TWI756411B - Addition-hardening polysiloxane composition, method for producing the composition, and optical semiconductor device - Google Patents
Addition-hardening polysiloxane composition, method for producing the composition, and optical semiconductor device Download PDFInfo
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- TWI756411B TWI756411B TW107114130A TW107114130A TWI756411B TW I756411 B TWI756411 B TW I756411B TW 107114130 A TW107114130 A TW 107114130A TW 107114130 A TW107114130 A TW 107114130A TW I756411 B TWI756411 B TW I756411B
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- -1 polysiloxane Polymers 0.000 title claims abstract description 155
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 143
- 239000000203 mixture Substances 0.000 title claims abstract description 136
- 230000003287 optical effect Effects 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000004065 semiconductor Substances 0.000 title claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 31
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 150000003961 organosilicon compounds Chemical class 0.000 claims abstract description 11
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 10
- 229920006136 organohydrogenpolysiloxane Polymers 0.000 claims abstract description 7
- 125000003342 alkenyl group Chemical group 0.000 claims description 47
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 29
- 150000002430 hydrocarbons Chemical group 0.000 claims description 28
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 26
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- 229910052684 Cerium Inorganic materials 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 6
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 5
- 150000003609 titanium compounds Chemical class 0.000 claims description 5
- 229910004283 SiO 4 Inorganic materials 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims 3
- 239000004593 Epoxy Substances 0.000 claims 1
- 238000002845 discoloration Methods 0.000 abstract description 14
- 230000004580 weight loss Effects 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 11
- 230000006866 deterioration Effects 0.000 abstract description 6
- 150000002894 organic compounds Chemical class 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 41
- 239000000047 product Substances 0.000 description 34
- 239000004205 dimethyl polysiloxane Substances 0.000 description 23
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 23
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 23
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 23
- 229920005989 resin Polymers 0.000 description 17
- 239000011347 resin Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 15
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 15
- 238000002834 transmittance Methods 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 10
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 229910052697 platinum Inorganic materials 0.000 description 8
- 239000003566 sealing material Substances 0.000 description 8
- 239000004480 active ingredient Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000013329 compounding Methods 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 4
- 229920005591 polysilicon Polymers 0.000 description 4
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 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 3
- 238000006459 hydrosilylation reaction Methods 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- FCCRGBVYSYHQRQ-UHFFFAOYSA-N [ethenyl(dimethyl)silyl]oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)(C)C=C FCCRGBVYSYHQRQ-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910002026 crystalline silica Inorganic materials 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 229910021485 fumed silica Inorganic materials 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 150000000703 Cerium Chemical class 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000001293 FEMA 3089 Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 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
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 241000779819 Syncarpia glomulifera Species 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 238000013006 addition curing Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- SHZIWNPUGXLXDT-UHFFFAOYSA-N caproic acid ethyl ester Natural products CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000007542 hardness measurement 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
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001624 naphthyl group Chemical group 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
- 239000003921 oil Substances 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
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000001739 pinus spp. Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002683 reaction inhibitor Substances 0.000 description 1
- 239000012779 reinforcing material 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
- 239000011833 salt mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- 229940036248 turpentine Drugs 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000011995 wilkinson's catalyst Substances 0.000 description 1
- UTODFRQBVUVYOB-UHFFFAOYSA-P wilkinson's catalyst Chemical compound [Cl-].C1=CC=CC=C1P(C=1C=CC=CC=1)(C=1C=CC=CC=1)[Rh+](P(C=1C=CC=CC=1)(C=1C=CC=CC=1)C=1C=CC=CC=1)P(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 UTODFRQBVUVYOB-UHFFFAOYSA-P 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
- C08G77/06—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
- C08G77/14—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
- C08G77/48—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
- 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
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- 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)
- Power Engineering (AREA)
- Computer Hardware Design (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Led Device Packages (AREA)
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Abstract
本發明之課題為，提供一種加成硬化型聚矽氧組成物，其係可賦予透明性及耐熱變色性優異，且高溫條件下之硬度變化，尤其是因軟化導致之劣化及重量減少小的硬化物。 本發明之解決手段為，一種加成硬化型聚矽氧組成物，其係含有：(a)以下述式(1)所表示，且25℃時之黏度為50～100,00mPa∙s的有機聚矽氧烷；
Description
本發明係關於適合於發光二極體(LED)元件等之合乎光學用途之密封材料等的加成硬化型聚矽氧組成物、該組成物之製造方法及使用該組成物作為密封材料之光學半導體裝置。The present invention relates to an addition-hardening polysiloxane composition suitable for a sealing material suitable for optical applications such as light emitting diode (LED) elements, a method for producing the composition, and an optical composition using the composition as a sealing material semiconductor device.
