CN108795053B - Addition-curable silicone composition, method for producing same, silicone cured product, and optical element - Google Patents
Addition-curable silicone composition, method for producing same, silicone cured product, and optical element Download PDFInfo
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- CN108795053B CN108795053B CN201810359283.7A CN201810359283A CN108795053B CN 108795053 B CN108795053 B CN 108795053B CN 201810359283 A CN201810359283 A CN 201810359283A CN 108795053 B CN108795053 B CN 108795053B
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- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 86
- 239000000203 mixture Substances 0.000 title claims abstract description 66
- 230000003287 optical effect Effects 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 44
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 13
- 229920006136 organohydrogenpolysiloxane Polymers 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 125000000962 organic group Chemical group 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 238000006459 hydrosilylation reaction Methods 0.000 claims abstract description 6
- -1 hydrocarbon radicals Chemical class 0.000 claims description 76
- 239000000047 product Substances 0.000 claims description 32
- 229910020388 SiO1/2 Inorganic materials 0.000 claims description 27
- 239000010936 titanium Substances 0.000 claims description 25
- 125000003118 aryl group Chemical group 0.000 claims description 22
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 20
- 229910052684 Cerium Inorganic materials 0.000 claims description 19
- 239000004215 Carbon black (E152) Substances 0.000 claims description 16
- 229930195733 hydrocarbon Natural products 0.000 claims description 16
- 125000003342 alkenyl group Chemical group 0.000 claims description 15
- 229910020487 SiO3/2 Inorganic materials 0.000 claims description 14
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- 229910020485 SiO4/2 Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 7
- 239000007859 condensation product Substances 0.000 claims description 5
- 150000003609 titanium compounds Chemical class 0.000 claims description 5
- 150000005840 aryl radicals Chemical class 0.000 claims description 4
- 150000007942 carboxylates Chemical class 0.000 claims description 4
- 150000002910 rare earth metals Chemical class 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 2
- 238000002845 discoloration Methods 0.000 abstract description 7
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 30
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 17
- 239000000377 silicon dioxide Substances 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 239000003566 sealing material Substances 0.000 description 9
- 229920002050 silicone resin Polymers 0.000 description 9
- 238000002834 transmittance Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001723 curing Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 241000779819 Syncarpia glomulifera Species 0.000 description 7
- NYMPGSQKHIOWIO-UHFFFAOYSA-N hydroxy(diphenyl)silicon Chemical class C=1C=CC=CC=1[Si](O)C1=CC=CC=C1 NYMPGSQKHIOWIO-UHFFFAOYSA-N 0.000 description 7
- 239000001739 pinus spp. Substances 0.000 description 7
- 239000002683 reaction inhibitor Substances 0.000 description 7
- 229940036248 turpentine Drugs 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 6
- 241000894007 species Species 0.000 description 6
- 238000013006 addition curing Methods 0.000 description 5
- SHZIWNPUGXLXDT-UHFFFAOYSA-N caproic acid ethyl ester Natural products CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- 238000007259 addition reaction Methods 0.000 description 4
- 125000005370 alkoxysilyl group Chemical group 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 229920001843 polymethylhydrosiloxane Polymers 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000004073 vulcanization 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
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 125000005388 dimethylhydrogensiloxy group Chemical group 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 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
- 238000002156 mixing Methods 0.000 description 2
- 150000003961 organosilicon compounds Chemical class 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000004945 silicone rubber Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- KWEKXPWNFQBJAY-UHFFFAOYSA-N (dimethyl-$l^{3}-silanyl)oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)C KWEKXPWNFQBJAY-UHFFFAOYSA-N 0.000 description 1
- VMAWODUEPLAHOE-UHFFFAOYSA-N 2,4,6,8-tetrakis(ethenyl)-2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O[Si](C)(C=C)O1 VMAWODUEPLAHOE-UHFFFAOYSA-N 0.000 description 1
- WZJUBBHODHNQPW-UHFFFAOYSA-N 2,4,6,8-tetramethyl-1,3,5,7,2$l^{3},4$l^{3},6$l^{3},8$l^{3}-tetraoxatetrasilocane Chemical compound C[Si]1O[Si](C)O[Si](C)O[Si](C)O1 WZJUBBHODHNQPW-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 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
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 150000000703 Cerium Chemical class 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- GNHNBNVTPVOERF-UHFFFAOYSA-N N-dimethylsilyl-N-tris(ethenyl)silylethenamine Chemical compound C[SiH](C)N(C=C)[Si](C=C)(C=C)C=C GNHNBNVTPVOERF-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical class C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 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
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- BITPLIXHRASDQB-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound C=C[Si](C)(C)O[Si](C)(C)C=C BITPLIXHRASDQB-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910021485 fumed silica Inorganic materials 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
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Substances OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- NOKUWSXLHXMAOM-UHFFFAOYSA-N hydroxy(phenyl)silicon Chemical class O[Si]C1=CC=CC=C1 NOKUWSXLHXMAOM-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- LAQFLZHBVPULPL-UHFFFAOYSA-N methyl(phenyl)silicon Chemical compound C[Si]C1=CC=CC=C1 LAQFLZHBVPULPL-UHFFFAOYSA-N 0.000 description 1
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- WKWOFMSUGVVZIV-UHFFFAOYSA-N n-bis(ethenyl)silyl-n-trimethylsilylmethanamine Chemical compound C[Si](C)(C)N(C)[SiH](C=C)C=C WKWOFMSUGVVZIV-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920003216 poly(methylphenylsiloxane) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012763 reinforcing filler Substances 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
- QBERHIJABFXGRZ-UHFFFAOYSA-M rhodium;triphenylphosphane;chloride Chemical compound [Cl-].[Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QBERHIJABFXGRZ-UHFFFAOYSA-M 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- 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
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/398—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing boron or metal atoms
-
- 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
-
- 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
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- C—CHEMISTRY; METALLURGY
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Abstract
一种加成固化型硅酮组合物，其包含苯基且能得到一种耐热性优异的固化物，该固化物在高温时的重量变化小，变色情形少。本发明的加成固化型硅酮组合物包含以下成分：(A‑1)由式(1)表示的分支状有机聚硅氧烷；(A‑2)由式(2)表示的直链状有机聚硅氧烷，(B)有机氢聚硅氧烷，其在一分子中具有至少2个以上的与硅原子键结的氢原子；(C)聚有机金属硅氧烷，含有Si‑O‑Ce键和Si‑O‑Ti键，Ce含量为50～5000ppm，Ti含量为50～5000ppm，25℃时的粘度为10～10000mPa·s，相对于一分子中包含的有机基团的总数，具有至少10摩尔％以上的芳基；以及(D)包含铂族金属的氢硅烷化催化剂。An addition-curable silicone composition containing a phenyl group and capable of obtaining a cured product excellent in heat resistance, the cured product having little weight change at high temperature and less discoloration. The addition-curable silicone composition of the present invention contains the following components: (A-1) a branched organopolysiloxane represented by the formula (1); (A-2) a straight-chain organopolysiloxane represented by the formula (2) organopolysiloxane, 
(B) organohydrogenpolysiloxane, which has at least 2 or more hydrogen atoms bonded to silicon atoms in one molecule; (C) polyorganometallic siloxane, which contains Si-O-Ce bonds and Si- O-Ti bond, Ce content is 50-5000ppm, Ti content is 50-5000ppm, viscosity at 25°C is 10-10000mPa·s, with at least 10 mol% or more relative to the total number of organic groups contained in one molecule and (D) a hydrosilylation catalyst comprising a platinum group metal.
