JP6456134B2 - Conductive resin composition, conductive resin composition for dispensing, die attach agent, and semiconductor device - Google Patents
Conductive resin composition, conductive resin composition for dispensing, die attach agent, and semiconductor device Download PDFInfo
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- JP6456134B2 JP6456134B2 JP2014259564A JP2014259564A JP6456134B2 JP 6456134 B2 JP6456134 B2 JP 6456134B2 JP 2014259564 A JP2014259564 A JP 2014259564A JP 2014259564 A JP2014259564 A JP 2014259564A JP 6456134 B2 JP6456134 B2 JP 6456134B2
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- 239000011342 resin composition Substances 0.000 title claims description 80
- 239000004065 semiconductor Substances 0.000 title claims description 17
- 239000000853 adhesive Substances 0.000 claims description 27
- 230000001070 adhesive effect Effects 0.000 claims description 27
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 230000001588 bifunctional effect Effects 0.000 claims description 6
- 229920000728 polyester Polymers 0.000 claims description 6
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 239000011231 conductive filler Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 claims description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 3
- VYQNWZOUAUKGHI-UHFFFAOYSA-N monobenzone Chemical compound C1=CC(O)=CC=C1OCC1=CC=CC=C1 VYQNWZOUAUKGHI-UHFFFAOYSA-N 0.000 claims description 3
- QROGIFZRVHSFLM-UHFFFAOYSA-N prop-1-enylbenzene Chemical class CC=CC1=CC=CC=C1 QROGIFZRVHSFLM-UHFFFAOYSA-N 0.000 claims description 3
- 230000000052 comparative effect Effects 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- ULQMPOIOSDXIGC-UHFFFAOYSA-N [2,2-dimethyl-3-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)(C)COC(=O)C(C)=C ULQMPOIOSDXIGC-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 229920002857 polybutadiene Polymers 0.000 description 5
- 239000003085 diluting agent Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- NOBYOEQUFMGXBP-UHFFFAOYSA-N (4-tert-butylcyclohexyl) (4-tert-butylcyclohexyl)oxycarbonyloxy carbonate Chemical compound C1CC(C(C)(C)C)CCC1OC(=O)OOC(=O)OC1CCC(C(C)(C)C)CC1 NOBYOEQUFMGXBP-UHFFFAOYSA-N 0.000 description 3
- DPGYCJUCJYUHTM-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-yloxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)CC(C)(C)C DPGYCJUCJYUHTM-UHFFFAOYSA-N 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 3
- -1 parachlorobenzoyl peroxide Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 2
- WVGXBYVKFQJQGN-UHFFFAOYSA-N 1-tert-butylperoxy-2-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC=C1OOC(C)(C)C WVGXBYVKFQJQGN-UHFFFAOYSA-N 0.000 description 2
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical group CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 125000004386 diacrylate group Chemical group 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000004945 silicone rubber Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical group CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- LTQBNYCMVZQRSD-UHFFFAOYSA-N (4-ethenylphenyl)-trimethoxysilane Chemical compound CO[Si](OC)(OC)C1=CC=C(C=C)C=C1 LTQBNYCMVZQRSD-UHFFFAOYSA-N 0.000 description 1
- 0 *[N+]([N-])[N+]([O-])O* Chemical compound *[N+]([N-])[N+]([O-])O* 0.000 description 1
- FYRCDEARNUVZRG-UHFFFAOYSA-N 1,1,5-trimethyl-3,3-bis(2-methylpentan-2-ylperoxy)cyclohexane Chemical compound CCCC(C)(C)OOC1(OOC(C)(C)CCC)CC(C)CC(C)(C)C1 FYRCDEARNUVZRG-UHFFFAOYSA-N 0.000 description 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- KRDXTHSSNCTAGY-UHFFFAOYSA-N 2-cyclohexylpyrrolidine Chemical compound C1CCNC1C1CCCCC1 KRDXTHSSNCTAGY-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- YAQDPWONDFRAHF-UHFFFAOYSA-N 2-methyl-2-(2-methylpentan-2-ylperoxy)pentane Chemical compound CCCC(C)(C)OOC(C)(C)CCC YAQDPWONDFRAHF-UHFFFAOYSA-N 0.000 description 1
- SZFABAXZLWVKDV-UHFFFAOYSA-N 2-methyloctanoyl 2-methyloctaneperoxoate Chemical compound CCCCCCC(C)C(=O)OOC(=O)C(C)CCCCCC SZFABAXZLWVKDV-UHFFFAOYSA-N 0.000 description 1
- KFGFVPMRLOQXNB-UHFFFAOYSA-N 3,5,5-trimethylhexanoyl 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOC(=O)CC(C)CC(C)(C)C KFGFVPMRLOQXNB-UHFFFAOYSA-N 0.000 description 1
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 235000014435 Mentha Nutrition 0.000 description 1
- 241001072983 Mentha Species 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- JWVAUCBYEDDGAD-UHFFFAOYSA-N bismuth tin Chemical compound [Sn].[Bi] JWVAUCBYEDDGAD-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QXJJQWWVWRCVQT-UHFFFAOYSA-K calcium;sodium;phosphate Chemical compound [Na+].[Ca+2].[O-]P([O-])([O-])=O QXJJQWWVWRCVQT-UHFFFAOYSA-K 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- BLCKNMAZFRMCJJ-UHFFFAOYSA-N cyclohexyl cyclohexyloxycarbonyloxy carbonate Chemical compound C1CCCCC1OC(=O)OOC(=O)OC1CCCCC1 BLCKNMAZFRMCJJ-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- XJOBOFWTZOKMOH-UHFFFAOYSA-N decanoyl decaneperoxoate Chemical compound CCCCCCCCCC(=O)OOC(=O)CCCCCCCCC XJOBOFWTZOKMOH-UHFFFAOYSA-N 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- YFQXEEXTCUCORR-UHFFFAOYSA-N ditert-butyl hexanediperoxoate Chemical compound CC(C)(C)OOC(=O)CCCCC(=O)OOC(C)(C)C YFQXEEXTCUCORR-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- QZEJHHGVNNHHSU-UHFFFAOYSA-N hexyl benzenecarboperoxoate Chemical compound CCCCCCOOC(=O)C1=CC=CC=C1 QZEJHHGVNNHHSU-UHFFFAOYSA-N 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000005040 ion trap Methods 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 229940105570 ornex Drugs 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000005634 peroxydicarbonate group Chemical group 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Description
本発明は、導電性樹脂組成物、ディスペンス用導電性樹脂組成物、ダイアタッチ剤、および半導体装置に関する。 The present invention relates to a conductive resin composition, a conductive resin composition for dispensing, a die attach agent, and a semiconductor device.
現在、チップコンデンサーや抵抗器などの表面実装部品を基板に実装するために、導電性樹脂組成物が用いられている。この表面実装では、複雑な形状の基板やアッセンブリの場合には、印刷工法による導電性接着剤の塗布が不適当になるため、導電性樹脂組成物を導電性接着剤として、ディスペンサーで塗布される場合が多い。 Currently, conductive resin compositions are used to mount surface mount components such as chip capacitors and resistors on a substrate. In this surface mounting, in the case of a substrate or assembly having a complicated shape, it is inappropriate to apply a conductive adhesive by a printing method, so that the conductive resin composition is applied as a conductive adhesive with a dispenser. There are many cases.
