JPWO2020121379A1 - Adhesives for semiconductors, cured products and semiconductor parts - Google Patents
Adhesives for semiconductors, cured products and semiconductor parts Download PDFInfo
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- JPWO2020121379A1 JPWO2020121379A1 JP2020558815A JP2020558815A JPWO2020121379A1 JP WO2020121379 A1 JPWO2020121379 A1 JP WO2020121379A1 JP 2020558815 A JP2020558815 A JP 2020558815A JP 2020558815 A JP2020558815 A JP 2020558815A JP WO2020121379 A1 JPWO2020121379 A1 JP WO2020121379A1
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- 239000004065 semiconductor Substances 0.000 title claims description 166
- 239000000853 adhesive Substances 0.000 title claims description 121
- 230000001070 adhesive effect Effects 0.000 title claims description 121
- 239000002245 particle Substances 0.000 claims abstract description 65
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910052709 silver Inorganic materials 0.000 claims abstract description 44
- 239000004332 silver Substances 0.000 claims abstract description 44
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims description 47
- 239000012790 adhesive layer Substances 0.000 claims description 21
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 239000007870 radical polymerization initiator Substances 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 80
- -1 for example Chemical compound 0.000 description 34
- 239000000047 product Substances 0.000 description 25
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- 239000005062 Polybutadiene Substances 0.000 description 14
- 229920001971 elastomer Polymers 0.000 description 14
- 229920002857 polybutadiene Polymers 0.000 description 14
- 239000005060 rubber Substances 0.000 description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 13
- 239000007788 liquid Substances 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 239000007822 coupling agent Substances 0.000 description 10
- 229920005992 thermoplastic resin Polymers 0.000 description 10
- 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 9
- 238000007789 sealing Methods 0.000 description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 229920000459 Nitrile rubber Polymers 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 230000009975 flexible effect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229910000679 solder Inorganic materials 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 3
- UMHKOAYRTRADAT-UHFFFAOYSA-N [hydroxy(octoxy)phosphoryl] octyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OP(O)(=O)OCCCCCCCC UMHKOAYRTRADAT-UHFFFAOYSA-N 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 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
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 150000002118 epoxides Chemical class 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000007561 laser diffraction method Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- RSVDRWTUCMTKBV-UHFFFAOYSA-N sbb057044 Chemical compound C12CC=CC2C2CC(OCCOC(=O)C=C)C1C2 RSVDRWTUCMTKBV-UHFFFAOYSA-N 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- HIQAWCBKWSQMRQ-UHFFFAOYSA-N 16-methylheptadecanoic acid;2-methylprop-2-enoic acid;propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(=C)C(O)=O.CC(=C)C(O)=O.CC(C)CCCCCCCCCCCCCCC(O)=O HIQAWCBKWSQMRQ-UHFFFAOYSA-N 0.000 description 1
- IEKHISJGRIEHRE-UHFFFAOYSA-N 16-methylheptadecanoic acid;propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)CCCCCCCCCCCCCCC(O)=O.CC(C)CCCCCCCCCCCCCCC(O)=O.CC(C)CCCCCCCCCCCCCCC(O)=O IEKHISJGRIEHRE-UHFFFAOYSA-N 0.000 description 1
- JMIZWXDKTUGEES-UHFFFAOYSA-N 2,2-di(cyclopenten-1-yloxy)ethyl 2-methylprop-2-enoate Chemical compound C=1CCCC=1OC(COC(=O)C(=C)C)OC1=CCCC1 JMIZWXDKTUGEES-UHFFFAOYSA-N 0.000 description 1
- YHYCMHWTYHPIQS-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-methoxyethanol Chemical compound COC(O)COCCO YHYCMHWTYHPIQS-UHFFFAOYSA-N 0.000 description 1
- HLIQLHSBZXDKLV-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-phenoxyethanol Chemical compound OCCOCC(O)OC1=CC=CC=C1 HLIQLHSBZXDKLV-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
- RKYJPYDJNQXILT-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxycarbonyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)OCCOC(=O)C=C RKYJPYDJNQXILT-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- CLYUOMVYYFJUBR-UHFFFAOYSA-N 2-[methyl-bis[2-(2-methylprop-2-enoyloxy)ethoxy]silyl]oxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCO[Si](C)(OCCOC(=O)C(C)=C)OCCOC(=O)C(C)=C CLYUOMVYYFJUBR-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- KKOHCQAVIJDYAF-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid;propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O.CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O.CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O KKOHCQAVIJDYAF-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- CEXQWAAGPPNOQF-UHFFFAOYSA-N 2-phenoxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC1=CC=CC=C1 CEXQWAAGPPNOQF-UHFFFAOYSA-N 0.000 description 1
- UDXXYUDJOHIIDZ-UHFFFAOYSA-N 2-phosphonooxyethyl prop-2-enoate Chemical compound OP(O)(=O)OCCOC(=O)C=C UDXXYUDJOHIIDZ-UHFFFAOYSA-N 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- KHVIAGJJSLUYIT-UHFFFAOYSA-N 3-(4,5-dihydro-1h-imidazol-2-yl)propyl-triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCC1=NCCN1 KHVIAGJJSLUYIT-UHFFFAOYSA-N 0.000 description 1
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 description 1
- 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 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- 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 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
- LVACOMKKELLCHJ-UHFFFAOYSA-N 3-trimethoxysilylpropylurea Chemical compound CO[Si](OC)(OC)CCCNC(N)=O LVACOMKKELLCHJ-UHFFFAOYSA-N 0.000 description 1
- UZDMJPAQQFSMMV-UHFFFAOYSA-N 4-oxo-4-(2-prop-2-enoyloxyethoxy)butanoic acid Chemical compound OC(=O)CCC(=O)OCCOC(=O)C=C UZDMJPAQQFSMMV-UHFFFAOYSA-N 0.000 description 1
- QOZVPNFFOMWHRW-UHFFFAOYSA-N CCO[SiH3].N=C=O.N=C=O.N=C=O Chemical compound CCO[SiH3].N=C=O.N=C=O.N=C=O QOZVPNFFOMWHRW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229920013646 Hycar Polymers 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 1
- QRSFFHRCBYCWBS-UHFFFAOYSA-N [O].[O] Chemical compound [O].[O] QRSFFHRCBYCWBS-UHFFFAOYSA-N 0.000 description 1
- OFLYIWITHZJFLS-UHFFFAOYSA-N [Si].[Au] Chemical compound [Si].[Au] OFLYIWITHZJFLS-UHFFFAOYSA-N 0.000 description 1
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000007718 adhesive strength test Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 1
- HUIQMPLLYXZKTI-UHFFFAOYSA-J butanoate pentane-2,4-dione zirconium(4+) Chemical compound [Zr+4].CCCC([O-])=O.CCCC([O-])=O.CCCC([O-])=O.CCCC([O-])=O.CC(=O)CC(C)=O HUIQMPLLYXZKTI-UHFFFAOYSA-J 0.000 description 1
- DZBZPOBRWKJBMH-UHFFFAOYSA-L butanoate;octadecanoate;zirconium(2+) Chemical compound [Zr+2].CCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O DZBZPOBRWKJBMH-UHFFFAOYSA-L 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- DDTBPAQBQHZRDW-UHFFFAOYSA-N cyclododecane Chemical compound C1CCCCCCCCCCC1 DDTBPAQBQHZRDW-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
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- HTDKEJXHILZNPP-UHFFFAOYSA-N dioctyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OCCCCCCCC HTDKEJXHILZNPP-UHFFFAOYSA-N 0.000 description 1
- XMQYIPNJVLNWOE-UHFFFAOYSA-N dioctyl hydrogen phosphite Chemical compound CCCCCCCCOP(O)OCCCCCCCC XMQYIPNJVLNWOE-UHFFFAOYSA-N 0.000 description 1
- VTIXMGZYGRZMAW-UHFFFAOYSA-N ditridecyl hydrogen phosphite Chemical compound CCCCCCCCCCCCCOP(O)OCCCCCCCCCCCCC VTIXMGZYGRZMAW-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
- H01L21/52—Mounting semiconductor bodies in containers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
- H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
- H01L2224/321—Disposition
- H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/32245—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/4805—Shape
- H01L2224/4809—Loop shape
- H01L2224/48091—Arched
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/481—Disposition
- H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
- H01L2224/48247—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
- H01L2224/732—Location after the connecting process
- H01L2224/73251—Location after the connecting process on different surfaces
- H01L2224/73265—Layer and wire connectors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
- H01L2924/181—Encapsulation
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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Die Bonding (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Conductive Materials (AREA)
Abstract
（Ａ）銀粒子と、（Ｂ）（メタ）アクリロイル基を有する単量体と、を含有し、前記（Ａ）成分が第１の銀粒子を含み、前記第１の銀粒子のＢＥＴ比表面積が０．３ｍ２／ｇ以下であり、前記第１の銀粒子の平均粒径が７．０μｍ以上である、半導体用接着剤。
It contains (A) silver particles and (B) a monomer having a (meth) acryloyl group, and the component (A) contains the first silver particles, and the BET specific surface area of the first silver particles. Is 0.3 m 2 / g or less, and the average particle size of the first silver particles is 7.0 μm or more.
Description
本発明は、半導体用接着剤、硬化物及び半導体部品に関する。 The present invention relates to semiconductor adhesives, cured products and semiconductor parts.
半導体装置に用いられる半導体部品は、一般に、半導体チップ等の半導体素子を接着剤（ダイボンディング材）によりリードフレーム等の支持部材に接着して製造されている。従来、半導体用接着剤としては、金−シリコン共晶、はんだ、ペースト状の樹脂組成物等が知られているが、近年、作業性及びコストの観点から、ペースト状の樹脂組成物が広く使用されている。 Semiconductor components used in semiconductor devices are generally manufactured by adhering semiconductor elements such as semiconductor chips to support members such as lead frames with an adhesive (die bonding material). Conventionally, gold-silicon eutectic, solder, paste-like resin compositions and the like are known as adhesives for semiconductors, but in recent years, paste-like resin compositions have been widely used from the viewpoint of workability and cost. Has been done.
半導体チップ等の半導体素子は、高集積化及び微細化に伴い集積密度が高くなり、単位面積当たりの発熱量が増加する傾向にある。そのため、半導体素子が搭載された半導体部品においては、半導体素子から発生した熱を外部に効率的に放散する必要がある。 Semiconductor elements such as semiconductor chips tend to have higher integration densities and heat generation per unit area as they become more integrated and miniaturized. Therefore, in a semiconductor component on which a semiconductor element is mounted, it is necessary to efficiently dissipate heat generated from the semiconductor element to the outside.
また、従来、パワーデバイス用パッケージの素子の接着では、はんだ接合が主流であるが、環境問題の観点から、はんだの脱鉛化の動きが盛んである。これに伴い、実装用途又はダイボンディング用途においては、はんだに代わる接着剤として、樹脂成分を含有する半導体用接着剤の要求が高まってきている。 Further, conventionally, solder bonding has been the mainstream for bonding elements of power device packages, but from the viewpoint of environmental problems, the movement of lead deleading of solder is active. Along with this, in mounting applications or die bonding applications, there is an increasing demand for semiconductor adhesives containing a resin component as an adhesive instead of solder.
しかしながら、樹脂成分を含有する従来の半導体用接着剤では、熱伝導率がはんだに比べて小さく、高熱伝導化が望まれている。これに対し、半導体用接着剤の構成成分として銀粒子を用いることが提案されている（例えば、下記特許文献１参照）。 However, conventional adhesives for semiconductors containing a resin component have a smaller thermal conductivity than solder, and high thermal conductivity is desired. On the other hand, it has been proposed to use silver particles as a constituent component of the semiconductor adhesive (see, for example, Patent Document 1 below).
ところで、半導体素子を支持部材に接着させるための半導体用接着剤に対しては、半導体素子から発生した熱を外部に更に効率的に放散する観点から、熱伝導性を向上させることが求められている。 By the way, with respect to the semiconductor adhesive for adhering a semiconductor element to a support member, it is required to improve the thermal conductivity from the viewpoint of more efficiently dissipating the heat generated from the semiconductor element to the outside. There is.
本発明は、優れた熱伝導性を有する半導体用接着剤及びその硬化物を提供することを目的とする。本発明は、前記半導体用接着剤又はその硬化物を用いた半導体部品を提供することを目的とする。 An object of the present invention is to provide an adhesive for a semiconductor having excellent thermal conductivity and a cured product thereof. An object of the present invention is to provide a semiconductor component using the adhesive for semiconductors or a cured product thereof.
本発明の一態様に係る半導体用接着剤は、（Ａ）銀粒子と、（Ｂ）（メタ）アクリロイル基を有する単量体と、を含有し、前記（Ａ）成分が第１の銀粒子を含み、前記第１の銀粒子のＢＥＴ比表面積が０．３ｍ２／ｇ以下であり、前記第１の銀粒子の平均粒径が７．０μｍ以上である。The adhesive for semiconductors according to one aspect of the present invention contains (A) silver particles and (B) a monomer having a (meth) acryloyl group, and the component (A) is the first silver particle. The BET specific surface area of the first silver particles is 0.3 m 2 / g or less, and the average particle size of the first silver particles is 7.0 μm or more.
上述の半導体用接着剤及びその硬化物は、優れた熱伝導性を有していることから、半導体素子から発生した熱を外部に効率的に放散することができる。 Since the above-mentioned adhesive for semiconductors and its cured product have excellent thermal conductivity, the heat generated from the semiconductor element can be efficiently dissipated to the outside.
本発明の他の態様に係る半導体部品は、支持部材と、半導体素子と、支持部材及び半導体素子の間に配置された接着剤層と、を備え、接着剤層が、上述の半導体用接着剤又はその硬化物を含む。 The semiconductor component according to another aspect of the present invention includes a support member, a semiconductor element, and an adhesive layer arranged between the support member and the semiconductor element, and the adhesive layer is the above-mentioned adhesive for semiconductors. Or the cured product thereof is included.
本発明によれば、優れた熱伝導性を有する半導体用接着剤及びその硬化物を提供することができる。本発明によれば、半導体素子から発生した熱を外部に効率的に放散することができる。本発明によれば、前記半導体用接着剤又はその硬化物を用いた半導体部品を提供することができる。 According to the present invention, it is possible to provide an adhesive for semiconductors having excellent thermal conductivity and a cured product thereof. According to the present invention, the heat generated from the semiconductor element can be efficiently dissipated to the outside. According to the present invention, it is possible to provide a semiconductor component using the adhesive for semiconductors or a cured product thereof.
本発明によれば、半導体用接着剤又はその硬化物の、半導体部品又はその製造への応用を提供することができる。本発明によれば、半導体用接着剤又はその硬化物の、半導体素子と支持部材との接着への応用を提供することができる。本発明によれば、半導体用接着剤の、ダイボンディング材への応用を提供することができる。 According to the present invention, it is possible to provide an application of a semiconductor adhesive or a cured product thereof to a semiconductor component or a manufacturing thereof. According to the present invention, it is possible to provide an application of an adhesive for semiconductors or a cured product thereof for adhesion between a semiconductor element and a support member. According to the present invention, it is possible to provide an application of a semiconductor adhesive to a die bonding material.