作為LED元件之密封材料一般是使用環氧樹脂，但，提案有使用聚矽氧樹脂作為取代環氧樹脂之密封材料(專利文獻1～3)。聚矽氧樹脂，由於耐熱性、耐候性、耐變色性比環氧樹脂更優異，因此尤其是主要使用於藍色LED、白色LED。Epoxy resin is generally used as a sealing material for LED elements, but it has been proposed to use polysiloxane resin as a sealing material instead of epoxy resin (Patent Documents 1 to 3). Polysiloxane resins are mainly used in blue LEDs and white LEDs because they are more excellent in heat resistance, weather resistance, and discoloration resistance than epoxy resins.
然而，近年來，伴隨著對LED之通電量的增加，LED元件周邊的溫度會上昇，即使是在使用聚矽氧樹脂的情況密封材料也會劣化，而引發裂縫發生，或是因變色而光透過率降低的問題。基於如此之背景，近年來，對LED元件之密封材料要求高溫環境下之長期可靠性(亦即，耐熱性)。However, in recent years, along with the increase in the amount of electricity supplied to the LED, the temperature around the LED element has risen, and even when polysiloxane is used, the sealing material has deteriorated, causing cracks to occur, or discoloration. The problem of reduced transmittance. Based on such a background, in recent years, long-term reliability (ie, heat resistance) in a high temperature environment has been required for sealing materials of LED elements.
作為對耐熱性已作改善的一般的聚矽氧材料，目前，報告有於成為基底的有機聚矽氧烷中，作為添加劑而摻合有將有機聚矽氧烷、鈰之羧酸鹽、及鈦化合物或氧化鋯化合物以150℃以上的溫度進行熱處理所得之反應生成物的耐熱性有機聚矽氧烷組成物(專利文獻4)，或摻合有相同之添加劑的聚矽氧凝膠組成物(專利文獻5)。然而，該等專利文獻所記載的並不是可賦予具有橡膠硬度之硬化物的加成硬化型之聚矽氧組成物，因而並非可使用於如上述般之LED元件的密封材料等之用途中者。As a general polysiloxane material with improved heat resistance, it has been reported that organopolysiloxane, a cerium carboxylate, and A heat-resistant organopolysiloxane composition of a reaction product obtained by heat-treating a titanium compound or a zirconia compound at a temperature of 150°C or higher (Patent Document 4), or a polysiloxane gel composition incorporating the same additives (Patent Document 5). However, what is described in these patent documents is not an addition-hardening type polysiloxane composition that can impart a hardened product with rubber hardness, and therefore is not applicable to the above-mentioned applications such as sealing materials for LED elements. .
