WO2019003995A1 - ダイボンディング用硬化性シリコーン組成物 - Google Patents
ダイボンディング用硬化性シリコーン組成物 Download PDFInfo
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- WO2019003995A1 WO2019003995A1 PCT/JP2018/023212 JP2018023212W WO2019003995A1 WO 2019003995 A1 WO2019003995 A1 WO 2019003995A1 JP 2018023212 W JP2018023212 W JP 2018023212W WO 2019003995 A1 WO2019003995 A1 WO 2019003995A1
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- sio
- formula
- die bonding
- silicone composition
- curable silicone
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- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 99
- 239000000203 mixture Substances 0.000 title claims abstract description 77
- -1 siloxane units Chemical group 0.000 claims abstract description 85
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 27
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 26
- 238000004073 vulcanization Methods 0.000 claims abstract description 24
- 238000006459 hydrosilylation reaction Methods 0.000 claims abstract description 14
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 239000002683 reaction inhibitor Substances 0.000 claims abstract description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 5
- 229910004283 SiO 4 Inorganic materials 0.000 claims description 33
- 229920005989 resin Polymers 0.000 claims description 28
- 239000011347 resin Substances 0.000 claims description 28
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 27
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 16
- 125000005372 silanol group Chemical group 0.000 claims description 8
- 238000005452 bending Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011541 reaction mixture Substances 0.000 claims description 6
- 150000001345 alkine derivatives Chemical class 0.000 claims description 5
- 125000003700 epoxy group Chemical group 0.000 claims description 5
- 229910021485 fumed silica Inorganic materials 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000004065 semiconductor Substances 0.000 abstract description 8
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 22
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 16
- 150000002430 hydrocarbons Chemical group 0.000 description 9
- 229910052697 platinum Inorganic materials 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 125000004122 cyclic group Chemical group 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 125000003710 aryl alkyl group Chemical group 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 125000001309 chloro group Chemical group Cl* 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 125000001153 fluoro group Chemical group F* 0.000 description 5
- 125000005843 halogen group Chemical group 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 230000001771 impaired effect Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- VMAWODUEPLAHOE-UHFFFAOYSA-N 2,4,6,8-tetrakis(ethenyl)-2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O[Si](C)(C=C)O1 VMAWODUEPLAHOE-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- BITPLIXHRASDQB-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane Chemical class C=C[Si](C)(C)O[Si](C)(C)C=C BITPLIXHRASDQB-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 3
- STJDTTBKCCNRPL-UHFFFAOYSA-N methyl-tris(2-phenylbut-3-yn-2-yloxy)silane Chemical compound C[Si](OC(C#C)(C)C1=CC=CC=C1)(OC(C#C)(C)C1=CC=CC=C1)OC(C#C)(C1=CC=CC=C1)C STJDTTBKCCNRPL-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- FSIJKGMIQTVTNP-UHFFFAOYSA-N bis(ethenyl)-methyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(C=C)C=C FSIJKGMIQTVTNP-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 125000006038 hexenyl group Chemical group 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 1
- KWEKXPWNFQBJAY-UHFFFAOYSA-N (dimethyl-$l^{3}-silanyl)oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)C KWEKXPWNFQBJAY-UHFFFAOYSA-N 0.000 description 1
- HMVBQEAJQVQOTI-SOFGYWHQSA-N (e)-3,5-dimethylhex-3-en-1-yne Chemical compound CC(C)\C=C(/C)C#C HMVBQEAJQVQOTI-SOFGYWHQSA-N 0.000 description 1
- GRGVQLWQXHFRHO-AATRIKPKSA-N (e)-3-methylpent-3-en-1-yne Chemical compound C\C=C(/C)C#C GRGVQLWQXHFRHO-AATRIKPKSA-N 0.000 description 1
- VEJOYRPGKZZTJW-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;platinum Chemical compound [Pt].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O VEJOYRPGKZZTJW-FDGPNNRMSA-N 0.000 description 1
- QWOVEJBDMKHZQK-UHFFFAOYSA-N 1,3,5-tris(3-trimethoxysilylpropyl)-1,3,5-triazinane-2,4,6-trione Chemical compound CO[Si](OC)(OC)CCCN1C(=O)N(CCC[Si](OC)(OC)OC)C(=O)N(CCC[Si](OC)(OC)OC)C1=O QWOVEJBDMKHZQK-UHFFFAOYSA-N 0.000 description 1
- CEBKHWWANWSNTI-UHFFFAOYSA-N 2-methylbut-3-yn-2-ol Chemical compound CC(C)(O)C#C CEBKHWWANWSNTI-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- NECRQCBKTGZNMH-UHFFFAOYSA-N 3,5-dimethylhex-1-yn-3-ol Chemical compound CC(C)CC(C)(O)C#C NECRQCBKTGZNMH-UHFFFAOYSA-N 0.000 description 1
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole 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
- 239000007767 bonding agent Substances 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000006482 condensation reaction Methods 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
- 125000003493 decenyl group Chemical group [H]C([*])=C([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])[H] 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
- 150000001993 dienes Chemical class 0.000 description 1
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 description 1
- RQCQBDUYEHRNPP-UHFFFAOYSA-N dimethyl-bis(2-methylbut-3-yn-2-yloxy)silane Chemical compound C#CC(C)(C)O[Si](C)(C)OC(C)(C)C#C RQCQBDUYEHRNPP-UHFFFAOYSA-N 0.000 description 1
- CEKBBZSCGNWGQU-UHFFFAOYSA-N dimethyl-bis(2-phenylbut-3-yn-2-yloxy)silane Chemical compound C[Si](OC(C#C)(C)C1=CC=CC=C1)(OC(C#C)(C1=CC=CC=C1)C)C CEKBBZSCGNWGQU-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 125000005066 dodecenyl group Chemical group C(=CCCCCCCCCCC)* 0.000 description 1
- 125000003438 dodecyl 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])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- KPWVUBSQUODFPP-UHFFFAOYSA-N ethenyl-(ethenyl-methyl-phenylsilyl)oxy-methyl-phenylsilane Chemical compound C=1C=CC=CC=1[Si](C)(C=C)O[Si](C)(C=C)C1=CC=CC=C1 KPWVUBSQUODFPP-UHFFFAOYSA-N 0.000 description 1
- HOMYFVKFSFMSFF-UHFFFAOYSA-N ethenyl-[ethenyl(diphenyl)silyl]oxy-diphenylsilane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(C=C)O[Si](C=C)(C=1C=CC=CC=1)C1=CC=CC=C1 HOMYFVKFSFMSFF-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- CRJSCSRODDRNDN-UHFFFAOYSA-N methyl-tris(2-methylbut-3-yn-2-yloxy)silane Chemical compound C#CC(C)(C)O[Si](C)(OC(C)(C)C#C)OC(C)(C)C#C CRJSCSRODDRNDN-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005187 nonenyl group Chemical group C(=CCCCCCCC)* 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([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])[H] 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- UMFJXASDGBJDEB-UHFFFAOYSA-N triethoxy(prop-2-enyl)silane Chemical compound CCO[Si](CC=C)(OCC)OCC UMFJXASDGBJDEB-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-UHFFFAOYSA-N 0.000 description 1
- 125000005065 undecenyl group Chemical group C(=CCCCCCCCCC)* 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([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])[H] 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
- C08G77/08—Preparatory processes characterised by the catalysts used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
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- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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- 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
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- H01L24/01—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
- H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
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- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
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- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
- H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
- H01L2224/29001—Core members of the layer connector
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- H01L2224/2919—Material with a principal constituent of the material being a polymer, e.g. polyester, phenolic based polymer, epoxy
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- H01L2924/11—Device type
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- H01L2924/11—Device type
- H01L2924/12—Passive devices, e.g. 2 terminal devices
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- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
Definitions
- the present invention relates to a curable silicone composition for die bonding.