本明細書において、「〜」を用いて示された数値範囲は、「〜」の前後に記載される数値をそれぞれ最小値及び最大値として含む範囲を示す。本明細書に段階的に記載されている数値範囲において、ある段階の数値範囲の上限値又は下限値は、他の段階の数値範囲の上限値又は下限値と任意に組み合わせることができる。本明細書に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。「Ａ又はＢ」とは、Ａ及びＢのどちらか一方を含んでいればよく、両方とも含んでいてもよい。本明細書に例示する材料は、特に断らない限り、１種を単独で又は２種以上を組み合わせて用いることができる。本明細書において、組成物中の各成分の使用量は、組成物中に各成分に該当する物質が複数存在する場合、特に断らない限り、組成物中に存在する当該複数の物質の合計量を意味する。本明細書において「層」との語は、平面図として観察したときに、全面に形成されている形状の構造に加え、一部に形成されている形状の構造も包含される。本明細書において「工程」との語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の所期の作用が達成されれば、本用語に含まれる。「（メタ）アクリレート」とは、アクリレート、及び、それに対応するメタクリレートの少なくとも一方を意味する。「（メタ）アクリロイル」等の他の類似の表現においても同様である。 In the present specification, the numerical range indicated by using "~" indicates a range including the numerical values before and after "~" as the minimum value and the maximum value, respectively. In the numerical range described stepwise in the present specification, the upper limit value or the lower limit value of the numerical range of one step can be arbitrarily combined with the upper limit value or the lower limit value of the numerical range of another step. In the numerical range described in the present specification, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples. "A or B" may include either A or B, or both. Unless otherwise specified, the materials exemplified in the present specification may be used alone or in combination of two or more. In the present specification, the amount of each component used in the composition is the total amount of the plurality of substances present in the composition unless otherwise specified, when a plurality of substances corresponding to each component are present in the composition. Means. In the present specification, the term "layer" includes not only a structure having a shape formed on the entire surface but also a structure having a shape partially formed when observed as a plan view. In the present specification, the term "process" is included in this term not only as an independent process but also as long as the desired action of the process is achieved even if it cannot be clearly distinguished from other processes. .. "(Meta) acrylate" means at least one of an acrylate and a corresponding methacrylate. The same is true for other similar expressions such as "(meta) acryloyl".
以下、本発明の実施形態について詳細に説明する。但し、本発明は、以下の実施形態に限定されるものではなく、その要旨の範囲内で種々変形して実施することができる。 Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and can be variously modified and implemented within the scope of the gist thereof.
＜半導体用接着剤及び硬化物＞
本実施形態に係る半導体用接着剤は、（Ａ）銀粒子（以下、場合により「（Ａ）成分」という。銀を含む粒子。例えば銀粉）と、（Ｂ）（メタ）アクリロイル基を有する単量体（以下、場合により「（Ｂ）成分」という）と、を含有し、（Ａ）成分が第１の銀粒子を含み、第１の銀粒子のＢＥＴ比表面積が０．３ｍ２／ｇ以下であり、第１の銀粒子の平均粒径が７．０μｍ以上である。<Adhesives for semiconductors and cured products>
The semiconductor adhesive according to the present embodiment is simply composed of (A) silver particles (hereinafter, sometimes referred to as "(A) component"; particles containing silver, for example, silver powder) and (B) (meth) acryloyl group. It contains a metric (hereinafter, sometimes referred to as "component (B)"), the component (A) contains the first silver particles, and the BET specific surface area of the first silver particles is 0.3 m 2 / g. The average particle size of the first silver particles is 7.0 μm or more.
本実施形態に係る半導体用接着剤は、導電性組成物であり、半導体素子を支持部材に接着させるための導電性組成物として用いることができる。本実施形態に係る半導体用接着剤は、例えば硬化性（例えば熱硬化性）の組成物である。本実施形態に係る半導体用接着剤は、ペースト状の樹脂組成物として用いることができる。本実施形態に係る硬化物は、本実施形態に係る半導体用接着剤の硬化物である。 The semiconductor adhesive according to the present embodiment is a conductive composition, and can be used as a conductive composition for adhering a semiconductor element to a support member. The semiconductor adhesive according to this embodiment is, for example, a curable (for example, thermosetting) composition. The semiconductor adhesive according to this embodiment can be used as a paste-like resin composition. The cured product according to the present embodiment is a cured product of the semiconductor adhesive according to the present embodiment.
本実施形態に係る半導体用接着剤及びその硬化物は、優れた熱伝導性を有していることから、半導体素子から発生した熱を外部に効率的に放散することができる。本実施形態に係る半導体用接着剤及びその硬化物が優れた熱伝導性を有する原因は明らかではないが、本発明者は下記のように推察している。但し、原因は下記の内容に限定されない。すなわち、ＢＥＴ比表面積が小さいと共に平均粒径が大きい第１の銀粒子を用いると、銀粒子同士の接触点が過剰に多くなることが抑制されやすいことにより、銀粒子の接触点における過剰な熱損失が抑制されやすいため、優れた熱伝導性が得られると推察される。 Since the semiconductor adhesive and the cured product thereof according to the present embodiment have excellent thermal conductivity, the heat generated from the semiconductor element can be efficiently dissipated to the outside. The reason why the semiconductor adhesive and the cured product thereof according to the present embodiment have excellent thermal conductivity is not clear, but the present inventor speculates as follows. However, the cause is not limited to the following contents. That is, when the first silver particles having a small BET specific surface area and a large average particle size are used, it is easy to prevent the number of contact points between the silver particles from becoming excessive, so that excessive heat at the contact points of the silver particles is easily suppressed. Since the loss is easily suppressed, it is presumed that excellent thermal conductivity can be obtained.
ところで、半導体用接着剤が多くの銀粒子を含有すると、粘度が高くなることに伴い塗布作業性が低くなる場合、又は、半導体用接着剤の硬化物が脆くなり半導体素子と支持部材との接着強度が低くなる場合がある。一方、本実施形態に係る半導体用接着剤によれば、半導体用接着剤が多くの銀粒子を含有する場合であっても、粘度が高くなることが抑制されやすいことから塗布作業性を高く維持することができると共に、半導体用接着剤の硬化物が脆くなることが抑制されやすいことから半導体素子と支持部材との接着強度を高く維持することができる。すなわち、本実施形態によれば、優れた熱伝導性、塗布作業性及び接着強度を有する半導体用接着剤及びその硬化物を提供することができる。 By the way, when the semiconductor adhesive contains a large number of silver particles, the coating workability decreases as the viscosity increases, or the cured product of the semiconductor adhesive becomes brittle and the semiconductor element and the support member adhere to each other. The strength may be low. On the other hand, according to the semiconductor adhesive according to the present embodiment, even when the semiconductor adhesive contains a large number of silver particles, it is easy to suppress the increase in viscosity, so that the coating workability is maintained high. At the same time, it is easy to prevent the cured product of the semiconductor adhesive from becoming brittle, so that the adhesive strength between the semiconductor element and the support member can be maintained high. That is, according to the present embodiment, it is possible to provide an adhesive for semiconductors having excellent thermal conductivity, coating workability and adhesive strength, and a cured product thereof.
（（Ａ）成分：銀粒子）
（Ａ）成分は、優れた熱伝導性を得る観点から、ＢＥＴ比表面積が０．３ｍ２／ｇ以下であると共に平均粒径が７．０μｍ以上である第１の銀粒子（以下、場合により「（Ａ１）成分」という）を含む。（Ａ）成分は、優れた接着強度を得やすい観点から、ＢＥＴ比表面積が０．３ｍ２／ｇを超える第２の銀粒子（以下、場合により「（Ａ２）成分」という）を更に含んでよい。（Ａ）成分は、１種を単独で又は２種以上を組み合わせて用いることができる。((A) component: silver particles)
From the viewpoint of obtaining excellent thermal conductivity, the component (A) is a first silver particle having a BET specific surface area of 0.3 m 2 / g or less and an average particle size of 7.0 μm or more (hereinafter, depending on the case). "(A1) component") is included. The component (A) further contains second silver particles having a BET specific surface area of more than 0.3 m 2 / g (hereinafter, sometimes referred to as “component (A2)”) from the viewpoint of easily obtaining excellent adhesive strength. good. As the component (A), one type can be used alone or two or more types can be used in combination.
（Ａ１）成分又は（Ａ２）成分の少なくとも一粒子における銀の含有量は、８０質量％以上が好ましく、９０質量％以上がより好ましく、９５質量％以上が更に好ましく、９８質量％以上が特に好ましく、９９質量％以上が極めて好ましい。（Ａ１）成分又は（Ａ２）成分の少なくとも一粒子は、実質的に銀からなる（実質的に粒子の１００質量％が銀である）態様であってよい。 The silver content in at least one particle of the component (A1) or the component (A2) is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and particularly preferably 98% by mass or more. , 99% by mass or more is extremely preferable. At least one particle of the component (A1) or the component (A2) may be in an embodiment substantially composed of silver (substantially 100% by mass of the particles is silver).
（Ａ１）成分の形状としては、鱗片状、球状、塊状、樹枝状、板状等が挙げられるが、優れた熱伝導性を得やすい観点から、鱗片状が好ましい。（Ａ２）成分の形状としては、鱗片状、球状、塊状、樹枝状、板状等が挙げられるが、優れた熱伝導性を得やすい観点から、鱗片状が好ましい。 Examples of the shape of the component (A1) include scaly, spherical, lumpy, dendritic, and plate-like, but scaly is preferable from the viewpoint of easily obtaining excellent thermal conductivity. Examples of the shape of the component (A2) include scaly, spherical, lumpy, dendritic, and plate-like, but scaly is preferable from the viewpoint of easily obtaining excellent thermal conductivity.
（Ａ２）成分としては、福田金属箔粉工業株式社製のＡｇＣ−２７１Ｂ（ＢＥＴ比表面積：０．５０ｍ２／ｇ）、ＡｇＣ−２２１Ｑ３（ＢＥＴ比表面積：０．３５ｍ２／ｇ）及びＡｇＣ−２１２ＤＨ（ＢＥＴ比表面積：１ｍ２／ｇ）；株式会社徳力化学研究所製のＴＣ−８８（ＢＥＴ比表面積：１．０５ｍ２／ｇ）、ＴＣ−５０５Ｃ（ＢＥＴ比表面積：０．６５ｍ２／ｇ）及びＴＣ−８７（ＢＥＴ比表面積：０．２５ｍ２／ｇ）；株式会社フェロ・ジャパン製のＳＦ−１２５（ＢＥＴ比表面積：０．１７ｍ２／ｇ）等が挙げられる。The components (A2) include AgC-271B (BET specific surface area: 0.50 m 2 / g), AgC-221Q3 (BET specific surface area: 0.35 m 2 / g) and AgC- manufactured by Fukuda Metal Foil Powder Industry Co., Ltd. 212DH (BET specific surface area: 1m 2 / g); CO., LTD Tokuriki chemical Laboratory, Ltd. of the TC-88 (BET specific surface area: 1.05m 2 / g), TC -505C (BET specific surface area: 0.65m 2 / g ) and TC-87 (BET specific surface area: 0.25m 2 / g); Co. ferro Japan in SF-125 (BET specific surface area: 0.17 m 2 / g), and the like.
（Ａ１）成分のＢＥＴ表面積は、優れた熱伝導性を得やすい観点から、０．３ｍ２／ｇ未満が好ましく、０．２７５ｍ２／ｇ以下がより好ましく、０．２５ｍ２／ｇ以下が更に好ましく、０．２２５ｍ２／ｇ以下が特に好ましく、０．２ｍ２／ｇ以下が極めて好ましい。（Ａ１）成分のＢＥＴ表面積は、半導体用接着剤の優れた粘度（ペースト使用時の粘度）を得やすい観点から、０．１ｍ２／ｇ以上が好ましく、０．１２５ｍ２／ｇ以上がより好ましく、０．１５ｍ２／ｇ以上が更に好ましく、０．１７５ｍ２／ｇ以上が特に好ましい。これらの観点から、（Ａ１）成分のＢＥＴ表面積は、０．１〜０．３ｍ２／ｇが好ましく、０．１〜０．２５ｍ２／ｇがより好ましい。(A1) BET surface area of the component, from easily obtained excellent thermal conductivity standpoint, is preferably less than 0.3 m 2 / g, more preferably 0.275M 2 / g or less, still is 0.25 m 2 / g or less preferably, particularly preferably 0.225 m 2 / g or less, very preferably 0.2 m 2 / g. (A1) BET surface area of the component, the easier the viewpoint of give excellent viscosity semiconductor adhesive (viscosity when the paste used), preferably at least 0.1 m 2 / g, more preferably at least 0.125 m 2 / g , more preferably not less than 0.15m 2 / g, 0.175m 2 / g or more is particularly preferable. From these viewpoints, (A1) BET surface area of the component is preferably 0.1~0.3m 2 / g, 0.1~0.25m 2 / g is more preferable.
（Ａ２）成分のＢＥＴ表面積は、半導体用接着剤の優れた粘度（ペースト使用時の粘度）を得やすい観点から、０．３５ｍ２／ｇ以上が好ましく、０．３７５ｍ２／ｇ以上がより好ましく、０．４ｍ２／ｇ以上が更に好ましく、０．４２５ｍ２／ｇ以上が特に好ましく、０．４５ｍ２／ｇ以上が極めて好ましく、０．４７５ｍ２／ｇ以上が非常に好ましく、０．５ｍ２／ｇ以上がより一層好ましい。（Ａ２）成分のＢＥＴ表面積は、優れた熱伝導性を得やすい観点から、１ｍ２／ｇ以下が好ましく、０．９ｍ２／ｇ以下がより好ましく、０．８ｍ２／ｇ以下が更に好ましく、０．７ｍ２／ｇ以下が特に好ましく、０．６ｍ２／ｇ以下が極めて好ましい。これらの観点から、（Ａ２）成分のＢＥＴ表面積は、０．３ｍ２／ｇを超え１ｍ２／ｇ以下が好ましく、０．３５〜１ｍ２／ｇがより好ましい。(A2) BET surface area of the component, the easier the viewpoint of give excellent viscosity semiconductor adhesive (viscosity when the paste used), preferably at least 0.35 m 2 / g, more preferably at least 0.375 M 2 / g , more preferably at least 0.4 m 2 / g, particularly preferably not less than 0.425m 2 / g, very preferably more than 0.45 m 2 / g, very preferably at least 0.475m 2 / g, 0.5m 2 / G or more is even more preferable. (A2) BET surface area of the component, from easily obtained excellent thermal conductivity standpoint, preferably 1 m 2 / g or less, more preferably 0.9 m 2 / g, still more preferably 0.8 m 2 / g or less, 0.7 m 2 / g or less is particularly preferable, and 0.6 m 2 / g or less is extremely preferable. From these viewpoints, BET surface area of the component (A2) is preferably from 1 m 2 / g or less exceed 0.3m 2 / g, 0.35~1m 2 / g is more preferable.