另一方面，於專利文獻6中，報告有含有2-乙基己酸之稀土類鹽混合物的耐熱性聚矽氧橡膠組成物，且報告有厚度2mm之薄片狀硬化物之波長600nm中之全光線透過率為90%以上。然而，於此耐熱性聚矽氧橡膠組成物中，存在有波長400nm附近之短波長光之光透過性差的問題。 [先前技術文獻] [專利文獻]On the other hand, in Patent Document 6, a heat-resistant polysiloxane rubber composition containing a rare-earth salt mixture of 2-ethylhexanoic acid is reported, and all of the wavelengths of 600 nm of the cured flakes with a thickness of 2 mm are reported. The light transmittance is more than 90%. However, in this heat-resistant silicone rubber composition, there is a problem that the light transmittance of short-wavelength light with a wavelength of around 400 nm is poor. [Prior Art Literature] [Patent Literature]
[專利文獻1] 日本特開平11-001619號公報 [專利文獻2] 日本特開2002-265787號公報 [專利文獻3] 日本特開2004-186168號公報 [專利文獻4] 日本特開昭60-163966號公報 [專利文獻5] 日本特開2008-291148號公報 [專利文獻6] 國際公開第WO2013/084699號[Patent Document 1] Japanese Patent Laid-Open No. 11-001619 [Patent Document 2] Japanese Patent Laid-Open No. 2002-265787 [Patent Document 3] Japanese Patent Laid-Open No. 2004-186168 [Patent Document 4] Japanese Patent Laid-Open No. 60- Publication No. 163966 [Patent Document 5] Japanese Patent Application Laid-Open No. 2008-291148 [Patent Document 6] International Publication No. WO2013/084699
[發明所欲解決之課題][The problem to be solved by the invention]
本發明係為了解決上述問題而完成者，其目的為，提供一種加成硬化型聚矽氧組成物，其係可賦予透明性及耐熱變色性優異，且高溫條件下之硬度變化，尤其是因軟化導致之劣化及重量減少小的硬化物。 [用以解決課題之手段]The present invention has been accomplished in order to solve the above-mentioned problems, and its object is to provide an addition-hardening polysiloxane composition, which can impart excellent transparency and thermal discoloration resistance, and has a hardness change under high temperature conditions, especially due to Hardened product with little deterioration and weight loss due to softening. [means to solve the problem]
為了解決上述課題，於本發明中， 提供一種加成硬化型聚矽氧組成物，其係含有： (a)以下述組成式(1)所表示，且25℃時之黏度為50～100,000mPa∙s的有機聚矽氧烷，
依據如此之加成硬化型聚矽氧組成物，可賦予透明性及耐熱變色性優異，且高溫條件下之硬度變化，尤其是因軟化導致之劣化及重量減少小的硬化物。According to such an addition-curable polysiloxane composition, excellent transparency and thermal discoloration resistance can be imparted to a cured product with little change in hardness under high temperature conditions, especially deterioration and weight loss due to softening.
又，較佳係於前述式(3)中，x＝0，且R4 的40%以上未達60%為氫原子。Moreover, it is preferable that in said formula (3), x=0, and 40% or more of R< 4 > but less than 60% are hydrogen atoms.
只要為如此者，則可適合使用作為(c)成分。As long as it is so, it can be used suitably as (c) component.
又，較佳係前述(e)成分為以下述組成式(4)所表示之含環氧基之有機矽化合物。
只要為如此者，則可適合使用作為(e)成分。As long as it is such, it can be used suitably as (e) component.
又，較佳係前述式(1)中之R為甲基，且前述(c)成分為包含苯基者。Moreover, it is preferable that R in said formula (1) is a methyl group, and the said (c) component contains a phenyl group.
只要為如此者，則可充分得到本發明之效果。As long as this is the case, the effects of the present invention can be sufficiently obtained.
上述加成硬化型聚矽氧組成物，較佳係進一步含有：(f)含有Si-O-Ce鍵及Si-O-Ti鍵，Ce含量為50～5,000ppm，Ti含量為50～5,000ppm，且25℃時之黏度為10～10,000mPa∙s的聚有機金屬矽氧烷：相對於前述(a)～(e)成分之合計100質量份而言，為0.01～2質量份之量者。The above-mentioned addition-hardening polysiloxane composition preferably further contains: (f) Si-O-Ce bond and Si-O-Ti bond, the Ce content is 50-5,000 ppm, and the Ti content is 50-5,000 ppm , and a polyorganometallic siloxane having a viscosity of 10 to 10,000 mPa∙s at 25°C: 0.01 to 2 parts by mass relative to 100 parts by mass of the total of components (a) to (e) above .
只要為如此者，則可更提昇加成硬化型聚矽氧組成物之耐熱性。As long as this is the case, the heat resistance of the addition-hardening polysiloxane composition can be further improved.
又，本發明係提供一種加成硬化型聚矽氧組成物之製造方法，其係上述加成硬化型聚矽氧組成物之製造方法，其包含： 將由下列(i)～(iii)所構成之混合物以150℃以上之溫度進行熱處理，而得到前述(f)成分之聚有機金屬矽氧烷的步驟，以及 將前述(a)～(f)成分混合的步驟， (i)25℃時之黏度為10～10,000mPa∙s的有機聚矽氧烷：100質量份； (ii)包含以下述一般式(f-1)所表示之鈰羧酸鹽的稀土類羧酸鹽：相對於前述(i)成分100質量份而言，以鈰換算計，為0.05～5質量份之量，
只要是如此之製造方法，則由於可容易地合成具有特定之Ce含量及Ti含量的聚有機金屬矽氧烷(亦即，上述(f)成分)，因此可容易地製造含有此等之加成硬化型聚矽氧組成物。With such a production method, since polyorganometallic siloxane (that is, the above-mentioned (f) component) having a specific Ce content and Ti content can be easily synthesized, the addition containing these can be easily produced. Hardened polysiloxane composition.
