TWI758469B - Addition-hardening polysiloxane composition, method for producing the composition, cured polysiloxane, and optical element - Google Patents
Addition-hardening polysiloxane composition, method for producing the composition, cured polysiloxane, and optical element Download PDFInfo
- Publication number
- TWI758469B TWI758469B TW107114129A TW107114129A TWI758469B TW I758469 B TWI758469 B TW I758469B TW 107114129 A TW107114129 A TW 107114129A TW 107114129 A TW107114129 A TW 107114129A TW I758469 B TWI758469 B TW I758469B
- Authority
- TW
- Taiwan
- Prior art keywords
- mass
- component
- group
- polysiloxane
- parts
- Prior art date
Links
- -1 polysiloxane Polymers 0.000 title claims abstract description 128
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 91
- 239000000203 mixture Substances 0.000 title claims abstract description 70
- 230000003287 optical effect Effects 0.000 title claims description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 125000003118 aryl group Chemical group 0.000 claims abstract description 24
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 13
- 229920006136 organohydrogenpolysiloxane Polymers 0.000 claims abstract description 13
- 239000010703 silicon Substances 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 125000000962 organic group Chemical group 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 238000006459 hydrosilylation reaction Methods 0.000 claims abstract description 6
- 239000010936 titanium Substances 0.000 claims description 24
- 125000003342 alkenyl group Chemical group 0.000 claims description 21
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 20
- 229910052684 Cerium Inorganic materials 0.000 claims description 19
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 18
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 229910004283 SiO 4 Inorganic materials 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 150000007942 carboxylates Chemical class 0.000 claims description 5
- 150000003609 titanium compounds Chemical class 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 2
- 125000002009 alkene group Chemical group 0.000 claims 1
- 238000002845 discoloration Methods 0.000 abstract description 10
- 230000008859 change Effects 0.000 abstract description 8
- 150000002894 organic compounds Chemical class 0.000 abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 21
- 239000000047 product Substances 0.000 description 18
- 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
- 229920001577 copolymer Polymers 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- 239000003566 sealing material Substances 0.000 description 11
- 239000000377 silicon dioxide Substances 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 238000002834 transmittance Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 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
- 239000000463 material Substances 0.000 description 7
- 239000002683 reaction inhibitor Substances 0.000 description 7
- 241000779819 Syncarpia glomulifera Species 0.000 description 6
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 6
- 238000013329 compounding Methods 0.000 description 6
- 239000001739 pinus spp. Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229940036248 turpentine Drugs 0.000 description 6
- SHZIWNPUGXLXDT-UHFFFAOYSA-N caproic acid ethyl ester Natural products CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 5
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 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
- 239000002253 acid Substances 0.000 description 4
- 125000005370 alkoxysilyl group Chemical group 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 125000003944 tolyl group Chemical group 0.000 description 4
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 125000004432 carbon atom Chemical group C* 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
- 239000006185 dispersion Substances 0.000 description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 150000003961 organosilicon compounds Chemical class 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005486 sulfidation Methods 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-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
- 239000002318 adhesion promoter Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 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
- 229920001971 elastomer Polymers 0.000 description 2
- 239000003623 enhancer Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000945 filler Substances 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
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920000620 organic polymer Polymers 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
- 229920000647 polyepoxide Polymers 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 238000007789 sealing Methods 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
- 238000012360 testing method Methods 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
- 239000013585 weight reducing agent Substances 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-$l^{3}-silanyl)oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)C KWEKXPWNFQBJAY-UHFFFAOYSA-N 0.000 description 1
- WZJUBBHODHNQPW-UHFFFAOYSA-N 2,4,6,8-tetramethyl-1,3,5,7,2$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
- 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
- 229910004298 SiO 2 Inorganic materials 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
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 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
- 125000000753 cycloalkyl 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
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 210000005069 ears Anatomy 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 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
- 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
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 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
- 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
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000004615 ingredient Substances 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
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 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
- 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
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 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
- BDDWSAASCFBVBK-UHFFFAOYSA-N rhodium;triphenylphosphane Chemical compound [Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 BDDWSAASCFBVBK-UHFFFAOYSA-N 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000008117 stearic acid Substances 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
- 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
- 230000004580 weight loss Effects 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
- C08L83/04—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
- C08G77/38—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
-
- 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
- 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
- C08G77/48—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/50—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
- C08G77/52—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages containing aromatic rings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
- H01L23/296—Organo-silicon compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- 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
- H01L33/52—Encapsulations
- H01L33/56—Materials, e.g. epoxy or silicone resin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本發明的課題為提供一種加成硬化型聚矽氧組成物，其係包含苯基之聚矽氧組成物，可給予於高溫時之重量變化小，尤其是變色少，且耐熱性優異之硬化物。 本發明的解決手段為一種加成硬化型聚矽氧組成物，其係包含： (A-1)式(1)表示之分枝狀有機聚矽氧烷、 (A-2)式(2)表示之直鏈狀有機聚矽氧烷、
Description
本發明係關於加成硬化型聚矽氧組成物、該組成物之製造方法、聚矽氧硬化物及以該硬化物密封之光學元件。The present invention relates to an addition-hardening polysiloxane composition, a method for producing the composition, a cured polysiloxane, and an optical element sealed with the cured material.
具有發光二極體(LED)作為光半導體元件，且已知作為光半導體裝置之LED燈，係將實裝於基板之LED以由透明之樹脂所構成之密封材料密封的構成。作為此密封LED之密封材料，自以往即泛用環氧樹脂基底之組成物。An LED lamp having a light emitting diode (LED) as an optical semiconductor element and known as an optical semiconductor device is constituted by sealing the LED mounted on a substrate with a sealing material made of a transparent resin. As the sealing material for sealing the LED, the composition of epoxy resin base has been widely used from the past.
惟，於環氧樹脂基底之密封材料，伴隨近年來半導體封裝之小型化，或LED之高亮度化的發熱量之增大或光之短波長化，而產生破裂或黃變，招致信賴性的下降。However, with the recent miniaturization of semiconductor packages, the increase in the calorific value of high-brightness LEDs, or the shortening of light wavelengths, the sealing materials on epoxy resin substrates have been cracked or yellowed, resulting in reliability problems. decline.
因此，從具有優異之耐熱性的觀點來看，使用聚矽氧樹脂組成物作為密封材料。尤其是加成反應硬化型之聚矽氧樹脂組成物，由於藉由加熱以短時間硬化，故生產性良好，適合作為LED之密封材料(專利文獻1)。此外，LED之密封材料中，雖要求高折射率與強度，但於主骨架使用苯基矽氧烷之組成物，變成可給予較以往之聚矽氧更高之折射率(專利文獻2、專利文獻3)。此外，已知如此之具有苯基的密封材料，係具有高耐硫化性，且可抑制因硫化氫導致之LED之銀基板的腐蝕，提供信賴性高之LED封裝。Therefore, from the viewpoint of having excellent heat resistance, the silicone resin composition is used as the sealing material. In particular, the polysiloxane composition of an addition reaction curing type is cured in a short time by heating, and thus has good productivity and is suitable as a sealing material for LEDs (Patent Document 1). In addition, although high refractive index and strength are required for sealing materials of LEDs, a composition using phenylsiloxane in the main skeleton can give a higher refractive index than conventional polysiloxane (Patent Document 2, Patent Reference 3). In addition, it is known that such a sealing material having a phenyl group has high sulfidation resistance, and can suppress the corrosion of the silver substrate of the LED due to hydrogen sulfide, thereby providing a highly reliable LED package.