Description
Technical Field
The present invention relates to an addition-curable silicone composition, a method for producing the composition, a cured silicone material, and an optical element sealed with the cured material.
Background
An LED lamp having a Light Emitting Diode (LED) as an optical semiconductor element is known as an optical semiconductor device, and is configured as follows: the LED mounted on the substrate is sealed with a sealing material composed of a transparent resin. As a sealing material for sealing the LED, a composition having an epoxy resin base has been widely used.
However, in recent years, with the miniaturization of semiconductor packages and the increase in luminance of LEDs, cracking and yellowing have occurred due to an increase in the amount of heat generated and a decrease in the wavelength of light, which has LED to a decrease in reliability.
Therefore, from the viewpoint of having excellent heat resistance, a silicone resin composition is used as a sealing material. In particular, an addition reaction curable silicone resin composition is excellent in productivity because it can be cured in a short time by heating, and is suitable as an LED sealing material (patent document 1). Further, although high refractive index and strength are required for the encapsulant for LED, a composition using phenylsiloxane as a main skeleton can provide a higher refractive index than conventional silicone (patent documents 2 and 3). Further, it is known that such a sealing material having a phenyl group has high resistance to vulcanization, and can suppress corrosion of the silver substrate of the LED by hydrogen sulfide, and thus can provide an LED package with high reliability.
However, such a composition containing a phenyl group is yellowed at a high temperature to decrease light transmittance, and thus the luminance of the LED may decrease. In recent years, as the output of LEDs has increased, the temperature of the sealing material has increased, and therefore, the thermal discoloration resistance of phenyl silicone has not been sufficient for this problem. Further, since cracking and lighting failure are observed due to a decrease in weight of the silicone resin, a material having a low weight loss rate at high temperature and little deterioration in light transmittance, that is, high heat resistance is further required.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2004-292714;
patent document 2: japanese patent laid-open publication No. 2005-105217;
patent document 3: japanese patent laid-open No. 2010-132795.
Disclosure of Invention
The present invention has been made in view of the above circumstances, and an object thereof is to provide an addition curing silicone composition which is a silicone composition containing a phenyl group and which can provide a cured product having excellent heat resistance, which shows little weight change at high temperatures, and in particular, shows little discoloration, and which improves the reliability of an LED.
In order to solve the above problems, the present invention provides an addition curable silicone composition comprising the following components:
(A-1) a branched organopolysiloxane represented by the following average compositional formula (1),
(R1 3SiO1/2)a(R2R1 2SiO1/2)b(R2R1SiO)c(R1 2SiO)d(R2SiO3/2)e(R1SiO3/2)f(SiO4/2)g(1)，
in the formula (1), R1Each being the same or different substituted or unsubstituted monovalent hydrocarbon radicals free of alkenyl radicals, all R1At least 10 mol% of (A) are aryl radicals, R2Is alkenyl, a, b, c, d, e, f, and g are each a number satisfying a.gtoreq.0, b.gtoreq.0, c.gtoreq.0, d.gtoreq.0, e.gtoreq.0, f.gtoreq.0, and g.gtoreq.0, wherein b + c + e > 0, e + f + g > 0, and a number satisfying a + b + c + d + e + f + g ═ 1;
(A-2) a linear organopolysiloxane represented by the following formula (2), which is contained in an amount of 10 to 40 parts by mass per 100 parts by mass of the total amount of the components (A-1) and (A-2),
in the formula (2), R1’Are identical or different substituted or unsubstituted monovalent hydrocarbon radicals which are free of alkenyl radicals, R3Is methyl or phenyl, h is a number from 0 to 50, i is a number from 0 to 100, wherein, when h is 0, R is3Is a phenyl group, and i is a number of 1 to 100, and the siloxane units in the parentheses with h and the siloxane units in the parentheses with i may be arranged randomly or in a block form;
(B) an organohydrogenpolysiloxane having at least 2 or more silicon atom-bonded hydrogen atoms in one molecule, wherein the amount of the component (B) is such that the number of silicon atom-bonded hydrogen atoms in the component (B) is 0.1 to 5.0 relative to 1 silicon atom-bonded alkenyl group in the components (A-1) and (A-2);
(C) a polyorgano-polysiloxane containing Si-O-Ce bonds and Si-O-Ti bonds, wherein the Ce content is 50-5000 ppm, the Ti content is 50-5000 ppm, the viscosity at 25 ℃ is 10-10000 mPa.s, the polyorgano-siloxane has at least 10 mol% of aryl groups relative to the total number of organic groups contained in one molecule, and the component (C) is 0.01-20 parts by mass relative to 100 parts by mass of the total amount of the component (A-1), the component (A-2) and the component (B); and the number of the first and second groups,
(D) a hydrosilylation catalyst comprising a platinum group metal.
The addition-curable silicone composition can provide a cured product having excellent heat resistance, which shows little weight change at high temperatures and is particularly little discolored.
Preferably, R in the formula (1)1And R in the aforementioned formula (2)1’Is phenyl or methyl.
Such a component is preferably used as the component (A-1) or the component (A-2).
Further, the present invention provides a method for producing an addition-curable silicone composition, the method comprising the steps of:
the component (a), the component (b) and the component (C) are reacted at a temperature of 150 ℃ or higher to produce a polyorgano-siloxane of the component (C),
(a) a polyorganosiloxane having a viscosity of 10 to 10000 mPas at 25 ℃, having at least 10 mol% or more of aryl groups relative to the total number of organic groups contained in one molecule, and containing 100 parts by mass of the component (a);
(b) a carboxylate of a rare earth represented by the following general formula (3), wherein the amount of the component (b) is 0.05 to 5 parts by mass in terms of the mass of cerium with respect to 100 parts by mass of the component (a),
(R4COO)jM1 (3)，
in the formula (3), R4Is a monovalent hydrocarbon radical of the same or different species, M1Is cerium or a rare earth element containing cerium, and j is an integer of 3 to 4;
(c) one or both of a titanium compound represented by the following general formula (4) and a hydrolysis-condensation product thereof, wherein the amount of the component (c) is 0.05 to 5 parts by mass in terms of the mass of titanium per 100 parts by mass of the component (a),
(R4O)4M2 (4)，
in the formula (4), R4Is a monovalent hydrocarbon radical of the same or different species, M2Is titanium; and the number of the first and second groups,
the component (A-1), the component (A-2), the component (B), the component (C) and the component (D) are mixed.
In such a production method, the polyorganopolysiloxane having the predetermined Ce content and Ti content (i.e., the component (C)) can be easily synthesized, and thus the addition-curable silicone composition of the present invention can be easily produced.
Further, the present invention provides a silicone cured product which is a cured product of the addition curing silicone composition.
The cured silicone material has high transparency, a high refractive index, and excellent heat resistance at high temperatures.
