and that in which separation such as a group pattern or a striped pattern was seen was judged to be incompatible. . The results are shown in Table 3 with “Good” indicating good compatibility and “Poor” indicating poor compatibility.
As is clear from Table 3, the adhesive composition of the present invention based on Examples 1 to 15 had good compatibility. On the other hand, those in Comparative Examples 4 and 6 had poor compatibility.
［埋め込み性（発泡及び充填状態）］
上記実施例１〜１５および比較例１〜６の接着剤組成物の塗料を、乾燥後の厚さが２５μｍとなるように、剥離処理を施した厚さ３８μｍのポリエステルフィルム上に塗布し、熱風循環型乾燥機中にて１３０℃で５分間乾燥して接着剤層を形成した後、剥離処理を施し厚さ５０μｍのポリエチレンフィルムを貼り合わせ接着シートを作製した。
また、フレキシブル基板（商品名：エスパネックス、新日鐵化学社製）にフォトレジスト膜を熱圧着、エッチング、レジスト膜剥離を経て、導体／導体間距離２５μｍ／２５μｍの梯子型回路を作製し、その回路上に、作製した接着シートを、ポリエチレンフィルムを剥離しながら熱圧着した。次いで、ポリエステルフィルムを剥がして１６０℃で１時間加熱して接着剤層を硬化させ、発泡及び埋め込み性評価試料とした。熱圧着温度はポリイミドフィルム（商品名：ユーピレックス５０Ｓ、宇部興産社製）に貼り合わせた場合反対から観て濡れて色が変わる温度とした。
その後、顕微鏡により、発泡及び充填状態を下記の基準で判定し、その結果を表３に示した。発泡に関しては、発泡が無いものを○、発泡が生じたものを×とした。また、充填状態に関しては、回路に十分充填できたものを○、できなかったものを×とした。なお、表３において、回路との接着性が悪く、試料として問題があるものは「−」と記載した。
表３から明らかなように、実施例１〜１５に基づく本発明の接着シートでは、発泡が生じず、回路への充填も良好で、埋め込み性が良好であった。これに対して、比較例１，２，４〜６では発泡および充填状態の少なくとも一方が悪く、半導体装置用としては、実用上、埋め込み性に問題のある結果であった。
[Embeddability (foamed and filled)]
The coating compositions of the adhesive compositions of Examples 1 to 15 and Comparative Examples 1 to 6 were applied onto a polyester film having a thickness of 38 μm subjected to a peeling treatment so that the thickness after drying was 25 μm. After drying for 5 minutes at 130 ° C. in a circulation type dryer to form an adhesive layer, a peeling treatment was performed to bond a polyethylene film having a thickness of 50 μm to produce an adhesive sheet.
In addition, a photoresist film is thermocompression-bonded to a flexible substrate (trade name: Espanex, manufactured by Nippon Steel Chemical Co., Ltd.), etched, and the resist film is peeled off to produce a ladder type circuit having a conductor / conductor distance of 25 μm / 25 μm. The produced adhesive sheet was thermocompression-bonded on the circuit while peeling the polyethylene film. Next, the polyester film was peeled off and heated at 160 ° C. for 1 hour to cure the adhesive layer, thereby obtaining a foam and embedding evaluation sample. The thermocompression bonding temperature was set to a temperature at which the color changes when wet when viewed from the opposite side when bonded to a polyimide film (trade name: Upilex 50S, manufactured by Ube Industries).
Thereafter, the foaming and filling states were determined by a microscope according to the following criteria, and the results are shown in Table 3. Regarding foaming, the case where foaming did not occur was marked with ◯, and the case where foaming occurred was marked with ×. In addition, regarding the filling state, the case where the circuit was sufficiently filled was marked with ◯, and the case where the circuit was not filled was marked with x. In Table 3, “−” indicates that the adhesion to the circuit is poor and there is a problem as a sample.
As is clear from Table 3, the adhesive sheets of the present invention based on Examples 1 to 15 did not cause foaming, had good filling into the circuit, and had good embeddability. On the other hand, in Comparative Examples 1, 2, 4 to 6, at least one of the foaming state and the filling state was bad, and as a result for semiconductor devices, there was a problem in terms of embedding properties.