また、半導体チップをリードフレーム等の金属板に接着・固定する際には、導電性樹脂組成物をダイアタッチ剤として、ディスペンサーで塗布し、使用している。 In addition, when the semiconductor chip is bonded and fixed to a metal plate such as a lead frame, the conductive resin composition is applied as a die attach agent with a dispenser and used.
ここで、ディスペンサーで塗布される導電性接着剤やダイアタッチ剤（以下、導電性接着剤等という）には、高い流動性が求められる。特に、５ｍｍ□チップ等の接合面積が２５ｍｍ２以上のような大型の部品を接着する場合には、導電性接着剤等を溶剤で希釈すると、揮発した溶剤がボイドを形成し、接続信頼性が低下するおそれがある。したがって、導電性接着剤等を、無溶剤で低粘度にする必要がある。 Here, high fluidity | liquidity is calculated | required by the conductive adhesive and die attach agent (henceforth conductive adhesive etc.) apply | coated with a dispenser. In particular, when bonding large parts such as a 5 mm square chip with a bonding area of 25 mm 2 or more, if the conductive adhesive is diluted with a solvent, the volatilized solvent forms a void, and connection reliability is improved. May decrease. Therefore, it is necessary to reduce the viscosity of the conductive adhesive or the like without using any solvent.
また、大型部品を実装する際には、寸法安定性や部品追従性の観点から、低反り性が求められる。この低反り性を実現するためには、硬化後の導電性接着剤等に低弾性が要求される。したがって、導電性接着剤等は、無溶剤で低粘度であり、かつ硬化後には低弾性である必要がある。 Further, when mounting a large component, low warpage is required from the viewpoint of dimensional stability and component followability. In order to realize this low warpage property, low elasticity is required for the conductive adhesive after curing. Therefore, a conductive adhesive or the like needs to be solventless and have a low viscosity and have a low elasticity after being cured.
硬化後に、低弾性となる樹脂組成物としては、シリコーンゴムと無機充填剤からなる、ガラス転移温度と−６５℃の貯蔵弾性率が所定の低弾性接着剤（特許文献１）、所定のエポキシ変性ブタジエンと、エポキシ樹脂と、硬化剤とを含有する硬化性組成物（特許文献２）が開示されている。 The resin composition having low elasticity after curing includes a low elastic adhesive (silicone rubber and inorganic filler) having a glass transition temperature and a storage elastic modulus of −65 ° C. (Patent Document 1), and a predetermined epoxy modification. A curable composition (Patent Document 2) containing butadiene, an epoxy resin, and a curing agent is disclosed.
しかしながら、上記のシリコーンゴムと無機充填剤からなる、ガラス転移温度と−６５℃の貯蔵弾性率が所定の低弾性接着剤（特許文献１）、所定のエポキシ変性ブタジエンと、エポキシ樹脂と、硬化剤とを含有する硬化性組成物（特許文献２）のいずれも、硬化前の粘度が高い、という問題がある。 However, a low elastic adhesive (Patent Document 1) having a glass transition temperature and a storage elastic modulus of −65 ° C. (Patent Document 1), a predetermined epoxy-modified butadiene, an epoxy resin, and a curing agent, comprising the silicone rubber and the inorganic filler Any of the curable compositions containing the above (Patent Document 2) has a problem that the viscosity before curing is high.
本発明は、無溶剤で低粘度であり、かつ硬化後には低弾性である導電性樹脂組成物を提供することを目的とする。 An object of the present invention is to provide a conductive resin composition that is solvent-free, has low viscosity, and has low elasticity after curing.
本発明は、以下の構成を有することによって上記問題を解決した導電性樹脂組成物、ディスペンス用導電性樹脂接着剤、ダイアタッチ剤、および半導体装置に関する。
〔１〕（Ａ）一般式（１）：
The present invention relates to a conductive resin composition, a conductive resin adhesive for dispensing, a die attach agent, and a semiconductor device that have solved the above problems by having the following configuration.
[1] (A) General formula (1):
（式中、Ｒは水素原子又はメチル基を示し、ｎは繰返し単位数を表し、平均値で４以上２０以下の数を示す）で表されるポリエチレングリコールジ（メタ）アクリレートと、
（Ｂ）ラジカル発生剤と、
（Ｃ）導電性フィラーと、
（Ｄ）炭素数５〜１４の直鎖アルキレン基を有する直鎖アルカンジオールジ（メタ）アクリレート、単官能および２官能性のポリエステル（メタ）アクリレート、ならびに末端変性ポリブタジエンゴムからなる群より選択される少なくとも１種と
を含むことを特徴とする、導電性樹脂組成物。
〔２〕（Ａ）成分の一般式（１）のｎが、５以上１４以下である、上記〔１〕記載の導電性樹脂組成物。
〔３〕さらに、（Ｅ）メチルヒドロキノン、ｔ−ブチルヒドロキノン、ｐ−ベンジルオキシフェノール、およびメチルスチレンダイマーからなる群より選択される少なくとも１種を含む、上記〔１〕または〔２〕記載の導電性樹脂組成物。
〔４〕上記〔１〕〜〔３〕のいずれか記載の導電性樹脂組成物を含む、ディスペンス用導電性樹脂組成物。
〔５〕上記〔１〕〜〔３〕のいずれか記載の導電性樹脂組成物を含む、ダイアタッチ剤。
〔６〕上記〔１〕〜〔３〕のいずれか記載の導電性樹脂組成物の硬化物を有する、半導体装置。
〔７〕上記〔４〕記載のディスペンス用導電性樹脂組成物の硬化物を有する、半導体装置。
〔８〕上記〔５〕記載のダイアタッチ剤の硬化物を有する、半導体装置。
(Wherein, R represents a hydrogen atom or a methyl group, n represents the number of repeating units, and represents an average value of 4 or more and 20 or less), and a polyethylene glycol di (meth) acrylate represented by:
(B) a radical generator;
(C) a conductive filler;
(D) selected from the group consisting of linear alkanediol di (meth) acrylates having a linear alkylene group of 5 to 14 carbon atoms, monofunctional and bifunctional polyester (meth) acrylates, and terminal-modified polybutadiene rubbers A conductive resin composition comprising at least one kind.
[2] The conductive resin composition according to [1], wherein n in the general formula (1) of the component (A) is 5 or more and 14 or less.
[3] The conductivity according to [1] or [2], further including (E) at least one selected from the group consisting of methylhydroquinone, t-butylhydroquinone, p-benzyloxyphenol, and methylstyrene dimer. Resin composition.
[4] A conductive resin composition for dispensing, comprising the conductive resin composition according to any one of [1] to [3].
[5] A die attach agent comprising the conductive resin composition according to any one of [1] to [3].
[6] A semiconductor device having a cured product of the conductive resin composition according to any one of [1] to [3].
[7] A semiconductor device having a cured product of the conductive resin composition for dispensing according to [4].
[8] A semiconductor device having a cured product of the die attach agent according to [5].