惟，由於如此之包含苯基之組成物於高溫下黃變，光透過率低下，LED之亮度低下成為問題。由伴隨近年來之LED的高輸出化，產生密封材料之溫度上昇，對於此課題之苯基聚矽氧的耐熱變色性尚不夠充分。此外，亦發現由聚矽氧樹脂的重量減少而產生裂痕，變成不點燈，故更加尋求在高溫時之重量減少率低，透過率劣化少，亦即耐熱性高之材料。 [先前技術文獻] [專利文獻]However, since the composition containing the phenyl group turns yellow at high temperature, the light transmittance is lowered, and the luminance of the LED is lowered as a problem. With the recent increase in the output of LEDs, the temperature of the sealing material has risen, and the thermal discoloration resistance of phenyl polysiloxane, which is the subject of this problem, is not sufficient. In addition, it was also found that cracks were generated due to the weight reduction of the polysiloxane resin, which made it impossible to light the lamp. Therefore, a material with low weight reduction rate and less transmittance deterioration at high temperature was sought, that is, a material with high heat resistance. [Prior Art Literature] [Patent Literature]
[專利文獻1]日本特開2004-292714號公報 [專利文獻2]日本特開2005-105217號公報 [專利文獻3]日本特開2010-132795號公報[Patent Document 1] Japanese Patent Laid-Open No. 2004-292714 [Patent Document 2] Japanese Patent Laid-Open No. 2005-105217 [Patent Document 3] Japanese Patent Laid-Open No. 2010-132795
[發明欲解決之課題][The problem to be solved by the invention]
本發明係鑑於上述事情而完成者，以提供一種加成硬化型聚矽氧組成物作為目的，其係包含苯基之聚矽氧組成物，可給予為了改善LED之信賴性之於高溫時之重量變化小，尤其是變色少，且耐熱性優異之硬化物。 [用以解決課題之手段]The present invention has been made in view of the above-mentioned matters, and aims to provide an addition-hardening polysiloxane composition, which is a polysiloxane composition containing a phenyl group, which can provide a high temperature resistance for improving the reliability of LEDs. A cured product with little weight change, especially little discoloration, and excellent heat resistance. [means to solve the problem]
為了解決上述課題，於本發明，提供一種加成硬化型聚矽氧組成物，其係包含： (A-1)下述平均組成式(1)表示之分枝狀有機聚矽氧烷，
若為如此之加成硬化型聚矽氧組成物，可成為可給予於高溫時之重量變化小，尤其是變色少，且耐熱性優異之硬化物。Such an addition-curable polysiloxane composition can be a cured product with little weight change at high temperature, especially less discoloration, and excellent heat resistance.
又，前述式(1)中之R1 及前述式(2)中之R1’ 較佳為苯基或甲基。Moreover, R 1 in the aforementioned formula (1) and R 1 ' in the aforementioned formula (2) are preferably a phenyl group or a methyl group.
若為如此者，可適合作為(A-1)及(A-2)成分使用。If so, it can be used suitably as (A-1) and (A-2) components.
進而，本發明係提供一種加成硬化型聚矽氧組成物之製造方法，係製造上述加成硬化型聚矽氧組成物之方法，其係包含以下步驟： 使下述(a)、(b)及(c)成分以150℃以上之溫度進行反應，生成前述(C)成分之聚有機金屬矽氧烷之步驟、與混合前述(A-1)、(A-2)、(B)、(C)及(D)成分之步驟； (a)在25℃之黏度為10～10,000mPa･s，相對於一分子中所包含之有機基的全數，具有至少10莫耳%以上芳基之聚有機矽氧烷：100質量份， (b)下述一般式(3)表示之稀土類元素之羧酸鹽：相對於前述(a)成分100質量份，以鈰之質量換算成為0.05～5質量份的量，
若為如此之製造方法，由於可輕易合成具有特定之Ce含量及Ti含量的聚有機金屬矽氧烷(即上述(C)成分)，故可輕易製造本發明之加成硬化型聚矽氧組成物。According to such a production method, since polyorganometallic siloxane having a specific Ce content and Ti content can be easily synthesized (ie, the above-mentioned component (C)), the addition-hardening polysiloxane composition of the present invention can be easily produced thing.
進而，本發明係提供一種聚矽氧硬化物，其係上述加成硬化型聚矽氧組成物的硬化物。Furthermore, the present invention provides a cured polysiloxane, which is a cured product of the above-mentioned addition-curable polysiloxane composition.
若為如此之聚矽氧硬化物，成為高透明，折射率高，且在高溫時之耐熱性優異者。Such a cured polysiloxane becomes highly transparent, has a high refractive index, and is excellent in heat resistance at high temperatures.
進而，本發明係提供一種光學元件，其係以上述聚矽氧硬化物密封者。Furthermore, the present invention provides an optical element sealed with the above-mentioned cured polysiloxane.
本發明之聚矽氧硬化物為高透明，折射率高，且在高溫時之耐熱性優異。據此，以如此之聚矽氧硬化物密封之光學元件成為信賴性高者。 [發明的效果]The polysiloxane cured product of the present invention is highly transparent, has a high refractive index, and is excellent in heat resistance at high temperatures. Accordingly, the optical element sealed with such a polysiloxane cured product becomes the one with high reliability. [Effect of invention]
如以上，若為本發明之加成硬化型聚矽氧組成物，係高透明，可給予與二甲基聚矽氧烷比較折射率高，且於高溫時之重量變化小，尤其是變色少，耐熱性優異之硬化物。據此，從如此之加成硬化型聚矽氧組成物所得之硬化物可適合使用在光學元件密封材料等。As above, if it is the addition-hardening polysiloxane composition of the present invention, it is highly transparent, can give a higher refractive index than dimethyl polysiloxane, and has less weight change at high temperature, especially less discoloration , a cured product with excellent heat resistance. Accordingly, the cured product obtained from such an addition-curable polysiloxane composition can be suitably used as an optical element sealing material and the like.
如上述，已尋求加成硬化型聚矽氧組成物的開發，其係包含苯基之聚矽氧組成物，可給予於高溫時之重量變化小，尤其是變色少，且耐熱性優異之硬化物。As mentioned above, the development of an addition hardening type polysiloxane composition has been sought, which is a polysiloxane composition containing phenyl groups, which can provide hardening with little weight change at high temperature, especially less discoloration, and excellent heat resistance thing.
本發明者們針對上述課題重複努力研究的結果，發現包含後述之(A-1)、(A-2)、(B)～(D)成分的加成硬化型聚矽氧組成物，藉由包含：包含苯基之特定聚矽氧樹脂、與含有Si-O-Ce鍵結及Si-O-Ti鍵結之聚有機金屬矽氧烷，可提昇耐熱性，達成上述課題，而完成本發明。The inventors of the present invention, as a result of repeated efforts to study the above-mentioned problems, have found that the addition-curable polysiloxane composition comprising the components (A-1), (A-2), (B) to (D) described later, has the following advantages: Including: a specific polysiloxane resin containing phenyl groups, and a polyorganometallic siloxane containing Si-O-Ce bonds and Si-O-Ti bonds, which can improve heat resistance, achieve the above problems, and complete the present invention .
即，本發明為加成硬化型聚矽氧組成物，其係包含： (A-1)下述平均組成式(1)表示之分枝狀有機聚矽氧烷、
以下，雖針對本發明進行詳細說明，但本發明並非被限定於此等。Hereinafter, although this invention is demonstrated in detail, this invention is not limited to these.
[加成硬化型聚矽氧組成物] 本發明之加成硬化型聚矽氧組成物係含有下述之(A-1)、(A-2)、(B)～(D)成分而成。以下，針對各成分進行詳細說明。[Addition-hardening polysiloxane composition] The addition-hardening polysiloxane composition of the present invention contains the following components (A-1), (A-2), (B) to (D) . Hereinafter, each component will be described in detail.
＜(A-1)成分＞ 在本發明之加成硬化型聚矽氧組成物之(A-1)成分，為下述平均組成式(1)表示之分枝狀有機聚矽氧烷。
(A-1)成分係為了得到聚矽氧組成物之補強性必要之成分，為具有分枝構造者。(A-1)成分雖將由SiO4/2 單位及/或SiO3/2 單位(即SiO4/2 單位、R2 SiO3/2 單位及/或R1 SiO3/2 單位)所構成之分枝構造作為必需，但可進一步包含甲基乙烯基矽烷氧基單位、二甲基矽烷氧基單位等之SiO2/2 單位、二甲基乙烯基矽烷氧基單位、三甲基矽烷氧基單位等之SiO1/2 單位。SiO4/2 單位及/或SiO3/2 單位的含量較佳為(A-1)成分之有機聚矽氧烷樹脂中之全矽氧烷單位的5莫耳%以上，更佳為10莫耳～95莫耳%，特佳為20～60莫耳%。The component (A-1) is a component necessary for obtaining the reinforcing properties of the polysiloxane composition, and has a branched structure. Although the component (A-1) will be composed of SiO 4/2 units and/or SiO 3/2 units (ie, SiO 4/2 units, R 2 SiO 3/2 units and/or R 1 SiO 3/2 units) A branched structure is required, but may further include SiO 2/2 units such as methylvinylsiloxy units, dimethylsiloxy units, dimethylvinylsiloxy units, trimethylsiloxy units, etc. Units are equal to SiO 1/2 units. The content of SiO 4/2 unit and/or SiO 3/2 unit is preferably 5 mol % or more of the total siloxane unit in the organopolysiloxane resin of the component (A-1), more preferably 10 mol % Ears to 95 mol%, preferably 20 to 60 mol%.