（２）硬化後評価
［ポリイミドフィルムとの接着力（ＰＩ接着力）］
（初期状態のＰＩ接着力）
実施例１〜１５および比較例１〜６の接着剤組成物の塗料を、乾燥後の厚さが２５μｍとなるように、剥離処理を施した厚さ３８μｍのポリエステルフィルム上に塗布し、熱風循環型乾燥機中にて１３０℃で５分間乾燥して接着剤層を形成した後、該接着剤層の表面に剥離処理を施した厚さ５０μｍのポリエチレンフィルムを貼り合わせ接着シートを作製した。
その後、ポリエチレンフィルムを剥離しながら、この接着シートを厚さ５０μｍのポリイミドフィルム（商品名：ユーピレックス５０Ｓ、宇部興産社製）に熱圧着した。熱圧着温度はポリイミドフィルム（商品名：ユーピレックス５０Ｓ、宇部興産社製）に貼り合わせた場合に、反対から観て濡れて色が変わる温度以上とした。
次いで、ポリエステルフィルムを剥がして、厚さ５０μｍのポリイミドフィルム（商品名：ユーピレックス５０Ｓ、宇部興産社製）に熱圧着し、さらに１６０℃で１時間加熱して接着剤層を硬化させた。接着力は、ポリイミドフィルム面を台に固定して、別のポリイミドフィルムの端をテンシロン（島津製作所社製）により１８０°方向に引き剥がして測定し、その結果を表４に示した。
（恒温恒湿試験（ＰＣＴ）後のＰＩ接着力）
また、上記と同様の評価用試料を用い、下記のＰＣＴ後の接着力を測定した。
ＰＣＴは、恒温恒湿槽を用いて、以下に示す条件で行った。温度：１２１℃、湿度：１００％ＲＨ、時間：３００時間。接着力は、ポリイミドフィルム面を台に固定して、別のポリイミドフィルムの端をテンシロン（島津製作所社製）により１８０°方向に引き剥がして測定し、その結果を表４に示した。
表４から明らかなように、実施例１〜１５に基づく本発明の接着シートでは、初期状態及びＰＣＴ後の接着力が４．２（Ｎ／ｃｍ）以上あり、ポリイミドフィルムに対して十分な接着力を有していた。
これに対し、比較例１〜６のものでは、ＰＣＴ後の接着力が０であり、半導体装置用としては使用に耐えうるものではなかった。
(2) Evaluation after curing [Adhesive strength with polyimide film (PI adhesive strength)]
(Initial PI adhesion)
The adhesive composition paints of Examples 1 to 15 and Comparative Examples 1 to 6 were applied onto a 38 μm thick polyester film that had been subjected to a release treatment so that the thickness after drying was 25 μm, and hot air circulation was performed. After drying for 5 minutes at 130 ° C. in a mold dryer to form an adhesive layer, a 50 μm-thick polyethylene film with a release treatment was bonded to the surface of the adhesive layer to prepare an adhesive sheet.
Then, this adhesive sheet was thermocompression bonded to a polyimide film having a thickness of 50 μm (trade name: Upilex 50S, manufactured by Ube Industries) while peeling the polyethylene film. The thermocompression bonding temperature was set to be equal to or higher than the temperature at which the color changes when wet from the opposite side when bonded to a polyimide film (trade name: Upilex 50S, manufactured by Ube Industries).
Next, the polyester film was peeled off, thermocompression bonded to a polyimide film having a thickness of 50 μm (trade name: Upilex 50S, manufactured by Ube Industries), and further heated at 160 ° C. for 1 hour to cure the adhesive layer. The adhesive force was measured by fixing the polyimide film surface to a base and peeling off the end of another polyimide film in a 180 ° direction with Tensilon (manufactured by Shimadzu Corporation). The results are shown in Table 4.
(PI adhesive strength after constant temperature and humidity test (PCT))
Moreover, the adhesive force after the following PCT was measured using the sample for evaluation similar to the above.
PCT was performed using the constant temperature and humidity chamber under the following conditions. Temperature: 121 ° C., humidity: 100% RH, time: 300 hours. The adhesive force was measured by fixing the polyimide film surface to a base and peeling off the end of another polyimide film in a 180 ° direction with Tensilon (manufactured by Shimadzu Corporation). The results are shown in Table 4.
As is clear from Table 4, the adhesive sheets of the present invention based on Examples 1 to 15 have an initial state and an adhesive force after PCT of 4.2 (N / cm) or more, and are sufficiently bonded to the polyimide film. Had power.
On the other hand, in Comparative Examples 1 to 6, the adhesive strength after PCT was 0, and it could not be used for semiconductor devices.