又，本發明係提供一種光學半導體裝置，其係以上述加成硬化型聚矽氧組成物之硬化物將光學元件密封而成者。Moreover, this invention provides the optical semiconductor device which sealed the optical element with the hardened|cured material of the said addition hardening-type polysiloxane composition.
藉由本發明之加成硬化型聚矽氧組成物所得之硬化物係透明性及耐熱變色性優異，且高溫條件下之硬度變化，尤其是因軟化導致之劣化及重量減少小者。因而，使用有如此之加成硬化型聚矽氧組成物之硬化物的光學半導體裝置係高溫條件下之可靠性優異者。 [發明效果]The cured product obtained by the addition-curable polysiloxane composition of the present invention is excellent in transparency and thermal discoloration resistance, and has a small change in hardness under high temperature conditions, especially deterioration and weight loss due to softening. Therefore, an optical semiconductor device using a cured product of such an addition-curable polysiloxane composition is excellent in reliability under high temperature conditions. [Inventive effect]
如以上般，只要是本發明之加成硬化型聚矽氧組成物，則可賦予透明性及耐熱變色性優異，具有適度的橡膠硬度，且高溫條件下之硬度變化，尤其是因軟化導致之劣化、重量減少小的硬化物。 只要是如此之加成硬化型聚矽氧組成物，則可賦予具備特別適合於LED等之光學元件的密封用途之透明性及耐熱性的硬化物。As described above, as long as it is the addition-curable polysiloxane composition of the present invention, it can impart excellent transparency and heat discoloration resistance, and has moderate rubber hardness, and the hardness changes under high temperature conditions, especially due to softening. Hardened product with little deterioration and weight loss. As long as such an addition-curable polysiloxane composition is used, it is possible to impart a cured product with transparency and heat resistance particularly suitable for sealing applications of optical elements such as LEDs.
如上述般，要求開發出可賦予透明性及耐熱變色性優異，且高溫條件下之硬度變化，尤其是因軟化導致之劣化及重量減少小的硬化物之加成硬化型聚矽氧組成物。As described above, it is required to develop an addition-curable polysiloxane composition which can impart excellent transparency and thermal discoloration resistance, and can exhibit a hardness change under high temperature conditions, especially a hardened product with little deterioration due to softening and weight loss.
本發明者們針對上述課題再三努力探討的結果，發現只要是包含後述之(a)～(e)成分的加成硬化型聚矽氧組成物，則藉由包含以特定的比例導入有苯基的有機聚矽氧烷及有機氫聚矽氧烷，可達成上述課題，而完成本發明。As a result of diligently examining the above-mentioned problems, the present inventors found that as long as it is an addition-curable polysiloxane composition containing the components (a) to (e) described later, by including a phenyl group introduced in a specific ratio The organopolysiloxane and organohydrogenpolysiloxane of the invention can achieve the above-mentioned subject, and the present invention is completed.
亦即，本發明係一種加成硬化型聚矽氧組成物，其係含有： (a)以下述組成式(1)所表示，且25℃時之黏度為50～100,000mPa∙s的有機聚矽氧烷，
以下，雖針對本發明來詳細地說明，但本發明並非限定於此等者。另外，於本說明書中，「Me」表示甲基，「Vi」表示乙烯基，「Ph」表示苯基。Hereinafter, although this invention is demonstrated in detail, this invention is not limited to these. In addition, in this specification, "Me" represents a methyl group, "Vi" represents a vinyl group, and "Ph" represents a phenyl group.
＜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)～(e)成分而成。以下，針對各成分詳細地說明。<Addition-curable polysiloxane composition> The addition-curable polysiloxane composition of the present invention contains the following components (a) to (e). Hereinafter, each component will be described in detail.