(A-1)成分較佳為在23℃，為蠟狀或固體之三次元網狀的有機聚矽氧烷樹脂。所謂「蠟狀」，係意指在23℃，為10,000Pa･s以上，尤其是100,000Pa･s以上之未顯示自我流動性之橡膠狀(生橡膠狀)。The component (A-1) is preferably a waxy or solid three-dimensional network organopolysiloxane resin at 23°C. The term "waxy" means a rubber-like (raw rubber-like) that does not exhibit self-fluidity at 23°C and is 10,000 Pa·s or more, especially 100,000 Pa·s or more.
在上述平均組成式(1)，全R1 中之至少10莫耳%，較佳為20莫耳%以上為芳基。藉由芳基的存在，可賦予折射率的提昇，或在LED封裝之光取出效率的提昇、用以抑制銀基板之黑色化的耐硫化性。作為芳基，可列舉苯基、甲苯基、二甲苯基、萘基等，特佳為苯基。In the above average composition formula (1), at least 10 mol %, preferably 20 mol % or more of all R 1 are aryl groups. The presence of the aryl group can improve the refractive index, improve the light extraction efficiency in the LED package, and suppress the sulfidation resistance of the silver substrate from blackening. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and the like, and a phenyl group is particularly preferred.
在上述R1 ，作為芳基以外者，若為未包含烯基之取代或非取代的一價烴基，則並未特別限定，例如可列舉甲基、乙基、丙基、丁基、戊基、己基、庚基等之烷基；環戊基、環己基等之環烷基；氯甲基、3-氯丙基、3,3,3-三氟丙基等之鹵素化烷基等之通常碳數為1～12，較佳為1～10，更佳為1～8之非取代或鹵素取代的一價烴基。特佳為甲基。The above-mentioned R 1 is not particularly limited as long as it is a substituted or unsubstituted monovalent hydrocarbon group that does not contain an alkenyl group other than the aryl group, and examples thereof include methyl group, ethyl group, propyl group, butyl group, and pentyl group. , alkyl groups such as hexyl, heptyl, etc.; cycloalkyl groups such as cyclopentyl, cyclohexyl, etc.; halogenated alkyl groups such as chloromethyl, 3-chloropropyl, 3,3,3-trifluoropropyl, etc. The carbon number is usually 1-12, preferably 1-10, more preferably 1-8 unsubstituted or halogen-substituted monovalent hydrocarbon groups. Particularly preferred is methyl.
上述R2 為烯基，較佳為乙烯基、烯丙基、乙炔基等之碳數2～10者，更佳為碳數2～6之烯基，特佳為乙烯基。The above R 2 is an alkenyl group, preferably a vinyl group, an allyl group, an ethynyl group and the like having 2 to 10 carbon atoms, more preferably an alkenyl group having 2 to 6 carbon atoms, and particularly preferably a vinyl group.
作為(A-1)成分之具體例，例如可列舉以下之分枝狀有機聚矽氧烷。
(A-1)成分可一種單獨亦可併用二種以上。The component (A-1) may be used alone or in combination of two or more.
＜(A-2)成分＞ (A-2)成分係下述式(2)表示之直鏈狀有機聚矽氧烷。
(A-2)成分係於1分子中具有2個乙烯基，於組成物之硬化後帶來應力緩和之成分，通常主鏈係由二有機矽氧烷單位的重複所構成，分子鏈兩末端被含有乙烯基之三有機矽烷氧基封鎖之具有直鏈狀的分子構造之有機聚矽氧烷。The component (A-2) is a component that has two vinyl groups in one molecule, and is a component that brings about stress relaxation after the hardening of the composition. Usually, the main chain is composed of repeating diorganosiloxane units, and both ends of the molecular chain are composed of repeating units. Organopolysiloxane with straight-chain molecular structure blocked by a vinyl group containing three organosilyloxy groups.
在(A-2)成分，作為式(2)中之R1’ ，可列舉與在(A-1)成分作為R1 例示者相同者。In the component (A-2), as R 1' in the formula (2), the same ones as those exemplified as R 1 in the component (A-1) can be mentioned.
式(2)中，h為0～50之數，i為0～100之數，較佳為h為3～20之數，i為0～30之數。h為0時，R3 為苯基，且i為1～100之數。h及i為上述範圍外時，有以本發明之組成物的硬化物密封之光學元件的耐硫化性或光取出效率降低之虞。In formula (2), h is a number of 0-50, i is a number of 0-100, preferably h is a number of 3-20, and i is a number of 0-30. When h is 0, R 3 is a phenyl group, and i is a number from 1 to 100. When h and i are outside the above-mentioned ranges, the sulfidation resistance or light extraction efficiency of the optical element sealed with the cured product of the composition of the present invention may be reduced.
(A-2)成分在25℃之黏度較佳為10～100,000 mPa･s，更佳為10～10,000mPa･s的範圍。若黏度為此範圍內，本成分不會有超過必要作為軟段(Soft segment)作用之虞，且可得到充分之硬度。又，不會產生組成物的黏度顯著提高使作業性劣化的問題之虞。The viscosity of the component (A-2) at 25°C is preferably in the range of 10 to 100,000 mPa･s, more preferably in the range of 10 to 10,000 mPa･s. If the viscosity is within this range, this component does not act as a soft segment more than necessary, and sufficient hardness can be obtained. In addition, there is no possibility that the viscosity of the composition is significantly increased and the workability is deteriorated.
作為(A-2)成分之具體例，可列舉兩末端甲基苯基乙烯基封鎖二苯基矽氧烷、單末端甲基苯基乙烯基單末端二苯基乙烯基封鎖二苯基矽氧烷、兩末端二苯基乙烯基封鎖二苯基矽氧烷、兩末端二苯基乙烯基封鎖二苯基矽氧烷･甲基苯基矽氧烷共聚物、兩末端二甲基乙烯基封鎖二苯基矽氧烷、單末端二甲基乙烯基單末端甲基苯基乙烯基封鎖二苯基矽氧烷、兩末端二甲基乙烯基封鎖甲基苯基矽氧烷、單末端二甲基乙烯基單末端甲基苯基乙烯基封鎖甲基苯基矽氧烷等。Specific examples of the component (A-2) include both-terminal methylphenylvinyl-blocked diphenylsiloxane and single-terminal methylphenylvinyl-blocked diphenylvinyl-blocked diphenylsiloxane. Alkane, Diphenylvinyl Blockade Diphenylsiloxane, Diphenylvinyl Blockade Diphenylsiloxane･Methylphenylsiloxane Copolymer, Dimethyl Vinyl Blockade Diphenylsiloxane, single-end dimethylvinyl, single-end methylphenylvinyl-blocked diphenylsiloxane, two-end dimethylvinyl-blocked methylphenylsiloxane, single-end dimethyl Methyl vinyl mono-terminal methyl phenyl vinyl block methyl phenyl siloxane and so on.
更具體而言，作為(A-2)成分，可列舉下述之直鏈狀有機聚矽氧烷。
(A-2)成分可一種單獨亦可併用二種以上。The component (A-2) may be used alone or in combination of two or more.
(A-2)成分的摻合量相對於(A-1)成分及(A-2)成分的合計100質量份，為10～40質量份，較佳為30～40質量份。(A-2) The compounding quantity of a component is 10-40 mass parts with respect to the total of 100 mass parts of (A-1) component and (A-2) component, Preferably it is 30-40 mass parts.
＜(B)成分＞ (B)成分係於1分子中具有至少2個以上矽原子鍵結氫原子之有機氫聚矽氧烷。<Component (B)> The component (B) is an organohydrogen polysiloxane having at least two or more silicon atoms bonded to hydrogen atoms in one molecule.
(B)成分之分子構造並未特別限制，例如可使用直鏈狀、環狀、分枝鏈狀、三次元網狀構造等之以往所製造之各種有機氫聚矽氧烷。進而，(B)成分於室溫(25℃)可為液狀，亦可為蠟狀或固體。The molecular structure of the component (B) is not particularly limited, and various organohydrogenpolysiloxanes conventionally produced, such as linear, cyclic, branched, and three-dimensional network structures, can be used. Furthermore, (B) component may be a liquid at room temperature (25 degreeC), and a waxy or solid may be sufficient as it.
(B)成分從對於(A-1)及(A-2)成分之相溶性的觀點來看，較佳為具有至少1個以上芳基。作為芳基，可列舉與(A-1)成分例示者相同者。The component (B) preferably has at least one aryl group from the viewpoint of compatibility with the components (A-1) and (A-2). As the aryl group, the same ones as those exemplified in the component (A-1) can be mentioned.