- a curable silicone composition is used to bond an optical semiconductor device such as an LED to a support such as sapphire.
- a curable silicone composition for example, in Patent Documents 1 and 2, substantially linear or cyclic alkenyl group-containing organopolysiloxane, branched alkenyl group-containing organopolysiloxane, molecular chain
- a curable silicone composition comprising a linear organopolysiloxane having a hydrogen atom bonded to a silicon atom in the inside, a branched organopolysiloxane having a silicon atom-bonded hydrogen atom, and a catalyst for hydrosilylation reaction is proposed
- Patent Document 3 discloses a linear organopolysiloxane having at least two alkenyl groups in one molecule, a branched organopolysiloxane having at least two alkenyl groups in one molecule, and one molecule. Branched organopolysiloxa having at least two silicon-bonded hydrogen
- An object of the present invention is to provide a curable silicone composition for die bonding capable of firmly bonding a semiconductor chip to a support.
- the curable silicone composition for die bonding of the present invention is (A) 100 parts by mass of organopolysiloxane having at least two alkenyl groups in one molecule, (B) At least two siloxane units represented by the formula: RHSiO (wherein R is a monovalent hydrocarbon group having 1 to 12 carbon atoms having no aliphatic unsaturated bond) in one molecule Organopolysiloxanes (the amount by which the molar ratio of silicon-bonded hydrogen atoms in this component is 0.1 to 10 with respect to the alkenyl groups in component (A)), (C) An amount such that the platinum group metal element in this component is at least 10 ppm by mass unit, relative to the total amount of platinum group metal based catalysts for hydrosilylation reaction (A) to (B) (D) Hydrosilylation reaction inhibitor 0.001 to 5 parts by mass with respect to a total of 100 parts by mass of the components (A) to (B), and the total of the components (A) to (B) The
- Component (A) formula: R 1 3 SiO 1/2 (wherein, R 1 is identical or different, monovalent hydrocarbon group having 1 to 12 carbon atoms free of aliphatic unsaturation. siloxane units represented by) the formula: R 1 2 R 2 SiO 1/2 (wherein, R 1 is as defined above, R 2 is represented by an alkenyl group having 2 to 12 carbon atoms).
- siloxane units and wherein: at least consists of siloxane units represented by SiO 4/2, wherein: for the siloxane units represented by SiO 4/2, wherein: the siloxane units represented by R 1 3 SiO 1/2 preparative formula: total molar ratio of siloxane units represented by R 1 2 R 2 SiO 1/2 is preferable to contain an organopolysiloxane resin is from 0.5 to 1.6.
- the component (B) has a formula: R 4 3 SiO 1/2 where R 4 is the same or different and is a monovalent hydrocarbon group having 1 to 12 carbon atoms which has no aliphatic unsaturated bond.
- the molar ratio of the siloxane unit represented by the formula: R 4 3 SiO 1/2 to the siloxane unit represented by the formula: SiO 4/2 is 0.6 to 1.5
- R Organopolysiloxane resin having a molar ratio of siloxane units represented by 4 HSiO 2/2 of 1.5 to 3, or the formula: R 4 3 SiO 1/2 (wherein R 4 is the same or different, C 1 to C 12 monovalent hydrocarbon groups having no aliphatic unsaturated bond .
- Table with SiO 4/2 Organopolysiloxanes which do not have any siloxane units.
- Component (D) is preferably an alkyne alcohol and / or a silylated form of an alkyne alcohol.
- the component (E) is preferably a reaction mixture of an alkenyl group-containing diorganosiloxane oligomer and an epoxy group-containing alkoxysilane, both of which are blocked on both molecular terminal silanol groups.
- composition further contains (F) fumed silica having a BET specific surface area of 20 to 200 m 2 / g in an amount of 1 to 20 parts by mass with respect to a total of 100 parts by mass of the components (A) to (B). Is preferred.
- the composition is preferably cured to form a cured product having a Type D durometer hardness of 50 or more as defined in JIS K 6253-1997.
- composition is preferably cured to form a cured product having a bending strain of 10% or more as defined in JIS K 7171-1994.
- such a present composition is a curable silicone composition for die bonding for bonding an LED element to a substrate.
- the curable silicone composition for die bonding of the present invention is characterized in that the semiconductor chip can be firmly adhered to the support.
- the component (A) is an organopolysiloxane having at least two alkenyl groups in one molecule.
- this alkenyl group include alkenyl groups having 2 to 12 carbon atoms such as vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl and dodecenyl groups.
- it is a vinyl group.
- the component (A) as a group to be bonded to a silicon atom other than the alkenyl group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, Alkyl group having 1 to 12 carbon atoms such as hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group and dodecyl group; 6 carbon atoms such as phenyl group, tolyl group, xylyl group and naphthyl group 12 to 12 aryl groups; aralkyl groups having 7 to 12 carbon atoms such as benzyl group, phenethyl group, phenylpropyl group and the like; some or all of the hydrogen atoms of these groups are hal
- the molecular structure of the component (A) is not limited, and examples thereof include linear, partially branched linear, cyclic, branched, or three-dimensional network structure.