Further, the present invention provides an optical element sealed with the silicone cured product.
The silicone cured product of the present invention is highly transparent, has a high refractive index, and has excellent heat resistance at high temperatures. Therefore, an optical element sealed with such a silicone cured product has high reliability.
As described above, the addition-curable silicone composition of the present invention can provide a cured product which is highly transparent, has a higher refractive index than dimethylpolysiloxane, shows a small weight change at high temperatures, and is particularly less likely to change color, and which has excellent heat resistance. Therefore, a cured product obtained from such an addition-curable silicone composition can be suitably used for an optical element sealing material or the like.
Detailed Description
As described above, development of an addition curing type silicone composition has been demanded which can give a cured product which is a silicone composition containing phenyl groups and which can give a cured product excellent in heat resistance and which shows little weight change at high temperatures and is less likely to be discolored in particular.
The present inventors have conducted extensive studies to solve the above problems, and as a result, have found that an addition-curable silicone composition containing components (a-1), (a-2), and (B) to (D) which contain a specific silicone resin and a polyorganopolysiloxane containing an Si-O-Ce bond and an Si-O-Ti bond, wherein the silicone resin contains a phenyl group, can improve heat resistance, and can achieve the above object, thereby completing the present invention.
That is, the present invention is an addition-curable silicone composition comprising the following components:
(A-1) a branched organopolysiloxane represented by the following average compositional formula (1),
(R1 3SiO1/2)a(R2R1 2SiO1/2)b(R2R1SiO)c(R1 2SiO)d(R2SiO3/2)e(R1SiO3/2)f(SiO4/2)g(1)，
in the formula (1), R1Each being the same or different substituted or unsubstituted monovalent hydrocarbon radicals free of alkenyl radicals, all R1At least 10 mol% of (A) are aryl radicals, R2Is alkenyl, a, b, c, d, e, f, and g are each a number satisfying a.gtoreq.0, b.gtoreq.0, c.gtoreq.0, d.gtoreq.0, e.gtoreq.0, f.gtoreq.0, and g.gtoreq.0, wherein b + c + e > 0, e + f + g > 0, and a number satisfying a + b + c + d + e + f + g ═ 1;
(A-2) a linear organopolysiloxane represented by the following formula (2), which is contained in an amount of 10 to 40 parts by mass per 100 parts by mass of the total amount of the components (A-1) and (A-2),
in the formula (2), R1’Are identical or different substituted or unsubstituted monovalent hydrocarbon radicals which are free of alkenyl radicals, R3Is methyl or phenyl, h is a number from 0 to 50, i is a number from 0 to 100, wherein, when h is 0, R is3Is a phenyl group, and i is a number of 1 to 100, and the siloxane units in the parentheses with h and the siloxane units in the parentheses with i may be arranged randomly with each other, orThe arrangement of blocks;
(B) an organohydrogenpolysiloxane having at least 2 or more silicon atom-bonded hydrogen atoms in one molecule, wherein the amount of the component (B) is such that the number of silicon atom-bonded hydrogen atoms in the component (B) is 0.1 to 5.0 relative to 1 silicon atom-bonded alkenyl group in the components (A-1) and (A-2);
(C) a polyorgano-polysiloxane containing Si-O-Ce bonds and Si-O-Ti bonds, wherein the Ce content is 50-5000 ppm, the Ti content is 50-5000 ppm, the viscosity at 25 ℃ is 10-10000 mPa.s, the polyorgano-siloxane has at least 10 mol% of aryl groups relative to the total number of organic groups contained in one molecule, and the component (C) is 0.01-20 parts by mass relative to 100 parts by mass of the total amount of the component (A-1), the component (A-2) and the component (B); and the number of the first and second groups,
(D) a hydrosilylation catalyst comprising a platinum group metal.
The present invention will be described in detail below, but the present invention is not limited to these descriptions.
[ addition-curable Silicone composition ]
The addition-curable silicone composition of the present invention comprises the following components (A-1), (A-2), (B) to (D). The components are described in detail below.
< (A-1) component
The component (a-1) in the addition-curable silicone composition of the present invention is a branched organopolysiloxane represented by the following average compositional formula (1).
(R1 3SiO1/2)a(R2R1 2SiO1/2)b(R2R1SiO)c(R1 2SiO)d(R2SiO3/2)e(R1SiO3/2)f(SiO4/2)g(1)
In the formula (1), R1Each being the same or different substituted or unsubstituted monovalent hydrocarbon radicals free of alkenyl radicals, all R1At least 10 mol% of (A) are aryl radicals, R2Is an alkenyl group. a. b, c, d, e, f and g are eachThe number of a is more than or equal to 0, b is more than or equal to 0, c is more than or equal to 0, d is more than or equal to 0, e is more than or equal to 0, f is more than or equal to 0, and g is more than or equal to 0, wherein b + c + e is more than 0, e + f + g is more than 0, and the number of a + b + c + d + e + f + g is more than 1.
The component (A-1) is a component necessary for obtaining the reinforcement of the silicone composition, and has a branched structure. (A-1) component consisting of SiO4/2Unit and/or SiO3/2Unit cell (i.e. SiO)4/2Unit, R2SiO3/2Unit, and/or R1SiO3/2Unit), but may further include the following unit: SiO such as methylvinylsiloxane unit, dimethylsiloxane unit2/2A unit; SiO such as dimethylvinylsiloxane unit, trimethylsiloxane unit, etc1/2And (4) units. SiO 24/2Unit and/or SiO3/2The content of the unit is preferably 5 mol% or more, more preferably 10 to 95 mol%, and particularly preferably 20 to 60 mol% of the total siloxane units in the organopolysiloxane resin of component (a-1).
The component (A-1) is preferably a wax-like or solid three-dimensional network organopolysiloxane at 23 ℃. "wax-like" means a gel-like material (raw rubber-like material) which has a viscosity of 10000 pas or more, particularly 100000 pas or more at 23 ℃ and does not exhibit self-fluidity.
In the above average composition formula (1), all R1At least 10 mol% of (A) are aryl groups, preferably 20 mol% or more are aryl groups. The presence of the aryl group can improve the refractive index, improve the light extraction efficiency (light extraction efficiency) in the LED package, and impart the resistance to vulcanization for suppressing blackening of the silver substrate. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group, and a phenyl group is particularly preferable.
R is as defined above1In (3), the group other than the aryl group is not particularly limited as long as it is a substituted or unsubstituted monovalent hydrocarbon group having no alkenyl group, and examples thereof include the following unsubstituted or halogen-substituted monovalent hydrocarbon groups having usually 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 8 carbon atoms: alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl and heptyl; cyclopentyl, cyclohexyl, etc. ringAn alkyl group; and halogenated alkyl groups such as chloromethyl, 3-chloropropyl, and 3,3, 3-trifluoropropyl. Methyl is particularly preferred.
R is as defined above2The alkenyl group is preferably an alkenyl group having 2 to 10 carbon atoms such as a vinyl group, allyl group, ethynyl group, etc., more preferably an alkenyl group having 2 to 6 carbon atoms, and particularly preferably a vinyl group.
Specific examples of the component (A-1) include the following branched organopolysiloxanes.