(B)成分之有機氫聚矽氧烷係於1分子中具有至少2個，較佳為3～300個，特佳為3～100個矽原子鍵結氫原子(即氫矽烷基(SiH基))。(B)成分之有機氫聚矽氧烷具有直鏈狀構造時，此等之SiH基可僅位於分子鏈末端及分子鏈途中(分子鏈非末端)的任一側，亦可位於其兩側。The organohydrogen polysiloxane of the component (B) has at least 2, preferably 3 to 300, particularly preferably 3 to 100 silicon atoms bonded to hydrogen atoms (that is, a hydrogen silyl group (SiH group) in one molecule )). When the organohydrogenpolysiloxane of the component (B) has a straight-chain structure, these SiH groups may be located only on either side of the molecular chain terminal and the middle of the molecular chain (non-terminal molecular chain), or may be located on both sides thereof .
(B)成分之於1分子中之矽原子的數(聚合度)較佳為2～300個，更佳為3～200個，再更佳為4～150個。The number (degree of polymerization) of the silicon atoms in one molecule of the component (B) is preferably 2 to 300, more preferably 3 to 200, still more preferably 4 to 150.
作為(B)成分，例如可使用下述平均組成式(5)表示之有機氫聚矽氧烷。
上述平均組成式(5)中，R5 之一價烴基的碳數較佳為1～12，更佳為1～10，再更佳為1～8，作為R5 之具體例，可列舉與作為在(A-1)成分之R1 及在(A-2)成分之R1’ 例示者相同者。In the above average composition formula (5), the carbon number of the monovalent hydrocarbon group of R 5 is preferably 1 to 12, more preferably 1 to 10, and even more preferably 1 to 8. Specific examples of R 5 include the following: Those exemplified as R 1 in the (A-1) component and R 1 ' in the (A-2) component are the same.
作為(B)成分之具體例，例如可列舉1,1,3,3-四甲基二矽氧烷、1,3,5,7-四甲基環四矽氧烷、參(氫二甲基矽烷氧基)甲基矽烷、參(氫二甲基矽烷氧基)苯基矽烷、甲基氫環聚矽氧烷、甲基氫矽氧烷･二甲基矽氧烷環狀共聚物、兩末端三甲基矽烷氧基封鎖甲基氫聚矽氧烷、兩末端三甲基矽烷氧基封鎖二甲基矽氧烷･甲基氫矽氧烷共聚物、兩末端二甲基氫矽烷氧基封鎖二甲基聚矽氧烷、兩末端二甲基氫矽烷氧基封鎖甲基氫聚矽氧烷二、兩末端二甲基氫矽烷氧基封鎖二甲基矽氧烷･甲基氫矽氧烷共聚物、兩末端三甲基矽烷氧基封鎖甲基氫矽氧烷･二苯基矽氧烷共聚物、兩末端三甲基矽烷氧基封鎖甲基氫矽氧烷･二苯基矽氧烷･二甲基矽氧烷共聚物、兩末端三甲基矽烷氧基封鎖甲基氫矽氧烷･甲基苯基矽氧烷･二甲基矽氧烷共聚物、兩末端二甲基氫矽烷氧基封鎖甲基氫矽氧烷･二甲基矽氧烷･二苯基矽氧烷共聚物、兩末端二甲基氫矽烷氧基封鎖甲基氫矽氧烷･二甲基矽氧烷･甲基苯基矽氧烷共聚物、由(CH3 )2 HSiO1/2 單位與(CH3 )3 SiO1/2 單位與SiO4/2 單位所構成之共聚物、由(CH3 )2 HSiO1/2 單位與SiO4/2 單位所構成之共聚物、由(CH3 )2 HSiO1/2 單位與SiO4/2 單位與(C6 H5 )3 SiO1/2 單位所構成之共聚物等。Specific examples of the component (B) include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, Methylsiloxy)methylsilane, gins(hydrodimethylsiloxy)phenylsilane, methylhydrocyclopolysiloxane, methylhydrosiloxane･dimethylsiloxane cyclic copolymer, Both-terminal trimethylsiloxy-blocked methylhydrogen polysiloxane, both-terminal trimethylsiloxy-blocked dimethylsiloxane･methylhydrosiloxane copolymer, both-terminal dimethylhydrosiloxane Base-blocked dimethylpolysiloxane, two-terminal dimethylhydrosiloxy-blocked methylhydrogenpolysiloxane, two-terminal dimethylhydrosiloxy-blocked dimethylsiloxane・methylhydrosiloxane Oxane copolymer, both-terminal trimethylsiloxy-blocked methylhydrosiloxane･diphenylsiloxane copolymer, both-terminal trimethylsiloxy-blocked methylhydrosiloxane･diphenylsiloxane Oxane･dimethylsiloxane copolymer, both-terminal trimethylsiloxy-blocked methylhydrosiloxane･methylphenylsiloxane･dimethylsiloxane copolymer, both-terminal dimethylsiloxane Hydrosiloxy-blocked methylhydrosiloxane･dimethylsiloxane･diphenylsiloxane copolymer, both ends of dimethylhydrosiloxane blocked methylhydrosiloxane･dimethylsiloxane Alkyl-methylphenylsiloxane copolymer, copolymer composed of (CH 3 ) 2 HSiO 1/2 unit, (CH 3 ) 3 SiO 1/2 unit and SiO 4/2 unit, (CH 3 ) ) 2 HSiO 1/2 unit and SiO 4/2 unit of the copolymer composed of (CH 3 ) 2 HSiO 1/2 unit and SiO 4/2 unit and (C 6 H 5 ) 3 SiO 1/2 unit composed of copolymers, etc.
更具體而言，作為(B)成分，可列舉下述表示之有機氫聚矽氧烷。
(B)成分之有機氫聚矽氧烷可一種單獨使用，亦可併用二種以上。The organohydrogen polysiloxane of the component (B) may be used alone or in combination of two or more.
(B)成分的摻合量，為相對於(A-1)成分及(A-2)成分中之矽原子鍵結烯基1個，(B)成分中之矽原子鍵結氫原子之數成為0.1～5.0個，較佳為0.5～3.0的範圍內的量，更佳為成為0.5～2.0的範圍內的量。為此範圍外時，無法對聚矽氧硬化物賦予高強度，無法適合作為密封材料使用。The compounding amount of the component (B) is the number of hydrogen atoms bonded to the silicon atom in the component (B) relative to one silicon atom-bonded alkenyl group in the components (A-1) and (A-2) It is 0.1 to 5.0 pieces, preferably an amount within a range of 0.5 to 3.0, and more preferably an amount within a range of 0.5 to 2.0. Outside this range, high strength cannot be imparted to the cured polysiloxane, and it is not suitable for use as a sealing material.
＜(C)成分＞ (C)成分為含有Si-O-Ce鍵結及Si-O-Ti鍵結，Ce含量為50～5,000ppm，Ti含量為50～5,000ppm，在25℃之黏度為10～10,000mPa･s，相對於一分子中所包含之有機基的全數，具有至少10莫耳%以上芳基之聚有機金屬矽氧烷。<Component (C)> Component (C) contains Si-O-Ce bond and Si-O-Ti bond, Ce content is 50-5,000ppm, Ti content is 50-5,000ppm, and the viscosity at 25°C is 10 to 10,000 mPa･s, a polyorganometallosiloxane having at least 10 mol% or more of aryl groups with respect to the total number of organic groups contained in one molecule.
(C)成分係用以對所得之聚矽氧組成物賦予耐熱性之添加劑。(C)成分的摻合量相對於(A-1)成分、(A-2)成分及(B)成分的合計100質量份，為0.01～20質量份，較佳為0.1～10質量份，更佳為0.5～5質量份。(C)成分的摻合量超過上述範圍時，有所得之聚矽氧組成物著色，或降低硬化物的硬度的情況。又，(C)成分的摻合量低於上述範圍時，得不到充分之耐熱變色性。The component (C) is an additive for imparting heat resistance to the obtained polysiloxane composition. The compounding quantity of (C) component is 0.01-20 mass parts with respect to the total of 100 mass parts of (A-1) component, (A-2) component, and (B) component, Preferably it is 0.1-10 mass parts, More preferably, it is 0.5-5 mass parts. When the blending amount of the component (C) exceeds the above range, the obtained polysiloxane composition may be colored or the hardness of the cured product may be lowered. Moreover, when the compounding quantity of (C)component is less than the said range, sufficient thermal discoloration resistance cannot be obtained.