- Component (A) is a single organopolysiloxane having these molecular structures, or a mixture of two or more organopolysiloxanes having these molecular structures, to obtain sufficient adhesion (chip die shear strength). It is preferable to contain an organopolysiloxane resin of at least a branched or three-dimensional network structure, and in particular, a linear or partially branched linear organopolysiloxane and a branched or tertiary one. It is preferably a mixture with an organopolysiloxane resin having an original network structure.
- linear organopolysiloxane for example, dimethylpolysiloxane blocked with dimethylvinylsiloxy at both ends of molecular chain, dimethylvinylsiloxy copolymer blocked with dimethylvinylsiloxy at both ends of molecular chain, dimethylvinylsiloxane with branched ends of molecular chain Siloxy group-capped dimethylsiloxane / methylvinylsiloxane copolymer, molecular chain both terminal dimethylvinylsiloxy group-capped methylphenylpolysiloxane, molecular chain both terminal trimethylsiloxy group-capped dimethylsiloxane / methylvinylsiloxane copolymer, molecular chain both terminal trimethyl And siloxy group-blocked dimethylsiloxane / methylvinylsiloxane / methylphenylsiloxane copolymers, and mixtures of two or more of these.
- the organopolysiloxane resin of the branched-chain or three dimensional network structure for example, the formula: the siloxane units represented by R 1 3 SiO 1/2, wherein: is represented by R 1 2 R 2 SiO 1/2 And at least one siloxane unit represented by the formula: SiO 4/2 .
- R 1 is the same or different and is a C 1-12 monovalent hydrocarbon group having no aliphatic unsaturated bond, the same C 1-12 alkyl group as described above, the C 6
- the aryl group of -12 and the aralkyl group having 7 to 12 carbon atoms are exemplified, and preferably a methyl group.
- R 2 is an alkenyl group having 2 to 12 carbon atoms, and the same alkenyl groups as those described above are exemplified, and preferably a vinyl group.
- Such organopolysiloxane resin has the formula: a siloxane unit represented by R 1 3 SiO 1/2, wherein: the siloxane units represented by R 1 2 R 2 SiO 1/2, and the formula: SiO 4/2 And at least one siloxane unit represented by the formula: R 1 SiO 3/2 may be included as long as the object of the present invention is not impaired.
- such organopolysiloxane resin may have a hydroxyl group or an alkoxy group bonded to a silicon atom in the molecule within a range that does not impair the object of the present invention, but rather a hydroxyl group or an alkoxy on a silicon atom in the molecule.
- the organopolysiloxane resin of the formula for the siloxane units represented by SiO 4/2, wherein: the siloxane units of the formula represented by R 1 3 SiO 1/2: R 1 2 R 2 SiO 1/2
- the total molar ratio of the siloxane units represented by is preferably in the range of 0.5 to 1.6, and more preferably in the range of 0.6 to 1.5, or 0.6 to 1. It is preferable to be in the range of 4.
- organopolysiloxane resin those represented by the following average composition formula are exemplified.
- Vi, Me and Ph each represent a vinyl group, a methyl group and a phenyl group.
- the component (A) preferably contains at least such an organopolysiloxane resin, and its content is not limited, but is preferably in the range of 40 to 90% by mass of the component (A), and more preferably The lower limit thereof is preferably 50% by mass or 60% by mass, while the upper limit thereof is preferably 80% by mass or 70% by mass. This is because the cured product obtained by curing the present composition can be made to have high hardness and toughness when the content of the organopolysiloxane resin is equal to or more than the lower limit, while the content is equal to or less than the upper limit. This is because the viscosity of the material does not increase excessively, and its handleability is improved.
- the organopolysiloxane described above is used to lower the viscosity of the present composition, to increase the hardness of the cured product obtained by curing the present composition, and to improve the mechanical strength.
- an organopolysiloxane resin having a high alkenyl group content represented by the following average composition formula and a relatively low viscosity may be used in combination.
- cyclic containing an alkenyl group It is preferable to contain the organopolysiloxane of Such cyclic organopolysiloxanes have an average unit formula: (R 3 2 SiO 2/2 ) n Is represented by
- R 3 is the same or different and is a monovalent hydrocarbon group having 1 to 12 carbon atoms, and specifically, the same alkyl group having 1 to 12 carbons and alkenyl having 2 to 12 carbon atoms as described above Groups, aryl groups having 6 to 12 carbon atoms, aralkyl groups having 7 to 12 carbon atoms, and groups in which part or all of the hydrogen atoms of these groups are substituted with a halogen atom such as a fluorine atom, chlorine atom or bromine atom Be done.
- at least two R 3 in one molecule are the above-mentioned alkenyl group, preferably a vinyl group.
- n is an integer within the range of 3 to 20, preferably an integer within the range of 3 to 10.
- cyclic organopolysiloxanes are as follows. In the formulae, Vi and Me are as defined above. (MeViSiO 2/2 ) 3 (MeViSiO 2/2 ) 4 (MeViSiO 2/2 ) 5
- the content of the cyclic organopolysiloxane in the component (A) is not limited, but 5% by mass or less of the component (A) because the mechanical strength of the cured product obtained by curing the present composition is good. Is preferably, and further preferably 3% by mass or less.
- the viscosity of the component (A) is not limited, the viscosity at 25 ° C. is in the range of 10 to 5,000,000 mPa ⁇ s, or 50 to 100,000 mPa ⁇ s, because the handling workability of the present composition is good. It is preferable to be in the range of s.
- the component (B) is an organopolysiloxane having at least two siloxane units represented by the formula: RHSiO in one molecule.
- RHSiO vulcanization time
- R is a monovalent hydrocarbon group having 1 to 12 carbon atoms which has no aliphatic unsaturated bond, and the same alkyl group having 1 to 12 carbons and an aryl group having 6 to 12 carbons as described above, Examples thereof include aralkyl groups having 7 to 12 carbon atoms and groups in which part or all of the hydrogen atoms of these groups are substituted with a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom, preferably a methyl group.
- the molecular structure of (B) component is not limited, For example, linear, the chain which has partial branch, branched chain, cyclic, or a three-dimensional network structure is mentioned.
- the component (B) may be a single organopolysiloxane having these molecular structures, or a mixture of two or more organopolysiloxanes having these molecular structures.
- the organopolysiloxane resin having a branched or three-dimensional network structure has, for example, a siloxane unit represented by the formula: R 4 3 SiO 1/2 , a siloxane unit represented by the formula: R 4 HSiO 2/2 , and a formula : in which at least consists of siloxane units represented by SiO 4/2, and the like, without impairing the object of the present invention, wherein: the siloxane units and formula represented by R 4 2 SiO 2/2: R 4 SiO It may also contain a siloxane unit represented by 3/2 .