本発明〔１〕によれば、無溶剤で低粘度であり、かつ硬化後には低弾性である導電性樹脂組成物を提供することができる。 According to the present invention [1], it is possible to provide a conductive resin composition that is solvent-free, has a low viscosity, and has low elasticity after curing.
本発明〔４〕によれば、無溶剤で低粘度であり、かつ硬化後には低弾性である導電性樹脂組成物を含むディスペンス用導電性樹脂組成物を得ることができる。本発明〔５〕によれば、無溶剤で低粘度であり、かつ硬化後には低弾性である導電性樹脂組成物を含むダイアタッチ剤を得ることができる。これらによれば、大型の部品を実装した際に低反り化を実現できる。 According to the present invention [4], it is possible to obtain a conductive resin composition for dispensing containing a conductive resin composition that is solvent-free and has low viscosity and low elasticity after curing. According to the present invention [5], it is possible to obtain a die attach agent containing a conductive resin composition which is solvent-free and has a low viscosity and has low elasticity after curing. According to these, low warpage can be realized when a large component is mounted.
本発明〔６〕〜〔８〕によれば、硬化後に低弾性である導電性樹脂組成物の硬化物による高信頼性の半導体装置を得ることができる。 According to the present invention [6] to [8], it is possible to obtain a highly reliable semiconductor device using a cured product of a conductive resin composition having low elasticity after curing.
本発明の導電性樹脂組成物（以下、導電性樹脂組成物という）は、
（Ａ）一般式（１）：
The conductive resin composition of the present invention (hereinafter referred to as a conductive resin composition)
(A) General formula (1):
（Ｂ）ラジカル発生剤と、
（Ｃ）導電性フィラーと、
（Ｄ）炭素数５〜１４の直鎖アルキレン基を有する直鎖アルカンジオールジ（メタ）アクリレート、単官能および２官能性のポリエステル（メタ）アクリレート、ならびに末端変性ポリブタジエンゴムからなる群より選択される少なくとも１種と
を含むことを特徴とする。
(B) a radical generator;
(C) a conductive filler;
(D) selected from the group consisting of linear alkanediol di (meth) acrylates having a linear alkylene group of 5 to 14 carbon atoms, monofunctional and bifunctional polyester (meth) acrylates, and terminal-modified polybutadiene rubbers And at least one kind.
（Ａ）成分は、硬化後の導電性樹脂組成物を低弾性にする。（Ａ）成分のポリエチレングリコールジ（メタ）アクリレートのエチレングリコール鎖の長さは、「−ＣＨ２ＣＨ２Ｏ−」を１単位として、平均で、４単位〜２０単位（一般式（１）におけるｎの平均値４〜２０）であり、流動性・揮発性の観点から、５〜１４単位（一般式（１）におけるｎの平均値５〜１４）であると好ましく、９単位〜１４単位（式（１）におけるｎの平均値９〜１４）が、より好ましい。 (A) A component makes the conductive resin composition after hardening low elasticity. The length of the ethylene glycol chain of the polyethylene glycol di (meth) acrylate as the component (A) is 4 units to 20 units on average with “—CH 2 CH 2 O—” as one unit (in the general formula (1)). The average value of n is 4 to 20), and from the viewpoint of fluidity and volatility, it is preferably 5 to 14 units (the average value of n in the general formula (1) is 5 to 14), and 9 units to 14 units ( The average value 9-14 of n in the formula (1) is more preferable.
エチレングリコール鎖が４単位未満では、成分が揮発しやすくボイド発生の原因となる。一方、２０単位を超えると、導電性樹脂組成物の硬化性が悪くなったり、粘度が上昇してしまったりする場合がある。 If the ethylene glycol chain is less than 4 units, the components are likely to volatilize and cause voids. On the other hand, when it exceeds 20 units, the curability of the conductive resin composition may deteriorate or the viscosity may increase.
ポリエチレングリコールジ（メタ）アクリレートとしては、アクリレート（Ｒが水素原子）でもメタクリレート（Ｒがメチル基）でもよいが、アクリレートであると、重合性が良好である点から好ましい。（Ａ）成分は、単独でも２種以上を併用してもよい。 The polyethylene glycol di (meth) acrylate may be an acrylate (R is a hydrogen atom) or a methacrylate (R is a methyl group), but an acrylate is preferred from the viewpoint of good polymerizability. (A) A component may be individual or may use 2 or more types together.
（Ｂ）成分であるラジカル発生剤は、（Ａ）成分を硬化させるために含有される。（Ｂ）成分としては、有機過酸化物が挙げられ、イソノナノイルペルオキシド、デカノイルペルオキシド、ラウロイルペルオキシド、パラクロロベンゾイルペルオキシド、ジ（３，５，５−トリメチルヘキサノイル）ペルオキシド等のジアシルペルオキシド類；２，２−ジ（４，４−ジ−（ジ−ｔｅｒｔ−ブチルペルオキシ）シクロヘキシル）プロパン等のペルオキシケタール類；ビス（４-ｔｅｒｔ-ブチルシクロヘキサニル）ペルオキシジカーボネート、ジ−３−メトキシブチルペルジカーボネート、ジシクロヘキシルペルジカーボネート等のペルオキシジカーボネート類；ｔｅｒｔ−ブチルペルベンゾエート、ｔｅｒｔ−ブチルペルアセテート、ｔｅｒｔ−ブチルペル−２−エチルへキサノエート、ｔｅｒｔ−ブチルペルイソブチレート、ｔｅｒｔ−ブチルペルピバレート、ｔｅｒｔ−ブチルジペルアジペート、キュミルペルネオデカノエート、ｔｅｒｔ−ブチルペルオキシベンゾエート、１，１，３，３−テトラメチルブチルペルオキシ−２−エチルヘキサノエート、２，５−ジメチル−２，５−ジ（ベンゾイルペルオキシ）ヘキサン等のペルオキシエステル類；メチルエチルケトンペルオキシド、シクロヘキサノンペルオキシド等のケトンペルオキシド類；ジ−ｔｅｒｔ−ブチルペルオキシド、ジキュミルペルオキシド、ｔｅｒｔ−ブチルキュミルペルオキシド、１，１−ジ（ｔ−ヘキシルペルオキシ）−３，３，５−トリメチルシクロヘキサン、ジ −ｔｅｒｔ−ヘキシルペルオキシド、ジ（２−ｔｅｒｔ−ブチルペルオキシイソプロピル）ベンゼン等のジアルキルペルオキシド類；キュメンヒドロキシペルオキシド、ｔｅｒｔ−ブチルハイドロペルオキシド、ｐ−メンタハイドロペルオキシド等のハイドロペルオキシド類等を使用することができる。 The radical generator as the component (B) is contained to cure the component (A). Examples of the component (B) include organic peroxides, and diacyl peroxides such as isononanoyl peroxide, decanoyl peroxide, lauroyl peroxide, parachlorobenzoyl peroxide, and di (3,5,5-trimethylhexanoyl) peroxide. Peroxyketals such as 2,2-di (4,4-di- (di-tert-butylperoxy) cyclohexyl) propane; bis (4-tert-butylcyclohexanyl) peroxydicarbonate, di-3-methoxy Peroxydicarbonates such as butyl perdicarbonate and dicyclohexyl perdicarbonate; tert-butyl perbenzoate, tert-butyl peracetate, tert-butyl per-2-ethylhexanoate, tert-butyl perisobutyrate tert-butylperpivalate, tert-butyldiperadipate, cumylperneodecanoate, tert-butylperoxybenzoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2, Peroxyesters such as 5-dimethyl-2,5-di (benzoylperoxy) hexane; ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; di-tert-butyl peroxide, dicumyl peroxide, tert-butyl cumyl peroxide, Dialkyl peroxides such as 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane, di-tert-hexyl peroxide, di (2-tert-butylperoxyisopropyl) benzene Sid like; particulate Men hydroperoxide, tert- butyl hydroperoxide, may be used hydro peroxides such as p- mentha hydroperoxide.