(CH2＝CH(CH3)(C6H5)SiO1/2)2((C6H5)2SiO)3.8(SiO2)4.3
((CH3)3SiO1/2)2.5(CH2＝CH(CH3)2SiO1/2)1.2((C6H5)2SiO)1.3(SiO2)5.0
The component (A-1) may be used alone or in combination of 2 or more.
< (A-2) component
The component (A-2) is a linear organopolysiloxane represented by the following formula (2).
In the formula (2), R1’Are identical or different substituted or unsubstituted monovalent hydrocarbon radicals which are free of alkenyl radicals, R3Is methyl or phenyl, h is a number from 0 to 50, and i is a number from 0 to 100. Wherein, when h is 0, R3Is a phenyl group, and i is a number of 1 to 100. The siloxane units in the parentheses attached with h and the siloxane units in the parentheses attached with i may be arranged randomly with each other or may be arranged in a block form.
The component (a-2) is a component having 2 vinyl groups in one molecule and serving to provide stress relaxation after the composition is cured, and is usually an organopolysiloxane having the following linear molecular structure: the main chain is composed of repeating diorganosiloxane units, and both ends of the molecular chain are blocked with vinyl-containing triorganosiloxy groups.
In the component (A-2), R in the formula (2) is1’Examples of the component (A-1) include R1The same groups as in (1).
In the formula (2), h is a number of 0 to 50, i is a number of 0 to 100, preferably, h is a number of 3 to 20, and i is a number of 0 to 30. When h is 0, R3Is a phenyl group, and i is a number of 1 to 100. If h and i are outside the above ranges, the optical element sealed with a cured product of the composition of the present invention may have reduced vulcanization resistance and light extraction efficiency.
The viscosity of the component (A-2) at 25 ℃ is preferably within a range of 10 to 100000 mPas, more preferably within a range of 10 to 10000 mPas. If the viscosity is within this range, there is no fear that the present component excessively acts as a soft segment (soft segment), and a sufficient hardness can be obtained. Further, there is no fear that the following problems occur: the viscosity of the composition became high and the workability was poor.
Specific examples of the component (A-2) include diphenylsiloxane having both terminals blocked with methylphenylvinyl groups, diphenylsiloxane having one terminal blocked with methylphenylvinyl groups and one terminal blocked with diphenylvinyl groups, diphenylsiloxane having both terminals blocked with diphenylvinyl groups, diphenylsiloxane/methylphenylsiloxane co-polymer having both terminals blocked with diphenylvinyl groups, diphenylsiloxane having both terminals blocked with dimethylvinyl groups, diphenylsiloxane having one terminal blocked with dimethylvinyl groups and one terminal blocked with methylphenylvinyl groups, methylphenylsiloxane having both terminals blocked with dimethylvinyl groups, methylphenylsiloxane having one terminal blocked with dimethylvinyl groups and one terminal blocked with methylphenylvinyl groups, and the like.
More specifically, the component (A-2) includes the following linear organopolysiloxane.
(CH2＝CH(CH3)(C6H5)SiO1/2)2((C6H5)2SiO)3
(CH2＝CH(CH3)2SiO1/2)2((C6H5)2SiO)15((CH3)2SiO)65
The component (A-2) may be used alone or in combination of 2 or more.
The amount of the component (A-2) to be blended is 10 to 40 parts by mass, preferably 30 to 40 parts by mass, based on 100 parts by mass of the total amount of the components (A-1) and (A-2).
< ingredient (B) >
(B) The component (A) is an organohydrogenpolysiloxane having at least 2 or more hydrogen atoms bonded to silicon atoms in one molecule.
(B) The molecular structure of the component (a) is not particularly limited, and various organohydrogenpolysiloxanes conventionally produced, such as linear, cyclic, branched, and three-dimensional network structures, can be used. Further, the component (B) may be in the form of a liquid, wax or solid at room temperature (25 ℃ C.).
From the viewpoint of compatibility with the (A-1) and (A-2) components, the component (B) preferably has at least 1 or more aryl groups. Examples of the aryl group include the same aryl groups as exemplified for the (A-1) component.
(B) The organohydrogenpolysiloxane of component (a) has at least 2, preferably 3 to 300, and particularly preferably 3 to 100 hydrogen atoms (i.e., hydrosilyl (SiH) groups) bonded to silicon atoms in one molecule. When the organohydrogenpolysiloxane of component (B) has a linear structure, these SiH groups may be located at either or both of the molecular chain ends and the molecular chain (non-ends of the molecular chain).
(B) The number of silicon atoms (polymerization degree) in one molecule of the component (A) is preferably 2 to 300, more preferably 3 to 200, and still more preferably 4 to 150.
As the component (B), for example, an organohydrogenpolysiloxane represented by the following average composition formula (5) can be used.
R5 lHkSiO(4-l-k)/2 (5)
In the formula (5), R5Are identical or different and are substituted or unsubstitutedA monovalent hydrocarbon group bonded to a silicon atom in an unsubstituted state, and l and k are positive numbers satisfying 0.7. ltoreq. l.ltoreq.2.1, 0.001. ltoreq. k.ltoreq.1.0, and 0.8. ltoreq. l + k.ltoreq.3.0.
In the above average composition formula (5), R5The monovalent hydrocarbon group (A) preferably has 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms, and further preferably 1 to 8 carbon atoms as R5Specific examples of (A) include R in the component (A-1)1And R in the component (A-2)1’The same groups.
Specific examples of the component (B) include 1,1,3, 3-tetramethyldisiloxane, 1,3,5, 7-tetramethylcyclotetrasiloxane, tris (hydrogendimethylsiloxy) methylsilane, tris (hydrogendimethylsiloxy) phenylsilane, methylhydrocyclopolysiloxane, methylhydrosiloxane/dimethylsiloxane cyclic copolymer, methylhydrogenpolysiloxane blocked at both ends by trimethylsiloxy groups, dimethylsiloxane/methylhydrosiloxane copolymer blocked at both ends by trimethylsiloxy groups, dimethylpolysiloxane blocked at both ends by dimethylhydrogensiloxane, methylhydrogenpolysiloxane blocked at both ends by dimethylhydrogensiloxane, dimethylsiloxane/methylhydrosiloxane copolymer blocked at both ends by dimethylhydrogensiloxane groups, methylhydrosiloxane/diphenylsiloxane copolymer blocked at both ends by trimethylsiloxy groups, and mixtures thereof, Methylhydrogensiloxane/diphenylsiloxane/dimethylsiloxane copolymer with both terminals blocked by trimethylsiloxy groups, methylhydrogensiloxane/methylphenylsiloxane/dimethylsiloxane copolymer with both terminals blocked by trimethylsiloxy groups, methylhydrogensiloxane/dimethylsiloxane/diphenylsiloxane copolymer with both terminals blocked by dimethylhydrogensiloxy groups, methylhydrogensiloxane/dimethylsiloxane/methylphenylsiloxane copolymer with both terminals blocked by dimethylhydrogensiloxy groups, and a Copolymer of (CH) with (C) and (C) as monomers3)2HSiO1/2Unit, (CH)3)3SiO1/2Unit and SiO4/2Copolymer of units of (CH)3)2HSiO1/2Units and SiO4/2Copolymer of units of (CH)3)2HSiO1/2Unit, SiO4/2Unit and (C)6H5)3SiO1/2Copolymers composed of units, and the like.