（Ａ１）成分の平均粒径は、優れた熱伝導性を得やすい（銀粒子同士の接触点が過剰に多くなることを抑制しやすいことにより、銀粒子の接触点における過剰な熱損失を抑制しやすい）観点から、７．０μｍ以上が好ましく、７．０μｍを超えることがより好ましく、７．２５μｍ以上が更に好ましく、７．５μｍ以上が特に好ましい。（Ａ１）成分の平均粒径は、半導体用接着剤の優れた吐出性（ディスペンス時の吐出性）を得やすい観点から、１０μｍ以下が好ましく、９．５μｍ以下がより好ましく、９μｍ以下が更に好ましく、８．５μｍ以下が特に好ましく、８．２５μｍ以下が極めて好ましく、８．０μｍ以下が非常に好ましい。これらの観点から、（Ａ１）成分の平均粒径は、７．０〜１０μｍが好ましく、７．０〜８．５μｍがより好ましく、７．５〜８．０μｍが更に好ましい。（Ａ１）成分の平均粒径は、レーザー回析式粒度分布測定装置（レーザー回析法）により測定することができる。 The average particle size of the component (A1) makes it easy to obtain excellent thermal conductivity (it is easy to suppress an excessive increase in the number of contact points between silver particles, thereby suppressing an excessive heat loss at the contact points of the silver particles. From the viewpoint of (easy to carry out), 7.0 μm or more is preferable, 7.0 μm or more is more preferable, 7.25 μm or more is further preferable, and 7.5 μm or more is particularly preferable. The average particle size of the component (A1) is preferably 10 μm or less, more preferably 9.5 μm or less, still more preferably 9 μm or less, from the viewpoint of easily obtaining excellent ejection properties (discharge properties at the time of dispensing) of the semiconductor adhesive. , 8.5 μm or less is particularly preferable, 8.25 μm or less is extremely preferable, and 8.0 μm or less is very preferable. From these viewpoints, the average particle size of the component (A1) is preferably 7.0 to 10 μm, more preferably 7.0 to 8.5 μm, and even more preferably 7.5 to 8.0 μm. The average particle size of the component (A1) can be measured by a laser diffraction type particle size distribution measuring device (laser diffraction method).
（Ａ２）成分の平均粒径は、優れた熱伝導性を得やすい観点から、１μｍ以上が好ましく、１．５μｍ以上がより好ましく、２μｍ以上が更に好ましい。（Ａ２）成分の平均粒径は、優れた熱伝導性を得やすい観点から、２０μｍ以下が好ましく、１５μｍ以下がより好ましく、１０μｍ以下が更に好ましく、８μｍ以下が特に好ましく、５μｍ以下が極めて好ましく、４μｍ以下が非常に好ましく、３μｍ以下がより一層好ましい。これらの観点から、（Ａ２）成分の平均粒径は、１〜２０μｍが好ましく、２〜５μｍがより好ましい。（Ａ２）成分の平均粒径は、レーザー回析式粒度分布測定装置（レーザー回析法）により測定することができる。 The average particle size of the component (A2) is preferably 1 μm or more, more preferably 1.5 μm or more, still more preferably 2 μm or more, from the viewpoint of easily obtaining excellent thermal conductivity. The average particle size of the component (A2) is preferably 20 μm or less, more preferably 15 μm or less, further preferably 10 μm or less, particularly preferably 8 μm or less, and extremely preferably 5 μm or less, from the viewpoint of easily obtaining excellent thermal conductivity. 4 μm or less is very preferable, and 3 μm or less is even more preferable. From these viewpoints, the average particle size of the component (A2) is preferably 1 to 20 μm, more preferably 2 to 5 μm. The average particle size of the component (A2) can be measured by a laser diffraction type particle size distribution measuring device (laser diffraction method).
（Ａ１）成分の含有量は、（Ａ）成分の総量を基準として下記の範囲が好ましい。（Ａ１）成分の含有量は、優れた熱伝導性を得やすい観点、及び、粘度を低減させやすい観点から、４０質量％以上が好ましく、５０質量％以上がより好ましく、５０質量％を超えることが更に好ましく、６０質量％以上が特に好ましく、７０質量％以上が極めて好ましい。（Ａ１）成分の含有量は、優れた接着強度を得やすい観点から、１００質量％以下であり、１００質量％未満が好ましく、９５質量％以下がより好ましく、９０質量％以下が更に好ましく、８５質量％以下が特に好ましく、８０質量％以下が極めて好ましく、７５質量％以下が非常に好ましい。これらの観点から、（Ａ１）成分の含有量は、４０〜１００質量％が好ましく、５０〜９５質量％がより好ましい。 The content of the component (A1) is preferably in the following range based on the total amount of the component (A). The content of the component (A1) is preferably 40% by mass or more, more preferably 50% by mass or more, and more than 50% by mass from the viewpoint of easily obtaining excellent thermal conductivity and easily reducing the viscosity. Is more preferable, 60% by mass or more is particularly preferable, and 70% by mass or more is extremely preferable. The content of the component (A1) is 100% by mass or less, preferably less than 100% by mass, more preferably 95% by mass or less, further preferably 90% by mass or less, and further preferably 85% by mass, from the viewpoint of easily obtaining excellent adhesive strength. It is particularly preferably mass% or less, extremely preferably 80% by mass or less, and very preferably 75% by mass or less. From these viewpoints, the content of the component (A1) is preferably 40 to 100% by mass, more preferably 50 to 95% by mass.
（Ａ２）成分の含有量は、（Ａ）成分の総量を基準として下記の範囲が好ましい。（Ａ２）成分の含有量は、優れた接着強度を得やすい観点から、０質量％を超えることが好ましく、５質量％以上がより好ましく、１０質量％以上が更に好ましく、１５質量％以上が特に好ましく、２０質量％以上が極めて好ましく、２５質量％以上が非常に好ましい。（Ａ２）成分の含有量は、優れた熱伝導性を得やすい観点、及び、粘度を低減させやすい観点から、６０質量％以下が好ましく、５０質量％以下がより好ましく、５０質量％未満が更に好ましく、４０質量％以下が特に好ましく、３０質量％以下が極めて好ましい。これらの観点から、（Ａ２）成分の含有量は、０質量％を超え６０質量％以下が好ましく、５〜５０質量％がより好ましい。 The content of the component (A2) is preferably in the following range based on the total amount of the component (A). The content of the component (A2) is preferably more than 0% by mass, more preferably 5% by mass or more, further preferably 10% by mass or more, and particularly preferably 15% by mass or more, from the viewpoint of easily obtaining excellent adhesive strength. Preferably, 20% by mass or more is extremely preferable, and 25% by mass or more is very preferable. The content of the component (A2) is preferably 60% by mass or less, more preferably 50% by mass or less, and further less than 50% by mass from the viewpoint of easily obtaining excellent thermal conductivity and easily reducing the viscosity. It is preferable, 40% by mass or less is particularly preferable, and 30% by mass or less is extremely preferable. From these viewpoints, the content of the component (A2) is preferably more than 0% by mass and 60% by mass or less, more preferably 5 to 50% by mass.
（Ａ１）成分の含有量は、半導体用接着剤の総量（固形分の総量。以下同様）を基準として下記の範囲が好ましい。（Ａ１）成分の含有量は、優れた熱伝導性を得やすい観点、及び、粘度を低減させやすい観点から、３０質量％以上が好ましく、３５質量％以上がより好ましく、４０質量％以上が更に好ましく、５０質量％以上が特に好ましく、５５質量％以上が極めて好ましく、６０質量％以上が非常に好ましい。（Ａ１）成分の含有量は、優れた接着強度を得やすい観点から、９５質量％以下が好ましく、９０質量％以下がより好ましく、８５質量％以下が更に好ましく、８５質量％未満が特に好ましく、８０質量％以下が極めて好ましく、７５質量％以下が非常に好ましく、７０質量％以下がより一層好ましく、６５質量％以下が更に好ましい。これらの観点から、（Ａ１）成分の含有量は、３０〜９５質量％が好ましく、５０〜９０質量％がより好ましく、５５〜８５質量％が更に好ましく、６０〜８０質量％が特に好ましい。 The content of the component (A1) is preferably in the following range based on the total amount of the semiconductor adhesive (total amount of solid content; the same applies hereinafter). The content of the component (A1) is preferably 30% by mass or more, more preferably 35% by mass or more, further preferably 40% by mass or more, from the viewpoint of easily obtaining excellent thermal conductivity and easily reducing the viscosity. Preferably, 50% by mass or more is particularly preferable, 55% by mass or more is extremely preferable, and 60% by mass or more is very preferable. The content of the component (A1) is preferably 95% by mass or less, more preferably 90% by mass or less, further preferably 85% by mass or less, and particularly preferably less than 85% by mass, from the viewpoint of easily obtaining excellent adhesive strength. 80% by mass or less is extremely preferable, 75% by mass or less is very preferable, 70% by mass or less is even more preferable, and 65% by mass or less is further preferable. From these viewpoints, the content of the component (A1) is preferably 30 to 95% by mass, more preferably 50 to 90% by mass, further preferably 55 to 85% by mass, and particularly preferably 60 to 80% by mass.
（Ａ２）成分の含有量は、半導体用接着剤の総量を基準として下記の範囲が好ましい。（Ａ２）成分の含有量は、優れた接着強度を得やすい観点から、２質量％以上が好ましく、５質量％以上がより好ましく、１０質量％以上が更に好ましく、１５質量％以上が特に好ましく、２０質量％以上が極めて好ましい。（Ａ２）成分の含有量は、優れた熱伝導性を得やすい観点、及び、粘度を低減させやすい観点から、５０質量％以下が好ましく、５０質量％未満がより好ましく、４５質量％以下が更に好ましく、４０質量％以下が特に好ましく、３５質量％以下が極めて好ましく、３０質量％以下が非常に好ましい。これらの観点から、（Ａ２）成分の含有量は、２〜５０質量％が好ましく、１０〜４０質量％がより好ましく、２０〜３５質量％が更に好ましい。 The content of the component (A2) is preferably in the following range based on the total amount of the semiconductor adhesive. The content of the component (A2) is preferably 2% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, and particularly preferably 15% by mass or more, from the viewpoint of easily obtaining excellent adhesive strength. 20% by mass or more is extremely preferable. The content of the component (A2) is preferably 50% by mass or less, more preferably less than 50% by mass, and further preferably 45% by mass or less from the viewpoint of easily obtaining excellent thermal conductivity and easily reducing the viscosity. Preferably, 40% by mass or less is particularly preferable, 35% by mass or less is extremely preferable, and 30% by mass or less is very preferable. From these viewpoints, the content of the component (A2) is preferably 2 to 50% by mass, more preferably 10 to 40% by mass, still more preferably 20 to 35% by mass.
（Ａ２）成分の含有量に対する（Ａ１）成分の含有量の質量比（（Ａ１）成分の含有量／（Ａ２）成分の含有量）は、下記の範囲が好ましい。前記質量比は、粘度を低減させやすい観点から、０．１以上が好ましく、０．５以上がより好ましく、１．０以上が更に好ましく、１．５以上が特に好ましく、２．０以上が極めて好ましく、２．５以上が非常に好ましい。前記質量比は、優れた接着強度を得やすい観点から、５．０以下が好ましく、４．０以下がより好ましく、３．０以下が更に好ましく、２．０以下が特に好ましく、１．５以下が極めて好ましく、１．０以下が非常に好ましい。これらの観点から、前記質量比は、０．１〜５．０が好ましい。 The mass ratio of the content of the component (A1) to the content of the component (A2) (content of component (A1) / content of component (A2)) is preferably in the following range. From the viewpoint of easily reducing the viscosity, the mass ratio is preferably 0.1 or more, more preferably 0.5 or more, further preferably 1.0 or more, particularly preferably 1.5 or more, and extremely preferably 2.0 or more. Preferably, 2.5 or more is very preferable. The mass ratio is preferably 5.0 or less, more preferably 4.0 or less, further preferably 3.0 or less, particularly preferably 2.0 or less, and 1.5 or less, from the viewpoint of easily obtaining excellent adhesive strength. Is extremely preferable, and 1.0 or less is very preferable. From these viewpoints, the mass ratio is preferably 0.1 to 5.0.
（Ａ）成分の含有量（（Ａ１）成分及び（Ａ２）成分の総量）は、半導体用接着剤の総量を基準として下記の範囲が好ましい。（Ａ）成分の含有量は、優れた熱伝導性を得やすい観点から、３０質量％以上が好ましく、４０質量％以上がより好ましく、５０質量％以上が更に好ましく、６０質量％以上が特に好ましく、７０質量％以上が極めて好ましく、８０質量％以上が非常に好ましく、８５質量％以上がより一層好ましい。（Ａ）成分の含有量は、半導体用接着剤の粘度を低減させやすい観点から、１００質量％未満が好ましく、９８質量％以下がより好ましく、９５質量％以下が更に好ましく、９２質量％以下が特に好ましく、９０質量％以下が極めて好ましい。これらの観点から、（Ａ）成分の含有量は、３０質量％以上１００質量％未満が好ましく、８０〜９２質量％がより好ましく、８５〜９０質量％が更に好ましい。 The content of the component (A) (the total amount of the component (A1) and the component (A2)) is preferably in the following range based on the total amount of the semiconductor adhesive. The content of the component (A) is preferably 30% by mass or more, more preferably 40% by mass or more, further preferably 50% by mass or more, and particularly preferably 60% by mass or more, from the viewpoint of easily obtaining excellent thermal conductivity. , 70% by mass or more is extremely preferable, 80% by mass or more is very preferable, and 85% by mass or more is even more preferable. The content of the component (A) is preferably less than 100% by mass, more preferably 98% by mass or less, further preferably 95% by mass or less, and 92% by mass or less from the viewpoint of easily reducing the viscosity of the semiconductor adhesive. It is particularly preferable, and 90% by mass or less is extremely preferable. From these viewpoints, the content of the component (A) is preferably 30% by mass or more and less than 100% by mass, more preferably 80 to 92% by mass, still more preferably 85 to 90% by mass.
平均粒径１μｍ以上４μ未満の銀粒子の含有量は、半導体用接着剤の総量を基準として、２質量％以下であってよく、２質量％未満であってよく、１質量％以下であってよく、１質量％未満であってよい。（Ａ）成分は、平均粒径１μｍ以上４μ未満の銀粒子を含まなくてよい。 The content of silver particles having an average particle size of 1 μm or more and less than 4 μm may be 2% by mass or less, may be less than 2% by mass, or 1% by mass or less, based on the total amount of the semiconductor adhesive. Well, it may be less than 1% by mass. The component (A) does not have to contain silver particles having an average particle size of 1 μm or more and less than 4 μm.