[(a)成分] 本發明之加成硬化型聚矽氧組成物中之(a)成分係以下述組成式(1)所表示，且25℃時之黏度為50～100,000mPa∙s的有機聚矽氧烷。
(a)成分於本發明之加成硬化型聚矽氧組成物中，係為了獲得硬化後之應力緩和所必要的成分，典型而言係主鏈由二有機矽氧烷單元之重複所構成，分子鏈兩末端被三有機矽氧基封鎖的直鏈狀之有機聚矽氧烷。The component (a) in the addition-hardening polysiloxane composition of the present invention is an essential component for obtaining stress relaxation after hardening, and typically the main chain is composed of repeating diorganosiloxane units, A linear organopolysiloxane in which both ends of the molecular chain are blocked by triorganosiloxyl groups.
(a)成分之黏度在25℃時為50～100,000 mPa∙s。在(a)成分之黏度超過100,000mPa∙s的情況，使用本發明之加成硬化型聚矽氧組成物進行密封時之作業性會惡化。另一方面，在(a)成分之黏度低於50mPa∙s的情況，由於(a)成分會成為低沸點，因此高溫環境下之重量減少變得容易發生。(a)成分之黏度，較佳為1,000～50,000 mPa∙s，更佳為1,000～10,000mPa∙s。(a) The viscosity of the component is 50 to 100,000 mPa∙s at 25°C. When the viscosity of the component (a) exceeds 100,000 mPa·s, the workability during sealing using the addition-curable polysiloxane composition of the present invention is deteriorated. On the other hand, when the viscosity of the component (a) is less than 50 mPa·s, since the component (a) has a low boiling point, weight loss in a high temperature environment tends to occur. The viscosity of the component (a) is preferably 1,000 to 50,000 mPa∙s, more preferably 1,000 to 10,000 mPa∙s.
於上述式(1)中之R中，作為一價烴基係只要不含芳香族烴基者則無特別限定，可列舉例如：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化烷基等之通常碳原子數為1～12，較佳為1～10，更佳為1～8之非取代或鹵素取代之一價烴基。特佳為甲基。 相對於R之合計數而言，為50莫耳%以上，較佳為90莫耳%以上為甲基。In R in the above formula (1), the monovalent hydrocarbon group is not particularly limited as long as it does not contain an aromatic hydrocarbon group, and examples thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl, and heptyl. The usual number of carbon atoms is: 1-12, preferably 1-10, more preferably 1-8 unsubstituted or halogen-substituted monovalent hydrocarbon groups. Particularly preferred is methyl. 50 mol% or more, preferably 90 mol% or more, are methyl groups relative to the total amount of R.
又，上述R之中2個以上為烯基，較佳係5個以上。作為烯基，較佳係乙烯基、烯丙基、乙炔基等之碳原子數2～10者，更佳係碳原子數2～6之烯基，特佳係乙烯基。Moreover, in the said R, 2 or more are alkenyl groups, Preferably it is 5 or more. The alkenyl group is preferably a vinyl group, an allyl group, and an ethynyl group having 2 to 10 carbon atoms, more preferably an alkenyl group having 2 to 6 carbon atoms, and particularly preferably a vinyl group.
j為40以上之整數，較佳為200～1,100之整數。j is an integer of 40 or more, preferably an integer of 200 to 1,100.
k為滿足0≦k/(j+k)≦0.04之整數。但，(a)成分或(c)成分之至少一者必須於分子中具有芳香族烴基，在(c)成分中不存在芳香族烴基的情況，較佳為0.001≦k/(j+k)≦0.04。若k/(j+k)超過0.04，則會成為耐熱變色性差的組成物。k is an integer satisfying 0≦k/(j+k)≦0.04. However, at least one of (a) component or (c) component must have an aromatic hydrocarbon group in the molecule, and when no aromatic hydrocarbon group is present in (c) component, preferably 0.001≦k/(j+k) ≦0.04. When k/(j+k) exceeds 0.04, a composition having poor thermal discoloration resistance will be obtained.
作為如此之(a)成分，較佳係可列舉以下述式所表示的有機聚矽氧烷。
上述式中，R’為不含烯基之一價烴基，較佳係碳原子數為10以下之一價烴基，更佳係甲基或苯基。c為0～5之整數，d為0～1000之整數，且c+d≧40。In the above formula, R' is a monovalent hydrocarbon group not containing an alkenyl group, preferably a monovalent hydrocarbon group having 10 or less carbon atoms, more preferably a methyl group or a phenyl group. c is an integer from 0 to 5, d is an integer from 0 to 1000, and c+d≧40.