More specifically, examples of the component (B) include organohydrogenpolysiloxanes represented by the following.
(H(CH3)(C6H5)SiO1/2)3((C6H5)SiO3/2)1
((CH3)3SiO1/2)2((C6H5)2SiO)2(H(CH3)SiO)6
(B) The organohydrogenpolysiloxane of component (a) may be used alone or in combination of 2 or more.
(B) The amount of the component (B) is an amount in which the number of hydrogen atoms bonded to silicon atoms in the component (B) is 0.1 to 5.0, preferably 0.5 to 3.0, and more preferably 0.5 to 2.0, relative to 1 alkenyl group bonded to silicon atoms in the component (A-1) and the component (A-2). If the amount is outside this range, high strength cannot be imparted to the cured silicone, and the silicone composition cannot be suitably used as a sealing material.
< ingredient (C) >
(C) The component (A) is a polyorgano-polysiloxane containing Si-O-Ce bond and Si-O-Ti bond, wherein the Ce content is 50-5000 ppm, the Ti content is 50-5000 ppm, the viscosity at 25 ℃ is 10-10000 mPa.s, and the total number of organic groups contained in one molecule is at least 10 mol% of aryl groups.
(C) The component (b) is an additive for imparting heat resistance to the obtained silicone composition. The amount of component (C) is 0.01 to 20 parts by mass, preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the total amount of component (A-1), component (A-2), and component (B). If the blending amount of the component (C) exceeds the above range, the obtained silicone composition may be colored or the hardness of the cured product may be lowered. If the amount of component (C) is less than the above range, sufficient thermal discoloration resistance cannot be obtained.
From the viewpoint of compatibility between the component (a) and the component (B), the component (C) contains 10 mol% or more of aryl groups in one molecule. When the content of the aryl group is less than 10 moles, it becomes impossible to obtain a highly transparent composition. Examples of the aryl group include the same aryl groups as those exemplified for the component (A-1).
The component (C) is preferably a reaction product obtained by heat-treating the following components (a), (b) and (C) at a temperature of 150 ℃ or higher.
(a) A polyorganosiloxane having a viscosity of 10 to 10000 mPas at 25 ℃, having at least 10 mol% or more of aryl groups relative to the total number of organic groups contained in one molecule, and containing 100 parts by mass of the component (a);
(b) a carboxylate of a rare earth represented by the following general formula (3), wherein the amount of the component (b) is 0.05 to 5 parts by mass in terms of the mass of cerium with respect to 100 parts by mass of the component (a),
(R4COO)jM1 (3)，
in the formula (3), R4Is a monovalent hydrocarbon radical of the same or different species, M1Is cerium or a rare earth element containing cerium, and j is an integer of 3 to 4;
(c) one or both of a titanium compound represented by the following general formula (4) and a hydrolysis-condensation product thereof, wherein the amount of the component (c) is 0.05 to 5 parts by mass in terms of the mass of titanium per 100 parts by mass of the component (a),
(R4O)4M2 (4)，
in the formula (4), R4Is a monovalent hydrocarbon radical of the same or different species, M2Is titanium.
The polyorganosiloxane as the component (a) may have a viscosity of 10 to 10000 mPas at 25 ℃ and at least 10 mol% or more of aryl groups based on the total number of organic groups contained in one molecule, and conventionally known polyorganosiloxanes can be used.
Examples of the rare earth carboxylate as the component (b) include cerium salts such as 2-ethylhexanoic acid, naphthenic acid (naphthecic acid), oleic acid, lauric acid, and stearic acid.
Examples of the titanium compound as the component (c) include titanium tetraalkoxide such as tetra-n-butyl titanate and a hydrolysis-condensation product thereof.
< ingredient (D) >
(D) The hydrosilylation catalyst containing a platinum group metal of component (a) may be any catalyst as long as it can promote the addition reaction between the alkenyl groups of components (a-1) and (a-2) and the hydrogen atoms bonded to silicon atoms of component (B). Specific examples thereof include the following platinum group metal compounds: platinum group metals such as platinum, palladium, and rhodium; or chloroplatinic acid, alcohol-modified chloroplatinic acid; a complex compound of chloroplatinic acid with an olefin, vinylsiloxane or acetylene compound; tetrakis (triphenylphosphine) palladium, tris (triphenylphosphine) rhodium chloride, and the like; but platinum group compounds are particularly preferred.
(D) The component (A) may be used alone or in combination of 2 or more.
(D) The amount of the component (B) is an effective amount of the catalyst, and is preferably in the range of 1 to 500ppm, more preferably 1 to 100ppm, in terms of catalyst metal element, based on the total amount of the component (A-1), the component (A-2) and the component (B), and based on the mass. When the amount is within the above range, the reaction rate of the addition reaction is appropriate, and a cured product having high strength can be obtained.
< other ingredients >
The addition-curable silicone composition of the present invention may contain components such as an adhesion improver and a reaction inhibitor, depending on the purpose.
The adhesion improver can be an organosilicon compound such as silane or siloxane, a non-silicone organic compound, or the like containing a functional group capable of imparting adhesion, from the viewpoint of imparting self-adhesion to the addition reaction curable composition of the present invention.
Specific examples of the functional group capable of imparting adhesiveness include an alkenyl group such as a vinyl group or an allyl group bonded to a silicon atom, and a hydrogen atom; an epoxy group (e.g., γ -glycidoxypropyl group,. beta. - (3, 4-epoxycyclohexyl) ethyl group, etc.), an acryloxy group (e.g., γ -acryloxypropyl group, etc.), or a methacryloxy group (e.g., γ -methacryloxypropyl group, etc.) bonded to a silicon atom via a carbon atom; an alkoxysilyl group (e.g., an alkoxysilyl group such as a trimethoxysilyl group, triethoxysilyl group, and methyldimethoxysilyl group, which may have 1 to 2 ester structures, urethane structures, or ether structures and is bonded to a silicon atom through an alkylene group).
Examples of the organosilicon compound containing a functional group capable of imparting adhesiveness include a silane coupling agent, a siloxane having an alkoxysilyl group and an organic functional group, and a compound obtained by introducing an alkoxysilyl group into an organic compound having a reactive organic group.
Examples of the non-silicone organic compound include allyl organo-acid, epoxy ring-opening catalysts, organotitanium compounds, organozirconium compounds, and organoaluminum compounds.
Examples of the reaction inhibitor include the following known compounds having a curing-inhibiting effect on the hydrosilylation catalyst of the component (D): phosphorus-containing compounds such as triphenylphosphine; nitrogen-containing compounds such as tributylamine, tetramethylethylenediamine and benzotriazole; a sulfur-containing compound; an acetylene-based compound; a hydrogen peroxide compound; a maleic acid derivative; 1-ethynylcyclohexanol, 3, 5-dimethyl-1-hexyn-3-ol, ethynylmethyldecylcarbinol, 1,3,5, 7-tetramethyl-1, 3,5, 7-tetravinylcyclotetrasiloxane and the like.