(C)成分從對於(A)成分及(B)成分之相溶性的觀點來看，係於一分子中包含10莫耳%以上之芳基。芳基的含量未滿10莫耳%時，變成無法得到高透明之組成物。作為該芳基之例，可列舉與在上述(A-1)成分所例示者相同者。(C) Component contains 10 mol% or more of aryl groups in one molecule from the viewpoint of compatibility with the (A) component and (B) component. When the content of the aryl group is less than 10 mol %, a highly transparent composition cannot be obtained. As an example of this aryl group, what was illustrated in the said (A-1) component is mentioned.
作為(C)成分，較佳為將下述(a)、(b)及(c)成分以150℃以上的溫度進行熱處理所得之反應生成物。 (a)在25℃之黏度為10～10,000mPa･s，相對於一分子中所包含之有機基的全數，具有至少10莫耳%以上芳基之聚有機矽氧烷：100質量份、 (b)下述一般式(3)表示之稀土類元素的羧酸鹽：相對於(a)成分100質量份，以鈰之質量換算成為0.05～5質量份的量、
作為(a)成分之聚有機矽氧烷，若為在25℃之黏度為10～10,000mPa･s，相對於一分子中所包含之有機基的全數，具有至少10莫耳%以上芳基者即可，可使用以往周知者。The polyorganosiloxane as the component (a) has at least 10 mol % or more of aryl groups with respect to the total number of organic groups contained in one molecule when the viscosity at 25°C is 10 to 10,000 mPa･s That is, those known in the past can be used.
作為(b)成分之稀土類元素的羧酸鹽，例示有2-乙基己酸、環烷酸、油酸、月桂酸、硬脂酸等之鈰鹽。As the carboxylate of the rare earth element as the component (b), cerium salts such as 2-ethylhexanoic acid, naphthenic acid, oleic acid, lauric acid, and stearic acid are exemplified.
作為(c)成分之鈦化合物，例示有四n-丁基鈦酸酯等之四烷氧基鈦或其水解縮合物等。As the titanium compound of the component (c), tetraalkoxytitanium such as tetran-butyl titanate or a hydrolysis condensate thereof is exemplified.
＜(D)成分＞ (D)成分之包含鉑族金屬之氫矽烷基化觸媒，若為促進(A-1)及(A-2)成分中之烯基與(B)成分中之矽原子鍵結氫原子的加成反應者，可為任何觸媒。作為其具體例，雖可列舉鉑、鈀、銠等之鉑族金屬或氯化鉑酸、醇改質氯化鉑酸、氯化鉑酸與烯烴類與乙烯基矽氧烷或乙炔化合物的配位化合物、肆(三苯基膦)鈀、氯參(三苯基膦)銠等之、鉑族金屬化合物，但特佳為鉑系化合物。<Component (D)> If the hydrosilylation catalyst of component (D) contains platinum group metals, if it promotes the alkenyl group in components (A-1) and (A-2) and the silicon in component (B) The addition reactant of atom-bonded hydrogen atoms may be any catalyst. Specific examples thereof include platinum group metals such as platinum, palladium, rhodium, chloroplatinic acid, alcohol-modified chloroplatinic acid, chloroplatinic acid, olefins, vinylsiloxane or acetylene compounds. A platinum-group metal compound, such as tetrakis (triphenylphosphine) palladium, chlorosine (triphenylphosphine) rhodium, etc., is particularly preferably a platinum-group compound.
(D)成分可一種單獨使用，亦可併用二種以上。(D) component may be used individually by 1 type, and may use 2 or more types together.
(D)成分的摻合量係作為觸媒之有效量，相對於(A-1)成分、(A-2)成分及(B)成分的合計量，換算成觸媒金屬元素，以質量基準較佳為1～500ppm的範圍，更佳為1～100ppm的範圍。若為上述範圍內，加成反應之反應速度成為適當者，可得到具有高強度之硬化物。The compounding amount of the component (D) is an effective amount as a catalyst, and is converted into a catalytic metal element with respect to the total amount of the (A-1) component, (A-2) component, and (B) component, and is based on mass The range of 1-500 ppm is preferable, and the range of 1-100 ppm is more preferable. Within the above range, the reaction rate of the addition reaction becomes appropriate, and a cured product having high strength can be obtained.
＜其他成分＞ 本發明之加成硬化型聚矽氧組成物中因應目的，可添加接著性提昇劑或反應抑制劑等之成分。<Other components> To the addition-curable polysiloxane composition of the present invention, components such as adhesion promoters and reaction inhibitors may be added according to the purpose.
作為接著性提昇劑，從對加成反應硬化型之本發明之組成物賦予自我接著性的觀點來看，係使用含有賦予接著性之官能基的矽烷、矽氧烷等之有機矽化合物、非聚矽氧系有機化合物等。As the adhesion promoter, from the viewpoint of imparting self-adhesion to the composition of the present invention of the addition reaction hardening type, organosilicon compounds, non- Polysiloxane-based organic compounds, etc.
作為賦予接著性之官能基之具體例，可列舉與矽原子鍵結之乙烯基、烯丙基等之烯基或氫原子；透過碳原子與矽原子鍵結之環氧基(例如γ-環氧丙氧基丙基、β-(3,4-環氧環己基)乙基等)、丙烯醯氧基(例如γ-丙烯醯氧基丙基等)、或甲基丙烯醯氧基(例如γ-甲基丙烯醯氧基丙基等)；烷氧基矽烷基(例如透過可含有1～2個酯構造、胺基甲酸酯構造、醚構造之伸烷基與矽原子鍵結之三甲氧基矽烷基、三乙氧基矽烷基、甲基二甲氧基矽烷基等之烷氧基矽烷基等)。Specific examples of the functional group imparting adhesiveness include alkenyl groups such as vinyl groups, allyl groups bonded to silicon atoms, and hydrogen atoms; epoxy groups (eg, γ-ring groups) bonded to silicon atoms through carbon atoms. oxypropoxypropyl, β-(3,4-epoxycyclohexyl)ethyl, etc.), acryloxy (eg, γ-acrylooxypropyl, etc.), or methacryloyloxy (eg γ-methacryloyloxypropyl group, etc.); alkoxysilyl group (for example, through the alkylene group which can contain 1-2 ester structure, urethane structure, ether structure and trimethyl bonded with silicon atom alkoxysilyl groups such as oxysilyl groups, triethoxysilyl groups, methyldimethoxysilyl groups, etc.).
作為含有賦予接著性之官能基的有機矽化合物，例示有矽烷耦合劑、具有烷氧基矽烷基與有機官能性基之矽氧烷、於具有反應性有機基之有機化合物導入烷氧基矽烷基之化合物等。Examples of the organosilicon compound containing a functional group imparting adhesiveness include silane coupling agents, siloxanes having an alkoxysilyl group and an organic functional group, and an alkoxysilyl group introduced into an organic compound having a reactive organic group. compounds, etc.
又，作為非聚矽氧系有機化合物，例如可列舉有機酸烯丙基酯、環氧基開環觸媒、有機鈦化合物、有機鋯化合物、有機鋁化合物等。Moreover, as a non-polysiloxane type organic compound, an organic acid allyl ester, an epoxy group ring-opening catalyst, an organotitanium compound, an organozirconium compound, an organoaluminum compound etc. are mentioned, for example.
作為反應抑制劑，例示有三苯基膦等之含有磷之化合物；三丁基胺或四甲基乙二胺、苯并***等之含有氮之化合物；含有硫之化合物；乙炔系化合物；氫過氧化合物；馬來酸衍生物；1-乙炔基環己醇、3,5-二甲基-1-己炔-3-醇、乙炔基甲基癸基甲醇(Carbinol)、1,3,5,7-四甲基-1,3,5,7-四乙烯基環四矽氧烷等之對於上述(D)成分之氫矽烷基化觸媒具有硬化抑制效果的周知化合物。Examples of reaction inhibitors include phosphorus-containing compounds such as triphenylphosphine; nitrogen-containing compounds such as tributylamine, tetramethylethylenediamine, and benzotriazole; sulfur-containing compounds; acetylene-based compounds; hydrogen Peroxy compounds; maleic acid derivatives; 1-ethynylcyclohexanol, 3,5-dimethyl-1-hexyn-3-ol, ethynylmethyldecylmethanol (Carbinol), 1,3, Well-known compounds such as 5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane which have a curing inhibitory effect on the hydrosilylation catalyst of the component (D) above.