（（Ｂ）成分：（メタ）アクリロイル基を有する単量体）
（Ｂ）成分としては、（メタ）アクリル酸、（メタ）アクリル酸エステル等を用いることができる。（Ｂ）成分は、イミド骨格及び／又はシロキサン骨格を含まなくてよい。（Ｂ）成分における（メタ）アクリロイル基の数は、優れた接着強度が得られやすい観点から、３以下が好ましく、２以下がより好ましく、１が更に好ましい。（Ｂ）成分における（メタ）アクリロイル基の数は、１以上であり、２以上であってよい。（Ｂ）成分の分子量は、２０００以下であってよく、１５００以下であってよく、１０００以下であってよく、８００以下であってよく、６００以下であってよい。（Ｂ）成分が２つの（メタ）アクリロイル基を有する場合、（Ｂ）成分の分子量は、４００以下であってよく、３００以下であってよい。(Component (B): Monomer having (meth) acryloyl group)
As the component (B), (meth) acrylic acid, (meth) acrylic acid ester and the like can be used. The component (B) does not have to contain an imide skeleton and / or a siloxane skeleton. The number of (meth) acryloyl groups in the component (B) is preferably 3 or less, more preferably 2 or less, and even more preferably 1 from the viewpoint that excellent adhesive strength can be easily obtained. The number of (meth) acryloyl groups in the component (B) is 1 or more, and may be 2 or more. The molecular weight of the component (B) may be 2000 or less, 1500 or less, 1000 or less, 800 or less, and 600 or less. When the component (B) has two (meth) acryloyl groups, the molecular weight of the component (B) may be 400 or less, and may be 300 or less.
（Ｂ）成分は、優れた接着強度が得られやすい観点から、下記一般式（ｂ１）で表される化合物を含むことが好ましい。 The component (B) preferably contains a compound represented by the following general formula (b1) from the viewpoint that excellent adhesive strength can be easily obtained.
式（ｂ１）で表される化合物としては、ジシクロペンテニルオキシエチル（メタ）アクリレート、ジシクロペンタニルオキシエチル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート等が挙げられる。ジシクロペンテニルアクリレートはＦＡ−５１１Ａとして、ジシクロペンテニルオキシエチルアクリレートはＦＡ−５１２Ａとして、ジシクロペンタニルアクリレートはＦＡ−５１３Ａとして、ジシクロペンテニルオキシエチルメタクリレートはＦＡ−５１２Ｍとして、ジシクロペンタニルメタクリレートはＦＡ−５１３Ｍとして、それぞれ商業的に日立化成株式会社より入手できる。 Examples of the compound represented by the formula (b1) include dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and dicyclopentanyl (meth) acrylate. Can be mentioned. Dicyclopentenyl acrylate as FA-511A, dicyclopentenyloxyethyl acrylate as FA-512A, dicyclopentanyl acrylate as FA-513A, dicyclopentenyloxyethyl methacrylate as FA-512M, dicyclopentanyl methacrylate Are commercially available from Hitachi Kasei Co., Ltd. as FA-513M.
式（ｂ１）で表される化合物の含有量は、（Ｂ）成分の総量を基準として下記の範囲が好ましい。式（ｂ１）で表される化合物の含有量は、優れた熱伝導性を得やすい観点から、１０質量％以上が好ましく、２０質量％以上がより好ましく、２５質量％以上が更に好ましく、３０質量％以上が特に好ましく、３５質量％以上が極めて好ましい。式（ｂ１）で表される化合物の含有量は、優れた熱伝導性を得やすい観点から、９５質量％以下が好ましく、９０質量％以下がより好ましく、８５質量％以下が更に好ましく、８０質量％以下が特に好ましく、７５質量％以下が極めて好ましい。これらの観点から、式（ｂ１）で表される化合物の含有量は、１０〜９５質量％が好ましく、２０〜９０質量％がより好ましい。 The content of the compound represented by the formula (b1) is preferably in the following range based on the total amount of the component (B). The content of the compound represented by the formula (b1) is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 25% by mass or more, and further preferably 30% by mass from the viewpoint of easily obtaining excellent thermal conductivity. % Or more is particularly preferable, and 35% by mass or more is extremely preferable. The content of the compound represented by the formula (b1) is preferably 95% by mass or less, more preferably 90% by mass or less, further preferably 85% by mass or less, and further preferably 80% by mass from the viewpoint of easily obtaining excellent thermal conductivity. % Or less is particularly preferable, and 75% by mass or less is extremely preferable. From these viewpoints, the content of the compound represented by the formula (b1) is preferably 10 to 95% by mass, more preferably 20 to 90% by mass.
式（ｂ１）で表される化合物の含有量は、半導体用接着剤の総量を基準として下記の範囲が好ましい。式（ｂ１）で表される化合物の含有量は、優れた熱伝導性を得やすい観点から、０．５質量％以上が好ましく、１質量％以上がより好ましく、１．２質量％以上が更に好ましく、１．５質量％以上が特に好ましく、１．８質量％以上が極めて好ましい。式（ｂ１）で表される化合物の含有量は、優れた熱伝導性を得やすい観点から、１０質量％以下が好ましく、８質量％以下がより好ましく、６質量％以下が更に好ましく、５質量％以下が特に好ましく、４質量％以下が極めて好ましい。これらの観点から、式（ｂ１）で表される化合物の含有量は、０．５〜１０質量％が好ましく、１〜８質量％がより好ましい。 The content of the compound represented by the formula (b1) is preferably in the following range based on the total amount of the semiconductor adhesive. The content of the compound represented by the formula (b1) is preferably 0.5% by mass or more, more preferably 1% by mass or more, and further preferably 1.2% by mass or more from the viewpoint of easily obtaining excellent thermal conductivity. Preferably, 1.5% by mass or more is particularly preferable, and 1.8% by mass or more is extremely preferable. The content of the compound represented by the formula (b1) is preferably 10% by mass or less, more preferably 8% by mass or less, further preferably 6% by mass or less, and 5% by mass from the viewpoint of easily obtaining excellent thermal conductivity. % Or less is particularly preferable, and 4% by mass or less is extremely preferable. From these viewpoints, the content of the compound represented by the formula (b1) is preferably 0.5 to 10% by mass, more preferably 1 to 8% by mass.
（Ｂ）成分は、優れた塗布作業性及び接着強度が得られやすい観点から、（メタ）アクリル酸エステルとして、下記一般式（ｂ２１）で表される化合物、下記一般式（ｂ２２）で表される化合物、及び、下記一般式（ｂ２３）で表される化合物からなる群より選ばれる少なくとも一種を含むことが好ましい。 The component (B) is represented as a (meth) acrylic acid ester as a compound represented by the following general formula (b21) and the following general formula (b22) from the viewpoint of easily obtaining excellent coating workability and adhesive strength. It is preferable to contain at least one selected from the group consisting of the following compounds and the compounds represented by the following general formula (b23).
式（ｂ２１）〜（ｂ２３）で表される化合物（式（ｂ２１）で表される化合物、式（ｂ２２）で表される化合物、又は、式（ｂ２３）で表される化合物。以下同様）としては、ベンジル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート等が挙げられる。ベンジルアクリレートはＦＡ−ＢＺＡ（日立化成株式会社製）として、フェノキシエチルアクリレートはＳＲ−３３９Ａ（サートマー社製）として、フェノキシエチルメタクリレートはＣＤ９０８７（サートマー社製）として、それぞれ商業的に入手できる。 As a compound represented by the formulas (b21) to (b23) (a compound represented by the formula (b21), a compound represented by the formula (b22), or a compound represented by the formula (b23); the same applies hereinafter). Examples include benzyl (meth) acrylate and phenoxyethyl (meth) acrylate. Benzyl acrylate is commercially available as FA-BZA (manufactured by Hitachi Kasei Co., Ltd.), phenoxyethyl acrylate as SR-339A (manufactured by Sartmer), and phenoxyethyl methacrylate as CD9087 (manufactured by Sartmer).
式（ｂ２１）〜（ｂ２３）で表される化合物の含有量は、（Ｂ）成分の総量を基準として下記の範囲が好ましい。式（ｂ２１）〜（ｂ２３）で表される化合物の含有量は、優れた熱伝導性を得やすい観点から、１０質量％以上が好ましく、２０質量％以上がより好ましく、２５質量％以上が更に好ましく、３０質量％以上が特に好ましく、３５質量％以上が極めて好ましい。式（ｂ２１）〜（ｂ２３）で表される化合物の含有量は、優れた熱伝導性を得やすい観点から、８０質量％以下が好ましく、７０質量％以下がより好ましく、６０質量％以下が更に好ましく、５０質量％以下が特に好ましく、４０質量％以下が極めて好ましい。これらの観点から、式（ｂ２１）〜（ｂ２３）で表される化合物の含有量は、１０〜８０質量％が好ましく、２０〜７０質量％がより好ましい。 The content of the compounds represented by the formulas (b21) to (b23) is preferably in the following range based on the total amount of the component (B). The content of the compounds represented by the formulas (b21) to (b23) is preferably 10% by mass or more, more preferably 20% by mass or more, and further preferably 25% by mass or more from the viewpoint of easily obtaining excellent thermal conductivity. It is preferable, 30% by mass or more is particularly preferable, and 35% by mass or more is extremely preferable. The content of the compounds represented by the formulas (b21) to (b23) is preferably 80% by mass or less, more preferably 70% by mass or less, and further preferably 60% by mass or less from the viewpoint of easily obtaining excellent thermal conductivity. It is preferable, 50% by mass or less is particularly preferable, and 40% by mass or less is extremely preferable. From these viewpoints, the content of the compounds represented by the formulas (b21) to (b23) is preferably 10 to 80% by mass, more preferably 20 to 70% by mass.
式（ｂ２１）〜（ｂ２３）で表される化合物の含有量は、半導体用接着剤の総量を基準として下記の範囲が好ましい。式（ｂ２１）〜（ｂ２３）で表される化合物の含有量は、優れた熱伝導性を得やすい観点から、０．５質量％以上が好ましく、１質量％以上がより好ましく、１．２質量％以上が更に好ましく、１．５質量％以上が特に好ましく、１．８質量％以上が極めて好ましい。式（ｂ２１）〜（ｂ２３）で表される化合物の含有量は、優れた熱伝導性を得やすい観点から、５質量％以下が好ましく、４質量％以下がより好ましく、３質量％以下が更に好ましく、２．５質量％以下が特に好ましく、２質量％以下が極めて好ましい。これらの観点から、式（ｂ２１）〜（ｂ２３）で表される化合物の含有量は、０．５〜５質量％が好ましく、１〜４質量％がより好ましい。 The content of the compounds represented by the formulas (b21) to (b23) is preferably in the following range based on the total amount of the semiconductor adhesive. The content of the compounds represented by the formulas (b21) to (b23) is preferably 0.5% by mass or more, more preferably 1% by mass or more, and 1.2% by mass from the viewpoint of easily obtaining excellent thermal conductivity. % Or more is more preferable, 1.5% by mass or more is particularly preferable, and 1.8% by mass or more is extremely preferable. The content of the compounds represented by the formulas (b21) to (b23) is preferably 5% by mass or less, more preferably 4% by mass or less, and further preferably 3% by mass or less, from the viewpoint of easily obtaining excellent thermal conductivity. It is preferable, 2.5% by mass or less is particularly preferable, and 2% by mass or less is extremely preferable. From these viewpoints, the content of the compounds represented by the formulas (b21) to (b23) is preferably 0.5 to 5% by mass, more preferably 1 to 4% by mass.
（Ｂ）成分は、式（ｂ１）で表される化合物、式（ｂ２１）で表される化合物、式（ｂ２２）で表される化合物、及び、式（ｂ２３）で表される化合物とは異なる単官能の（メタ）アクリル酸エステルを含んでよい。このような単官能の（メタ）アクリル酸エステルとしては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、アミル（メタ）アクリレート、イソアミル（メタ）アクリレート、ヘキシル（メタ）アクリレート、ヘプチル（メタ）アクリレート、オクチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ノニル（メタ）アクリレート、デシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、トリデシル（メタ）アクリレート、ヘキサデシル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソステアリル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、ダイマージオールモノ（メタ）アクリレート、ジエチレングリコール（メタ）アクリレート、ポリエチレングリコール（メタ）アクリレート、ポリプロピレングリコール（メタ）アクリレート、２−メトキシエチル（メタ）アクリレート、２−エトキシエチル（メタ）アクリレート、２−ブトキシエチル（メタ）アクリレート、メトキシジエチレングリコール（メタ）アクリレート、メトキシポリエチレングリコール（メタ）アクリレート、フェノキシジエチレングリコール（メタ）アクリレート、フェノキシポリエチレングリコール（メタ）アクリレート、２−ベンゾイルオキシエチル（メタ）アクリレート、２−ヒドロキシ−３−フェノキシプロピル（メタ）アクリレート、２−シアノエチル（メタ）アクリレート、γ−（メタ）アクリロキシプロピルトリメトキシシラン、グリシジル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、テトラヒドロピラニル（メタ）アクリレート、ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、（メタ）アクリロキシエチルホスフェート、（メタ）アクリロキシエチルフェニルアシッドホスフェート、β−（メタ）アクリロイルオキシエチルハイドロジェンフタレート、β−（メタ）アクリロイルオキシエチルハイドロジェンサクシネート等が挙げられる。 The component (B) is different from the compound represented by the formula (b1), the compound represented by the formula (b21), the compound represented by the formula (b22), and the compound represented by the formula (b23). It may contain a monofunctional (meth) acrylic acid ester. Examples of such monofunctional (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. ) Acrylate, t-butyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (Meta) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, hexadecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) Meta) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, dimerdiol mono (meth) acrylate, diethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene Glycol (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxydiethylene glycol (Meta) acrylate, phenoxypolyethylene glycol (meth) acrylate, 2-benzoyloxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-cyanoethyl (meth) acrylate, γ- (meth) acrylic Loxypropyltrimethoxysilane, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tetrahydropyranyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, (meth) acryloxyethyl phosphate , (Meta) acryloyloxyethyl phenyl acid phosphate, β- (meth) acryloyloxyethyl hydrogen phthalate, β- (meth) acryloyloxyethyl hydrogen succinate, etc. Is done.
（Ｂ）成分は、下記一般式（ｂ３）で表される化合物を含んでいてよく、含んでいなくてもよい。式（ｂ３）で表される化合物の含有量は、（Ｂ）成分の総量を基準として、１質量％以下であってよく、０．１質量％以下であってよく、０．０１質量％以下であってよい。式（ｂ３）で表される化合物の含有量は、半導体用接着剤の総量を基準として、１質量％以下であってよく、０．１質量％以下であってよく、０．０１質量％以下であってよい。 The component (B) may or may not contain the compound represented by the following general formula (b3). The content of the compound represented by the formula (b3) may be 1% by mass or less, 0.1% by mass or less, and 0.01% by mass or less based on the total amount of the component (B). May be. The content of the compound represented by the formula (b3) may be 1% by mass or less, 0.1% by mass or less, and 0.01% by mass or less based on the total amount of the semiconductor adhesive. May be.
（Ｂ）成分は、多官能の（メタ）アクリル酸エステルを含んでよい。（Ｂ）成分は、多官能の（メタ）アクリル酸エステルとして、１分子中に２個の（メタ）アクリロイルオキシ基を有する化合物を含むことが好ましい。この場合、熱硬化時において耐リフロー性の低下の原因となる接着剤中の気泡の発生を低減しやすい。 The component (B) may include a polyfunctional (meth) acrylic acid ester. The component (B) preferably contains a compound having two (meth) acryloyloxy groups in one molecule as a polyfunctional (meth) acrylic acid ester. In this case, it is easy to reduce the generation of air bubbles in the adhesive, which causes a decrease in reflow resistance during thermosetting.