［銅箔との接着力（Ｃｕ接着力）］
（初期状態のＣｕ接着力）
実施例１〜１５および比較例１〜６の接着剤組成物の塗料を、乾燥後の厚さが２５μｍとなるように、剥離処理を施した厚さ３８μｍのポリエステルフィルム上に塗布し、熱風循環型乾燥機中にて１３０℃で５分間乾燥して接着剤層を形成した後、該接着剤層の表面に、剥離処理を施した厚さ５０μｍのポリエチレンフィルムを貼り合わせて接着シートを作製した。
その後、ポリエチレンフィルムを剥離しながら、この接着シートを厚さ１８μｍの銅箔（商品名：ＪＴＣ−Ａ、ジャパンエナジー社製）に熱圧着した。熱圧着温度は、先の評価でポリイミドフィルム（商品名：ユーピレックス５０Ｓ、宇部興産社製）に貼り合わせた場合と同様、反対から観て濡れて色が変わる温度以上とする。
次いで、ポリエステルフィルムを剥がして、厚さ１８μｍの銅箔（商品名：ＪＴＣ−Ａ、ジャパンエナジー社製）に熱圧着し、さらに１６０℃で１時間加熱して接着剤層を硬化させた。接着力は、銅箔面を台に固定して、別の銅箔の端をテンシロン（島津製作所社製）により１８０°方向に引き剥がして測定し、その結果を表４に示した。
（ＰＣＴ後のＣｕ接着力）
また、同様の評価用試料を使いＰＣＴ後の接着力を測定した。
恒温恒湿試験は恒温恒湿槽を用いて、以下に示す条件で行った。温度：１２１℃、湿度：１００％ＲＨ、時間：３００時間。接着力は、銅箔面を台に固定して、別の銅箔の端をテンシロン（島津製作所社製）により１８０°方向に引き剥がして測定し、その結果を表４に示した。
表４から明らかなように、実施例１〜１５に基づく本発明の接着シートでは、初期状態及びＰＣＴ後のＣｕ接着力が５．１（Ｎ／ｃｍ）以上あり、銅箔に対して十分な接着力を有していた。
これに対し、比較例１〜６のものでは、ＰＣＴ後の接着力が２．５（Ｎ／ｃｍ）以下であり、半導体装置用としては使用に耐えうるものではなかった。
[Adhesive strength with copper foil (Cu adhesive strength)]
(Initial Cu adhesion)
The adhesive composition paints of Examples 1 to 15 and Comparative Examples 1 to 6 were applied onto a 38 μm thick polyester film that had been subjected to a release treatment so that the thickness after drying was 25 μm, and hot air circulation was performed. After forming an adhesive layer by drying at 130 ° C. for 5 minutes in a mold dryer, an adhesive sheet was prepared by laminating a 50 μm-thick polyethylene film with a release treatment on the surface of the adhesive layer. .
Then, this adhesive sheet was thermocompression bonded to a copper foil (trade name: JTC-A, manufactured by Japan Energy Co., Ltd.) having a thickness of 18 μm while peeling the polyethylene film. The thermocompression bonding temperature is set to a temperature equal to or higher than the temperature at which the color changes when viewed from the opposite side, similarly to the case where the film is bonded to a polyimide film (trade name: Upilex 50S, manufactured by Ube Industries) in the previous evaluation.
Next, the polyester film was peeled off and thermocompression bonded to a 18 μm thick copper foil (trade name: JTC-A, manufactured by Japan Energy Co., Ltd.), and further heated at 160 ° C. for 1 hour to cure the adhesive layer. The adhesive strength was measured by fixing the copper foil surface to a base and peeling off the end of another copper foil in a 180 ° direction with Tensilon (manufactured by Shimadzu Corporation). The results are shown in Table 4.
(Cu adhesive strength after PCT)
Moreover, the adhesive force after PCT was measured using the same sample for evaluation.
The constant temperature and humidity test was performed using a constant temperature and humidity chamber under the following conditions. Temperature: 121 ° C., humidity: 100% RH, time: 300 hours. The adhesive strength was measured by fixing the copper foil surface to a base and peeling off the end of another copper foil in a 180 ° direction with Tensilon (manufactured by Shimadzu Corporation). The results are shown in Table 4.
As is apparent from Table 4, in the adhesive sheets of the present invention based on Examples 1 to 15, the initial state and the Cu adhesive force after PCT are 5.1 (N / cm) or more, which is sufficient for the copper foil. It had adhesive strength.
On the other hand, in the comparative examples 1-6, the adhesive force after PCT is 2.5 (N / cm) or less, and it cannot be used for semiconductor devices.