The degree of the curing inhibition effect by the reaction inhibitor varies depending on the chemical structure of the reaction inhibitor, and therefore the amount of the reaction inhibitor to be blended is desirably adjusted to an optimum amount in accordance with the reaction inhibitor to be used. Preferably, the amount of the component (A-1), the component (A-2), the component (B), the component (C) and the component (D) is 0.001 to 5 parts by mass in total. When the amount of the compound is 0.001 part by mass or more, the long-term storage stability of the composition at room temperature can be sufficiently obtained. If the amount of the additive is 5 parts by mass or less, there is no fear that the curing of the composition is inhibited.
In addition, for the purpose of enhancing the reinforcing property, for example, an inorganic filler such as fine powder silica, crystalline silica, hollow filler, silsesquioxane (silsequioxane) or the like; and fillers obtained by hydrophobizing the surfaces of these fillers with an organic silicon compound such as an organoalkoxysilane compound, an organochlorosilane compound, an organoazane compound, or a low-molecular-weight siloxane compound; silicone rubber powder, silicone resin powder, and the like.
The fine powder silica preferably has a specific surface area (BET method) of 50m2More preferably 50 to 400 m/g2A specific preferred range is 100 to 300m2(ii) in terms of/g. If the specific surface area is 50m2At least g, sufficient reinforcing properties can be imparted to the cured product.
As the fine powder silica, known fine powder silica conventionally used as a reinforcing filler for silicone rubber can be used, and examples thereof include fumed silica (dry silica), precipitated silica (wet silica), and the like. The fine powder silica may be used as it is, but in order to impart good fluidity to the composition, it is preferable to use fine powder silica treated with the following organic silicon compounds: methylchlorosilanes such as trimethylchlorosilane, dimethyldichlorosilane and methyltrichlorosilane; and hexaorganodisilazanes such as dimethylpolysiloxane, hexamethyldisilazane, divinyltetramethyldisilazane, and dimethyltetravinyldisilazane. The reinforcing silica may be used alone or in combination of 1 or more.
[ method for producing addition-curable Silicone composition ]
Further, the present invention provides a method for producing the addition-curable silicone composition.
The addition-curable silicone composition of the present invention can be produced by: the following component (a), component (B) and component (C) are reacted at a temperature of 150 ℃ or higher to produce a polyorgano-siloxane as component (C), and component (A-1), component (A-2), component (B), component (C) and component (D) are mixed.
(a) A polyorganosiloxane having a viscosity of 10 to 10000 mPas at 25 ℃, having at least 10 mol% or more of aryl groups relative to the total number of organic groups contained in one molecule, and containing 100 parts by mass of the component (a);
(b) a carboxylate of a rare earth represented by the following general formula (3), wherein the amount of the component (b) is 0.05 to 5 parts by mass in terms of the mass of cerium with respect to 100 parts by mass of the component (a),
(R4COO)jM1 (3)，
in the formula (3), R4Is a monovalent hydrocarbon radical of the same or different species, M1Is cerium or a rare earth element containing cerium, and j is an integer of 3 to 4;
(c) one or both of a titanium compound represented by the following general formula (4) and a hydrolysis-condensation product thereof, wherein the amount of the component (c) is 0.05 to 5 parts by mass in terms of the mass of titanium per 100 parts by mass of the component (a),
(R4O)4M2 (4)，
in the formula (4), R4Is a monovalent hydrocarbon radical of the same or different species, M2Is titanium.
Examples of the components (a), (b) and (C) used as the raw material of the component (C) are as described above.
In such a production method, since the polyorganopolysiloxane having the predetermined Ce content and Ti content can be easily synthesized, the addition-curable silicone composition of the present invention can be easily produced.
[ cured Silicone product ]
Further, the present invention provides a cured product (silicone cured product) obtained by curing the addition-curable silicone composition.
As the curing method and conditions of the silicone resin composition of the present invention, known curing methods and conditions can be used. As an example, the curing can be carried out at 100 to 180 ℃ for 10 minutes to 5 hours.
The refractive index of the cured silicone material at a wavelength of 589nm is preferably 1.44 or more.
The silicone cured product obtained by curing the addition curing silicone composition of the present invention has a high refractive index, is excellent in heat resistance at high temperatures, and has high light transmittance, and therefore can be used as a covering material and a sealing material for semiconductor devices, particularly semiconductor devices for optical use, and a protective covering material for electric and electronic devices.
[ optical element ]
Further, the present invention provides an optical element sealed with the silicone cured product.
As described above, the silicone cured product of the present invention is highly transparent, has a high refractive index, and has excellent heat resistance at high temperatures. Therefore, an optical element sealed with such a silicone cured product has high reliability.
[ examples ]
The present invention will be described in detail below using synthesis examples, examples and comparative examples, but the present invention is not limited to these examples. In the following examples, the viscosity is a value at 25 ℃ measured using a rotational viscometer.
[ Synthesis example 1]
13 parts by mass (0.55 part by mass in terms of cerium) of a turpentine (turpentine) solution of 2-ethylhexanoate containing cerium as a main component (6 mass% rare earth element content) and 2.7 parts by mass of tetra-n-butyl titanate (titanium mass 0.3 times the mass of cerium in the above 2-ethylhexanoate) were thoroughly mixed in advance, and then added to 130 parts by mass of a mixture ((CH) with stirring3)3SiO1/2)2((C6H5)2SiO)3.9((CH3)2SiO)8.6Expressed and having a viscosity of 400 mPas, to obtain a yellowish white dispersion. Heating while passing a small amount of nitrogen gas through the dispersion to allow turpentine to flow out, followed by heating at 300 ℃ for 1 hour, resulted in obtaining a dark yellowish brown transparent uniform composition of polyorgano-polysiloxane (C-1). After the obtained polyorganosiloxanes were analyzed by ICP-OES (inductively coupled plasma optical emission spectroscopy), the Ce content was 3200ppm and the Ti content was 2700 ppm. The viscosity of the polyorgano-siloxane (C-1) was 175 mPas.
[ Synthesis example 2]
13 parts by mass (0.55 part by mass in terms of cerium) of cerium as a main component was stirredA turpentine solution of 2-ethylhexanoate (rare earth element content: 6% by mass) as a component was added to 130 parts by mass of a mixture of ((CH)3)3SiO1/2)2((C6H5)2SiO)3.9((CH3)2SiO)8.6Expressed and having a viscosity of 400 mPas, to obtain a yellowish white dispersion. Heating while passing a small amount of nitrogen gas through the dispersion to allow turpentine to flow out, followed by heating at 300 ℃ for 1 hour, resulted in obtaining a dark yellowish brown transparent uniform composition of polyorgano-polysiloxane (C-2). After the obtained polyorganosiloxanes were analyzed by ICP-OES (inductively coupled plasma optical emission spectrometry), the Ce content was 3300 ppm. Furthermore, the viscosity of the polyorganopolysiloxane (C-2) was 220 mPas.