１分子中に２個の（メタ）アクリロイルオキシ基を有する化合物としては、エチレングリコールジ（メタ）アクリレート、１，４−ブタンジオールジ（メタ）アクリレート、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、１，３−ブタンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ダイマージオールジ（メタ）アクリレート、ジメチロールトリシクロデカンジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート等のジ（メタ）アクリレート化合物；ビスフェノールＡ、ビスフェノールＦ又はビスフェノールＡＤ１モルとグリシジル（メタ）アクリレート２モルとの反応物；ビスフェノールＡ、ビスフェノールＦ又はビスフェノールＡＤのポリエチレンオキサイド付加物のジ（メタ）アクリレート；ビスフェノールＡ、ビスフェノールＦ又はビスフェノールＡＤのポリプロピレンオキサイド付加物のジ（メタ）アクリレート；ビス（アクリロキシプロピル）ポリジメチルシロキサン、ビス（アクリロキシプロピル）メチルシロキサン−ジメチルシロキサンコポリマー、ビス（メタクリロキシプロピル）ポリジメチルシロキサン、ビス（メタクリロキシプロピル）メチルシロキサン−ジメチルシロキサンコポリマー等のシロキサン化合物などが挙げられる。 Examples of the compound having two (meth) acryloyloxy groups in one molecule include ethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexanediol di (meth) acrylate. , 1,9-Nonandiol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, dimerdiol di (meth) acrylate, dimethylol tricyclodecandi (meth) ) Acrylate, Diethylene glycol di (meth) acrylate, Triethylene glycol di (meth) acrylate, Tetraethylene glycol di (meth) acrylate, Polyethylene glycol di (meth) acrylate, Tripropylene glycol di (meth) acrylate, Polypropylene glycol di (meth) ) Di (meth) acrylate compound such as acrylate; reaction product of 1 mol of bisphenol A, bisphenol F or bisphenol AD and 2 mol of glycidyl (meth) acrylate; di (meth) of polyethylene oxide adduct of bisphenol A, bisphenol F or bisphenol AD. ) Acrylate; Di (meth) acrylate of polypropylene oxide adduct of bisphenol A, bisphenol F or bisphenol AD; bis (acryloxypropyl) polydimethylsiloxane, bis (acryloxypropyl) methylsiloxane-dimethylsiloxane copolymer, bis (methacryloxy) Examples thereof include siloxane compounds such as propyl) polydimethylsiloxane and bis (methacryloxypropyl) methylsiloxane-dimethylsiloxane copolymer.
（Ｂ）成分は、優れた接着強度が得られやすい観点から、１分子中に２個の（メタ）アクリロイルオキシ基を有する化合物として、下記一般式（ｂ４）で表される化合物を含むことが好ましい。 The component (B) may contain a compound represented by the following general formula (b4) as a compound having two (meth) acryloyloxy groups in one molecule from the viewpoint that excellent adhesive strength can be easily obtained. preferable.
（Ｂ）成分は、多官能の（メタ）アクリル酸エステルとして、１分子中に３個以上の（メタ）アクリロイルオキシ基を有する化合物を用いることができる。１分子中に３個以上の（メタ）アクリロイルオキシ基を有する化合物としては、トリメチロールプロパントリ（メタ）アクリレート、エチレンオキシド変性トリメチロールプロパントリ（メタ）アクリレート、プロピレンオキシド変性トリメチロールプロパントリ（メタ）アクリレート、エチレンオキシド・プロピレンオキシド変性トリメチロールプロパントリ（メタ）アクリレート、テトラメチロールメタントリ（メタ）アクリレート、テトラメチロールメタンテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート等が挙げられる。 As the component (B), a compound having three or more (meth) acryloyloxy groups in one molecule can be used as the polyfunctional (meth) acrylic acid ester. Examples of the compound having three or more (meth) acryloyloxy groups in one molecule include trimethylolpropane tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, and propylene oxide-modified trimethylolpropane tri (meth). Acrylate, ethylene oxide / propylene oxide modified trimethylolpropane tri (meth) acrylate, tetramethylolmethanetri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) Examples thereof include acrylate and pentaerythritol tri (meth) acrylate.
多官能の（メタ）アクリル酸エステルの含有量は、（Ｂ）成分の総量を基準として下記の範囲が好ましい。多官能の（メタ）アクリル酸エステルの含有量は、優れた熱伝導性を得やすい観点から、５質量％以上が好ましく、１０質量％以上がより好ましく、１５質量％以上が更に好ましく、２０質量％以上が特に好ましく、２５質量％以上が極めて好ましい。多官能の（メタ）アクリル酸エステルの含有量は、優れた熱伝導性を得やすい観点から、５０質量％以下が好ましく、４５質量％以下がより好ましく、４０質量％以下が更に好ましく、３５質量％以下が特に好ましく、３０質量％以下が極めて好ましい。これらの観点から、多官能の（メタ）アクリル酸エステルの含有量は、５〜５０質量％が好ましく、１０〜４５質量％がより好ましい。 The content of the polyfunctional (meth) acrylic acid ester is preferably in the following range based on the total amount of the component (B). The content of the polyfunctional (meth) acrylic acid ester is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and further preferably 20% by mass from the viewpoint of easily obtaining excellent thermal conductivity. % Or more is particularly preferable, and 25% by mass or more is extremely preferable. The content of the polyfunctional (meth) acrylic acid ester is preferably 50% by mass or less, more preferably 45% by mass or less, further preferably 40% by mass or less, and further preferably 35% by mass from the viewpoint of easily obtaining excellent thermal conductivity. % Or less is particularly preferable, and 30% by mass or less is extremely preferable. From these viewpoints, the content of the polyfunctional (meth) acrylic acid ester is preferably 5 to 50% by mass, more preferably 10 to 45% by mass.
多官能の（メタ）アクリル酸エステルの含有量は、半導体用接着剤の総量を基準として下記の範囲が好ましい。多官能の（メタ）アクリル酸エステルの含有量は、優れた熱伝導性を得やすい観点から、０．５質量％以上が好ましく、０．８質量％以上がより好ましく、１質量％以上が更に好ましく、１．２質量％以上が特に好ましく、１．４質量％以上が極めて好ましい。多官能の（メタ）アクリル酸エステルの含有量は、優れた熱伝導性を得やすい観点から、３質量％以下が好ましく、２．５質量％以下がより好ましく、２質量％以下が更に好ましく、１．８質量％以下が特に好ましく、１．５質量％以下が極めて好ましい。これらの観点から、多官能の（メタ）アクリル酸エステルの含有量は、０．５〜３質量％が好ましく、０．８〜２．５質量％がより好ましい。 The content of the polyfunctional (meth) acrylic acid ester is preferably in the following range based on the total amount of the semiconductor adhesive. The content of the polyfunctional (meth) acrylic acid ester is preferably 0.5% by mass or more, more preferably 0.8% by mass or more, further preferably 1% by mass or more, from the viewpoint of easily obtaining excellent thermal conductivity. Preferably, 1.2% by mass or more is particularly preferable, and 1.4% by mass or more is extremely preferable. The content of the polyfunctional (meth) acrylic acid ester is preferably 3% by mass or less, more preferably 2.5% by mass or less, still more preferably 2% by mass or less, from the viewpoint of easily obtaining excellent thermal conductivity. 1.8% by mass or less is particularly preferable, and 1.5% by mass or less is extremely preferable. From these viewpoints, the content of the polyfunctional (meth) acrylic acid ester is preferably 0.5 to 3% by mass, more preferably 0.8 to 2.5% by mass.
（Ｂ）成分の含有量は、半導体用接着剤の総量を基準として下記の範囲が好ましい。（Ｂ）成分の含有量は、優れた熱伝導性を得やすい観点から、１質量％以上が好ましく、２質量％以上がより好ましく、３質量％以上が更に好ましく、４質量％以上が特に好ましく、５質量％以上が極めて好ましい。（Ｂ）成分の含有量は、優れた熱伝導性を得やすい観点から、１０質量％以下が好ましく、１０質量％未満がより好ましく、９質量％以下が更に好ましく、８質量％以下が特に好ましく、７質量％以下が極めて好ましく、６質量％以下が非常に好ましい。これらの観点から、（Ｂ）成分の含有量は、１〜１０質量％が好ましく、２〜９質量％がより好ましい。 The content of the component (B) is preferably in the following range based on the total amount of the semiconductor adhesive. The content of the component (B) is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 3% by mass or more, and particularly preferably 4% by mass or more, from the viewpoint of easily obtaining excellent thermal conductivity. 5, 5% by mass or more is extremely preferable. The content of the component (B) is preferably 10% by mass or less, more preferably less than 10% by mass, further preferably 9% by mass or less, and particularly preferably 8% by mass or less, from the viewpoint of easily obtaining excellent thermal conductivity. , 7% by mass or less is extremely preferable, and 6% by mass or less is very preferable. From these viewpoints, the content of the component (B) is preferably 1 to 10% by mass, more preferably 2 to 9% by mass.
（Ｂ）成分の含有量は、（Ａ）成分１００質量部に対して下記の範囲が好ましい。（Ｂ）成分の含有量は、優れた熱伝導性を得やすい観点から、１質量部以上が好ましく、３質量部以上がより好ましく、４質量部以上が更に好ましく、５質量部以上が特に好ましく、６質量部以上が極めて好ましい。（Ｂ）成分の含有量は、優れた熱伝導性を得やすい観点から、２０質量部以下が好ましく、１５質量部以下がより好ましく、１０質量部以下が更に好ましく、８質量部以下が特に好ましく、７質量部以下が極めて好ましい。これらの観点から、（Ｂ）成分の含有量は、１〜２０質量部が好ましく、３〜１５質量部がより好ましい。 The content of the component (B) is preferably in the following range with respect to 100 parts by mass of the component (A). The content of the component (B) is preferably 1 part by mass or more, more preferably 3 parts by mass or more, further preferably 4 parts by mass or more, and particularly preferably 5 parts by mass or more, from the viewpoint of easily obtaining excellent thermal conductivity. , 6 parts by mass or more is extremely preferable. The content of the component (B) is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, further preferably 10 parts by mass or less, and particularly preferably 8 parts by mass or less from the viewpoint of easily obtaining excellent thermal conductivity. , 7 parts by mass or less is extremely preferable. From these viewpoints, the content of the component (B) is preferably 1 to 20 parts by mass, more preferably 3 to 15 parts by mass.
（（Ｃ）成分：ラジカル重合開始剤）
本実施形態に係る半導体用接着剤は、ラジカル重合開始剤（以下、場合により「（Ｃ）成分」という）を含有してよい。（Ｃ）成分は、ボイド等の発生を抑制しやすい観点から、過酸化物を含むことが好ましい。急速加熱試験における過酸化物の分解温度は、半導体用接着剤の優れた硬化性及び粘度安定性が得られやすい観点から、７０〜１７０℃が好ましい。(Component (C): Radical Polymerization Initiator)
The semiconductor adhesive according to the present embodiment may contain a radical polymerization initiator (hereinafter, in some cases, referred to as “component (C)”). The component (C) preferably contains a peroxide from the viewpoint of easily suppressing the generation of voids and the like. The decomposition temperature of the peroxide in the rapid heating test is preferably 70 to 170 ° C. from the viewpoint that excellent curability and viscosity stability of the semiconductor adhesive can be easily obtained.
（Ｃ）成分としては、１，１，３，３−テトラメチルパーオキシ２−エチルヘキサノエート、１，１−ビス（ｔ−ブチルパーオキシ）シクロヘキサン、１，１−ビス（ｔ−ブチルパーオキシ）シクロドデカン、ジ−ｔ−ブチルパーオキシイソフタレート、ｔ−ブチルパーベンゾエート、ジクミルパーオキサイド、ｔ−ブチルクミルパーオキサイド、２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキサン、２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキシン、クメンハイドロパーオキサイド等が挙げられる。 The components (C) include 1,1,3,3-tetramethylperoxy2-ethylhexanoate, 1,1-bis (t-butylperoxy) cyclohexane, and 1,1-bis (t-butylper). Oxy) Cyclododecane, di-t-butylperoxyisophthalate, t-butylperbenzoate, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) ) Hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexine, cumenehydroperoxide and the like.
（Ｃ）成分の含有量は、（Ｂ）成分１００質量部に対して下記の範囲が好ましい。（Ｃ）成分の含有量は、優れた熱伝導性を得やすい観点から、３質量部以上が好ましく、４質量部以上がより好ましく、５質量部以上が更に好ましく、８質量部以上が特に好ましく、１０質量部以上が極めて好ましい。（Ｃ）成分の含有量は、優れた熱伝導性を得やすい観点から、３０質量部以下が好ましく、２０質量部以下がより好ましく、１５質量部以下が更に好ましい。これらの観点から、（Ｃ）成分の含有量は、３〜３０質量部が好ましく、４〜２０質量部がより好ましく、５〜１５質量部が更に好ましい。 The content of the component (C) is preferably in the following range with respect to 100 parts by mass of the component (B). The content of the component (C) is preferably 3 parts by mass or more, more preferably 4 parts by mass or more, further preferably 5 parts by mass or more, and particularly preferably 8 parts by mass or more from the viewpoint of easily obtaining excellent thermal conductivity. 10 parts by mass or more is extremely preferable. The content of the component (C) is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 15 parts by mass or less, from the viewpoint of easily obtaining excellent thermal conductivity. From these viewpoints, the content of the component (C) is preferably 3 to 30 parts by mass, more preferably 4 to 20 parts by mass, and even more preferably 5 to 15 parts by mass.
（（Ｄ）成分：可とう化剤）
本実施形態に係る半導体用接着剤は、可とう化剤（以下、場合により「（Ｄ）成分」という。（Ａ）〜（Ｃ）成分に該当する化合物を除く）を含有してよい。（Ｄ）成分は、液状ゴム及び熱可塑性樹脂（液状ゴムに該当する化合物を除く）からなる群より選ばれる少なくとも一種を含むことが好ましい。(Component (D): Flexible agent)
The semiconductor adhesive according to the present embodiment may contain a flexible agent (hereinafter, in some cases, referred to as "component (D)", excluding compounds corresponding to components (A) to (C)). The component (D) preferably contains at least one selected from the group consisting of liquid rubber and thermoplastic resins (excluding compounds corresponding to liquid rubber).