作為(a)成分之具體例，可列舉以下述式所表示的有機聚矽氧烷。
(a)成分可一種單獨，亦可併用二種以上。The component (a) may be used alone or in combination of two or more.
[(b)成分] (b)成分係以下述平均組成式(2)所表示，且25℃時之黏度為1,000Pa∙s以上之液體或固體的有機聚矽氧烷。
另外，(b)成分，典型而言係具有R1 SiO3/2 單元或SiO4/2 單元等之分支構造的分支狀的有機聚矽氧烷。又，(b)成分係比上述之(a)成分黏度更高的液體或固體的有機聚矽氧烷。In addition, the component (b) is typically a branched organopolysiloxane having a branched structure such as R 1 SiO 3/2 unit or SiO 4/2 unit. In addition, the (b) component is a liquid or solid organopolysiloxane having a higher viscosity than the above-mentioned (a) component.
於上述平均組成式(2)中，R1 為烯基，其中，以碳原子數2～12，尤其是2～6者為佳。作為如此之R1 ，具體而言，可列舉乙烯基、烯丙基等。又，R2 為不具有烯基之一價烴基，其中，以碳原子數1～12，尤其是1～6者為佳。作為如此之R2 ，具體而言，可列舉：甲基、乙基、丙基、丁基、環己基等。另外，全R2 之中80%以上為甲基。又，R3 為氫原子或烷基，作為烷基係以碳原子數1～6，尤其是1～3者為佳。作為如此之R3 ，具體而言，可列舉：甲基、乙基、丙基等。In the above average composition formula (2), R 1 is an alkenyl group, and among them, those having 2 to 12 carbon atoms, especially 2 to 6 carbon atoms are preferred. As such R1, a vinyl group, an allyl group, etc. are mentioned specifically,. Moreover, R< 2 > is a monovalent hydrocarbon group which does not have an alkenyl group, and it is especially preferable that it has 1-12 carbon atoms, especially 1-6. As such R< 2 >, a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, etc. are mentioned specifically,. In addition, 80% or more of all R 2 are methyl groups. Further, R 3 is a hydrogen atom or an alkyl group, and the alkyl group is preferably one having 1 to 6 carbon atoms, especially 1 to 3 carbon atoms. As such R< 3 >, a methyl group, an ethyl group, a propyl group etc. are mentioned specifically,.
(b)成分為具有烯基者，作為(b)成分中之烯基，就取得之容易度、價格面而言，最佳為乙烯基。烯基之量，較佳係相對於(b)成分之固體成分而言，為0.01～1莫耳/100g之範圍，更佳為0.05～0.5莫耳/100g。只要(b)成分之烯基之量，相對於固體成分而言，為0.01莫耳/100g以上，則(b)成分會充分導入至交聯，因此，不會有硬化物之硬度變得過低的疑慮。又，只要(b)成分之烯基之量，相對於固體成分而言，為1莫耳/100g以下，則由於系內之烯基不會變得過多，因此可將(b)成分之摻合量相對於後述之(c)成分(交聯劑)之摻合量設為適量。因而，不會有交聯不充分進行而無法得到所期望的硬度，或導致硬化物變脆的疑慮。The component (b) has an alkenyl group, and the alkenyl group in the component (b) is preferably a vinyl group in terms of availability and price. The amount of the alkenyl group is preferably in the range of 0.01 to 1 mol/100 g, more preferably 0.05 to 0.5 mol/100 g, relative to the solid content of the component (b). As long as the amount of the alkenyl group of the component (b) is 0.01 mol/100 g or more with respect to the solid content, the component (b) will be sufficiently introduced into the crosslinking, so that the hardness of the cured product will not become too low. of doubts. In addition, as long as the amount of the alkenyl group of the component (b) is 1 mol/100 g or less relative to the solid content, the alkenyl group in the system will not become too much, so the amount of the component (b) can be mixed The compounding amount is an appropriate amount with respect to the compounding amount of the (c) component (crosslinking agent) described later. Therefore, there is no possibility that the desired hardness cannot be obtained due to insufficient crosslinking, or that the hardened product becomes brittle.