[ Synthesis example 3]
10 parts by mass (0.43 parts by mass in terms of cerium) of a turpentine solution of 2-ethylhexanoate containing cerium as a main component (the rare earth element content is 6% by mass) and 2.1 parts by mass of tetra-n-butyl titanate (titanium mass is 0.3 times the mass of cerium in the 2-ethylhexanoate) were thoroughly mixed in advance, and then added to 100 parts by mass of a mixture of ((CH)3)3SiO1/2)2((CH3)2SiO)57Expressed and having a viscosity of 100 mPas, to obtain a yellowish white dispersion. Heating while passing a small amount of nitrogen gas through the dispersion to allow turpentine to flow out, followed by heating at 300 ℃ for 1 hour, resulted in obtaining a dark reddish brown transparent uniform composition of polyorganopolysiloxane (C-3). After the obtained polyorganosiloxanes were analyzed by ICP-OES (inductively coupled plasma optical emission spectrometry), the Ce content was 3400ppm and the Ti content was 3700 ppm. The viscosity of the polyorgano-siloxane (C-3) was 115 mPas.
[ Synthesis example 4]
A platinum catalyst was prepared by diluting a reaction product of hexachloroplatinic acid and 1, 3-divinyltetramethyldisiloxane with a methylphenylorganopolysiloxane containing 30 mol% of phenyl groups and having a viscosity of 700mPa · s so that the platinum content became 1.0 mass%.
Examples 1 to 4 and comparative examples 1 to 4
The following components were mixed in the blending amounts shown in table 1 to prepare addition-curable silicone compositions. In addition, the numerical values of the respective components in table 1 represent parts by mass. [ Si-H ]/[ Si-Vi ] indicates the molar ratio of hydrogen atoms bonded to silicon atoms in component (B) to alkenyl groups bonded to silicon atoms in all of components (A-1) and (A-2).
(A-1) component:
(A-1-1) is Composed of (CH)2＝CH(CH3)(C6H5)SiO1/2)2((C6H5)2SiO)3.8(SiO2)4.3The branched phenyl silicone resin
(A-1-2) is composed of ((CH)3)3SiO1/2)2.5(CH2＝CH(CH3)2SiO1/2)1.2((C6H5)2SiO)1.3(SiO2)5.0A branched methyl phenyl silicone resin
(A-2) component:
(A-2-1) is Composed of (CH)2＝CH(CH3)(C6H5)SiO1/2)2((C6H5)2SiO)3A straight-chain phenyl silicone oil having a viscosity of 2000 mPas
(A-2-2) is Composed of (CH)2＝CH(CH3)2SiO1/2)2((C6H5)2SiO)15((CH3)2SiO)65A linear methylphenyl silicone oil having a viscosity of 700 mPas
(B) The components:
(B-1) is composed of (H (CH)3)(C6H5)SiO1/2)3((C6H5)SiO3/2)1The organohydrogenpolysiloxane of
(B-2) is composed of ((CH)3)3SiO1/2)2((C6H5)2SiO)2(H(CH3)SiO)6The organohydrogenpolysiloxane of
(C) The components:
(C-1) Polyorganometasiloxane obtained in Synthesis example 1
(C-2) Polyorganometasiloxane obtained in Synthesis example 2
(C-3) Polyorganometasiloxane obtained in Synthesis example 3
(D) The components: synthesis of platinum catalyst obtained in Synthesis example 4
Other components:
(E) reaction inhibitors: ethynyl cyclohexanol
(F-1) adhesion improving agent: siloxane represented by the following formula (6)
(F-2) adhesion improving agent: siloxane represented by the following formula (7)
The results of evaluation of the addition-curable silicone compositions obtained in examples 1 to 4 and comparative examples 1 to 4 are shown in table 2.
[ appearance ]
Each composition was cured by heating at 150 ℃ for 2 hours, and the appearance of the obtained cured product was visually confirmed.
[ refractive index ]
Each composition was cured by heating at 150 ℃ for 2 hours, and the refractive index at a wavelength of 589nm of the cured product at 25 ℃ was measured using a digital refractometer RX-5000 manufactured by ATAGO.
[ light transmittance ]
An addition curing type silicone composition was poured into a mold so as to have a thickness of 2mm, and cured under conditions of 150 ℃ for 4 hours. Using spectrophotometer U-3900(Hitachi High-Tech Scien)ce Corporation) to measure an initial linear light transmittance T of the cured product at a wavelength of 400nm0. Further, after the cured product was exposed to 180 ℃ for 1000 hours, the linear light transmittance T at a wavelength of 400nm was measured. Difference from initial transmittance (T)0The smaller the-T), the more excellent the heat discoloration resistance was evaluated. As (T)0The value of-T) is preferably 10 points or less.
[ weight after Heat resistance test ]
The addition-curable silicone composition was cured at 150 ℃ for 2 hours, and the initial weight of the cured product was set to 100, compared with the weight after exposure to 180 ℃ for 1000 hours. The smaller the difference from the initial value, the less the weight loss and the more excellent the heat resistance.
[ Table 1]
[ Table 2]
As shown in Table 2, the cured silicone materials of examples 1 to 4 have excellent transparency and excellent thermal discoloration resistance because of small deterioration in light transmittance at 180 ℃ for 1000 hours. In addition, it was confirmed that examples 1 to 2 have excellent heat resistance because the weight change after the heat resistance test is small as compared with comparative example 1; in examples 3 to 4, the weight change after the heat resistance test was small as compared with comparative example 2, and thus the heat resistance was excellent.
On the other hand, comparative examples 1 and 2 containing no component (C), and comparative example 3 containing no Si-O-Ti bond as component (C) have high initial transparency, but have less reliability because deterioration of light transmittance and change in weight are large after 180 ℃ for 1000 hours, as compared with examples 1 to 4. Further, comparative example 4 in which component (C) does not have an aryl group is poor in compatibility with a composition containing a phenyl group, and is found to be unsuitable for LED applications because initial transparency is significantly reduced.
From the above, it is understood that, if the addition curable silicone composition of the present invention is used, a cured product for LED applications can be obtained, which has a small weight change at high temperatures and excellent thermal discoloration resistance.
The present invention is not limited to the above-described embodiments. The above-described embodiments are illustrative, and any embodiments having substantially the same configuration as the technical idea described in the claims of the present invention and exhibiting the same operational effects are included in the technical scope of the present invention.