- a hydroxyl group or an alkoxy group may be bonded to a silicon atom in the molecule, as long as the object of the present invention is not impaired.
- the molar ratio of the siloxane unit represented by the formula: R 4 3 SiO 1/2 to the siloxane unit represented by the formula: SiO 4/2 is 0.6 to 1.5.
- the molar ratio of the siloxane unit represented by the formula: R 4 HSiO 2/2 is preferably in the range of 1.5 to 3.
- R 4 is the same or different and is a monovalent hydrocarbon group having 1 to 12 carbon atoms having no aliphatic unsaturated carbon bond, and the same alkyl group having 1 to 12 carbons as described above, the carbon number Examples thereof include aryl groups of 6 to 12 and aralkyl groups having 7 to 12 carbon atoms, and groups in which part or all of the hydrogen atoms of these groups are substituted with a halogen atom such as a fluorine atom, chlorine atom or bromine atom. , Methyl group.
- organopolysiloxane resin what is represented by the following average unit formula is illustrated.
- Me is as defined above. (Me 3 SiO 1/2 ) 0.23 (MeHSiO 2/2 ) 0.51 (SiO 4/2 ) 0.26 (Me 3 SiO 1/2 ) 0.24 (MeHSiO 2/2 ) 0.49 (SiO 4/2 ) 0.27 (Me 3 SiO 1/2 ) 0.24 (Me 2 SiO 2/2 ) 0.10 (MeHSiO 2/2 ) 0.40 (SiO 4/2 ) 0.26
- straight-chain or partially branched straight-chain organopolysiloxanes are, for example, siloxane units represented by the formula: R 4 3 SiO 1/2 and siloxanes represented by the formula: R 4 HSiO 2/2
- siloxane units represented by the formula: R 4 3 SiO 1/2 What contains at least a unit and does not have a siloxane unit represented by the formula: SiO 4/2 is mentioned, and a siloxane represented by the formula: R 4 2 HSiO 1/2 as long as the object of the present invention is not impaired
- a unit, a siloxane unit represented by the formula: R 4 2 SiO 2/2 , or a siloxane unit represented by the formula: R 4 SiO 3/2 may be included.
- R 4 is the same or different and is a monovalent hydrocarbon group having 1 to 12 carbon atoms having no aliphatic unsaturated carbon bond, and the same alkyl group having 1 to 12 carbons as described above, the carbon number Examples thereof include aryl groups of 6 to 12 and aralkyl groups having 7 to 12 carbon atoms, and groups in which part or all of the hydrogen atoms of these groups are substituted with a halogen atom such as a fluorine atom, chlorine atom or bromine atom. , Methyl group.
- organopolysiloxane one represented by the following formula is exemplified.
- Me and Ph are as defined above.
- Me 3 SiO (MeHSiO) 36 SiMe 3 HMe 2 SiO (Me 2 SiO) 36 SiMe 2 H Me 3 SiO (MeHSiO) 80 SiMe 3 Me 3 SiO (Me 2 SiO) 30 (MeHSiO) 30 SiMe 3 Me 2 PhSiO (MeHSiO) 35 SiMe 2 Ph
- the weight average molecular weight (Mw) of the component (B) is not limited, it is preferably 6,000 or more and 8,000 or more, because the adhesion of the cured product obtained by curing the present composition is good. Or it is 10,000 or more.
- the content of the component (B) is such that the silicon-bonded hydrogen atoms in the component (B) are in the range of 0.1 to 10 moles with respect to 1 mole in total of the alkenyl groups in the component (A) And an amount such that it is preferably in the range of 0.5 to 5 moles, or in the range of 0.5 to 3 moles, because the resulting cured product has good hardness, mechanical properties and adhesiveness. Amount.
- Component (C) is a platinum group metal based catalyst for hydrosilylation reaction to promote the hydrosilylation reaction of the present composition.
- the platinum group metal is exemplified by platinum, ruthenium, rhodium, palladium and iridium, preferably platinum.
- the platinum-based catalyst for hydrosilylation reaction of component (C) includes fine platinum powder, platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complex of chloroplatinic acid and diolefin, platinum-olefin complex, platinum bis (Acetoacetate), platinum-carbonyl complexes such as platinum bis (acetylacetonate), chloroplatinic acid / alkenylsiloxane such as chloroplatinic acid / divinyltetramethyldisiloxane complex, chloroplatinic acid / tetravinyltetramethylcyclotetrasiloxane complex, etc.
- platinum / alkenyl siloxane complexes such as platinum / divinyl tetramethyldisiloxane complex, platinum / tetravinyl tetramethyl cyclotetrasiloxane complex, and complexes of chloroplatinic acid and acetylene alcohols, which can significantly accelerate the hydrosilylation reaction From the platinum-alkenyl white San complexes are preferred.
- alkenyl siloxane 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane,
- the alkenyl siloxane oligomer which substituted a part of the methyl group of these alkenyl siloxane by the ethyl group, the phenyl group, etc., and the vinyl group of these anyl siloxanes by the allyl group, the hexenyl group etc. is illustrated.
- 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is preferable because the stability of the resulting platinum-alkenyl siloxane complex is good.
- platinum-alkenyl siloxane complexes may be added to 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3-diallyl-1 1,3,3-Tetramethyldisiloxane, 1,3-Divinyl-1,3-dimethyl-1,3-diphenyldisiloxane, 1,3-Divinyl-1,1,3,3-tetraphenyldisiloxane It is preferable that it is dissolved in an organosiloxane oligomer such as an alkenyl siloxane oligomer such as 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane or a dimethylsiloxane oligomer, and in particular, It is preferable that it is dissolved in the alkenyl siloxane oligomer.
- organosiloxane oligomer such as an alkenyl siloxane
- the content of the component (C) is an amount such that at least 10 ppm of a platinum-based element in the component can be obtained in mass units with respect to the total amount of the components (A) to (B).
- the amount is in the range of 500 ppm, in the range of 10 to 100 ppm, or in the range of 10 to 50 ppm. This is because when the content of the component (C) is at least the lower limit of the above range, the curability of the present composition is good, and in particular, the curability at a die bonding thickness of 10 ⁇ m or less is good. On the other hand, when it is below the upper limit of the said range, it is because it becomes difficult to produce problems, such as coloring, in the obtained hardened
- the component (D) is a hydrosilylation reaction inhibitor for extending the pot life at room temperature of the composition and improving the storage stability.