これらの中でも、ペルオキシジカーボネート類、ペルオキシエステル類およびジアルキルペルオキサイド類が好ましく、ｔｅｒｔ−ブチルペルオキシベンゾエート、１，１，３，３−テトラメチルブチルペルオキシ−２−エチルヘキサノエート、ビス（４−ｔｅｒｔ−ブチルシクロヘキサニル）ペルオキシジカーボネート、およびジ（２−ｔｅｒｔ−ブチルペルオキシイソプロピル）ベンゼンが、導電性樹脂組成物の保存安定性が良好なことから、より好ましい。（Ｂ）成分は、単独でも２種以上を併用してもよい。 Among these, peroxydicarbonates, peroxyesters and dialkyl peroxides are preferable, and tert-butyl peroxybenzoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, bis (4- tert-Butylcyclohexanyl) peroxydicarbonate and di (2-tert-butylperoxyisopropyl) benzene are more preferable because the storage stability of the conductive resin composition is good. (B) A component may be individual or may use 2 or more types together.
（Ｃ）成分の導電性フィラーは、特に限定する必要はなく、（Ｃ）成分としては、銀、銅、金、パラジウム、白金、ビスマス、錫、ビスマス−錫合金、インジウム錫酸化物、銀被覆銅、銀被覆アルミニウム、金属被覆ガラス球、およびこれらの混合物が挙げられる。（Ｃ）成分の平均粒径は、作業性及び低粘度化の観点から、０．１〜５０μｍであると好ましく、２〜２０μｍであるとより好ましい。ここで、（Ｃ）成分の平均粒径は、レーザー回折法によって測定した体積基準のメジアン径である。また、（Ｃ）成分の形状は、リン片状であると、低抵抗化の観点から、より好ましい。市販品としては、ＤＯＷＡエレクトロニクス製銀粉末（品名：ＦＡ６−１８）、メタロー テクノロジーズ ユーエスエイ（Ｍｅｔａｌｏｒ Ｔｅｃｈｎｏｌｏｇｉｅｓ ＵＳＡ）製銀粉末（品名：Ｋ−００８２Ｐ）、三井金属鉱業製銀粉末（品名：ＳＬ０２）が挙げられる。（Ｃ）成分は、単独でも２種以上を併用してもよい。 The conductive filler of the component (C) is not particularly limited. Examples of the component (C) include silver, copper, gold, palladium, platinum, bismuth, tin, bismuth-tin alloy, indium tin oxide, and silver coating. Examples include copper, silver coated aluminum, metal coated glass spheres, and mixtures thereof. The average particle size of the component (C) is preferably 0.1 to 50 μm and more preferably 2 to 20 μm from the viewpoint of workability and low viscosity. Here, the average particle diameter of the component (C) is a volume-based median diameter measured by a laser diffraction method. In addition, the shape of the component (C) is more preferably a flake shape from the viewpoint of reducing resistance. Commercially available products include silver powder manufactured by DOWA Electronics (product name: FA6-18), silver powder manufactured by Metallo Technologies USA (product name: K-0082P), and silver powder manufactured by Mitsui Mining & Smelting Co., Ltd. (product name: SL02). It is done. (C) A component may be individual or may use 2 or more types together.
さらに、（Ｃ）成分として、タップ密度：０．１〜１．０ｇ／ｃｍ３、ＢＥＴ比表面積：１〜２ｍ２／ｇのものを含むと、（Ｃ）成分の沈降防止を図ることができ、例えば、２５℃で２４時間〜４８時間放置した後でも、導電性樹脂組成物中で（Ｃ）成分を均一に分散させることができる。よって、導電性樹脂組成物が低粘度であっても、導電性を維持することができる。 Further, when the component (C) includes one having a tap density of 0.1 to 1.0 g / cm 3 and a BET specific surface area of 1 to 2 m 2 / g, the precipitation of the component (C) can be prevented. For example, the component (C) can be uniformly dispersed in the conductive resin composition even after being left at 25 ° C. for 24 hours to 48 hours. Therefore, even if the conductive resin composition has a low viscosity, the conductivity can be maintained.
（Ｄ）成分は、炭素数５〜１４の直鎖アルキレン基を有する直鎖アルカンジオールジ（メタ）アクリレート、単官能および２官能性のポリエステル（メタ）アクリレート、ならびに末端変性ポリブタジエンゴムからなる群より選択される少なくとも１種であり、導電性樹脂組成物に接着性と、硬化後の更なる低弾性化を付与する低弾性の接着性付与剤である。（Ｄ）成分は、（Ａ）成分に比べ低弾性率化への寄与度は小さいが、接着性への寄与度が大きい。 The component (D) is composed of a linear alkanediol di (meth) acrylate having a linear alkylene group having 5 to 14 carbon atoms, a monofunctional and bifunctional polyester (meth) acrylate, and a terminal-modified polybutadiene rubber. It is at least one selected, and is a low-elasticity imparting agent that imparts adhesiveness and further low elasticity after curing to the conductive resin composition. The component (D) contributes less to the lower modulus of elasticity than the component (A), but has a greater contribution to adhesiveness.
炭素数５〜１４の直鎖アルキレン基を有する直鎖アルカンジオールジ（メタ）アクリレートとしては、１，６−ヘキサンジオールジ（メタ）アクリレート、１，９−ノナンジオールジ（メタ）アクリレート等が挙げられ、硬化後の弾性率と接着強度の観点から１，９−ノナンジオールジ（メタ）アクリレートが好ましい。 Examples of the linear alkanediol di (meth) acrylate having a linear alkylene group having 5 to 14 carbon atoms include 1,6-hexanediol di (meth) acrylate and 1,9-nonanediol di (meth) acrylate. 1,9-nonanediol di (meth) acrylate is preferred from the viewpoint of the elastic modulus after curing and the adhesive strength.