［耐リフロー性］
実施例１〜１５および比較例１〜６の接着剤組成物の塗料を、乾燥後の厚さが２５μｍとなるように、剥離処理を施した厚さ３８μｍのポリエステルフィルム上に塗布し、熱風循環型乾燥機中にて１３０℃で５分間乾燥して接着シートを作製した後、剥離処理を施した厚さ５０μｍのポリエチレンフィルムを貼り合わせた。
その後、ポリエチレンフィルムを剥離しながら、この接着シートを厚さ２００μｍ、大きさ２．５ｃｍ×２．５ｃｍの銅部分をエッチングしたガラスエポキシ基板（商品名；ＣＣＬ−ＥＬ１７０、三菱瓦斯化学社製）に熱圧着した。熱圧着温度は、ガラスエポキシ基板（商品名；ＣＣＬ−ＥＬ１７０、三菱瓦斯化学社製）に貼り合わせた場合に、反対から観て濡れて色が変わる温度以上とした。
次いで、ポリエステルフィルムを剥がして、０．９ｃｍ×０．７ｃｍのガラスチップを、熱圧着温度で３分間、０．１ＭＰａの圧力で熱圧着し、９０℃で１時間、さらに１６０℃で１時間加熱して接着剤層を硬化させ、各実施例及び比較例共に５個の耐リフロー性評価試料を得た。
この評価試料を、恒温恒湿槽中に８５℃、８５％ＲＨの条件で４８時間曝露し、その後２６０℃に設定されたＩＲリフロー炉を通過させ、層間剥離、発泡の有無を観察して、結果を表４に示した。表４には５個の試料の中で層間剥離及び発泡が無いものの数（良好なものの個数／５個）を記した。
表４から明らかなように、実施例１〜１５に基づく本発明の接着シートでは、層間剥離及び発泡が無く、５個全てが良好であった。
これに対して、比較例１〜６の接着シートでは、５個全てが良好なものはなく、少なくとも２個以上に、層間剥離および発泡のいずれかが生じていた。
[Reflow resistance]
The adhesive composition paints of Examples 1 to 15 and Comparative Examples 1 to 6 were applied onto a 38 μm thick polyester film that had been subjected to a release treatment so that the thickness after drying was 25 μm, and hot air circulation was performed. An adhesive sheet was prepared by drying at 130 ° C. for 5 minutes in a mold dryer, and then a polyethylene film having a thickness of 50 μm subjected to a peeling treatment was bonded.
Then, while peeling the polyethylene film, this adhesive sheet was applied to a glass epoxy substrate (trade name; CCL-EL170, manufactured by Mitsubishi Gas Chemical Co., Ltd.) with a copper part having a thickness of 200 μm and a size of 2.5 cm × 2.5 cm etched. Thermocompression bonding was performed. The thermocompression bonding temperature was set to be equal to or higher than the temperature at which the color changes when wet from the opposite side when bonded to a glass epoxy substrate (trade name; CCL-EL170, manufactured by Mitsubishi Gas Chemical Company).
Next, the polyester film is peeled off, and a glass chip of 0.9 cm × 0.7 cm is thermocompression bonded at a thermocompression temperature for 3 minutes at a pressure of 0.1 MPa, and heated at 90 ° C. for 1 hour and further at 160 ° C. for 1 hour. Then, the adhesive layer was cured, and five reflow resistance evaluation samples were obtained for each of the examples and comparative examples.
This evaluation sample was exposed to a constant temperature and humidity chamber at 85 ° C. and 85% RH for 48 hours, then passed through an IR reflow furnace set at 260 ° C., and observed for delamination and foaming. The results are shown in Table 4. Table 4 shows the number of samples having no delamination and foaming among the five samples (the number of good ones / 5).
As is clear from Table 4, the adhesive sheets of the present invention based on Examples 1 to 15 were free from delamination and foaming, and all five were good.
On the other hand, none of the five adhesive sheets of Comparative Examples 1 to 6 were satisfactory, and at least two of the adhesive sheets had either delamination or foaming.
［耐熱温度サイクル性（ＴＣＴ性）］
上記実施例１〜１５および比較例１〜６の接着剤組成物の塗料を、乾燥後の厚さが５０μｍとなるように、剥離処理を施した厚さ３８μｍのポリエステルフィルム上に塗布し、熱風循環型乾燥機中にて１３０℃で５分間乾燥して接着シートを作製した後、剥離処理を施した厚さ５０μｍのポリエチレンフィルムを貼り合わせた。
その後、ポリエチレンフィルムを剥離しながら、この接着シートを厚さ２００μｍ、大きさ２．５ｃｍ×２．５ｃｍの銅部分をエッチングしたガラスエポキシ基板（商品名：ＣＣＬ−ＥＬ１７０、三菱瓦斯化学社製）に熱圧着した。熱圧着温度は、ガラスエポキシ基板（商品名；ＣＣＬ−ＥＬ１７０、三菱瓦斯化学社製）に貼り合わせた場合に、反対から観て濡れて色が変わる温度以上とした。
次いで、ポリエステルフィルムを剥がして、０．９ｃｍ×０．７ｃｍのガラスチップを、熱圧着温度で３分間、０．１ＭＰａの圧力で熱圧着し、９０℃で１時間、さらに１６０℃で１時間加熱して接着剤層を硬化させ、各実施例及び比較例共に５個の耐温度サイクル性評価試料を得た。
この評価試料を用いて、−６５℃〜１５０℃の温度サイクル試験を行った。
但し、この場合、１５０℃および−６５℃ではそれぞれ３０分間の温度履歴を必須とし、［高温−低温］を１サイクルとして、１０００サイクルの条件で実施した。
温度サイクル試験実施後、層間剥離、発泡の有無を観察し結果を表４に示した。表４には５個の試料の中で層間剥離及び発泡が無く良好なものの数（良好の個数／５個）を記した。
表４から明らかなように、実施例１〜１５に基づく本発明の接着シートでは、層間剥離及び発泡が無く５個全てが良好であった。これに対して比較例１〜６の接着シートでは、層間剥離又は発泡のいずれかが生じて５個全てが良好なものはなかった。
[Heat-resistant temperature cycle (TCT)]
The coating compositions of the adhesive compositions of Examples 1 to 15 and Comparative Examples 1 to 6 were applied on a polyester film having a thickness of 38 μm subjected to a peeling treatment so that the thickness after drying was 50 μm. An adhesive sheet was prepared by drying at 130 ° C. for 5 minutes in a circulation dryer, and then a polyethylene film having a thickness of 50 μm subjected to a peeling treatment was bonded.