於本發明中，(b)成分相對於(a)成分之比率亦為重要，(b)成分之摻合量，相對於(a)成分與(b)成分之合計100質量份而言，(b)成分為多於0質量份未達80質量份之量。由於(b)成分之摻合量越增加硬化物之硬度越增大，因此可配合光學半導體裝置等之設計來改變(b)成分之摻合量而調整硬度。更具體而言，例如，在對硬化物要求應力緩和的情況，較佳係相對於(a)成分與(b)成分之合計100質量份而言，(b)成分為多於0質量份未達50質量份之量。另一方面，例如，在對硬化物要求高硬度的情況，較佳係相對於(a)成分與(b)成分之合計100質量份而言，(b)成分為50質量份以上未達80質量份之量。In the present invention, the ratio of the component (b) to the component (a) is also important, and the blending amount of the component (b) is ( b) The component is more than 0 parts by mass and less than 80 parts by mass. Since the hardness of the cured product increases as the blending amount of the component (b) increases, the hardness can be adjusted by changing the blending amount of the component (b) in accordance with the design of an optical semiconductor device or the like. More specifically, for example, when stress relaxation is required for a cured product, it is preferable that the (b) component is more than 0 parts by mass relative to 100 parts by mass of the total of the (a) component and the (b) component. up to 50 parts by mass. On the other hand, for example, when high hardness is required for the cured product, it is preferable that the (b) component is 50 parts by mass or more and less than 80 parts by mass with respect to 100 parts by mass of the total of the (a) component and the (b) component. The amount of parts by mass.
[(c)成分] 本發明之加成硬化型聚矽氧組成物中之(c)成分係以下述平均組成式(3)所表示，且25℃時之黏度為1,000mPa∙s以下的有機氫聚矽氧烷。
(c)成分係發揮作為本組成物之交聯部分的作用，藉由使用該成分，而可賦予高溫條件下之硬度變化及重量減少為少，且裂縫耐性為良好的硬化物。The component (c) functions as a cross-linking part of the present composition, and by using this component, a hardened product with less hardness change and weight loss under high temperature conditions and good crack resistance can be provided.
(c)成分之黏度於25℃時為1,000mPa∙s以下，較佳為0.5～500mPa∙s，更佳為2～100mPa∙s。在(c)成分之黏度超過1,000mPa∙s的情況，使用本發明之加成硬化型聚矽氧組成物進行密封時之作業性會惡化。The viscosity of the component (c) is 1,000 mPa∙s or less at 25°C, preferably 0.5 to 500 mPa∙s, more preferably 2 to 100 mPa∙s. When the viscosity of the component (c) exceeds 1,000 mPa·s, the workability during sealing using the addition-hardening polysiloxane composition of the present invention is deteriorated.
又，就交聯之均衡的觀點而言，(c)成分之摻合量，相對於(a)成分及(b)成分之烯基數的合計而言，(c)成分之SiH鍵之數為0.5～5.0倍之量，較佳為0.7～3.0倍之量。In addition, from the viewpoint of the balance of crosslinking, the compounding amount of the component (c) relative to the total number of alkenyl groups of the component (a) and the component (b), the number of SiH bonds in the component (c) is: The amount is 0.5 to 5.0 times, preferably 0.7 to 3.0 times.
於上述平均組成式(3)中，R4 為不含烯基及芳香族烴基之一價烴基或氫原子，針對一價烴基，以碳原子數1～10，尤其是1～8者為佳。作為如此之一價烴基，具體而言可列舉：甲基、乙基、丙基、異丙基、丁基、異丁基、tert-丁基、戊基、新戊基、己基、環己基、辛基、壬基、癸基等之烷基等，尤其是以甲基為佳。In the above average composition formula (3), R 4 is a monovalent hydrocarbon group or hydrogen atom that does not contain an alkenyl group and an aromatic hydrocarbon group, and for the monovalent hydrocarbon group, the number of carbon atoms is preferably 1-10, especially 1-8. . Specific examples of such monovalent hydrocarbon groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, Alkyl groups such as octyl, nonyl, decyl, etc., especially methyl groups are preferred.