藉由反應抑制劑所致之硬化抑制效果的程度，由於因反應抑制劑的化學構造而異，故反應抑制劑的摻合量，期望為依照使用之反應抑制劑之不同調整至最適當的量。較佳為相對於(A-1)成分、(A-2)成分、(B)成分、(C)成分及(D)成分的合計30質量份，為0.001～5質量份。若摻合量為0.001質量份以上，可充分得到於室溫之組成物的長期儲藏安定性。若摻合量為5質量份以下，無阻礙組成物的硬化之虞。Since the degree of the hardening inhibitory effect by the reaction inhibitor varies depending on the chemical structure of the reaction inhibitor, it is desirable to adjust the amount of the reaction inhibitor to an optimum amount according to the reaction inhibitor to be used. . It is preferable that it is 0.001-5 mass parts with respect to the total 30 mass parts of (A-1) component, (A-2) component, (B) component, (C) component, and (D) component. When the compounding amount 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 blending amount is 5 parts by mass or less, there is no possibility of inhibiting the hardening of the composition.
又，本發明之組成物中為了提昇補強性，例如可摻合微粉末二氧化矽、結晶性二氧化矽、中空填料、倍半矽氧烷等之無機質填充劑及將此等之填充劑藉由有機烷氧基矽烷化合物、有機氯矽烷化合物、有機矽氮烷化合物、低分子量矽氧烷化合物等之有機矽化合物經表面疏水化處理之填充劑等；聚矽氧橡膠粉末、聚矽氧樹脂粉末等。In addition, in order to enhance the reinforcement, the composition of the present invention can be mixed with inorganic fillers such as micro-powder silica, crystalline silica, hollow fillers, silsesquioxane, etc. Fillers with surface hydrophobized treatment of organosilicon compounds such as organoalkoxysilane compounds, organochlorosilane compounds, organosilazanine compounds, low molecular weight siloxane compounds, etc.; polysiloxane rubber powder, polysiloxane resin powder etc.
作為微粉末二氧化矽，較佳為比表面積(BET法)為50m2 /g以上者，更佳為50～400m2 /g，特佳為100～300m2 /g。若比表面積為50m2 /g以上，可對硬化物賦予充分之補強性。The fine powder silica is preferably one having a specific surface area (BET method) of 50 m 2 /g or more, more preferably 50 to 400 m 2 /g, and particularly preferably 100 to 300 m 2 /g. When the specific surface area is 50 m 2 /g or more, sufficient reinforcement can be imparted to the cured product.
作為如此之微粉末二氧化矽，可使用自以往作為聚矽氧橡膠之補強性填充劑使用之周知者，例如可列舉煙霧質二氧化矽(乾式二氧化矽)、沉澱二氧化矽(濕式二氧化矽)等。微粉末二氧化矽雖可直接使用，但為了對組成物賦予良好的流動性，較佳為使用以三甲基氯矽烷、二甲基二氯矽烷、甲基三氯矽烷等之甲基氯矽烷類、二甲基聚矽氧烷、六甲基二矽氮烷、二乙烯基四甲基二矽氮烷、二甲基四乙烯基二矽氮烷等之六有機二矽氮烷等之有機矽化合物處理者。如此之補強性二氧化矽可一種單獨使用，亦可併用二種以上。As such fine powder silica, well-known ones used as reinforcing fillers for polysiloxane rubbers can be used. For example, aerosol silica (dry silica), precipitated silica (wet silica) can be used. silica), etc. Although fine powder silica can be used directly, in order to impart good fluidity to the composition, it is preferable to use methylchlorosilane such as trimethylchlorosilane, dimethyldichlorosilane, and methyltrichlorosilane. Organic compounds such as hexamethylene disilazane, dimethylpolysiloxane, hexamethyldisilazane, divinyltetramethyldisilazane, dimethyltetravinyldisilazane, etc. Silicon compound handler. Such reinforcing silica may be used alone or in combination of two or more.
[加成硬化型聚矽氧組成物之製造方法] 又，於本發明，提供製造上述之加成硬化型聚矽氧組成物之方法。 本發明之加成硬化型聚矽氧組成物可藉由使下述(a)、(b)及(c)成分以150℃以上之溫度進行反應，生成(C)成分之聚有機金屬矽氧烷，混合上述之(A-1)、(A-2)、(B)、(C)及(D)成分製造。 (a)在25℃之黏度為10～10,000mPa･s，相對於一分子中所包含之有機基的全數，具有至少10莫耳%以上芳基之聚有機矽氧烷：100質量份、 (b)下述一般式(3)表示之稀土類元素的羧酸鹽：相對於前述(a)成分100質量份，以鈰的質量換算成為0.05～5質量份的量、
作為(C)成分之原料使用之(a)、(b)及(c)成分之例係如上述。Examples of the components (a), (b) and (c) used as the raw material of the component (C) are as described above.
若為如此之製造方法，由於可輕易合成具有特定Ce含量及Ti含量之聚有機金屬矽氧烷，故可輕易製造本發明之加成硬化型聚矽氧組成物。According to such a manufacturing method, since the polyorganosiloxane having a specific Ce content and a Ti content can be easily synthesized, the addition-hardening polysiloxane composition of the present invention can be easily manufactured.
[聚矽氧硬化物] 進而，本發明係提供一種硬化上述加成硬化型聚矽氧組成物所得之硬化物(聚矽氧硬化物)。[Cured Polysiloxane] Furthermore, the present invention provides a cured product (cured polysiloxane) obtained by curing the above-mentioned addition-curable polysiloxane composition.
本發明之聚矽氧樹脂組成物之硬化方法，作為條件，可採用周知之硬化方法、條件。作為一例，可用在100～180℃以10分鐘～5小時的條件硬化。The hardening method of the polysiloxane resin composition of the present invention can be a well-known hardening method and condition as a condition. As an example, it can be hardened at 100 to 180° C. for 10 minutes to 5 hours.
在上述聚矽氧硬化物之波長589nm的折射率較佳為1.44以上。The refractive index of the above-mentioned cured polysiloxane at a wavelength of 589 nm is preferably 1.44 or more.
硬化本發明之加成硬化型聚矽氧組成物所得之上述聚矽氧硬化物，由折射率高，且在高溫時之耐熱性優異，尤其是光透過率高，可作為半導體元件，尤其是光學用途之半導體元件的塗佈材料或密封材料、電氣･電子用之保護塗佈材料使用。The above-mentioned cured polysiloxane obtained by curing the addition-curable polysiloxane composition of the present invention has high refractive index, excellent heat resistance at high temperature, especially high light transmittance, and can be used as a semiconductor element, especially It is used as a coating material or sealing material for semiconductor elements for optical applications, and as a protective coating material for electrical and electronic applications.
[光學元件] 進而，本發明係提供一種以上述聚矽氧硬化物密封之光學元件。[Optical element] Furthermore, the present invention provides an optical element sealed with the above-mentioned cured polysiloxane.
如上述，本發明之聚矽氧硬化物係高透明，折射率高，且在高溫時之耐熱性優異。據此，以如此之聚矽氧硬化物密封之光學元件成為信賴性高者。 [實施例]As described above, the cured polysiloxane of the present invention is highly transparent, has a high refractive index, and is excellent in heat resistance at high temperatures. Accordingly, the optical element sealed with such a polysiloxane cured product becomes the one with high reliability. [Example]
以下，雖使用合成例、實施例及比較例，具體說明本發明，但本發明並非被限定於此等者。又，在以下，黏度係使用回轉黏度計測定之於25℃之值。Hereinafter, the present invention will be specifically described using synthesis examples, examples, and comparative examples, but the present invention is not limited to these. In addition, in the following, the viscosity is the value at 25 degreeC measured using the rotational viscometer.
[合成例1] 於((CH3 )3 SiO1/2 )2 ((C6 H5 )2 SiO)3.9 ((CH3 )2 SiO)8.6 表示之黏度400mPa･s的甲基苯基有機聚矽氧烷130質量份，邊攪拌邊添加預先充分混合將鈰作為主成分之2-乙基己酸鹽之松節油溶液(稀土類元素含量6質量%)13質量份(作為鈰量為0.55份)與四n-丁基鈦酸酯2.7質量份(鈦質量為上述2-乙基己酸鹽中之鈰質量的0.3倍)者，而得到黃白色之分散液。邊於此少量流通氮氣體，邊加熱使松節油流出，其次以300℃加熱1小時後，得到濃黃褐色且透明之聚有機金屬矽氧烷(C-1)的均一組成物。將所得之聚有機金屬矽氧烷以ICP-OES(高頻電感耦合電漿發光分光分析法)解析後，Ce含量為3,200ppm，Ti含量為2,700ppm。又，聚有機金屬矽氧烷(C-1)的黏度為175mPa･s。[Synthesis Example 1] A methylphenyl organic compound having a viscosity of 400 mPa･s expressed in ((CH 3 ) 3 SiO 1/2 ) 2 ((C 6 H 5 ) 2 SiO) 3.9 ((CH 3 ) 2 SiO) 8.6 130 parts by mass of polysiloxane, 13 parts by mass of a turpentine solution (rare earth element content of 6 mass %) of 2-ethylhexanoate containing cerium as the main component, and 13 parts by mass (0.55 part of cerium) were added while stirring. ) and 2.7 parts by mass of tetra-n-butyl titanate (the mass of titanium is 0.3 times the mass of cerium in the above-mentioned 2-ethylhexanoate) to obtain a yellow-white dispersion. While flowing a small amount of nitrogen gas, the turpentine was heated to flow out, and then heated at 300° C. for 1 hour to obtain a homogeneous composition of a dark brown and transparent polyorganometallic siloxane (C-1). The obtained polyorganometallic siloxane was analyzed by ICP-OES (high-frequency inductively coupled plasma optical emission spectrometry), and the Ce content was 3,200 ppm, and the Ti content was 2,700 ppm. In addition, the viscosity of the polyorganometallic siloxane (C-1) was 175 mPa·s.