Then, while peeling the polyethylene film, this adhesive sheet was applied to a glass epoxy substrate (trade name: CCL-EL170, manufactured by Mitsubishi Gas Chemical Co., Ltd.) obtained by etching a copper part having a thickness of 200 μm and a size of 2.5 cm × 2.5 cm. Thermocompression bonding was performed. The thermocompression bonding temperature was set to be equal to or higher than the temperature at which the color changes when wet from the opposite side when bonded to a glass epoxy substrate (trade name; CCL-EL170, manufactured by Mitsubishi Gas Chemical Company).
Next, the polyester film is peeled off, and a glass chip of 0.9 cm × 0.7 cm is thermocompression bonded at a thermocompression temperature for 3 minutes at a pressure of 0.1 MPa, and heated at 90 ° C. for 1 hour and further at 160 ° C. for 1 hour. Then, the adhesive layer was cured, and five temperature cycle resistance evaluation samples were obtained in each example and comparative example.
Using this evaluation sample, a temperature cycle test of −65 ° C. to 150 ° C. was performed.
However, in this case, a temperature history of 30 minutes was essential at 150 ° C. and −65 ° C., and [high temperature-low temperature] was set as one cycle, and the test was performed under conditions of 1000 cycles.
After the temperature cycle test, the presence or absence of delamination and foaming was observed, and the results are shown in Table 4. Table 4 shows the number of good samples without delamination and foaming among the five samples (good number / 5 pieces).
As is clear from Table 4, the adhesive sheets of the present invention based on Examples 1 to 15 were free from delamination and foaming, and all five were good. On the other hand, in the adhesive sheets of Comparative Examples 1 to 6, either delamination or foaming occurred and none of the five sheets was satisfactory.
［動的弾性率］
上記実施例１〜１５および比較例１〜６の接着剤組成物の塗料を、乾燥後の厚さが２５μｍとなるように、剥離処理を施した厚さ３８μｍのポリエステルフィルム上に塗布し、熱風循環型乾燥機中にて１３０℃で５分間乾燥して接着剤層を形成した。次に、得られた接着剤層を、ポリエステルフィルムから剥離して単層とし、この単層の接着剤層を複数重ねた後、この積層体の両面に、ポリエステルフィルム上の接着剤層を更に重ね、全体の接着剤層の厚さが０．１ｍｍとなるようにしてラミネーターで貼り合わせた。ラミネーター温度は、ポリイミドフィルム（商品名：ユーピレックス５０Ｓ、宇部興産社製）に貼り合わせた場合に、反対から観て濡れて色が変わる温度＋３℃〜＋１３℃以内とした。貼り合わせ速度１ｍ／ｍｉｎとした。次に、両面のポリエステルフィルムを剥離して、接着剤層が複数積層された未硬化フィルムを得た。
その後、未硬化フィルムをさらに１６０℃で１時間加熱して接着剤層を硬化させ、４ｍｍ×５ｃｍの動的弾性率評価用試料を作製し、硬化後の２００℃〜２８０℃における動的弾性率（硬化後の動的弾性率）を評価した。
測定条件はオリエンテック社製のレオバイブロンＤＤＶ−ＩＩを用いて周波数１１Ｈｚ、昇温速度３℃／分で測定した値である。
また、同様の評価用試料を使い、硬化後、さらに１５０℃の環境に２４時間放置した後の２００℃〜２８０℃における動的弾性率（熱履歴後の動的弾性率）を測定した。
オーブンにて、温度：１５０℃、時間：２４時間（Ｈ）後、オリエンテック社製のレオバイブロンＤＤＶ−ＩＩを用いて周波数１１Ｈｚ、昇温速度３℃／分で測定した。
これらの結果を表４に示した。
表４から明らかなように、実施例１〜１５に基づく本発明の接着シートでは、硬化後の動的弾性率と熱履歴後の弾性率とを比較すると、その変化が少なかった。この結果から、耐熱劣化性が良好であったことがわかる。
一方、比較例１〜４に基づく接着シートでは、硬化後の動的弾性率と熱履歴後の弾性率との変化が大きく、耐熱劣化性が悪かった。
[Dynamic elastic modulus]
The coating compositions of the adhesive compositions of Examples 1 to 15 and Comparative Examples 1 to 6 were applied onto a polyester film having a thickness of 38 μm subjected to a peeling treatment so that the thickness after drying was 25 μm. It dried for 5 minutes at 130 degreeC in the circulation type dryer, and formed the adhesive bond layer. Next, the obtained adhesive layer is peeled from the polyester film to form a single layer, and a plurality of the single-layer adhesive layers are stacked, and then an adhesive layer on the polyester film is further formed on both sides of the laminate. The laminate was laminated with a laminator so that the thickness of the entire adhesive layer was 0.1 mm. The laminator temperature was set to a temperature within + 3 ° C. to + 13 ° C. when the film was bonded to a polyimide film (trade name: Upilex 50S, manufactured by Ube Industries Co., Ltd.). The bonding speed was 1 m / min. Next, the polyester films on both sides were peeled to obtain an uncured film in which a plurality of adhesive layers were laminated.