単官能および２官能性のポリエステル（メタ）アクリレートは、硬化後の組成物の架橋密度が高くなりすぎないよう、低弾性化の観点から用いられる。このような単官能および２官能性のポリエステル（メタ）アクリレートとしては、ダイセル・オルネクス社のＥＢＥＣＲＹＬ（登録商標）シリーズや、サートマー社製のＣＮシリーズのものを用いることができる。ＥＢＥＣＲＹＬ（登録商標）シリーズとしては、ＥＢＥＣＲＹＬ５２４（６００００ｍＰａ・ｓ＠２５℃）、 ＥＢＥＣＲＹＬ５２５（４００００ｍＰａ・ｓ ＠２５℃）、ＣＮシリーズとしては、ＣＮ２２０３、ＣＮ２２７０（５５ｃｐｓ＠２５℃）、ＣＮ２２７１（７０ｃｐｓ＠２５℃）、ＣＮ２２７３（１００ｃｐｓ＠２５℃）、ＣＮ２２７４（１３０ｃｐｓ＠２５℃）、ＣＮ２２８３（１０５ｃｐｓ＠２５℃）等が挙げられ、特に粘度の観点からＣＮ２２７０、ＣＮ２２７１、ＣＮ２２７３、ＣＮ２２７４、ＣＮ２２８３が好ましい。 Monofunctional and bifunctional polyester (meth) acrylates are used from the viewpoint of low elasticity so that the crosslinked density of the cured composition does not become too high. As such a monofunctional and bifunctional polyester (meth) acrylate, those of the EBECRYL (registered trademark) series manufactured by Daicel Ornex and the CN series manufactured by Sartomer can be used. EBECRYL (registered trademark) series includes EBECRYL 524 (60000 mPa · s @ 25 ° C), EBECRYL 525 (40000 mPa · s @ 25 ° C), CN series includes CN2203, CN2270 (55 cps @ 25 ° C), CN2271 (70 cps @ 25 ° C) ), CN2273 (100 cps @ 25 ° C.), CN2274 (130 cps @ 25 ° C.), CN2283 (105 cps @ 25 ° C.) and the like. CN2270, CN2271, CN2273, CN2274, and CN2283 are particularly preferable from the viewpoint of viscosity.
末端変性ポリブタジエンゴムとしては、無水マレイン酸変性のように、末端基に二重結合を有することが望ましい。末端変性ポリブタジエンゴムは、市販品を用いることができる。市販品としては、クレイバレー社製のＲＩＣＯＮ（登録商標）シリーズを用いることができる。 The terminal-modified polybutadiene rubber preferably has a double bond in the terminal group as in maleic anhydride modification. A commercially available product can be used as the terminal-modified polybutadiene rubber. As a commercially available product, RICON (registered trademark) series manufactured by Clay Valley can be used.
（Ｄ）成分は、固体、液状いずれの形態であってもよい。（Ｄ）成分は、単独でも２種以上を併用してもよい。 The component (D) may be in a solid or liquid form. (D) A component may be individual or may use 2 or more types together.
（Ａ）成分は、導電性樹脂組成物１００質量部に対して、１〜８質量部であると、硬化後の導電性樹脂組成物の弾性率の観点から、好ましい。（Ａ）成分が８質量部を超えると、硬化後の導電性樹脂組成物の耐湿性が悪くなる場合がある。（Ａ）成分は、導電性樹脂組成物１００質量部に対して、２〜７質量部であると、より好ましい。 (A) A component is preferable from a viewpoint of the elasticity modulus of the conductive resin composition after hardening that it is 1-8 mass parts with respect to 100 mass parts of conductive resin compositions. (A) When a component exceeds 8 mass parts, the moisture resistance of the conductive resin composition after hardening may worsen. (A) A component is more preferable in it being 2-7 mass parts with respect to 100 mass parts of conductive resin compositions.
（Ｂ）成分は、導電性樹脂組成物の硬化性の観点から、導電性樹脂組成物１００質量部に対して、０．０５〜３質量部であると好ましく、０．１〜２質量部であると、より好ましい。 The component (B) is preferably 0.05 to 3 parts by mass, and 0.1 to 2 parts by mass with respect to 100 parts by mass of the conductive resin composition, from the viewpoint of curability of the conductive resin composition. More preferably.
（Ｃ）成分は、導電性樹脂組成物自体の導電性の観点から、導電性樹脂組成物１００質量部に対して、５０〜９０質量部であると好ましく、６０〜８６質量部であると、より好ましい。 The component (C) is preferably 50 to 90 parts by mass, and 60 to 86 parts by mass with respect to 100 parts by mass of the conductive resin composition, from the viewpoint of the conductivity of the conductive resin composition itself. More preferred.
また、（Ｃ）成分は、導電性樹脂組成物の硬化物の場合も、導電性樹脂組成物１００質量部に対して、５０〜９０質量部であると好ましく、６０〜８６質量部であると、より好ましい。ここで、（Ｃ）成分の定量分析は、質量分析法で行う。 Moreover, also in the case of the hardened | cured material of a conductive resin composition, (C) component is preferable in it being 50-90 mass parts with respect to 100 mass parts of conductive resin compositions, and being 60-86 mass parts. More preferable. Here, the quantitative analysis of the component (C) is performed by mass spectrometry.
（Ｄ）成分は、硬化物の部品接着強度、弾性率の観点から、導電性樹脂組成物１００質量部に対して、５〜３０質量部であると好ましく、８〜２０質量部であると、より好ましい。 The component (D) is preferably 5 to 30 parts by mass, and 8 to 20 parts by mass with respect to 100 parts by mass of the conductive resin composition from the viewpoint of component adhesive strength and elastic modulus of the cured product. More preferred.
導電性樹脂組成物は、さらに、重合禁止剤として、（Ｅ）メチルヒドロキノン、ｔ−ブチルヒドロキノン、ｐ−ベンジルオキシフェノール、およびメチルスチレンダイマーからなる群より選択される少なくとも１種を含むと、導電性樹脂組成物のゲル化を防止し、ポットライフが長くなるため、好ましい。（Ｅ）成分は、単独でも２種以上を併用してもよい。 When the conductive resin composition further contains at least one selected from the group consisting of (E) methylhydroquinone, t-butylhydroquinone, p-benzyloxyphenol, and methylstyrene dimer as a polymerization inhibitor, This is preferable because it prevents gelation of the conductive resin composition and prolongs the pot life. (E) A component may be individual or may use 2 or more types together.
導電性樹脂組成物は、さらに、（Ｆ）カップリング剤を含むと、導電性樹脂組成物の密着性の観点から好ましい。（Ｆ）成分としては、３−グリシドキシプロピルトリメトキシシラン、３−アミノプロピルトリメトキシシラン、ビニルトリメトキシシラン、ｐ−スチリルトリメトキシシラン、３−メタクリロキシプロピルメチルジメトキシシラン、３−メタクリロキシプロピルトリメトキシシラン、３−アクリロキシプロピルトリメトキシシラン、３−ウレイドプロピルトリエトキシシラン、３−メルカプトプロピルトリメトキシシラン、ビス（トリエトキシシリルプロピル）テトラスルフィド、３−イソシアネートプロピルトリエトキシシラン等が挙げられ、３−メタクリロキシプロピルメチルジメトキシシラン、３−メタクリロキシプロピルトリメトキシシランが、導電性樹脂組成物の密着性の観点から好ましい。市販品としては、信越化学工業製シランカップリング剤（品名：ＫＢＭ５０２、ＫＢＭ５０３）、日美商事製シランカップリング剤（品名：Ｓ５１０）等が挙げられるが、（Ｆ）成分は、これら品名に限定されるものではない。（Ｆ）成分は、単独でも２種以上を併用してもよい。 When the conductive resin composition further contains a coupling agent (F), it is preferable from the viewpoint of the adhesiveness of the conductive resin composition. As the component (F), 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, vinyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxy Examples include propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane, and the like. 3-methacryloxypropylmethyldimethoxysilane and 3-methacryloxypropyltrimethoxysilane are preferable from the viewpoint of the adhesiveness of the conductive resin composition. Examples of commercially available products include silane coupling agents manufactured by Shin-Etsu Chemical Co., Ltd. (product names: KBM502, KBM503), silane coupling agents manufactured by Nimi Shoji (product name: S510), and the component (F) is limited to these product names. Is not to be done. (F) A component may be individual or may use 2 or more types together.