Claims (5)
1. An addition-curable silicone composition characterized by comprising the following components:
(A-1) a branched organopolysiloxane represented by the following average compositional formula (1),
(R1 3SiO1/2)a(R2R1 2SiO1/2)b(R2R1SiO)c(R1 2SiO)d(R2SiO3/2)e(R1SiO3/2)f(SiO4/2)g (1)，
in the formula (1), R1Each being the same or different substituted or unsubstituted monovalent hydrocarbon radicals free of alkenyl radicals, all R1At least 10 mol% of (A) are aryl radicals, R2Is alkenyl, a, b, c, d, e, f, and g are each a number satisfying a.gtoreq.0, b.gtoreq.0, c.gtoreq.0, d.gtoreq.0, e.gtoreq.0, f.gtoreq.0, and g.gtoreq.0, b + c + e > 0, e + f + g > 0, and a number satisfying a + b + c + d + e + f + g ═ 1;
(A-2) a linear organopolysiloxane represented by the following formula (2), which is 10 to 40 parts by mass per 100 parts by mass of the total amount of the component (A-1) and the component (A-2),
in the formula (2), R1’Are the same or differentA substituted or unsubstituted monovalent hydrocarbon radical free of alkenyl radicals, R3Is methyl or phenyl, h is a number of 0 to 50, i is a number of 0 to 100, and when h is 0, R is3Is a phenyl group, and i is a number of 1 to 100, the siloxane units in the parentheses with h and the siloxane units in the parentheses with i being arranged randomly with respect to each other, or in a block form;
(B) an organohydrogenpolysiloxane having at least 2 or more hydrogen atoms bonded to silicon atoms in one molecule, and an amount of the component (B) being an amount of 0.1 to 5.0 hydrogen atoms bonded to silicon atoms in the component (B) with respect to 1 silicon atom-bonded alkenyl group in the component (a-1) and the component (a-2);
(C) a polyorgano-polysiloxane containing Si-O-Ce bonds and Si-O-Ti bonds, wherein the Ce content is 50-5000 ppm, the Ti content is 50-5000 ppm, the viscosity at 25 ℃ is 10-10000 mPa.s, the polyorgano-siloxane contains at least 10 mol% of aryl groups relative to the total number of organic groups contained in one molecule, and the component (C) is 0.01-20 parts by mass relative to 100 parts by mass of the total amount of the component (A-1), the component (A-2) and the component (B); and the number of the first and second groups,
(D) a hydrosilylation catalyst comprising a platinum group metal.
2. The addition-curable silicone composition according to claim 1, wherein R in the formula (1)1And R in the formula (2)1’Is phenyl or methyl.
3. A method for producing an addition-curable silicone composition according to claim 1 or 2, the method comprising:
a polyorganosiloxane which is obtained by reacting the component (a), the component (b) and the component (C) at a temperature of 150 ℃ or higher,
(a) a polyorganosiloxane having a viscosity of 10 to 10000 mPas at 25 ℃, having at least 10 mol% or more of aryl groups relative to the total number of organic groups contained in one molecule, and containing 100 parts by mass of the component (a);
(b) a carboxylate of a rare earth represented by the following general formula (3), wherein the amount of the component (b) is 0.05 to 5 parts by mass in terms of the mass of cerium with respect to 100 parts by mass of the component (a),
(R4COO)jM1 (3)，
in the formula (3), R4Is a monovalent hydrocarbon radical of the same or different species, M1Is a rare earth element containing cerium, and j is an integer of 3 to 4;
(c) one or both of a titanium compound represented by the following general formula (4) and a hydrolysis-condensation product thereof, wherein the amount of the component (c) is 0.05 to 5 parts by mass in terms of the mass of titanium per 100 parts by mass of the component (a),
(R4O)4M2 (4)，
in the formula (4), R4Is a monovalent hydrocarbon radical of the same or different species, M2Is titanium; and the number of the first and second groups,
the component (A-1), the component (A-2), the component (B), the component (C) and the component (D) are mixed.
4. A silicone cured product which is a cured product of the addition curable silicone composition according to claim 1 or 2.
5. An optical element sealed with the silicone cured product according to claim 4.
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| JP2020125430A (en) * | 2019-02-06 | 2020-08-20 | 信越化学工業株式会社 | Organic modified silicone resin composition for die bonding, and cured product thereof and optical semiconductor element |
| JP2020132743A (en) * | 2019-02-18 | 2020-08-31 | 信越化学工業株式会社 | Die-bonding silicone resin composition, cured product, light-emitting diode element, and method for producing said composition |
| JP7084343B2 (en) * | 2019-03-11 | 2022-06-14 | 信越化学工業株式会社 | Additive-curable silicone composition, cured product thereof, and opto-semiconductor device |
| JP7088880B2 (en) * | 2019-05-30 | 2022-06-21 | 信越化学工業株式会社 | Additive-curable silicone resin composition, manufacturing method of the composition, and optical semiconductor device |
| KR20230037595A (en) * | 2020-07-13 | 2023-03-16 | 다우 도레이 캄파니 리미티드 | Silicone gel composition, cured product thereof and use thereof |
| JP7581352B2 (en) * | 2020-07-22 | 2024-11-12 | 信越化学工業株式会社 | Anti-sulfuration coating material, cured product thereof, and electronic device |
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| US7790292B2 (en) * | 1999-05-18 | 2010-09-07 | Sabic Innovative Plastics Ip B.V. | Polysiloxane copolymers, thermoplastic composition, and articles formed therefrom |
| JP2004292714A (en) | 2003-03-28 | 2004-10-21 | Kanegafuchi Chem Ind Co Ltd | Curable composition, cured product, its manufacturing method and light emitting diode encapsulated by cured product |
| JP4908736B2 (en) * | 2003-10-01 | 2012-04-04 | 東レ・ダウコーニング株式会社 | Curable organopolysiloxane composition and semiconductor device |
| JP2005327777A (en) * | 2004-05-12 | 2005-11-24 | Shin Etsu Chem Co Ltd | Silicone resin composition for light emitting diode |
| JP2008291148A (en) * | 2007-05-25 | 2008-12-04 | Shin Etsu Chem Co Ltd | Silicone gel composition with excellent heat resistance |
| JP4862032B2 (en) | 2008-12-05 | 2012-01-25 | 信越化学工業株式会社 | Addition-curable silicone composition that provides a cured product having a high refractive index, and an optical element sealing material comprising the composition |
| JP5524017B2 (en) * | 2010-10-08 | 2014-06-18 | 信越化学工業株式会社 | Addition-curable silicone composition and semiconductor device in which semiconductor element is coated with cured product of the composition |
| WO2014004969A1 (en) * | 2012-06-29 | 2014-01-03 | Dow Corning Corporation | Polyorganometallosiloxane, curable polymer compositions, cured product thereof, and optical semiconductor device |
| JP5524424B1 (en) * | 2012-09-27 | 2014-06-18 | モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 | Silicone composition for optical semiconductor element sealing and optical semiconductor device |
| WO2014092196A1 (en) * | 2012-12-11 | 2014-06-19 | 東レ・ダウコーニング株式会社 | High-refractive index heat-conductive composition of exceptional transparence, heat-conductive grease comprising same, cured heat-conductive material, thermal-softening heat-conductive composition, and applications for same |
| JP6297070B2 (en) * | 2013-02-22 | 2018-03-20 | 東レ・ダウコーニング株式会社 | Curable silicone composition, cured product thereof, and optical semiconductor device |
| KR20160013872A (en) * | 2013-05-29 | 2016-02-05 | 다우 코닝 도레이 캄파니 리미티드 | Semiconductor device and curable silicone composition for sealing semiconductor element |
| US9493634B2 (en) * | 2013-09-03 | 2016-11-15 | Dow Corning Corporation | Additive for a silicone encapsulant |
| JP6240593B2 (en) * | 2014-10-09 | 2017-11-29 | 信越化学工業株式会社 | Thermally conductive silicone composition and cured product thereof |
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| TWI758469B (en) | 2022-03-21 |
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| CN108795053A (en) | 2018-11-13 |
| JP2018184579A (en) | 2018-11-22 |
| KR20180120594A (en) | 2018-11-06 |
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