Thereafter, the uncured film is further heated at 160 ° C. for 1 hour to cure the adhesive layer, to prepare a 4 mm × 5 cm sample for dynamic elastic modulus evaluation, and after curing, the dynamic elastic modulus at 200 ° C. to 280 ° C. (Dynamic elastic modulus after curing) was evaluated.
The measurement conditions are values measured at a frequency of 11 Hz and a heating rate of 3 ° C./min using Leovibron DDV-II manufactured by Orientech.
Moreover, using the same sample for evaluation, after curing, the dynamic elastic modulus at 200 ° C. to 280 ° C. (dynamic elastic modulus after thermal history) after standing in an environment of 150 ° C. for 24 hours was measured.
After measurement in an oven at a temperature of 150 ° C. and a time of 24 hours (H), the measurement was performed at a frequency of 11 Hz and a heating rate of 3 ° C./min using a Leo Vibron DDV-II manufactured by Orientec.
These results are shown in Table 4.
As is apparent from Table 4, the adhesive sheets of the present invention based on Examples 1 to 15 showed little change when compared between the dynamic elastic modulus after curing and the elastic modulus after thermal history. From this result, it can be seen that the heat resistance deterioration was good.
On the other hand, in the adhesive sheet based on Comparative Examples 1-4, the change with the dynamic elastic modulus after hardening and the elastic modulus after a heat history was large, and its heat-resistant deterioration property was bad.
［吸湿率］
上記実施例１〜１５および比較例１〜６の接着剤組成物の塗料を、乾燥後の厚さが６０μｍとなるように、剥離処理を施した厚さ３８μｍのポリエステルフィルム上に塗布し、熱風循環型乾燥機中にて１３０℃で５分間乾燥して接着剤層を形成し、接着シートを作製した後、剥離処理を施した厚さ５０μｍのポリエチレンフィルムを貼り合わせた。
その後、ポリエチレンフィルムとポリエステルフィルムを剥がして、さらに１６０℃で１時間加熱して接着剤層を硬化させ、５ｃｍ×５ｃｍの吸湿率評価用試料を作製し吸湿率を測定した。吸湿条件は恒温恒湿槽を用いて、以下に示す条件で行った。温度：１２１℃、湿度：１００％ＲＨ、時間：２４時間。その後下記式により吸湿率を算出し結果を表４に示した。
吸湿率（％）＝（吸湿後の試料重量−吸湿前の試料重量）／吸湿前の試料重量×１００
表４から明らかなように、実施例１〜１５に基づく本発明の接着シートでは、吸湿率が０．７％以下であって、実用上問題の無い結果であった。
これに対して比較例１、３では吸湿率が１．３％以上あり、半導体装置用として実用上問題のある結果であった。
[Hygroscopic rate]
The coating compositions of the adhesive compositions of Examples 1 to 15 and Comparative Examples 1 to 6 were applied on a polyester film having a thickness of 38 μm subjected to a release treatment so that the thickness after drying was 60 μm. After drying for 5 minutes at 130 ° C. in a circulation type dryer to form an adhesive layer and preparing an adhesive sheet, a polyethylene film having a thickness of 50 μm subjected to a release treatment was bonded.
Thereafter, the polyethylene film and the polyester film were peeled off, and further heated at 160 ° C. for 1 hour to cure the adhesive layer, thereby preparing a 5 cm × 5 cm moisture absorption rate evaluation sample and measuring the moisture absorption rate. Hygroscopic conditions were performed under the following conditions using a constant temperature and humidity chamber. Temperature: 121 ° C., humidity: 100% RH, time: 24 hours. Thereafter, the moisture absorption rate was calculated by the following formula, and the results are shown in Table 4.
Moisture absorption rate (%) = (sample weight after moisture absorption−sample weight before moisture absorption) / sample weight before moisture absorption × 100
As is apparent from Table 4, the adhesive sheets of the present invention based on Examples 1 to 15 had a moisture absorption rate of 0.7% or less, and there were no practical problems.