液状ゴムとしては、ポリブタジエン、エポキシ化ポリブタジエン、マレイン化ポリブタジエン、アクリロニトリルブタジエンゴム、カルボキシ基を有するアクリロニトリルブタジエンゴム（例えば、カルボキシ基を有するアクリロニトリルポリブタジエン共重合体）、アミノ末端アクリロニトリルブタジエンゴム、ビニル末端アクリロニトリルブタジエンゴム、スチレンブタジエンゴム等の、ポリブタジエン骨格を有する樹脂などが挙げられる。 Examples of the liquid rubber include polybutadiene, epoxidized polybutadiene, maleated polybutadiene, acrylonitrile butadiene rubber, acrylonitrile butadiene rubber having a carboxy group (for example, an acrylonitrile polybutadiene copolymer having a carboxy group), amino-terminated acrylonitrile butadiene rubber, and vinyl-terminated acrylonitrile butadiene. Examples thereof include resins having a polybutadiene skeleton such as rubber and styrene butadiene rubber.
液状ゴムは、半導体用接着剤の弾性率を低減させやすい観点から、エポキシ化ポリブタジエン、及び、カルボキシ基を有するアクリロニトリルブタジエンゴムからなる群より選ばれる少なくとも一種を含むことが好ましい。優れた塗布作業性及び接着強度を得やすい観点から、エポキシ化ポリブタジエン、及び、カルボキシ基を有するアクリロニトリルブタジエンゴムを併用することが好ましい。 The liquid rubber preferably contains at least one selected from the group consisting of epoxidized polybutadiene and acrylonitrile butadiene rubber having a carboxy group from the viewpoint of easily reducing the elastic modulus of the semiconductor adhesive. From the viewpoint of obtaining excellent coating workability and adhesive strength, it is preferable to use epoxidized polybutadiene and acrylonitrile butadiene rubber having a carboxy group in combination.
エポキシ化ポリブタジエンは、市販されているポリブタジエンを過酸化水素水又は過酸類によりエポキシ化することによって容易に得ることができる。エポキシ化ポリブタジエンは、例えば、Ｂ−１０００、Ｂ−３０００、Ｇ−１０００、Ｇ−３０００（以上、日本曹達株式会社製）、Ｂ−１０００、Ｂ−２０００、Ｂ−３０００、Ｂ−４０００（以上、日本石油株式会社製）、Ｒ−１５ＨＴ、Ｒ−４５ＨＴ、Ｒ−４５Ｍ（以上、出光石油株式会社製）、エポリードＰＢ−３６００、エポリードＰＢ−４７００（以上、ダイセル化学工業株式会社製）等が市販品として入手できる。エポキシ化ポリブタジエンのオキシラン酸素濃度は、３〜１８％が好ましく、６〜１２％がより好ましい。 Epoxidized polybutadiene can be easily obtained by epoxidizing commercially available polybutadiene with hydrogen peroxide solution or peracids. The epoxidized polybutadiene is, for example, B-1000, B-3000, G-1000, G-3000 (above, manufactured by Nippon Soda Co., Ltd.), B-1000, B-2000, B-3000, B-4000 (above, Nippon Oil Co., Ltd.), R-15HT, R-45HT, R-45M (above, manufactured by Idemitsu Petroleum Co., Ltd.), Epoxide PB-3600, Epoxide PB-4700 (above, manufactured by Daicel Chemical Industry Co., Ltd.), etc. are commercially available. Available as a product. The oxygen oxygen concentration of the epoxidized polybutadiene is preferably 3 to 18%, more preferably 6 to 12%.
カルボキシ基を有するアクリロニトリルブタジエンゴムを用いることにより、優れた接着強度が得られやすい。カルボキシ基を有するアクリロニトリルブタジエンゴムは、優れた接着強度が得られやすい観点から、下記一般式（ｄ１）で表される化合物を含むことが好ましい。 By using acrylonitrile butadiene rubber having a carboxy group, excellent adhesive strength can be easily obtained. The acrylonitrile butadiene rubber having a carboxy group preferably contains a compound represented by the following general formula (d1) from the viewpoint that excellent adhesive strength can be easily obtained.
カルボキシ基を有するアクリロニトリルポリブタジエンとしては、Ｈｙｃａｒ ＣＴＢＮ−２００９×１６２，ＣＴＢＮ−１３００×３１，ＣＴＢＮ−１３００×８、ＣＴＢＮ−１３００×１３、ＣＴＢＮ−１００９ＳＰ−Ｓ、ＣＴＢＮＸ−１３００×９（いずれも宇部興産株式会社製）等が市販品として入手できる。 Examples of acrylonitrile polybutadiene having a carboxy group include Hycar CTBN-2009 × 162, CTBN-1300 × 31, CTBN-1300 × 8, CTBN-1300 × 13, CTBN-1009SP-S, and CTBNX-1300 × 9 (all from Ube Industries). (Made by Co., Ltd.) etc. are available as commercial products.
液状ゴムの数平均分子量は、充分な可とう化効果が得られやすい観点から、５００以上が好ましく、１０００以上がより好ましい。液状ゴムの数平均分子量は、半導体用接着剤の粘度の過剰な上昇が抑制されて優れた塗布作業性が得られやすい観点から、１００００以下が好ましく、５０００以下がより好ましい。これらの観点から、液状ゴムの数平均分子量は、５００〜１００００が好ましく、１０００〜５０００がより好ましい。液状ゴムの数平均分子量は、下記条件のゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定し、標準ポリスチレンを用いた検量線から換算して得ることができる。
［ＧＰＣ条件］
ポンプ：日立 Ｌ−６０００型（株式会社日立製作所製）
検出器：日立 Ｌ−３３００ ＲＩ（株式会社日立製作所製）
カラム：Ｇｅｌｐａｃｋ ＧＬ−Ｒ４２０＋Ｇｅｌｐａｃｋ ＧＬ−Ｒ４３０＋Ｇｅｌｐａｃｋ ＧＬ−Ｒ４３０（計３本）（日立化成株式会社製、商品名）
溶離液：ＴＨＦ
試料濃度：２５０ｍｇ／５ｍＬ
注入量：５０μＬ
圧力：４４１Ｐａ（４５ｋｇｆ／ｃｍ２）
流量：１．７５ｍＬ／分The number average molecular weight of the liquid rubber is preferably 500 or more, more preferably 1000 or more, from the viewpoint that a sufficient flexible effect can be easily obtained. The number average molecular weight of the liquid rubber is preferably 10,000 or less, and more preferably 5,000 or less, from the viewpoint that an excessive increase in the viscosity of the semiconductor adhesive is suppressed and excellent coating workability can be easily obtained. From these viewpoints, the number average molecular weight of the liquid rubber is preferably 500 to 10000, more preferably 1000 to 5000. The number average molecular weight of the liquid rubber can be measured by gel permeation chromatography (GPC) under the following conditions and converted from a calibration curve using standard polystyrene.
[GPC conditions]
Pump: Hitachi L-6000 (manufactured by Hitachi, Ltd.)
Detector: Hitachi L-3300 RI (manufactured by Hitachi, Ltd.)
Column: Gelpack GL-R420 + Gelpack GL-R430 + Gelpack GL-R430 (3 in total) (manufactured by Hitachi Kasei Co., Ltd., product name)
Eluent: THF
Sample concentration: 250 mg / 5 mL
Injection volume: 50 μL
Pressure: 441 Pa (45 kgf / cm 2 )
Flow rate: 1.75 mL / min
液状ゴムの含有量は、（Ｄ）成分の総量を基準として下記の範囲が好ましい。液状ゴムの含有量は、優れた熱伝導性を得やすい観点、及び、優れた接着強度を得やすい観点から、５質量％以上が好ましく、８質量％以上がより好ましく、１０質量％以上が更に好ましく、１４質量％以上が特に好ましい。液状ゴムの含有量は、優れた熱伝導性を得やすい観点、及び、優れた接着強度を得やすい観点から、５０質量％以下が好ましく、４０質量％以下がより好ましく、３５質量％以下が更に好ましく、３０質量％以下が特に好ましい。これらの観点から、液状ゴムの含有量は、５〜５０質量％が好ましく、８〜４０質量％がより好ましい。 The content of the liquid rubber is preferably in the following range based on the total amount of the component (D). The content of the liquid rubber is preferably 5% by mass or more, more preferably 8% by mass or more, further preferably 10% by mass or more, from the viewpoint of easily obtaining excellent thermal conductivity and excellent adhesive strength. It is preferable, and 14% by mass or more is particularly preferable. The content of the liquid rubber is preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 35% by mass or less, from the viewpoint of easily obtaining excellent thermal conductivity and excellent adhesive strength. It is preferable, and 30% by mass or less is particularly preferable. From these viewpoints, the content of the liquid rubber is preferably 5 to 50% by mass, more preferably 8 to 40% by mass.
熱可塑性樹脂としては、ポリ酢酸ビニル、ポリアクリル酸メチル、ε−カプロラクトン変性ポリエステル、フェノキシ樹脂、ポリイミド、下記一般式（ｄ２）で表される共重合体等が挙げられる。 Examples of the thermoplastic resin include polyvinyl acetate, methyl polyacrylate, ε-caprolactone-modified polyester, phenoxy resin, polyimide, and a copolymer represented by the following general formula (d2).
熱可塑性樹脂の数平均分子量は、充分な可とう化効果が得られやすい観点から、１００００以上が好ましく、２００００以上がより好ましい。熱可塑性樹脂の数平均分子量は、半導体用接着剤の粘度の過剰な上昇が抑制されて優れた塗布作業性が得られやすい観点から、３０００００以下が好ましく、２０００００以下がより好ましい。これらの観点から、熱可塑性樹脂の数平均分子量は、１００００〜３０００００が好ましく、２００００〜２０００００がより好ましい。熱可塑性樹脂の数平均分子量は、液状ゴムの数平均分子量と同様の方法により測定できる。 The number average molecular weight of the thermoplastic resin is preferably 10,000 or more, more preferably 20,000 or more, from the viewpoint that a sufficient plasticizing effect can be easily obtained. The number average molecular weight of the thermoplastic resin is preferably 300,000 or less, more preferably 200,000 or less, from the viewpoint that an excessive increase in the viscosity of the semiconductor adhesive is suppressed and excellent coating workability can be easily obtained. From these viewpoints, the number average molecular weight of the thermoplastic resin is preferably 1000 to 300,000, more preferably 2000 to 20000. The number average molecular weight of the thermoplastic resin can be measured by the same method as the number average molecular weight of the liquid rubber.
熱可塑性樹脂の含有量は、（Ｄ）成分の総量を基準として下記の範囲が好ましい。熱可塑性樹脂の含有量は、優れた熱伝導性を得やすい観点、及び、優れた接着強度を得やすい観点から、５０質量％以上が好ましく、６０質量％以上がより好ましく、６５質量％以上が更に好ましく、７０質量％以上が特に好ましい。熱可塑性樹脂の含有量は、優れた熱伝導性を得やすい観点、及び、優れた接着強度を得やすい観点から、９５質量％以下が好ましく、９２質量％以下がより好ましく、９０質量％以下が更に好ましく、８６質量％以下が特に好ましい。これらの観点から、熱可塑性樹脂の含有量は、５０〜９５質量％が好ましく、６０〜９２質量％がより好ましい。 The content of the thermoplastic resin is preferably in the following range based on the total amount of the component (D). The content of the thermoplastic resin is preferably 50% by mass or more, more preferably 60% by mass or more, and 65% by mass or more from the viewpoint of easily obtaining excellent thermal conductivity and excellent adhesive strength. More preferably, 70% by mass or more is particularly preferable. The content of the thermoplastic resin is preferably 95% by mass or less, more preferably 92% by mass or less, and 90% by mass or less from the viewpoint of easily obtaining excellent thermal conductivity and excellent adhesive strength. More preferably, 86% by mass or less is particularly preferable. From these viewpoints, the content of the thermoplastic resin is preferably 50 to 95% by mass, more preferably 60 to 92% by mass.
（Ｄ）成分の含有量は、（Ｂ）成分１００質量部に対して下記の範囲が好ましい。（Ｄ）成分の含有量は、充分な可とう化効果が得られやすい観点から、３０質量部以上が好ましく、４０質量部以上がより好ましく、５０質量部以上が更に好ましく、６０質量部以上が特に好ましい。（Ｄ）成分の含有量は、半導体用接着剤の粘度の過剰な上昇が抑制されて優れた塗布作業性が得られやすい観点から、１００質量部以下が好ましく、８０質量部以下がより好ましく、７０質量部以下が更に好ましい。これらの観点から、（Ｄ）成分の含有量は、３０〜１００質量部が好ましく、４０〜８０質量部がより好ましく、５０〜７０質量部が更に好ましい。 The content of the component (D) is preferably in the following range with respect to 100 parts by mass of the component (B). The content of the component (D) is preferably 30 parts by mass or more, more preferably 40 parts by mass or more, further preferably 50 parts by mass or more, and 60 parts by mass or more from the viewpoint that a sufficient flexible effect can be easily obtained. Especially preferable. The content of the component (D) is preferably 100 parts by mass or less, more preferably 80 parts by mass or less, from the viewpoint of suppressing an excessive increase in the viscosity of the semiconductor adhesive and easily obtaining excellent coating workability. More preferably, it is 70 parts by mass or less. From these viewpoints, the content of the component (D) is preferably 30 to 100 parts by mass, more preferably 40 to 80 parts by mass, and even more preferably 50 to 70 parts by mass.
（（Ｅ）成分：カップリング剤）
本実施形態に係る半導体用接着剤は、カップリング剤（以下、場合により「（Ｅ）成分」という）を含有してよい。（Ｅ）成分としては、シランカップリング剤、チタネート系カップリング剤、アルミニウム系カップリング剤、ジルコネート系カップリング剤、ジルコアルミネート系カップリング剤等が挙げられる。((E) component: coupling agent)
The semiconductor adhesive according to the present embodiment may contain a coupling agent (hereinafter, in some cases, referred to as “component (E)”). Examples of the component (E) include a silane coupling agent, a titanate-based coupling agent, an aluminum-based coupling agent, a zirconeate-based coupling agent, a zircoaluminate-based coupling agent, and the like.