- component (D) 1-ethynylcyclohexan-1-ol, 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyn-3-ol, 2-phenyl-3-butyne- Alkyne alcohols such as 2-ol; ene compounds such as 3-methyl-3-penten-1-yne and 3,5-dimethyl-3-hexen-1-yne; methyl tris (1-methyl-1-phenyl-propyne Oxy) silane, dimethylbis (1-methyl-1-phenyl-propynoxy) silane, methyltris (1,1-dimethyl-propynoxy) silane, dimethylbis (1,1-dimethyl-propynoxy) silane, etc.
- Other examples are benzotriazole, and preferably, alkyn alcohol and / or silylated alkyn
- the content of the component (D) is in the range of 0.0001 to 5 parts by mass, 0.01 to 5 parts by mass, or 100 parts by mass of the components (A) to (B). And preferably in the range of 0.01 to 3 parts by mass. This is because gelation or curing can be sufficiently suppressed when the components (A), (B) and (C) are mixed, if the content of the (D) component is at least the lower limit of the above range. On the other hand, if it is below the upper limit of the above range, the vulcanization characteristics of the present composition are not significantly reduced.
- the scorch time (ts1) at temperature is 20 to 60 seconds
- the 90% vulcanization time [tc (90)] can be 300 to 500 seconds for the maximum torque value up to a vulcanization time of 600 seconds.
- the component (E) is an adhesion-imparting agent for imparting adhesiveness to the composition.
- adhesion promoter known ones which can be blended in a curable silicone composition which cures by a hydrosilylation reaction can be used.
- (E) component vinyltrimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, hydrogentrilyoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, Alkoxysilanes such as 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, etc .; Dimethyl siloxane ⁇ methyl vinyl with blocking of both terminal silanol groups.
- Alkenyl group-containing diorganosiloxane oligomers such as siloxane copolymer oligomers, methyl vinyl siloxane oligomers having a molecular chain both terminal silanol group blocked, and a molecular chain both terminal silanol group blocked, and 3-glycidoxypropyl Reaction mixtures with epoxy group-containing alkoxysilanes such as dimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; alkenyl group-containing diorganosiloxane oligomers as described above for blocking both terminal silanol groups, -A reaction mixture with methacryloxypropyltrimethoxysilane; a reaction mixture of the epoxy group-containing alkoxysilane and 3-aminopropyltriethoxysilane; and others, tris (3-trimethoxysilylpropyl) isocyanurate, preferably It is
- the content of the component (E) is in the range of 0.01 to 10 parts by mass, preferably 0.01 to 5 parts by mass, with respect to a total of 100 parts by mass of the components (A) to (B).
- the content of the component (E) is at least the lower limit of the above range, sufficient adhesiveness can be given to the present composition, while when the content is at most the upper limit of the above range, the present composition is It is because it is hard to produce discoloration of the hardened
- the composition preferably contains fumed silica having a BET specific surface area of 20 to 200 m 2 / g for the purpose of improving handling workability and adhesion.
- the content of the component (F) is not limited, it is in the range of 1 to 20 parts by mass with respect to a total of 100 parts by mass of the components (A) to (B) because the mechanical properties of the obtained cured product become good. It is preferably inside.
- inorganic fillers such as silica, glass, alumina, zinc oxide other than the component (F); silicone rubber powder; silicone resin, polymethacrylate Resin powder such as resin; heat resisting agent, dye, pigment, flame retarder, solvent and the like may be blended.
- the curing proceeds by heating, but in order to cure rapidly, the composition is preferably heated within a range of 50 to 200.degree.
- the composition is preferably cured to form a cured product having a Type D durometer hardness of 50 or more as defined in JIS K 6253-1997 "Test method for hardness of vulcanized rubber and thermoplastic rubber". Further, it is preferable to form a cured product of 50 to 70. This is because when the hardness is 50 or more, the cured product has sufficient cohesion and sufficient strength and adhesiveness can be obtained under the conditions of a film thickness of 10 ⁇ m or less, while 70 or less. Also, the cured product is flexible and sufficient adhesion can be obtained.
- the composition is preferably cured to form a cured product having a bending strain of 10% or more as defined in JIS K 7171-1994 "Plastics-Test method of flexural properties". This is because when the bending strain is 10% or more, the cured product has flexibility and sufficient adhesion can be obtained.
- This composition has a scorch time (ts1) of 20 to 60 seconds as measured by MDR (Moving Die Rheometer) at a die bonding temperature, and a 90% vulcanization time [tc (90)] of 300 to 500 seconds.
- ts1 scorch time
- tc 90% vulcanization time
- an organopolysiloxane having at least two siloxane units represented by the formula: RHSiO in one molecule is further used as the component (B).
- Examples of the method include adjusting the content of the component C) or adjusting the type and content of the component (D).
- the curable silicone composition for die bonding of the present invention will be described in detail by way of examples / comparative examples.
- the viscosity is a value at 25 ° C.
- the following components were used to prepare the curable silicone composition for die bonding of Examples / Comparative Examples.
- Vi represents a vinyl group and Me represents a methyl group.
- (A1): Dimethylvinylsiloxy group-blocked dimethylpolysiloxane having a viscosity of 60 mPa ⁇ s and having both chain ends (content of vinyl group 1.53% by mass)
- (A2): Dimethylvinylsiloxy group-blocked dimethylpolysiloxane having a viscosity of 350 mPa ⁇ s and having both chains (content of vinyl group 0.45% by mass)
- (A3): average formula: (MeViSiO) 4 Cyclic methyl vinyl polysiloxane having a viscosity of 4 mPa ⁇ s (content of vinyl group 30% by mass)
- (A4): average formula: HO (MeViSiO) 20 H Methyl vinyl polysiloxane having a viscosity of 30 mPa ⁇ s (content of vinyl group 30% by mass)
- B2 viscosity is 510 mPa ⁇ s, average unit formula: (Me 3 SiO 1/2 ) 0.24 (MeHSiO 2/2 ) 0.49 (SiO 4/2 ) 0.27
- B3 viscosity is 10 mPa ⁇ s, average formula: Me 3 SiO (MeHSiO) 36 SiMe 3 Organopolysiloxane represented by (weight average molecular weight
- component (C) 1,3-divinyl-1,1,1,3,1 of a 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum wherein the content of platinum metal is about 4% by weight , 3-Tetramethyldisiloxane solution
- (D1) methyltris (1-methyl-1-phenyl-propynoxy) silane
- (d2) 1-ethynylcyclohexane-1-ol
- (F) Fumed silica having a BET specific surface area of 115 to 165 m 2 / g and whose surface is hydrophobized with hexamethyldisilazane (trade name: RX200 manufactured by Nippon Aerosil Co., Ltd.)