On the other hand, Comparative Examples 1 and 3 had a moisture absorption rate of 1.3% or more, which was a practically problematic result for semiconductor devices.
［伸び率］
上記実施例１〜１５および比較例１〜６の接着剤組成物の塗料を、乾燥後の厚さが６０μｍとなるように、剥離処理を施した厚さ３８μｍのポリエステルフィルム上に塗布し、熱風循環型乾燥機中にて１３０℃で５分間乾燥して接着剤層を形成し接着シートを作製した後、剥離処理を施した厚さ５０μｍのポリエチレンフィルムを貼り合わせた。
その後、ポリエチレンフィルムとポリエステルフィルムを剥がして、さらに１６０℃で１時間加熱して接着剤層を硬化させ、１ｃｍ×１２ｃｍの伸び率評価用試料を作製し伸び率を評価した。
伸び率の測定方法はテンシロン（島津製作所社製）により測定して下記式により伸び率を算出し結果を表４に示した。
伸び率（％）＝（引張り後の試料長さ−引張り前の試料の長さ）／引張り前の試料の長さ×１００
表４から明らかなように、実施例１〜１５に基づく本発明の接着シートでは、伸び率が３０％以上であって応力緩和性に優れていることが確認された。これに対して比較例１，３では伸び率が１０％以下であり、応力緩和性に劣ることが確認された。
[Growth rate]
The coating compositions of the adhesive compositions of Examples 1 to 15 and Comparative Examples 1 to 6 were applied on a polyester film having a thickness of 38 μm subjected to a release treatment so that the thickness after drying was 60 μm. After drying for 5 minutes at 130 ° C. in a circulation type dryer to form an adhesive layer and preparing an adhesive sheet, a polyethylene film having a thickness of 50 μm subjected to a peeling treatment was bonded.
Thereafter, the polyethylene film and the polyester film were peeled off, and further heated at 160 ° C. for 1 hour to cure the adhesive layer, and a 1 cm × 12 cm elongation rate evaluation sample was prepared to evaluate the elongation rate.
The elongation percentage was measured with Tensilon (manufactured by Shimadzu Corporation), the elongation percentage was calculated according to the following formula, and the results are shown in Table 4.
Elongation rate (%) = (sample length after tension−length of sample before tension) / length of sample before tension × 100
As is clear from Table 4, it was confirmed that the adhesive sheets of the present invention based on Examples 1 to 15 had an elongation rate of 30% or more and excellent stress relaxation properties. In contrast, in Comparative Examples 1 and 3, the elongation was 10% or less, and it was confirmed that the stress relaxation properties were inferior.
［電気特性］
上記実施例１〜１５および比較例１〜６の接着剤組成物の塗料を、乾燥後の厚さが２５μｍとなるように、剥離処理を施した厚さ３８μｍのポリエステルフィルム上に塗布し、熱風循環型乾燥機中にて１３０℃で５分間乾燥して接着剤層を形成した後、剥離処理を施した厚さ５０μｍのポリエチレンフィルムを貼り合わせ接着シートを作製した。
またフレキシブル基板（商品名：エスパネックス、新日鐵化学社製）にフォトレジスト膜を熱圧着、エッチング、レジスト膜剥離を経て、導体／導体間距離２５μｍ／２５μｍのくし型回路を作製し、その回路上にポリエチレンフィルムを剥離しながら、この接着シートを熱圧着した。次いで、ポリエステルフィルムを剥がして１６０℃で１時間加熱して接着剤層を硬化させ、電気特性評価試料とした。
次に、この試料を温度：１３０℃、湿度：８５％ＲＨの恒温恒湿槽に、直流電圧５Ｖを加えながら３００時間曝した。その後、恒温恒湿槽から取り出して、くし型回路の導体（銅箔部）への電食の有無について観察し、くし型回路の導体（銅箔部）への電食が無いものを○、電食があるもの×とした。なお、表４において、回路との接着性が悪く、試料として問題があるものは「−」と記載した。その結果を表４に示した。
表４から明らかなように、実施例１〜１５に基づく本発明の接着シートでは、くし型回路の導体（銅箔部）への電食が無く、実用上問題がないものであった。これに対して、比較例２〜６のものでは、電食が発生し半導体装置用としては実用上問題のある結果であった。
[Electrical characteristics]
The coating compositions of the adhesive compositions of Examples 1 to 15 and Comparative Examples 1 to 6 were applied onto a polyester film having a thickness of 38 μm subjected to a peeling treatment so that the thickness after drying was 25 μm. After drying for 5 minutes at 130 ° C. in a circulation type dryer to form an adhesive layer, a 50 μm-thick polyethylene film having been subjected to a release treatment was bonded to prepare an adhesive sheet.