（Ｅ）成分は、導電性樹脂組成物１００質量部に対して、０．０１〜０．５質量部であると、ポットライフの観点から、好ましい。 (E) It is preferable from a viewpoint of a pot life that a component is 0.01-0.5 mass part with respect to 100 mass parts of conductive resin compositions.
（Ｆ）成分は、導電性樹脂組成物１００質量部に対して、好ましくは０．０５〜５質量部、より好ましくは０．１〜２質量部含有される。０．０５質量部以上であると、密着性が向上し、５質量部以下であると、導電性樹脂組成物の発泡が抑制される。 The component (F) is preferably contained in an amount of 0.05 to 5 parts by mass, more preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the conductive resin composition. Adhesiveness improves that it is 0.05 mass part or more, and foaming of a conductive resin composition is suppressed as it is 5 mass parts or less.
導電性樹脂組成物には、本発明の目的を損なわない範囲で、更に必要に応じ、レベリング剤、イオントラップ剤、その他の添加剤等を配合することができる。 In the conductive resin composition, a leveling agent, an ion trap agent, other additives, and the like can be further blended as necessary within a range not impairing the object of the present invention.
導電性樹脂組成物は、例えば、（Ａ）成分〜（Ｄ）成分およびその他添加剤等を同時にまたは別々に、撹拌、溶融、混合、分散させることにより得ることができる。これらの混合、撹拌、分散等の装置としては、特に限定されるものではないが、撹拌、３本ロールミル、プラネタリーミキサー、遊星式ミキサー等を使用することができる。また、これら装置を適宜組み合わせて使用してもよい。 The conductive resin composition can be obtained, for example, by stirring, melting, mixing, and dispersing the components (A) to (D) and other additives simultaneously or separately. The mixing, stirring, and dispersing devices are not particularly limited, and a stirring, three roll mill, planetary mixer, planetary mixer, and the like can be used. Moreover, you may use combining these apparatuses suitably.
導電性樹脂組成物は、温度：２５℃での粘度が３〜２０Ｐａ・ｓであると、ディスペンス作業性の観点から好ましい。ここで、粘度は、ＥＨＤ型粘度計として、東機産業株式会社製ＴＶＥ−２２形粘度計（３°コーン、Ｒ９．７）を用い、５ｒｐｍ、２５℃で測定する。 The conductive resin composition preferably has a viscosity at a temperature of 25 ° C. of 3 to 20 Pa · s from the viewpoint of dispensing workability. Here, the viscosity is measured at 5 rpm and 25 ° C. using a TVE-22 type viscometer (3 ° cone, R9.7) manufactured by Toki Sangyo Co., Ltd. as an EHD type viscometer.
導電性樹脂組成物は、ディスペンサー等で、基板の導電部やダイアタッチ部（ダイ取り付け部）、半導体素子の電極部等の電子部品の所望の位置に形成・塗布される。 The conductive resin composition is formed and applied to a desired position of an electronic component such as a conductive portion of a substrate, a die attach portion (die attachment portion), or an electrode portion of a semiconductor element with a dispenser or the like.
導電性樹脂組成物の硬化は、６０〜２００℃が好ましい。導電性樹脂組成物の硬化物の弾性率は３ＧＰａ以下が好ましく、より好ましくは２ＧＰａ以下であり、さらに好ましくは１．５ＧＰａ以下である。このため、特に大型の部品を実装した際に低反り化を実現できる。 The curing of the conductive resin composition is preferably 60 to 200 ° C. The elastic modulus of the cured product of the conductive resin composition is preferably 3 GPa or less, more preferably 2 GPa or less, and even more preferably 1.5 GPa or less. For this reason, low warpage can be realized particularly when a large component is mounted.
本発明の導電性樹脂組成物は、ディスペンス用導電性樹脂組成物やダイアタッチ剤として好適である。 The conductive resin composition of the present invention is suitable as a conductive resin composition for dispensing or a die attach agent.
〔半導体装置〕
本発明の半導体装置は、導電性樹脂組成物の硬化物により、基板とダイ等が接合されている。導電性樹脂組成物が、ディスペンス用導電性樹脂組成物として使用される場合には、例えば、チップコンデンサーや抵抗器などの表面実装部品を基板に実装するために、ディスペンス用導電性樹脂組成物を硬化させて用いられる。導電性樹脂組成物が、ダイアタッチ剤として使用される場合には、例えば、リードフレーム等の金属板と、半導体チップ（ダイ）との接着に、ダイアタッチ剤を硬化させて用いられる。
[Semiconductor device]
In the semiconductor device of the present invention, the substrate and the die are joined by a cured product of the conductive resin composition. When the conductive resin composition is used as a conductive resin composition for dispensing, for example, in order to mount a surface mount component such as a chip capacitor or a resistor on a substrate, the conductive resin composition for dispensing is used. Used after curing. When the conductive resin composition is used as a die attach agent, for example, the die attach agent is cured for adhesion between a metal plate such as a lead frame and a semiconductor chip (die).
本発明の半導体装置は、硬化後に低弾性である導電性樹脂組成物の硬化物により、表面実装部品、金属板、半導体チップ等が接合されているので、高信頼性である。 The semiconductor device of the present invention has high reliability because a surface-mounted component, a metal plate, a semiconductor chip, and the like are joined by a cured product of a conductive resin composition that has low elasticity after curing.
本発明について、実施例により説明するが、本発明はこれらに限定されるものではない。なお、以下の実施例において、部、％はことわりのない限り、質量部、質量％を示す。 The present invention will be described with reference to examples, but the present invention is not limited thereto. In the following examples, parts and% indicate parts by mass and mass% unless otherwise specified.
〔評価用サンプルの作製〕
表１、表２に示す材料のうち、（Ｂ）成分と反応性希釈剤以外を混合し、３本ロールにより最大粒径が１５μｍ以下になるまで分散させ、混合物を得た。分散度の測定は、ＪＩＳ−Ｋ５６００−２−５に準拠して行った。別途、（Ｂ）成分を反応性希釈剤（反応性希釈剤を使用しない場合には、（Ｄ）成分またはその他のアクリレート樹脂）に溶解させた。作製した混合物と、（Ｂ）成分を溶解した反応性希釈剤とを混合し、遊星式ミキサーで、均一に攪拌・混合し、導電性樹脂組成物を得た。混合が完了した導電性樹脂組成物は、真空状態で静置し、内部の気泡を除去した。使用した材料と配合割合を表１、表２に示した。
[Preparation of sample for evaluation]
Among the materials shown in Tables 1 and 2, components other than the component (B) and the reactive diluent were mixed and dispersed with a three roll until the maximum particle size became 15 μm or less to obtain a mixture. The degree of dispersion was measured according to JIS-K5600-2-5. Separately, the component (B) was dissolved in a reactive diluent (in the case where no reactive diluent is used, the component (D) or other acrylate resin). The prepared mixture was mixed with a reactive diluent in which component (B) was dissolved, and the mixture was uniformly stirred and mixed with a planetary mixer to obtain a conductive resin composition. The conductive resin composition after mixing was allowed to stand in a vacuum state to remove internal bubbles. Tables 1 and 2 show the materials and blending ratios used.