- vulcanization characteristics and the characteristics of the cured product of the curable silicone composition for die bonding in Examples and Comparative Examples were measured as follows.
- a curable silicone composition for die bonding is prepared according to the method specified in JIS K 6300-2: 2001 "Unvulcanized rubber-Physical characteristics-Part 2: Determination of vulcanization characteristics using a vibration vulcanization tester". It was measured after curing for 600 seconds at a general die bonding temperature (150 ° C.) using a curastometer (PREMIERMDR manufactured by Alpha Technologies, Inc.). The measurement was carried out by placing 5 ml of the curable liquid silicone composition on the lower die and starting the measurement when the upper die was closed. In addition, it measured by making an amplitude angle into 0.5 degree, a frequency of 100 times / min, and making a torque range into 230 kgf * cm of the maximum using R-die for rubber
- a sheet-like cured product was produced by press-molding the curable silicone composition for die bonding at 150 ° C. for 2 hours.
- the hardness of the sheet-like cured product was measured using a type D durometer specified by JIS K 6253-1997 "Hardness testing method of vulcanized rubber and thermoplastic rubber".
- Chip die shear strength A curable silicone composition for die bonding was applied to the LED substrate by a die bonder (AD 830 PLUS manufactured by ASM), an LED chip of 300 ⁇ m 2 was placed thereon, and cured at 150 ° C. for 2 hours. Thereafter, chip die shear strength was measured with a die shear tester (DAGE 4000 bond tester manufactured by Nordson DAGE).
- Examples 1 to 4 Comparative Examples 1 to 8
- a curable silicone composition for die bonding was prepared with the compositions shown in Tables 1 and 2.
- "SiH / Vi" in Tables 1 and 2 represents the value of the total number of moles of silicon-bonded hydrogen atoms in the component (B) to 1 mole in total of the vinyl groups in the component (A). Further, the vulcanizing properties and the properties of the cured product of this curable silicone composition are shown in Tables 1 and 2.
- the present composition can firmly bond the semiconductor element to the support, die bonding of semiconductor elements such as light emitting diode (LED), semiconductor laser, photodiode, phototransistor, solid imaging, light emitter for photo coupler and light receiver It is suitable as an agent.
- LED light emitting diode
- semiconductor laser semiconductor laser
- photodiode phototransistor
- solid imaging solid imaging
- light emitter for photo coupler light receiver
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Abstract
Description
(A)一分子中にアルケニル基を少なくとも2個有するオルガノポリシロキサン 100質量部、
(B)一分子中に、式:RHSiO(式中、Rは脂肪族不飽和結合を有さない炭素数1~12の一価炭化水素基である。)で表されるシロキサン単位を少なくとも2個有するオルガノポリシロキサン{(A)成分中のアルケニル基に対する、本成分中のケイ素原子結合水素原子のモル比が0.1~10となる量}、
(C)ヒドロシリル化反応用白金族金属系触媒 (A)~(B)成分の合計量に対して、質量単位で、本成分中の白金族金属元素が少なくとも10ppmとなる量、
(D)ヒドロシリル化反応抑制剤 (A)~(B)成分の合計100質量部に対して0.001~5質量部、および
(E)接着性付与剤 (A)~(B)成分の合計100質量部に対して0.01~10質量部
から少なくともなり、JIS K 6300-2で規定される、ダイボンディング温度におけるスコーチタイム(ts1)が20~60秒であり、加硫時間600秒までの最大トルク値に対する90%加硫時間[tc(90)]が300~500秒であることを特徴とする。
(ViMe2SiO1/2)0.10(Me3SiO1/2)0.33(SiO4/2)0.57(HO1/2)0.03
(ViMe2SiO1/2)0.13(Me3SiO1/2)0.35(SiO4/2)0.52(HO1/2)0.02
(ViMePhSiO1/2)0.10(Me3SiO1/2)0.45(SiO4/2)0.45(HO1/2)0.03
(ViMe2SiO1/2)0.09(Me3SiO1/2)0.31(SiO4/2)0.60(HO1/2)0.04
(ViMe2SiO1/2)0.10(Me3SiO1/2)0.40(SiO4/2)0.50(HO1/2)0.03
(ViMe2SiO1/2)0.55(Me3SiO1/2)0.05(SiO4/2)0.40