Further, a photoresist circuit is thermocompression-bonded to a flexible substrate (trade name: Espanex, manufactured by Nippon Steel Chemical Co., Ltd.), etched, and the resist film is peeled off to produce a comb-type circuit having a conductor / conductor distance of 25 μm / 25 μm. The adhesive sheet was thermocompression bonded while peeling the polyethylene film on the circuit. Next, the polyester film was peeled off and heated at 160 ° C. for 1 hour to cure the adhesive layer, thereby obtaining an electrical property evaluation sample.
Next, this sample was exposed to a constant temperature and humidity chamber having a temperature of 130 ° C. and a humidity of 85% RH for 300 hours while applying a DC voltage of 5V. Then, take out from the constant temperature and humidity chamber, observe the presence or absence of electrolytic corrosion on the conductor (copper foil portion) of the comb-shaped circuit, ○ It was set to x with electric corrosion. In Table 4, “−” indicates that the adhesiveness to the circuit is poor and there is a problem as a sample. The results are shown in Table 4.
As is apparent from Table 4, the adhesive sheets of the present invention based on Examples 1 to 15 had no electrical corrosion on the conductor (copper foil portion) of the comb circuit, and had no practical problems. On the other hand, in Comparative Examples 2 to 6, electrolytic corrosion occurred, and there were practically problematic results for semiconductor devices.
上記結果から明らかなように、本発明の接着剤組成物および接着シートは、埋め込み性、電気特性、接着力、耐リフロー性及びＴＣＴ性に優れ、吸湿率が小さく、伸び率が大きく、応力緩和性に優れ、かつ耐熱劣化性にも優れている。このことから、本発明の接着剤組成物および接着シートによれば、半導体装置における層間剥離、発泡、反り等の不具合の発生が抑制され、また加工性にも優れているため、半導体装置の信頼性を向上させることができる。
As is apparent from the above results, the adhesive composition and adhesive sheet of the present invention are excellent in embedding property, electrical property, adhesive force, reflow resistance and TCT property, have a low moisture absorption rate, a high elongation rate, and a stress relaxation. Excellent in heat resistance and heat deterioration resistance. Therefore, according to the adhesive composition and the adhesive sheet of the present invention, the occurrence of defects such as delamination, foaming and warping in the semiconductor device is suppressed, and the processability is excellent, so that the reliability of the semiconductor device can be improved. Can be improved.
Claims (10)
前記エポキシ樹脂（Ａ）の含有量が、全固形量の３〜４５質量％であり、前記フェノール樹脂（Ｂ）の含有量が、全固形量の２〜３０質量％であり、前記ビニル共重合体（Ｃ）の含有量が、全固形量の２０〜８０質量％であり、前記シロキサン化合物（Ｄ）の含有量が、全固形量の０．０５〜１０質量％であり、かつ
硬化前の動的粘弾性測定における最低溶融粘度が４００〜５００００Ｐａ．ｓの範囲内であることを特徴とする半導体装置用接着剤組成物。
The content of the epoxy resin (A) is 3 to 45% by mass of the total solid amount, the content of the phenol resin (B) is 2 to 30% by mass of the total solid amount, and the vinyl copolymer The content of the coalescence (C) is 20 to 80% by mass of the total solid content, the content of the siloxane compound (D) is 0.05 to 10% by mass of the total solid content, and before curing The minimum melt viscosity in the dynamic viscoelasticity measurement is 400 to 50000 Pa. It is in the range of s, The adhesive composition for semiconductor devices characterized by the above-mentioned.
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| JP2005181711A JP4691401B2 (en) | 2005-06-22 | 2005-06-22 | Adhesive composition for semiconductor device and adhesive sheet for semiconductor device |
| TW095103025A TWI323275B (en) | 2005-02-04 | 2006-01-26 | Adhesive composition and adhesive sheet for semiconductor device |
| KR1020060009848A KR100727550B1 (en) | 2005-02-04 | 2006-02-01 | Adhesive composition and adhesive sheet for semiconductor device |
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| JP4933281B2 (en) * | 2007-01-17 | 2012-05-16 | 日東シンコー株式会社 | Insulation paper for motor |
| JP5303326B2 (en) * | 2008-06-18 | 2013-10-02 | 積水化学工業株式会社 | Adhesive film, dicing die-bonding tape, and semiconductor device manufacturing method |
| WO2012043450A1 (en) * | 2010-09-30 | 2012-04-05 | 住友ベークライト株式会社 | Liquid resin composition and semiconductor device |
| KR101799499B1 (en) * | 2014-12-24 | 2017-12-20 | 주식회사 엘지화학 | Adhesive composition for semiconductor, adhesive film, dicing die bonding film, and semiconductor device |
| JP6553427B2 (en) * | 2015-06-30 | 2019-07-31 | デクセリアルズ株式会社 | Method for producing reinforced flexible printed wiring board, thermosetting resin composition, and thermosetting adhesive sheet |
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