[合成例2] 於((CH3 )3 SiO1/2 )2 ((C6 H5 )2 SiO)3.9 ((CH3 )2 SiO)8.6 表示之黏度400mPa･s的甲基苯基有機聚矽氧烷130質量份，邊攪拌邊添加將鈰作為主成分之2-乙基己酸鹽的松節油溶液(稀土類元素含量6質量%)13質量份(作為鈰量為0.55份)，而得到黃白色之分散液。邊於此少量流通氮氣體，邊加熱使松節油流出，其次以300℃加熱1小時後，得到濃黃褐色且透明之聚有機金屬矽氧烷(C-2)的均一組成物。將所得之聚有機金屬矽氧烷以ICP-OES(高頻電感耦合電漿發光分光分析法)解析後，Ce含量為3,300ppm。又，聚有機金屬矽氧烷(C-2)的黏度為220mPa･s。[Synthesis Example 2] Methylphenyl organic compound with a viscosity of 400 mPa･s represented by ((CH 3 ) 3 SiO 1/2 ) 2 ((C 6 H 5 ) 2 SiO) 3.9 ((CH 3 ) 2 SiO) 8.6 130 parts by mass of polysiloxane, 13 parts by mass of a turpentine solution of 2-ethylhexanoate containing cerium as the main component (content of rare earth element: 6 mass %), and 13 parts by mass (0.55 part of cerium) were added while stirring, and A yellowish-white dispersion was obtained. While flowing a small amount of nitrogen gas, the turpentine was heated to flow out, and then heated at 300° C. for 1 hour to obtain a homogeneous composition of a dark brown and transparent polyorganometallic siloxane (C-2). After analyzing the obtained polyorganometallosiloxane by ICP-OES (high-frequency inductively coupled plasma emission spectrometry), the Ce content was 3,300 ppm. In addition, the viscosity of the polyorganometallic siloxane (C-2) was 220 mPa·s.
[合成例3] 於((CH3 )3 SiO1/2 )2 ((CH3 )2 SiO)57 表示之黏度100mPa･s的甲基有機聚矽氧烷100質量份，邊攪拌邊添加預先充分混合將鈰作為主成分之2-乙基己酸鹽的松節油溶液(稀土類元素含量6質量%)10質量份(作為鈰量為0.43份)與四n-丁基鈦酸酯2.1質量份(鈦質量為上述2-乙基己酸鹽中之鈰質量的0.3倍)者，而得到黃白色之分散液。邊於此少量流通氮氣體，邊加熱使松節油流出，其次以300℃加熱1小時後，得到濃紅褐色且透明之聚有機金屬矽氧烷(C-3)的均一組成物。將所得之聚有機金屬矽氧烷以ICP-OES(高頻電感耦合電漿發光分光分析法)解析後，Ce含量為3,400 ppm，Ti含量為3,700ppm。又，聚有機金屬矽氧烷(C-3)的黏度為115mPa･s。[Synthesis Example 3] To 100 parts by mass of methylorganopolysiloxane having a viscosity of 100 mPa･s represented by ((CH 3 ) 3 SiO 1/2 ) 2 ((CH 3 ) 2 SiO) 57 , a preliminary addition was added while stirring. 10 parts by mass of a turpentine solution of 2-ethylhexanoate containing cerium as the main component (content of rare earth elements: 6 mass %) (0.43 parts by mass as cerium) and 2.1 parts by mass of tetra-n-butyl titanate were thoroughly mixed (the mass of titanium is 0.3 times the mass of cerium in the above-mentioned 2-ethylhexanoate), a yellow-white dispersion is obtained. While flowing a small amount of nitrogen gas, the turpentine was heated to flow out, and then heated at 300° C. for 1 hour to obtain a homogeneous composition of a dark reddish-brown and transparent polyorganometallic siloxane (C-3). After analyzing the obtained polyorganometallic siloxane by ICP-OES (high frequency inductively coupled plasma optical emission spectrometry), the Ce content was 3,400 ppm and the Ti content was 3,700 ppm. In addition, the viscosity of the polyorganometallosiloxane (C-3) was 115 mPa·s.
[合成例4] 將六氯化鉑酸與1,3-二乙烯基四甲基二矽氧烷的反應生成物以鉑含量成為1.0質量%的方式，以含有30莫耳%苯基之黏度700mPa･s的甲基苯基有機聚矽氧烷稀釋，來調製鉑觸媒。[Synthesis Example 4] The reaction product of platinic acid hexachloride and 1,3-divinyltetramethyldisiloxane was prepared so that the content of platinum was 1.0 mass %, and the viscosity of 30 mol % of phenyl was included. 700mPa･s of methylphenylorganopolysiloxane was diluted to prepare a platinum catalyst.
[實施例1～4、比較例1～4] 以表1所示之摻合量混合下述之各成分，調製加成硬化型聚矽氧組成物。尚，在表1之各成分的數值係表示質量份。[Si-H]/[Si-Vi]值係表示(B)成分中之與矽原子鍵結之氫原子對於(A-1)成分及(A-2)成分中之全矽原子鍵結烯基的莫耳比。[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 an addition-curable polysiloxane composition. In addition, the numerical system of each component in Table 1 represents parts by mass. The [Si-H]/[Si-Vi] value represents the hydrogen atom bonded to the silicon atom in the (B) component to the all-silicon atom-bonded olefin in the (A-1) component and (A-2) component Key Morby.
(A-1)成分：
其他成分： (E)反應抑制劑：乙炔基環己醇 (F-1)接著性提昇劑：下述式(6)表示之矽氧烷
針對實施例1～4、比較例1～4所得之加成硬化型聚矽氧組成物，進行下述之評估，將結果示於表2。The following evaluations were performed for the addition-curable polysiloxane compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 4, and Table 2 shows the results.
[外觀] 將各組成物以150℃加熱2小時使其硬化，將所得之硬化物的外觀以目視確認。[Appearance] Each composition was heated at 150°C for 2 hours to be hardened, and the appearance of the obtained hardened product was visually confirmed.
[折射率] 將各組成物以150℃加熱2小時使其硬化，使用ATAGO製數位折射儀RX-5000，測定在25℃之硬化物的波長589nm之折射率。[Refractive Index] Each composition was heated at 150°C for 2 hours to be hardened, and a digital refractometer RX-5000 manufactured by ATAGO was used to measure the refractive index of the hardened product at a wavelength of 589 nm at 25°C.
[光透過率] 將加成硬化型聚矽氧組成物以成為2mm厚的方式流入模型，以150℃×4小時的條件使其硬化。將該硬化物在波長400nm之初期的直線光透過率T0 以分光光度計U-3900(日立高科技公司製)測定。進而，將硬化物以180℃之條件曝露1000小時後，測定在波長400nm之直線光透過率T。與初期之光透過率的差(T0 -T)越小，評估為耐熱變色性越優異之材料。作為(T0 -T)之值，較佳為10點以下。[Light transmittance] The addition-hardening polysiloxane composition was poured into a mold so as to have a thickness of 2 mm, and was cured under the conditions of 150° C.×4 hours. The linear light transmittance T 0 of the cured product at the initial stage of the wavelength of 400 nm was measured with a spectrophotometer U-3900 (manufactured by Hitachi High-Technologies). Furthermore, after exposing the hardened|cured material on the condition of 180 degreeC for 1000 hours, the linear light transmittance T at wavelength 400nm was measured. The smaller the difference (T 0 -T) from the initial light transmittance, the more excellent the thermal discoloration resistance is evaluated. The value of (T 0 -T) is preferably 10 points or less.