シランカップリング剤としては、メチルトリメトキシシラン、メチルトリエトキシシラン、フェニルトリメトキシシラン、フェニルトリエトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリアセトキシシラン、ビニル−トリス（２−メトキシエトキシ）シラン、γ−メタクリロキシプロピルトリメトキシシラン、γ−メタクリロキシプロピルメチルジメトキシシラン、メチルトリ（メタクリロキシエトキシ）シラン、γ−アクリロキシプロピルトリメトキシシラン、γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、Ｎ−β−（アミノエチル）−γ−アミノプロピルトリメトキシシラン、Ｎ−β−（アミノエチル）−γ−アミノプロピルメチルジメトキシシラン、Ｎ−β−（Ｎ−ビニルベンジルアミノエチル）−γ−アミノプロピルトリメトキシシラン、γ−アニリノプロピルトリメトキシシラン、γ−ウレイドプロピルトリメトキシシラン、γ−ウレイドプロピルトリエトキシシラン、３−（４，５−ジヒドロイミダゾリル）プロピルトリエトキシシラン、β−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルメチルジエトキシシラン、γ−グリシドキシプロピルメチルジイソプロペノキシシラン、メチルトリグリシドキシシラン、γ−メルカプトプロピルトリメトキシシラン、γ−メルカプトプロピルトリエトキシシラン、γ−メルカプトプロピルメチルジメトキシシラン、トリメチルシリルイソシアネート、ジメチルシリルイソシアネート、フェニルシリルトリイソシアネート、テトライソシアネートシラン、メチルシリルトリイソシアネート、ビニルシリルトリイソシアネート、エトキシシラントリイソシアネート等が挙げられる。チタネート系カップリング剤としては、イソプロピルトリイソステアロイルチタネート、イソプロピルトリドデシルベンゼンスルホニルチタネート、イソプロピルトリス（ジオクチルパイロホスフェート）チタネート、テトライソプロピルビス（ジオクチルホスファイト）チタネート、テトラオクチルビス（ジトリデシルホスファイト）チタネート、テトラ（２，２−ジアリルオキシメチル−１−ブチル）ビス（ジ−トリデシル）ホスファイトチタネート、ビス（ジオクチルパイロホスフェート）オキシアセテートチタネート、ビス（ジオクチルパイロホスフェート）エチレンチタネート、イソプロピルトリオクタノイルチタネート、イソプロピルジメタクリルイソステアロイルチタネート、イソプロピル（ジオクチルホスフェート）チタネート、イソプロピルトリクミルフェニルチタネート、イソプロピルトリ（Ｎ−アミノエチル・アミノエチル）チタネート、ジクミルフェニルオキシアセテートチタネート、ジイソステアロイルエチレンチタネート等が挙げられる。アルミニウム系カップリング剤としては、アセトアルコキシアルミニウムジイソプロピオネート等が挙げられる。ジルコネート系カップリング剤としては、テトラプロピルジルコネート、テトラブチルジルコネート、テトラ（トリエタノールアミン）ジルコネート、テトライソプロピルジルコネート、ジルコニウムアセチルアセトネート、アセチルアセトンジルコニウムブチレート、ステアリン酸ジルコニウムブチレート等が挙げられる。 Examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, and vinyl-tris (2-methoxyethoxy). ) Silane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, methyltri (methacryloxyethoxy) silane, γ-acryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyl Triethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -Γ-Aminopropyltrimethoxysilane, γ-anilinopropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, 3- (4,5-dihydroimidazolyl) propyltriethoxysilane, β -(3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldiisopropenoxysilane, methyltriglycyl Sidoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, trimethylsilylisocyanate, dimethylsilylisocyanate, phenylsilyltriisocyanate, tetraisocyanatesilane, methylsilyltriisocyanate, vinyl Examples thereof include silyl triisocyanate and ethoxysilane triisocyanate. Examples of titanate-based coupling agents include isopropyltriisostearoyl titanate, isopropyltridodecylbenzenesulfonyl titanate, isopropyltris (dioctylpyrophosphate) titanate, tetraisopropylbis (dioctylphosphite) titanate, and tetraoctylbis (ditridecylphosphite) titanate. , Tetra (2,2-diallyloxymethyl-1-butyl) bis (di-tridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, Examples thereof include isopropyldimethacrylisostearoyl titanate, isopropyl (dioctylphosphate) titanate, isopropyltricylphenyl titanate, isopropyltri (N-aminoethyl / aminoethyl) titanate, dicumylphenyloxyacetate titanate, diisostearoylethylene titanate and the like. Examples of the aluminum-based coupling agent include acetalkoxyaluminum diisopropionate. Examples of the zirconate-based coupling agent include tetrapropyl zirconate, tetrabutyl zirconate, tetra (triethanolamine) zirconate, tetraisopropyl zirconate, zirconium acetylacetonate, acetylacetone zirconium butyrate, zirconium stearate butyrate and the like. ..
（Ｅ）成分の含有量は、（Ｂ）成分１００質量部に対して下記の範囲が好ましい。（Ｅ）成分の含有量は、優れた接着強度を得やすい観点から、３質量部以上が好ましく、５質量部以上がより好ましく、８質量部以上が更に好ましい。（Ｅ）成分の含有量は、優れた接着強度を得やすい観点から、３０質量部以下が好ましく、２０質量部以下がより好ましく、１０質量部以下が更に好ましい。これらの観点から、（Ｅ）成分の含有量は、３〜３０質量部が好ましく、５〜２０質量部がより好ましい。 The content of the component (E) is preferably in the following range with respect to 100 parts by mass of the component (B). The content of the component (E) is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, and further preferably 8 parts by mass or more from the viewpoint of easily obtaining excellent adhesive strength. The content of the component (E) is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, from the viewpoint of easily obtaining excellent adhesive strength. From these viewpoints, the content of the component (E) is preferably 3 to 30 parts by mass, more preferably 5 to 20 parts by mass.
（その他の成分）
本実施形態に係る半導体用接着剤は、必要に応じて、酸化カルシウム、酸化マグネシウム等の吸湿剤；フッ素系界面活性剤、ノニオン系界面活性剤、高級脂肪酸等の濡れ性向上剤；シリコーン油等の消泡剤；無機イオン交換体等のイオントラップ剤；溶剤などを含有してよい。溶剤を用いることにより粘度を調整してもよい。溶剤を用いる場合、溶剤の含有量は、ボイド等の発生を抑制しやすい観点から、半導体用接着剤の総量を基準として３質量％以下が好ましい。本実施形態に係る半導体用接着剤は、アウトガスの発生を抑制しやすいと共に、支持部材に対する接着剤の良好な濡れ性が得られやすい観点から、溶剤を含有しなくてよい（無溶剤であってよい）。(Other ingredients)
The semiconductor adhesive according to the present embodiment may be a hygroscopic agent such as calcium oxide or magnesium oxide; a wettability improver such as a fluorine-based surfactant, a nonionic surfactant, or a higher fatty acid; a silicone oil or the like, if necessary. Defoaming agent; ion trapping agent such as an inorganic ion exchanger; solvent and the like may be contained. The viscosity may be adjusted by using a solvent. When a solvent is used, the content of the solvent is preferably 3% by mass or less based on the total amount of the semiconductor adhesive from the viewpoint of easily suppressing the generation of voids and the like. The semiconductor adhesive according to the present embodiment does not have to contain a solvent from the viewpoint that it is easy to suppress the generation of outgas and it is easy to obtain good wettability of the adhesive to the support member (solvent-free). good).
本実施形態に係る半導体用接着剤の回転数０．５ｒｐｍにおける粘度（２５℃）は、優れた塗布作業性が得られやすい観点から、３００Ｐａ・ｓ以下が好ましく、２００Ｐａ・ｓ以下がより好ましく、１５０Ｐａ・ｓ以下が更に好ましく、１００Ｐａ・ｓ以下が特に好ましく、８０Ｐａ・ｓ以下が極めて好ましく、７０Ｐａ・ｓ以下が非常に好ましく、６５Ｐａ・ｓ以下がより一層好ましい。本実施形態に係る半導体用接着剤の回転数０．５ｒｐｍにおける粘度（２５℃）は、銀粒子の沈降を抑制しやすいことから半導体用接着剤の優れた保管安定性を得やすい観点から、３０Ｐａ・ｓ以上が好ましく、４０Ｐａ・ｓ以上がより好ましく、５０Ｐａ・ｓ以上が更に好ましい。これらの観点から、半導体用接着剤の回転数０．５ｒｐｍにおける粘度（２５℃）は、３０〜３００Ｐａ・ｓが好ましい。本実施形態に係る半導体用接着剤の回転数５ｒｐｍにおける粘度（２５℃）は、優れた塗布作業性が得られやすい観点から、４０Ｐａ・ｓ以下が好ましく、３５Ｐａ・ｓ以下がより好ましく、３０Ｐａ・ｓ以下が更に好ましく、２５Ｐａ・ｓ以下が特に好ましい。本実施形態に係る半導体用接着剤の回転数５ｒｐｍにおける粘度（２５℃）は、銀粒子の沈降を抑制しやすいことから半導体用接着剤の優れた保管安定性を得やすい観点から、１０Ｐａ・ｓ以上が好ましく、１５Ｐａ・ｓ以上がより好ましく、２０Ｐａ・ｓ以上が更に好ましい。これらの観点から、半導体用接着剤の回転数５ｒｐｍにおける粘度（２５℃）は、１０〜４０Ｐａ・ｓが好ましい。粘度は、ブルックフィールド型粘度計を用いて測定できる。 The viscosity (25 ° C.) of the semiconductor adhesive according to the present embodiment at a rotation speed of 0.5 rpm is preferably 300 Pa · s or less, more preferably 200 Pa · s or less, from the viewpoint of easily obtaining excellent coating workability. 150 Pa · s or less is further preferable, 100 Pa · s or less is particularly preferable, 80 Pa · s or less is extremely preferable, 70 Pa · s or less is very preferable, and 65 Pa · s or less is even more preferable. The viscosity (25 ° C.) of the semiconductor adhesive according to the present embodiment at a rotation speed of 0.5 rpm is 30 Pa from the viewpoint that it is easy to suppress the sedimentation of silver particles and therefore it is easy to obtain excellent storage stability of the semiconductor adhesive. -S or more is preferable, 40 Pa · s or more is more preferable, and 50 Pa · s or more is further preferable. From these viewpoints, the viscosity (25 ° C.) of the semiconductor adhesive at a rotation speed of 0.5 rpm is preferably 30 to 300 Pa · s. The viscosity (25 ° C.) of the semiconductor adhesive according to the present embodiment at a rotation speed of 5 rpm is preferably 40 Pa · s or less, more preferably 35 Pa · s or less, and more preferably 30 Pa · s, from the viewpoint that excellent coating workability can be easily obtained. It is more preferably s or less, and particularly preferably 25 Pa · s or less. The viscosity (25 ° C.) of the semiconductor adhesive according to the present embodiment at a rotation speed of 5 rpm is 10 Pa · s from the viewpoint of easily obtaining excellent storage stability of the semiconductor adhesive because it is easy to suppress the sedimentation of silver particles. The above is preferable, 15 Pa · s or more is more preferable, and 20 Pa · s or more is further preferable. From these viewpoints, the viscosity (25 ° C.) of the semiconductor adhesive at a rotation speed of 5 rpm is preferably 10 to 40 Pa · s. Viscosity can be measured using a Brookfield viscometer.
＜半導体部品＞
本実施形態に係る半導体部品は、支持部材と、半導体素子と、支持部材及び半導体素子の間に配置された接着剤層と、を備え、接着剤層が、本実施形態に係る半導体用接着剤又はその硬化物を含む。半導体素子は、接着剤層を介して支持部材上に搭載されている。接着剤層は、支持部材及び半導体素子に接している。本実施形態に係る半導体部品では、本実施形態に係る半導体用接着剤を用いることにより、半導体素子から発生した熱を外部に効率的に放散することができると共に、半導体素子と支持部材との高い接着強度を得ることができる。本実施形態に係る半導体装置は、本実施形態に係る半導体部品を備える。<Semiconductor parts>
The semiconductor component according to the present embodiment includes a support member, a semiconductor element, and an adhesive layer arranged between the support member and the semiconductor element, and the adhesive layer is an adhesive for semiconductors according to the present embodiment. Or the cured product thereof is included. The semiconductor element is mounted on the support member via an adhesive layer. The adhesive layer is in contact with the support member and the semiconductor element. In the semiconductor component according to the present embodiment, by using the semiconductor adhesive according to the present embodiment, the heat generated from the semiconductor element can be efficiently dissipated to the outside, and the semiconductor element and the support member are high. Adhesive strength can be obtained. The semiconductor device according to the present embodiment includes the semiconductor parts according to the present embodiment.
支持部材（半導体素子搭載用支持部材）としては、４２アロイリードフレーム、銅リードフレーム、パラジウムＰＰＦリードフレーム等のリードフレーム；ガラスエポキシ基板（ガラス繊維強化エポキシ樹脂からなる基板）、ＢＴ基板（シアネートモノマー及びそのオリゴマーとビスマレイミドからなるＢＴレジン使用基板）等の有機基板などが挙げられる。半導体素子としては、ＩＣ、ＬＳＩ、ＬＥＤチップ等が挙げられる。半導体素子の厚さは、６００μｍ以下であってよく、５００μｍ以下であってよく、４００μｍ以下であってよい。 As the support member (support member for mounting a semiconductor element), a lead frame such as a 42 alloy lead frame, a copper lead frame, or a palladium PPF lead frame; a glass epoxy substrate (a substrate made of a glass fiber reinforced epoxy resin), a BT substrate (cyanate monomer). BT resin-based substrate composed of the oligomer and bismaleimide) and the like. Examples of semiconductor elements include ICs, LSIs, LED chips, and the like. The thickness of the semiconductor element may be 600 μm or less, 500 μm or less, and 400 μm or less.
本実施形態に係る半導体部品は、半導体素子の一部又は全部を封止する封止部を備えていてよい。封止部の構成材料としては、透光性樹脂を用いることができる。封止部は、支持部材の一部又は全部を封止していてもよい。 The semiconductor component according to the present embodiment may include a sealing portion that seals a part or all of the semiconductor element. A translucent resin can be used as a constituent material of the sealing portion. The sealing portion may seal a part or all of the support member.
本実施形態に係る半導体部品の製造方法は、本実施形態に係る半導体用接着剤を支持部材と半導体素子との間に配置して接着剤層を形成する接着剤層形成工程を備える。本実施形態に係る半導体用接着剤は、構成成分を一括又は分割して攪拌機、ハイブリッドミキサー、ライカイ機、３本ロール、プラネタリーミキサー等を用いて混合することにより得ることができる。 The method for manufacturing a semiconductor component according to the present embodiment includes an adhesive layer forming step of arranging the semiconductor adhesive according to the present embodiment between a support member and a semiconductor element to form an adhesive layer. The semiconductor adhesive according to the present embodiment can be obtained by collectively or dividing the constituent components and mixing them using a stirrer, a hybrid mixer, a Raikai machine, a three-roll, a planetary mixer, or the like.
本実施形態に係る半導体部品の製造方法は、接着剤層形成工程の後に、接着剤層を硬化（熱硬化等）して硬化物を得る工程を備えてよい。本実施形態に係る半導体部品の製造方法は、接着剤層形成工程の後に、半導体素子をワイヤボンディングするワイヤボンド工程を備えていてよい。本実施形態に係る半導体部品の製造方法は、接着剤層形成工程の後に、半導体素子を封止する工程を備えていてよい。 The method for manufacturing a semiconductor component according to the present embodiment may include a step of curing the adhesive layer (thermosetting or the like) to obtain a cured product after the adhesive layer forming step. The method for manufacturing a semiconductor component according to the present embodiment may include a wire bonding step of wire bonding the semiconductor element after the adhesive layer forming step. The method for manufacturing a semiconductor component according to the present embodiment may include a step of sealing the semiconductor element after the step of forming the adhesive layer.
半導体用接着剤を用いて半導体素子を支持部材に接着させるには、例えば、まず、支持部材上に半導体用接着剤をディスペンス法、スクリーン印刷法、スタンピング法等により塗布した後、半導体素子を圧着し、その後、加熱装置（オーブン、ヒートブロック等）を用いて半導体用接着剤を加熱硬化することにより行うことができる。さらに、ワイヤボンド工程を経た後、通常の方法により半導体素子を封止することができる。 To attach a semiconductor element to a support member using a semiconductor adhesive, for example, first, the semiconductor adhesive is applied onto the support member by a dispensing method, a screen printing method, a stamping method, or the like, and then the semiconductor element is crimped. Then, it can be carried out by heating and curing the semiconductor adhesive using a heating device (orange, heat block, etc.). Further, after passing through the wire bonding step, the semiconductor element can be sealed by a usual method.