(ViMe2SiO1/2)0.15(Me3SiO1/2)0.45(SiO4/2)0.40
(R3 2SiO2/2)n
で表される。
(MeViSiO2/2)3
(MeViSiO2/2)4
(MeViSiO2/2)5
(Me3SiO1/2)0.23(MeHSiO2/2)0.51(SiO4/2)0.26
(Me3SiO1/2)0.24(MeHSiO2/2)0.49(SiO4/2)0.27
(Me3SiO1/2)0.24(Me2SiO2/2)0.10(MeHSiO2/2)0.40(SiO4/2)0.26
Me3SiO(MeHSiO)36SiMe3
HMe2SiO(Me2SiO)36SiMe2H
Me3SiO(MeHSiO)80SiMe3
Me3SiO(Me2SiO)30(MeHSiO)30SiMe3
Me2PhSiO(MeHSiO)35SiMe2Ph
(a1):粘度60mPa・sの分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン(ビニル基の含有量=1.53質量%)
(a2):粘度350mPa・sの分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン(ビニル基の含有量=0.45質量%)
(a3):平均式:
(MeViSiO)4
で表される、粘度4mPa・sの環状メチルビニルポリシロキサン(ビニル基の含有量=30質量%)
(a4):平均式:
HO(MeViSiO)20H
で表される、粘度30mPa・sのメチルビニルポリシロキサン(ビニル基の含有量=30質量%)
(a5):平均単位式:
(Me2ViSiO1/2)0.55(Me3SiO1/2)0.05(SiO4/2)0.40
で表される、粘度300mPa・sのオルガノポリシロキサンレジン(ビニル基の含有量=19.0質量%)
(a6):平均単位式:
(Me2ViSiO1/2)0.15(Me3SiO1/2)0.45(SiO4/2)0.40
で表される、粘度350mPa・sのオルガノポリシロキサンレジン(ビニル基の含有量=5.1質量%)
(a7)成分:平均単位式:
(Me2ViSiO1/2)0.09(Me3SiO1/2)0.43(SiO4/2)0.48(HO1/2)0.03
で表される、室温で固体のオルガノポリシロキサンレジン(ビニル基の含有量=3.0質量%)
(a8)成分:平均単位式:
(Me2ViSiO1/2)0.10(Me3SiO1/2)0.45(SiO4/2)0.45(HO1/2)0.02
で表される、室温で固体のオルガノポリシロキサンレジン(ビニル基の含有量=3.0質量%)
(b1):粘度が2,000mPa・sであり、平均単位式:
(Me3SiO1/2)0.23(MeHSiO2/2)0.51(SiO4/2)0.26
で表されるオルガノポリシロキサンレジン(重量平均分子量=18,000、ケイ素原子結合水素原子の含有量=0.78質量%)
(b2):粘度が510mPa・sであり、平均単位式:
(Me3SiO1/2)0.24(MeHSiO2/2)0.49(SiO4/2)0.27
で表されるオルガノポリシロキサンレジン(重量平均分子量=16,300、ケイ素原子結合水素原子の含有量=0.75質量%)
(b3):粘度が10mPa・sであり、平均式:
Me3SiO(MeHSiO)36SiMe3
で表されるオルガノポリシロキサン(重量平均分子量=8,800、ケイ素原子結合水素原子の含有量=1.6質量%)
(b4):粘度が120mPa・sであり、平均単位式:
(HMe2SiO1/2)0.67(SiO4/2)0.33
で表されるオルガノポリシロキサンレジン(重量平均分子量=1310、ケイ素原子結合水素原子の含有量=0.95質量%)
(c):白金金属の含有量が約4重量%である、白金の1,3-ジビニル-1,1,3,3-テトラメチルジシロキサン錯体の1,3-ジビニル-1,1,3,3-テトラメチルジシロキサン溶液
(d1):メチルトリス(1-メチル-1-フェニル-プロピンオキシ)シラン
(d2):1-エチニルシクロヘキサン-1-オール
(e):25℃における粘度が30mPa・sである分子鎖両末端シラノール基封鎖メチルビニルシロキサンオリゴマーと3-グリシドキシプロピルトリメトキシシランの縮合反応物
(f):BET比表面積が115~165m2/gであり、その表面がヘキサメチルジシラザンで疎水化処理されたフュームドシリカ(日本アエロジル社製の商品名:RX200)
ダイボンディング用硬化性シリコーン組成物を、JIS K 6300-2:2001「未加硫ゴム-物理特性-第2部:振動式加硫試験機による加硫特性の求め方」で規定される方法に従い、キュラストメーター(アルファテクノロジーズ社製のPREMIERMDR)を用いて、一般的なダイボンディング温度(150℃)において600秒間加硫して測定した。なお、測定は、硬化性液状シリコーン組成物 5mlを下側ダイスに載せ、上側ダイスが閉まった時点を測定開始とした。なお、ゴム用R型ダイスを用い、振幅角度は0.5°、振動数は100回/分、トルクレンジを最大の230kgf・cmにして測定した。
ダイボンディング用硬化性シリコーン組成物を150℃で2時間プレス成形することによりシート状硬化物を作製した。JIS K 6253-1997「加硫ゴム及び熱可塑性ゴムの硬さ試験方法」で規定されるタイプDデュロメータにより、このシート状硬化物の硬さを測定した。
ダイボンディング用硬化性シリコーン組成物を150℃で2時間加熱して硬化物を作製した。JIS K 7171-1994「プラスチック-曲げ特性の試験方法」で規定される方法に従って、この硬化物の曲げひずみ(%)を求めた。
ダイボンディング用硬化性シリコーン組成物をダイボンダー(ASM社製のAD830PLUS)によりLED基板に塗布し、300μm2のLEDチップを載せ、150℃、2時間の硬化条件で硬化させた。その後、ダイシェアテスター(Nordson DAGE社製のDAGE4000 bond tester)にて、チップダイシェア強度を測定した。
表1および表2に示した組成でダイボンディング用硬化性シリコーン組成物を調製した。なお、表1および表2中の「SiH/Vi」は、(A)成分中のビニル基の合計1モルに対する、(B)成分中のケイ素原子結合水素原子の合計モル数の値を表す。また、この硬化性シリコーン組成物の加硫特性および硬化物の特性を表1および表2に示した。
Claims (10)
- (A)一分子中にアルケニル基を少なくとも2個有するオルガノポリシロキサン 100質量部、
(B)一分子中に、式:RHSiO(式中、Rは脂肪族不飽和結合を有さない炭素数1~12の一価炭化水素基である。)で表されるシロキサン単位を少なくとも2個有するオルガノポリシロキサン{(A)成分中のアルケニル基に対する、本成分中のケイ素原子結合水素原子のモル比が0.1~10となる量}、
(C)ヒドロシリル化反応用白金族金属系触媒 (A)~(B)成分の合計量に対して、質量単位で、本成分中の白金族金属元素が少なくとも10ppmとなる量、
(D)ヒドロシリル化反応抑制剤 (A)~(B)成分の合計100質量部に対して0.001~5質量部、および
(E)接着性付与剤 (A)~(B)成分の合計100質量部に対して0.01~10質量部
から少なくともなり、JIS K 6300-2で規定される、ダイボンディング温度におけるスコーチタイム(ts1)が20~60秒であり、加硫時間600秒までの最大トルク値に対する90%加硫時間[tc(90)]が300~500秒であるダイボンディング用硬化性シリコーン組成物。 - (A)成分が、式:R1 3SiO1/2(式中、R1は同じかまたは異なる、脂肪族不飽和結合を有さない炭素数1~12の一価炭化水素基である。)で表されるシロキサン単位、式:R1 2R2SiO1/2(式中、R1は前記と同じであり、R2は炭素数2~12のアルケニル基である。)で表されるシロキサン単位、および式:SiO4/2で表されるシロキサン単位から少なくともなり、式:SiO4/2で表されるシロキサン単位に対する、式:R1 3SiO1/2で表されるシロキサン単位と式:R1 2R2SiO1/2で表されるシロキサン単位の合計のモル比が0.5~1.6であるオルガノポリシロキサンレジンを含有する、請求項1に記載のダイボンディング用硬化性シリコーン組成物。