[耐熱試驗後之重量] 使加成硬化型聚矽氧組成物以150℃、2小時的條件硬化，相對於將該硬化物之初期重量定為100時，比較曝露於180℃、1000小時的條件下以後之重量。與初期的差越小，重量減少越少，評估為耐熱性越優異之材料。[Weight after heat resistance test] The addition-hardening polysiloxane composition was cured at 150°C for 2 hours, and the initial weight of the cured product was set at 100, compared with exposure to 180°C for 1000 hours. Weight after condition. The smaller the difference from the initial stage, the smaller the weight loss, and the more excellent the heat resistance is evaluated.
如表2所示，實施例1～4之聚矽氧硬化物係透明性優異，且180℃×1000小時後之透過率劣化小，耐熱變色性優異。又，確認實施例1～2相對於比較例1，實施例3～4相對於比較例2，耐熱試驗後之重量變化小，耐熱性優異。As shown in Table 2, the cured polysiloxanes of Examples 1 to 4 are excellent in transparency, have little transmittance deterioration after 180° C.×1000 hours, and are excellent in thermal discoloration resistance. In addition, it was confirmed that Examples 1 to 2 have less weight change after the heat resistance test than Comparative Example 1 and Examples 3 to 4 are excellent in heat resistance compared to Comparative Example 2.
另一方面，於未包含(C)成分之比較例1及2，(C)成分未包含Si-O-Ti鍵結之比較例3，初期之透明性雖高，但180℃×1000小時後之透過率劣化及重量變化與實施例1～4進行比較較大，為信賴性低之材料。又，於(C)成分不具有芳基之比較例4，與包含苯基之組成物的相溶性不良，初期之透明性顯著降低，瞭解到不適合作為LED用途。On the other hand, in Comparative Examples 1 and 2 that did not contain the component (C), and Comparative Example 3 that did not contain the Si-O-Ti bond as the component (C), although the initial transparency was high, after 180°C × 1000 hours The transmittance deterioration and weight change were larger than those of Examples 1 to 4, and the materials were low in reliability. Moreover, in the comparative example 4 which does not have an aryl group in (C)component, the compatibility with the composition containing a phenyl group was unsatisfactory, and the transparency of the initial stage fell remarkably, and it turned out that it is not suitable for LED use.
由以上，顯示若為本發明之加成硬化型聚矽氧組成物，可得到於高溫時之重量變化小，耐熱變色性優異之適合於LED用途之硬化物。From the above, it has been shown that the addition-curable polysiloxane composition of the present invention can obtain a cured product suitable for LED applications, which exhibits little weight change at high temperature and is excellent in thermal discoloration resistance.
尚，本發明並非限定於上述實施形態者。上述實施形態為例示，具有與本發明之申請專利範圍所記載之技術思想實質上相同之構成，發揮同樣作用效果者，無論何者皆可包含在本發明之技術範圍內。However, the present invention is not limited to the above-mentioned embodiments. The above-described embodiments are examples, and those having substantially the same configuration as the technical idea described in the scope of the present invention, and exhibiting the same functions and effects, can be included in the technical scope of the present invention.
Claims (5)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017-088879 | 2017-04-27 | ||
| JP2017088879A JP6754317B2 (en) | 2017-04-27 | 2017-04-27 | Additive-curable silicone composition, method for producing the composition, silicone cured product, and optical element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201843239A TW201843239A (en) | 2018-12-16 |
| TWI758469B true TWI758469B (en) | 2022-03-21 |
Family
ID=64093414
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW107114129A TWI758469B (en) | 2017-04-27 | 2018-04-26 | Addition-hardening polysiloxane composition, method for producing the composition, cured polysiloxane, and optical element |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6754317B2 (en) |
| KR (1) | KR102414395B1 (en) |
| CN (1) | CN108795053B (en) |
| TW (1) | TWI758469B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7021046B2 (en) * | 2018-10-22 | 2022-02-16 | 信越化学工業株式会社 | Additive-curable silicone composition, silicone cured product, and optical element |
| 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 |
| US20230250284A1 (en) * | 2020-07-13 | 2023-08-10 | Dow Toray Co., Ltd. | Silicone gel composition, cured product thereof, and use therefor |
| WO2022019056A1 (en) * | 2020-07-22 | 2022-01-27 | 信越化学工業株式会社 | Anti-sulfurization coating material, cured product thereof, and electronic device |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200831565A (en) * | 2006-08-07 | 2008-08-01 | Gen Electric | Polysiloxane copolymers, thermoplastic composition, and articles formed therefrom |
| JP2008291148A (en) * | 2007-05-25 | 2008-12-04 | Shin Etsu Chem Co Ltd | Silicone gel composition excellent in heat resistance |
| TW201406863A (en) * | 2012-06-29 | 2014-02-16 | Dow Corning | Polyorganometallosiloxane, curable polymer composition, cured product thereof, and optical semiconductor device |
| TW201430064A (en) * | 2012-12-11 | 2014-08-01 | Dow Corning Toray Co Ltd | 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 |
| TW201510095A (en) * | 2013-09-03 | 2015-03-16 | Dow Corning | Curable silicone composition, cured product thereof, and optical semiconductor device |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 constituent for light emitting diode |
| 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 |
| 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 |
| KR101747160B1 (en) * | 2013-02-22 | 2017-06-14 | 다우 코닝 도레이 캄파니 리미티드 | 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 |
| 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 |
-
2017
- 2017-04-27 JP JP2017088879A patent/JP6754317B2/en active Active
-
2018
- 2018-04-20 CN CN201810359283.7A patent/CN108795053B/en active Active
- 2018-04-24 KR KR1020180047125A patent/KR102414395B1/en active IP Right Grant
- 2018-04-26 TW TW107114129A patent/TWI758469B/en active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200831565A (en) * | 2006-08-07 | 2008-08-01 | Gen Electric | Polysiloxane copolymers, thermoplastic composition, and articles formed therefrom |
| JP2008291148A (en) * | 2007-05-25 | 2008-12-04 | Shin Etsu Chem Co Ltd | Silicone gel composition excellent in heat resistance |
| TW201406863A (en) * | 2012-06-29 | 2014-02-16 | Dow Corning | Polyorganometallosiloxane, curable polymer composition, cured product thereof, and optical semiconductor device |
| TW201430064A (en) * | 2012-12-11 | 2014-08-01 | Dow Corning Toray Co Ltd | 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 |
| TW201510095A (en) * | 2013-09-03 | 2015-03-16 | Dow Corning | Curable silicone composition, cured product thereof, and optical semiconductor device |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201843239A (en) | 2018-12-16 |
| KR20180120594A (en) | 2018-11-06 |
| CN108795053B (en) | 2021-03-09 |
| KR102414395B1 (en) | 2022-06-30 |
| JP2018184579A (en) | 2018-11-22 |
| CN108795053A (en) | 2018-11-13 |
| JP6754317B2 (en) | 2020-09-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI758469B (en) | Addition-hardening polysiloxane composition, method for producing the composition, cured polysiloxane, and optical element | |
| KR101266635B1 (en) | Addition-Curable Silicone Composition Capable of Producing a Cured Product Having Excellent Crack-Resistance | |
| KR101265886B1 (en) | Addition-curable silicone resin composition for light emitting diode | |
| KR102065203B1 (en) | Silicone composition for sealing optical semiconductor element, and optical semiconductor device | |
| TWI798283B (en) | Addition hardening polysiloxane composition, cured product, optical element | |
| WO2014108954A1 (en) | Addition-cure-type silicone composition, sealing material for optical elements, and optical element | |
| TWI756411B (en) | Addition-hardening polysiloxane composition, method for producing the composition, and optical semiconductor device | |
| JP6313722B2 (en) | Addition-curing silicone composition and semiconductor device | |
| JP2016204423A (en) | Addition curing type silicone composition and semiconductor device | |
| JP7270574B2 (en) | Addition-curable silicone composition, cured silicone product, and optical element | |
| JP6393659B2 (en) | Addition-curing silicone composition and semiconductor device | |
| JP6998905B2 (en) | Additive-curable silicone compositions, cured products and opto-semiconductor devices | |
| JP7088880B2 (en) | Additive-curable silicone resin composition, manufacturing method of the composition, and optical semiconductor device | |
| KR20210027139A (en) | Addition-curable silicone composition and optical element | |
| TWI756574B (en) | Addition-hardening polysiloxane compositions, cured polysiloxanes, and optical components | |
| TWI837415B (en) | Addition hardening polysiloxane compositions and optical components | |
| TWI834881B (en) | Addition-hardening polysilicone resin composition, method of manufacturing the composition, and optical semiconductor device | |
| JP6307470B2 (en) | Addition-curing silicone composition and semiconductor device |