使用したビス（４−ｔ−ブチルシクロヘキサニル）ペルオキシジカーボネートは、下記式で表される。 The bis (4-t-butylcyclohexanyl) peroxydicarbonate used is represented by the following formula.
１，１，３，３−テトラメチルブチルペルオキシ−２−エチルヘキサノエートは、下記式で表される。 1,1,3,3-Tetramethylbutylperoxy-2-ethylhexanoate is represented by the following formula.
ネオペンチルグルコールジメタクリレートは、下記式で表される。 Neopentyl glycol dimethacrylate is represented by the following formula.
ジメチロール−トリシクロデカンジアクリレートは、下記式で表される。 Dimethylol-tricyclodecane diacrylate is represented by the following formula.
イソボルニルアクリレートは、下記式で表される。 Isobornyl acrylate is represented by the following formula.
〔評価方法〕
〈導電性樹脂組成物の粘度の測定〉
得られた導電性樹脂組成物の粘度を、東機産業株式会社製粘度計ＴＶＥ−２２形粘度計（３°コーン、Ｒ９．７）を用い、５ｒｐｍ、２５℃で測定した。導電性樹脂組成物の粘度は、３〜２０Ｐａ・ｓであると好ましい。表１、表２に、粘度の測定結果を示す。なお、比較例９は、粘度が高すぎたため、測定できなかった。
〔Evaluation method〕
<Measurement of viscosity of conductive resin composition>
The viscosity of the obtained conductive resin composition was measured at 5 rpm and 25 ° C. using a viscometer TVE-22 type viscometer (3 ° cone, R9.7) manufactured by Toki Sangyo Co., Ltd. The viscosity of the conductive resin composition is preferably 3 to 20 Pa · s. Tables 1 and 2 show the viscosity measurement results. Note that Comparative Example 9 could not be measured because the viscosity was too high.
〈１５０℃、３０分硬化後の常温での弾性率の測定〉
テフロン（登録商標）シート上に膜厚が約１５０μｍになるように、導電性樹脂組成物を塗布し、１５０℃×１０分でシート状に硬化させた。４０ｍｍ×１０ｍｍの短冊状に切り出し、エスアイアイ・ナノテクノロジー社製のＤＭＳ６１００を用いて、室温での引張弾性率を求めた。引張弾性率は、３．０ＧＰａ以下が好ましく、より好ましくは１．５ＧＰａ以下である。表１、表２に測定結果を示す。なお、比較例９は、硬化しなかったため、測定できなかった。
<Measurement of elastic modulus at room temperature after curing at 150 ° C. for 30 minutes>
A conductive resin composition was applied on a Teflon (registered trademark) sheet so that the film thickness was about 150 μm, and cured in a sheet form at 150 ° C. for 10 minutes. Cut into a 40 mm × 10 mm strip, the tensile modulus at room temperature was determined using DMS6100 manufactured by SII Nanotechnology. The tensile modulus is preferably 3.0 GPa or less, more preferably 1.5 GPa or less. Tables 1 and 2 show the measurement results. Note that Comparative Example 9 could not be measured because it was not cured.
〈接着強度の測定〉
２０ｍｍ×２０ｍｍのアルミナ基板上に、１．５ｍｍ×１．５ｍｍの印刷パターンを膜厚２０〜５０μｍ程度になるようにスクリーン印刷で導電性樹脂組成物を塗布し、３．２ｍｍ×１．６ｍｍのアルミナチップを搭載し、荷重をかけたものを１５０℃×１０分で硬化させて、試験片を作製した（ｎ＝１０）。このアルミナ基板上のアルミナチップを、アイコーエンジニアリング社製ＭＯＤＥＬ−１６０５ＨＴＰ型強度試験機で側面から突き、アルミナチップが剥がれた時の数値からせん断強度を算出した。せん断強度は、好ましくは８Ｎ／ｍｍ２以上、さらに好ましくは１０Ｎ／ｍｍ２以上である。表１、表２に測定結果を示す。また、実施例１〜３については、プレッシャークッカー試験（Ｐｒｅｓｓｕｒｅ Ｃｏｏｋｅｒ Ｔｅｓｔ；以下、ＰＣＴ）（２ａｔｍ、１２１℃、２０時間）を行った後、同様にしてせん断強度を算出した。表３に結果を示す。なお、表３には、ＰＣＴ前のせん断強度を「初期の接着強度」、ＰＣＴ後のせん断強度を「ＰＣＴ後の接着強度」と記載した。
<Measurement of adhesive strength>
A conductive resin composition is applied on a 20 mm × 20 mm alumina substrate by screen printing so that a 1.5 mm × 1.5 mm printed pattern has a film thickness of about 20 to 50 μm. A test piece was prepared by mounting an alumina chip and applying a load thereto and curing at 150 ° C. for 10 minutes (n = 10). The alumina chip on the alumina substrate was struck from the side surface with a MODEL-1605 HTP type strength tester manufactured by Aiko Engineering, and the shear strength was calculated from the numerical value when the alumina chip was peeled off. The shear strength is preferably 8 N / mm 2 or more, more preferably 10 N / mm 2 or more. Tables 1 and 2 show the measurement results. Moreover, about Examples 1-3, after performing the pressure cooker test (Pressure Cooker Test; Hereafter, PCT) (2 atm, 121 degreeC, 20 hours), the shear strength was computed similarly. Table 3 shows the results. In Table 3, the shear strength before PCT is described as “initial adhesive strength”, and the shear strength after PCT is described as “adhesive strength after PCT”.
〈総合評価〉
総合評価を行った。導電性樹脂組成物の粘度が３〜２０Ｐａ・ｓ、弾性率が３．０ＧＰａ以下、接着強度が８Ｎ／ｍｍ２以上の全てを満たすときに、総合評価を「○」、ひとつでも満たさないものがあるときに、総合評価を「×」とした。総合評価「○」のうち、弾性率が１．５ＧＰａ以下と、特に優れていた場合には総合評価を「◎」とした。表１、表２に、評価結果を示す。
<Comprehensive evaluation>
A comprehensive evaluation was conducted. When the viscosity of the conductive resin composition is 3 to 20 Pa · s, the elastic modulus is 3.0 GPa or less, and the adhesive strength is 8 N / mm 2 or more, the overall evaluation is “◯”. In some cases, the overall evaluation was “x”. Of the overall evaluation “◯”, when the elastic modulus was particularly excellent at 1.5 GPa or less, the overall evaluation was “◎”. Tables 1 and 2 show the evaluation results.