- (B)成分が、式:R4 3SiO1/2(式中、R4は同じかまたは異なる、脂肪族不飽和結合を有さない炭素数1~12の一価炭化水素基である。)で表されるシロキサン単位、式:R4HSiO2/2(式中、R4は前記と同じである。)で表されるシロキサン単位、および式:SiO4/2で表されるシロキサン単位から少なくともなり、式:SiO4/2で表されるシロキサン単位に対する、式:R4 3SiO1/2で表されるシロキサン単位のモル比が0.6~1.5であり、式:R4HSiO2/2で表されるシロキサン単位のモル比が1.5~3であるオルガノポリシロキサンレジンである、請求項1に記載のダイボンディング用硬化性シリコーン組成物。
- (B)成分が、式:R4 3SiO1/2(式中、R4は同じかまたは異なる、脂肪族不飽和結合を有さない炭素数1~12の一価炭化水素基である。)で表されるシロキサン単位および式:R4HSiO2/2(式中、R4は前記と同じである。)で表されるシロキサン単位から少なくともなり、式:SiO4/2で表されるシロキサン単位を有さないオルガノポリシロキサンである、請求項1に記載のダイボンディング用硬化性シリコーン組成物。
- (D)成分がアルキンアルコールおよび/またはアルキンアルコールのシリル化物である、請求項1に記載のダイボンディング用硬化性シリコーン組成物。
- (E)成分が、分子鎖両末端シラノール基封鎖のアルケニル基含有ジオルガノシロキサンオリゴマーとエポキシ基含有アルコキシシランとの反応混合物である、請求項1に記載のダイボンディング用硬化性シリコーン組成物。
- さらに、(F)BET比表面積が20~200m2/gであるフュームドシリカを、(A)~(B)成分の合計100質量部に対して1~20質量部含有する、請求項1に記載のダイボンディング用硬化性シリコーン組成物。
- 硬化して、JIS K 6253-1997で規定されるタイプDデュロメータ硬さが50以上である硬化物を形成する、請求項1乃至7のいずれか1項に記載のダイボンディング用硬化性シリコーン組成物。
- 硬化して、JIS K 7171-1994で規定される曲げひずみが10%以上である硬化物を形成する、請求項1乃至8のいずれか1項に記載のダイボンディング用硬化性シリコーン組成物。
- LED素子を基板に接着するための、請求項1乃至9のいずれか1項に記載のダイボンディング用硬化性シリコーン組成物。
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CN111534274A (zh) * | 2019-02-06 | 2020-08-14 | 信越化学工业株式会社 | 管芯键合用有机改性硅酮树脂组合物、其固化物及光学半导体元件 |
JP2020189908A (ja) * | 2019-05-21 | 2020-11-26 | 信越化学工業株式会社 | ダイボンディング用シリコーン組成物、その硬化物、及び光半導体装置 |
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WO2022030120A1 (ja) * | 2020-08-06 | 2022-02-10 | ダウ・東レ株式会社 | 硬化性シリコーン組成物およびその硬化物 |
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WO2024090403A1 (ja) * | 2022-10-24 | 2024-05-02 | ダウ・東レ株式会社 | 半導体製造用導電性ピラーモジュール前駆体、半導体製造用導電性ピラーモジュール、半導体または半導体前駆体、並びにその製造方法 |
WO2024135805A1 (ja) * | 2022-12-23 | 2024-06-27 | ダウ・東レ株式会社 | 硬化性シリコーン組成物、その硬化生成物、及び前記組成物の使用 |
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JP2022042170A (ja) * | 2020-09-02 | 2022-03-14 | デュポン・東レ・スペシャルティ・マテリアル株式会社 | 熱硬化性シリコーン組成物 |
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CN111534274A (zh) * | 2019-02-06 | 2020-08-14 | 信越化学工业株式会社 | 管芯键合用有机改性硅酮树脂组合物、其固化物及光学半导体元件 |
JP2020125430A (ja) * | 2019-02-06 | 2020-08-20 | 信越化学工業株式会社 | ダイボンディング用有機変性シリコーン樹脂組成物、その硬化物及び光半導体素子 |
JP2020189908A (ja) * | 2019-05-21 | 2020-11-26 | 信越化学工業株式会社 | ダイボンディング用シリコーン組成物、その硬化物、及び光半導体装置 |
JP7041094B2 (ja) | 2019-05-21 | 2022-03-23 | 信越化学工業株式会社 | ダイボンディング用シリコーン組成物、その硬化物、及び光半導体装置 |
JP7041094B6 (ja) | 2019-05-21 | 2023-12-18 | 信越化学工業株式会社 | ダイボンディング用シリコーン組成物、その硬化物、及び光半導体装置 |
JP2021042132A (ja) * | 2019-09-06 | 2021-03-18 | 信越化学工業株式会社 | アルキニル基含有オルガノポリシロキサン及びヒドロシリル化反応制御剤 |
JP7175249B2 (ja) | 2019-09-06 | 2022-11-18 | 信越化学工業株式会社 | アルキニル基含有オルガノポリシロキサン及びヒドロシリル化反応制御剤 |
WO2022030120A1 (ja) * | 2020-08-06 | 2022-02-10 | ダウ・東レ株式会社 | 硬化性シリコーン組成物およびその硬化物 |
WO2022138341A1 (ja) * | 2020-12-25 | 2022-06-30 | ダウ・東レ株式会社 | 一体型ダイシングダイボンディング用シートおよび半導体装置の製造方法 |
WO2024090403A1 (ja) * | 2022-10-24 | 2024-05-02 | ダウ・東レ株式会社 | 半導体製造用導電性ピラーモジュール前駆体、半導体製造用導電性ピラーモジュール、半導体または半導体前駆体、並びにその製造方法 |
WO2024135805A1 (ja) * | 2022-12-23 | 2024-06-27 | ダウ・東レ株式会社 | 硬化性シリコーン組成物、その硬化生成物、及び前記組成物の使用 |
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JP6965346B2 (ja) | 2021-11-10 |
JPWO2019003995A1 (ja) | 2020-04-09 |
TWI762649B (zh) | 2022-05-01 |
US11384268B2 (en) | 2022-07-12 |
EP3648149A4 (en) | 2021-03-24 |
TW201905149A (zh) | 2019-02-01 |
MY195006A (en) | 2022-12-30 |
KR20200010425A (ko) | 2020-01-30 |
US20200115603A1 (en) | 2020-04-16 |
CN110832627A (zh) | 2020-02-21 |
EP3648149A1 (en) | 2020-05-06 |
KR102282547B1 (ko) | 2021-07-29 |
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