上述の加熱硬化の温度は、低温での長時間硬化、高温での速硬化等の条件により異なるが、例えば、１５０〜２２０℃（好ましくは１８０〜２００℃）で３０秒〜２時間（好ましくは１時間〜１時間３０分）行うことができる。 The temperature of the above-mentioned heat curing varies depending on conditions such as long-term curing at a low temperature and rapid curing at a high temperature, but for example, it is 150 to 220 ° C. (preferably 180 to 200 ° C.) for 30 seconds to 2 hours (preferably). 1 hour to 1 hour 30 minutes) can be done.
図１は、本実施形態に係る半導体部品の一例を示す模式断面図である。図１に示すように、半導体部品１０は、支持部材１１、半導体素子１３、接着剤層１５、及び、封止部１７を備える。接着剤層１５は、支持部材１１と半導体素子１３との間に配置されており、本実施形態に係る半導体用接着剤又はその硬化物を含む。封止部１７は、支持部材１１、半導体素子１３及び接着剤層１５を封止している。半導体素子１３は、ワイヤ１９ａを介してリードフレーム１９ｂに接続されている。
FIG. 1 is a schematic cross-sectional view showing an example of a semiconductor component according to the present embodiment. As shown in FIG. 1, the
図２は、本実施形態に係る半導体部品の他の例を示す模式断面図である。図２に示すように、半導体部品２０は、支持部材２１、半導体素子（ＬＥＤチップ）２３、接着剤層２５、及び、封止部２７を備える。支持部材２１は、基板２１ａと、基板２１ａを囲むように形成されたリードフレーム２１ｂと、を有している。接着剤層２５は、支持部材２１と半導体素子２３との間に配置されており、本実施形態に係る半導体用接着剤又はその硬化物を含む。封止部２７は、半導体素子２３及び接着剤層２５を封止している。半導体素子２３は、ワイヤ２９を介してリードフレーム２１ｂに接続されている。
FIG. 2 is a schematic cross-sectional view showing another example of the semiconductor component according to the present embodiment. As shown in FIG. 2, the
以下、実施例及び比較例を用いて本発明の内容を更に詳細に説明するが、本発明は以下の実施例に限定されるものではない。 Hereinafter, the contents of the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.
＜半導体用接着剤の構成成分＞
（銀粒子）
ＡｇＣ−２２１ＰＡ（福田金属箔粉工業株式会社製、商品名、形状：鱗片状、ＢＥＴ比表面積：０．２０ｍ２／ｇ、平均粒径：７．５μｍ）
ＡｇＣ−２７１Ｂ（福田金属箔粉工業株式会社製、商品名、形状：鱗片状、ＢＥＴ比表面積：０．５０ｍ２／ｇ、平均粒径：２．１μｍ）
ＡｇＣ−２２１Ｑ３（福田金属箔粉工業株式会社製、商品名、形状：鱗片状、ＢＥＴ比表面積：０．３５ｍ２／ｇ）
ＴＣ−８８（株式会社徳力化学研究所製、商品名、形状：鱗片状、ＢＥＴ比表面積：１．０５ｍ２／ｇ）<Components of semiconductor adhesives>
(Silver particles)
AgC-221PA (manufactured by Fukuda Metal Foil Powder Industry Co., Ltd., trade name, shape: scaly, BET specific surface area: 0.20 m 2 / g, average particle size: 7.5 μm)
AgC-271B (manufactured by Fukuda Metal Foil Powder Industry Co., Ltd., trade name, shape: scaly, BET specific surface area: 0.50 m 2 / g, average particle size: 2.1 μm)
AgC-221Q3 (manufactured by Fukuda Metal Foil Powder Industry Co., Ltd., trade name, shape: scaly, BET specific surface area: 0.35 m 2 / g)
TC-88 (manufactured by Tokuri Kagaku Kenkyusho Co., Ltd., trade name, shape: scaly, BET specific surface area: 1.05 m 2 / g)
（（メタ）アクリロイル基を有する単量体）
ＦＡ−５１２Ａ（ジシクロペンテニルオキシエチルアクリレート、日立化成株式会社製、商品名、下記式（ｂ５１）で表される化合物）
ＳＲ−３３９Ａ（２−フェノキシエチルアクリレート、サートマー社製、商品名、下記式（ｂ５２）で表される化合物）
ＳＲ−３４９（ＥＯ変性ビスフェノールＡジアクリレート、サートマー社製、商品名、下記式（ｂ５３）で表される化合物）
FA-512A (dicyclopentenyloxyethyl acrylate, manufactured by Hitachi Kasei Co., Ltd., trade name, compound represented by the following formula (b51))
SR-339A (2-phenoxyethyl acrylate, manufactured by Sartmer, trade name, compound represented by the following formula (b52))
SR-349 (EO-modified bisphenol A diacrylate, manufactured by Sartomer, trade name, compound represented by the following formula (b53))
（ラジカル重合開始剤）
トリゴノックス２２−７０Ｅ（１，１−ビス（ｔ−ブチルパーオキシ）シクロヘキサン、化薬アクゾ株式会社製、商品名）(Radical polymerization initiator)
Trigonox 22-70E (1,1-bis (t-butylperoxy) cyclohexane, manufactured by Kayaku Akzo Corporation, trade name)
（可とう化剤）
エポリードＰＢ−４７００（エポキシ化ポリブタジエン、ダイセル化学工業株式会社製、商品名、エポキシ当量：１５２．４〜１７７．８、数平均分子量：３５００）
ＣＴＢＮ−１００９ＳＰ−Ｓ（カルボキシ基を有するアクリロニトリルポリブタジエン共重合体、宇部興産株式会社製、商品名、数平均分子量：３６００）(Flexible agent)
Epolide PB-4700 (epoxidized polybutadiene, manufactured by Daicel Chemical Industry Co., Ltd., trade name, epoxy equivalent: 152.4 to 177.8, number average molecular weight: 3500)
CTBN-1009SP-S (Acrylonitrile polybutadiene copolymer having a carboxy group, manufactured by Ube Industries, Ltd., trade name, number average molecular weight: 3600)
（カップリング剤）
ＫＢＭ−４０３（γ−グリシドキシプロピルトリメトキシシラン、信越化学工業株式会社製、商品名）(Coupling agent)
KBM-403 (γ-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., trade name)
＜半導体用接着剤の調製＞
表１の各成分（配合量の単位：質量部）を混合した後、ハイブリットミキサを用いて混練した。次に、６６６．６１Ｐａ（５Ｔｏｒｒ）以下で３分間脱泡処理を行うことにより半導体用接着剤（導電性組成物）を得た。<Preparation of adhesive for semiconductors>
After mixing each component in Table 1 (unit of blending amount: parts by mass), the mixture was kneaded using a hybrid mixer. Next, a semiconductor adhesive (conductive composition) was obtained by performing a defoaming treatment at 666.61 Pa (5 Torr) or less for 3 minutes.
＜評価＞
熱伝導率、粘度及びダイシェア強度（接着強度）を下記に示す方法で評価した。結果を表１に示す。ダイシェア強度は実施例についてのみ評価した。<Evaluation>
The thermal conductivity, viscosity and die shear strength (adhesive strength) were evaluated by the methods shown below. The results are shown in Table 1. Die-share strength was evaluated only for the examples.
（熱伝導率）
オーブンを用いて半導体用接着剤を１８０℃まで１時間で昇温した後に１８０℃で１時間保持することにより硬化物を得た。そして、下記測定装置を用いて熱拡散率、比重及び比熱を測定した後、下記式によって熱伝導率を算出した。
［測定装置］
熱拡散率：レーザフラッシュ法熱定数測定装置（Ｎｅｔｚｓｃｈ製、ＬＦＡ ４６７ ＨｙｐｅｒＦｌａｓｈ）
比熱：ＤＳＣ（ティー・エイ・インスツルメント・ジャパン株式会社製、Ｑ−２００）
比重：電子比重計（アルファミラージュ株式会社製、ＳＤ−２００Ｌ）
［算出式］
λ＝α×ρ×Ｃｐ
λ：熱伝導率（Ｗ／ｍ／Ｋ）
α：熱拡散率（ｍｍ２／ｓ）
ρ：比重（ｇ／ｃｍ３）
Ｃｐ：比熱（Ｊ／ｇ／Ｋ）(Thermal conductivity)
A cured product was obtained by heating the semiconductor adhesive to 180 ° C. for 1 hour using an oven and then holding it at 180 ° C. for 1 hour. Then, after measuring the thermal diffusivity, the specific gravity and the specific heat using the following measuring device, the thermal conductivity was calculated by the following formula.
[measuring device]
Thermal diffusivity: Laser flash method thermal constant measuring device (manufactured by Netzsch, LFA 467 HyperFlash)
Specific heat: DSC (TA Instruments Japan Co., Ltd., Q-200)
Specific gravity: Electronic hydrometer (manufactured by Alpha Mirage Co., Ltd., SD-200L)
[Calculation formula]
λ = α × ρ × C p
λ: Thermal conductivity (W / m / K)
α: Thermal diffusivity (mm 2 / s)
ρ: Specific gravity (g / cm 3 )
C p : Specific heat (J / g / K)
（粘度）
ブルックフィールド型粘度計（Ｂｒｏｏｋｆｉｅｌｄ Ｅｎｇｉｎｅｅｒｉｎｇ Ｌａｂｏｒａｔｏｒｉｅｓ製、ＨＡＤＶ−ＩＩＩ Ｕ ＣＰ）を用いて、接着剤量０．５ｍＬ、温度２５℃、回転数０．５ｒｐｍ又は５ｒｐｍで３分間回転後の半導体用接着剤の粘度を得た。(viscosity)
Using a Brookfield viscometer (HADV-III UCP, manufactured by Brookfield Engineering Laboratories), the adhesive amount for semiconductors after rotation at 0.5 mL,
（ダイシェア強度）
半導体用接着剤を銀リングめっき付き銅リードフレーム上に約１．５ｍｇ塗布した後、半導体用接着剤上に５ｍｍ×５ｍｍのシリコンチップ（厚さ：４００μｍ）を圧着した。さらに、オーブンを用いて１８０℃まで３０分で昇温した後に１８０℃で１時間保持して半導体用接着剤を硬化させて半導体部品を得た。自動接着力試験装置（ＢＴ４０００、Ｄａｇｅ社製）を用いて、半導体部品の２５０℃における剪断接着強度（ＭＰａ）を測定した。１０個の半導体部品の測定結果の平均値をダイシェア強度の測定結果として得た。(Die share strength)
After applying about 1.5 mg of the semiconductor adhesive onto a copper lead frame with silver ring plating, a 5 mm × 5 mm silicon chip (thickness: 400 μm) was pressure-bonded onto the semiconductor adhesive. Further, the temperature was raised to 180 ° C. in 30 minutes using an oven, and then the temperature was maintained at 180 ° C. for 1 hour to cure the semiconductor adhesive to obtain a semiconductor component. The shear adhesive strength (MPa) of the semiconductor component at 250 ° C. was measured using an automatic adhesive strength test device (BT4000, manufactured by Dage). The average value of the measurement results of 10 semiconductor parts was obtained as the measurement result of the die shear strength.
表１に示すように、実施例では、比較例と比較して熱伝導率が高いことが確認される。また、実施例では、優れた熱伝導性、塗布作業性（粘度）及び接着強度が得られることが確認される。 As shown in Table 1, it is confirmed that the thermal conductivity of the examples is higher than that of the comparative examples. Further, in the examples, it is confirmed that excellent thermal conductivity, coating workability (viscosity) and adhesive strength can be obtained.
１０，２０…半導体部品、１１，２１…支持部材、１３，２３…半導体素子、１５，２５…接着剤層、１７，２７…封止部、１９ａ，２９…ワイヤ、１９ｂ，２１ｂ…リードフレーム、２１ａ…基板。 10,20 ... Semiconductor parts, 11,21 ... Support members, 13,23 ... Semiconductor elements, 15,25 ... Adhesive layers, 17,27 ... Sealing parts, 19a, 29 ... Wires, 19b, 21b ... Lead frames, 21a ... Substrate.
Claims (11)
前記（Ａ）成分が第１の銀粒子を含み、
前記第１の銀粒子のＢＥＴ比表面積が０．３ｍ２／ｇ以下であり、
前記第１の銀粒子の平均粒径が７．０μｍ以上である、半導体用接着剤。It contains (A) silver particles and (B) a monomer having a (meth) acryloyl group.
The component (A) contains the first silver particles, and the component (A) contains the first silver particles.
The BET specific surface area of the first silver particles is 0.3 m 2 / g or less.
An adhesive for semiconductors in which the average particle size of the first silver particles is 7.0 μm or more.
前記第２の銀粒子のＢＥＴ比表面積が０．３ｍ２／ｇを超える、請求項１〜５のいずれか一項に記載の半導体用接着剤。The component (A) further contains a second silver particle, and the component (A) further contains a second silver particle.
The adhesive for semiconductors according to any one of claims 1 to 5, wherein the BET specific surface area of the second silver particles exceeds 0.3 m 2 / g.
前記ラジカル重合開始剤の含有量が、前記（Ｂ）成分１００質量部に対して３〜３０質量部である、請求項１〜８のいずれか一項に記載の半導体用接着剤。Further containing a radical polymerization initiator,
The semiconductor adhesive according to any one of claims 1 to 8, wherein the content of the radical polymerization initiator is 3 to 30 parts by mass with respect to 100 parts by mass of the component (B).
前記接着剤層が、請求項１〜９のいずれか一項に記載の半導体用接着剤又はその硬化物を含む、半導体部品。A support member, a semiconductor element, and an adhesive layer arranged between the support member and the semiconductor element are provided.
A semiconductor component in which the adhesive layer contains the semiconductor adhesive according to any one of claims 1 to 9 or a cured product thereof.
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| JP2010225312A (en) * | 2009-03-19 | 2010-10-07 | Hitachi Chem Co Ltd | Resin paste composition and semiconductor device |
| JP2015135805A (en) * | 2013-12-16 | 2015-07-27 | 日立化成株式会社 | Resin paste composition and semiconductor device |
| WO2018034234A1 (en) * | 2016-08-19 | 2018-02-22 | 住友ベークライト株式会社 | Die attach paste and semiconductor device |
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| JP2010225312A (en) * | 2009-03-19 | 2010-10-07 | Hitachi Chem Co Ltd | Resin paste composition and semiconductor device |
| JP2015135805A (en) * | 2013-12-16 | 2015-07-27 | 日立化成株式会社 | Resin paste composition and semiconductor device |
| WO2018034234A1 (en) * | 2016-08-19 | 2018-02-22 | 住友ベークライト株式会社 | Die attach paste and semiconductor device |
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