表１、表２からわかるように、実施例１〜８の全てで、粘度と硬化後の弾性率が低く、接着強度が高く、総合評価も良好であった。特に、実施例６、７では、総合評価が非常に良好であった。これに対して、（Ｄ）成分の代わりにネオペンチルグリコールジメタクリレートを用いた比較例１は、粘度が低すぎ、硬化後の弾性率が高すぎ、接着強度が低かった。（Ｄ）成分の代わりにネオペンチルグリコールジメタクリレートを用いた比較例２は、硬化後の弾性率が高すぎ、接着強度が低かった。（Ｄ）成分の代わりにネオペンチルグリコールジメタクリレートを用いた比較例３は、粘度が低すぎ、硬化後の弾性率が高すぎ、接着強度が低かった。（Ｄ）成分の代わりにネオペンチルグリコールジメタクリレートを用いた比較例４は、粘度が低すぎ、硬化後の弾性率が高すぎた。（Ｄ）成分の代わりにジメチロールトリシクロデカンジアクリレートを用いた比較例５は、硬化後の弾性率が高すぎた。（Ｄ）成分の代わりにウレタン（メタ）クリレートを用いた比較例６は、接着強度が低かった。（Ａ）成分を含有させず（Ｄ）成分の代わりにネオペンチルグリコールジメタクリレートを用いた比較例７は、粘度が低すぎ、硬化後の弾性率が高すぎ、接着強度が低かった。（Ａ）成分を含まない比較例８は、粘度が低すぎた。（Ａ）成分と（Ｄ）成分を含まない比較例９は、粘度が高すぎたため、粘度測定ができず、硬化しなかったため、弾性率測定ができなかった。
また、表３からわかるように、（Ａ）成分の含有量が低い実施例１が、実施例１〜３の中で最も接着強度、およびＰＣＴ後の接着強度が高かった。
As can be seen from Tables 1 and 2, in all of Examples 1 to 8, the viscosity and the elastic modulus after curing were low, the adhesive strength was high, and the overall evaluation was also good. In particular, in Examples 6 and 7, the overall evaluation was very good. On the other hand, Comparative Example 1 using neopentyl glycol dimethacrylate instead of the component (D) had too low a viscosity, too high an elastic modulus after curing, and low adhesive strength. In Comparative Example 2 using neopentyl glycol dimethacrylate instead of the component (D), the elastic modulus after curing was too high and the adhesive strength was low. In Comparative Example 3 using neopentyl glycol dimethacrylate instead of the component (D), the viscosity was too low, the elastic modulus after curing was too high, and the adhesive strength was low. In Comparative Example 4 using neopentyl glycol dimethacrylate instead of the component (D), the viscosity was too low and the elastic modulus after curing was too high. In Comparative Example 5 using dimethylol tricyclodecane diacrylate instead of the component (D), the elastic modulus after curing was too high. In Comparative Example 6 using urethane (meth) acrylate instead of the component (D), the adhesive strength was low. The comparative example 7 which did not contain (A) component but used neopentylglycol dimethacrylate instead of (D) component was too low in viscosity, too high in elasticity after curing, and low in adhesive strength. The viscosity of Comparative Example 8 containing no component (A) was too low. In Comparative Example 9, which did not contain the component (A) and the component (D), the viscosity was too high, the viscosity could not be measured, and the cured product did not cure, so the elastic modulus could not be measured.
Further, as can be seen from Table 3, Example 1 having a low content of the component (A) had the highest adhesive strength among Examples 1 to 3 and the adhesive strength after PCT.
上記のように、本発明の導電性樹脂組成物は、無溶剤で低粘度であり、かつ硬化後には低弾性である。 As described above, the conductive resin composition of the present invention has no solvent and low viscosity, and has low elasticity after curing.
Claims (8)
（Ｂ）ラジカル発生剤と、
（Ｃ）導電性フィラーと、
（Ｄ）炭素数５〜１４の直鎖アルキレン基を有する直鎖アルカンジオールジ（メタ）アクリレート、ならびに単官能および２官能性のポリエステル（メタ）アクリレートからなる群より選択される少なくとも１種と
を含むことを特徴とする、導電性樹脂組成物。 (A) General formula (1):
(B) a radical generator;
(C) a conductive filler;
(D) at least one selected from the group consisting of a linear alkanediol di (meth) acrylate having a linear alkylene group having 5 to 14 carbon atoms and a monofunctional and bifunctional polyester (meth) acrylate. A conductive resin composition comprising the conductive resin composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014259564A JP6456134B2 (en) | 2014-12-23 | 2014-12-23 | Conductive resin composition, conductive resin composition for dispensing, die attach agent, and semiconductor device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| JP2014259564A JP6456134B2 (en) | 2014-12-23 | 2014-12-23 | Conductive resin composition, conductive resin composition for dispensing, die attach agent, and semiconductor device |
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| WO2017090759A1 (en) * | 2015-11-26 | 2017-06-01 | 株式会社スリーボンド | Thermosetting composition and conductive adhesive using same |
| CN108884310B (en) | 2016-03-31 | 2021-05-14 | 日本瑞翁株式会社 | Polyether polymer composition |
| EP3438203B1 (en) | 2016-03-31 | 2021-06-30 | Zeon Corporation | Polyether polymer composition and sheet |
| US10982120B2 (en) * | 2016-09-06 | 2021-04-20 | Threebond Co., Ltd. | Thermocurable electroconductive adhesive |
| US11359116B2 (en) | 2016-09-06 | 2022-06-14 | Threebond Co., Ltd. | Thermocurable electroconductive adhesive |
| KR102516241B1 (en) * | 2016-12-27 | 2023-03-29 | 주식회사 엘지화학 | Acrylic emulsion adhesive and method for preparing the same |
| EP3907252A1 (en) | 2020-05-06 | 2021-11-10 | Henkel AG & Co. KGaA | Adhesive composition and cured product |
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| JP3511129B2 (en) * | 1998-09-28 | 2004-03-29 | 日立化成工業株式会社 | Resin paste composition and semiconductor device using the same |
| JP3929220B2 (en) * | 2000-01-26 | 2007-06-13 | 住友ベークライト株式会社 | Die attach paste and semiconductor device |
| DE602006006665D1 (en) * | 2005-05-19 | 2009-06-18 | Lord Corp | AT ROOM TEMPERATURE HARDENABLE, PROTECTIVE SEALANT |
| JP4830430B2 (en) * | 2005-09-29 | 2011-12-07 | 住友ベークライト株式会社 | Resin composition and semiconductor device produced using resin composition |
| JP2009193005A (en) * | 2008-02-18 | 2009-08-27 | Sekisui Chem Co Ltd | Curable resin composition, column spacer, and liquid crystal display element |
| JP5423262B2 (en) * | 2009-09-10 | 2014-02-19 | 住友ベークライト株式会社 | Resin composition and semiconductor device produced using resin composition |
| JP5563268B2 (en) * | 2009-10-02 | 2014-07-30 | 電気化学工業株式会社 | (Meth) acrylic resin composition, adhesive composition and temporary fixing / peeling method |
| JP5577845B2 (en) * | 2010-05-20 | 2014-08-27 | 住友ベークライト株式会社 | Resin composition and semiconductor device produced using resin composition |
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