於(c)成分中，於一分子中所包含之R4 之中2個以上為氫原子，較佳係2～100個、更佳係3～30個、再更佳係4～20個為氫原子。該等SiH鍵可位於分子鏈末端、分子鏈途中之任一個位置，又，亦可位於此兩個位置。In the component (c), 2 or more of R 4 contained in one molecule are hydrogen atoms, preferably 2 to 100, more preferably 3 to 30, and still more preferably 4 to 20. A hydrogen atom. These SiH bonds may be located at any position at the end of the molecular chain, in the middle of the molecular chain, or may be located at these two positions.
於上述平均組成式(3)中，R5
為不含烯基之一價烴基或氫原子，針對一價烴基係以碳原子數1～10，尤其是1～8者為佳。作為如此之一價烴基，具體而言，可列舉：甲基、乙基、丙基、異丙基、丁基、異丁基、tert-丁基、戊基、新戊基、己基、環己基、辛基、壬基、癸基等之烷基；苯基、
於上述平均組成式(3)中，w為4～100之整數，x為滿足0≦x/(w+x)≦0.3之整數。若x/(w+x)超過0.3，則會成為於高溫條件下耐熱變色性差之組成物。In the above average composition formula (3), w is an integer of 4 to 100, and x is an integer satisfying 0≦x/(w+x)≦0.3. When x/(w+x) exceeds 0.3, it will become a composition with poor thermal discoloration resistance under high temperature conditions.
又，(a)成分或(c)成分之至少一方必須於分子中具有芳香族烴基。亦即，在(a)成分中不存在芳香族烴基的情況，必須滿足x為1以上或R5 為包含芳香族烴基之至少一者。 (a)成分及(c)成分中所包含之芳香族烴基之合計，相對於加成硬化型聚矽氧組成物中之鍵結於矽原子的有機基之總數而言，較佳為0.002～10%，更佳為0.004～8%。Moreover, at least one of (a) component or (c) component must have an aromatic hydrocarbon group in a molecule|numerator. That is, when an aromatic hydrocarbon group does not exist in (a) component, it must satisfy|fill that x is 1 or more or R< 5 > contains at least one of an aromatic hydrocarbon group. The total of the aromatic hydrocarbon groups contained in the components (a) and (c) is preferably 0.002 to 10%, more preferably 0.004 to 8%.
作為(c)成分，可列舉例如：於上述平均組成式(3)中，x＝0，R4 的40%以上未達60%為氫原子者。只要為如此者，則可適合使用作為(c)成分。 於此情況中，作為(c)成分，雖可考慮不存在芳香族烴基者(亦即，式(3)中之R5 不含芳香族烴基的情況)與包含芳香族烴基者(亦即，式(3)中之R5 之中至少一個為芳香族烴基的情況)，但於前者的情況中，(a)成分必須包含芳香族烴基。As the component (c), for example, in the above-mentioned average composition formula (3), x=0, and 40% or more of R 4 and less than 60% are hydrogen atoms. As long as it is so, it can be used suitably as (c) component. In this case, as the component (c), those without an aromatic hydrocarbon group (that is, the case where R 5 in the formula (3) does not contain an aromatic hydrocarbon group) and those containing an aromatic hydrocarbon group (that is, In the case where at least one of R 5 in the formula (3) is an aromatic hydrocarbon group), in the former case, the component (a) must contain an aromatic hydrocarbon group.
另外，作為(a)成分及(c)成分之組合，較佳係(a)成分為式(1)中之R為甲基者，且(c)成分為包含苯基者。 只要為如此者，則可充分得到本發明之效果。Moreover, as a combination of (a) component and (c) component, it is preferable that (a) component is what R in Formula (1) is a methyl group, and (c) component is what contains a phenyl group. As long as this is the case, the effects of the present invention can be sufficiently obtained.
作為以上述平均組成式(3)所表示之有機氫聚矽氧烷，可列舉例如：以下述式所表示之直鏈狀之有機氫聚矽氧烷。
[(d)成分] (d)成分為鉑族金屬系觸媒。此(d)成分係發揮作為促進上述之(a)成分及(b)成分中之烯基與鍵結於(c)成分中之矽原子的氫原子之反應(氫化矽烷化反應)的反應觸媒之功用的成分。[Component (d)] The component (d) is a platinum group metal-based catalyst. This (d) component acts as a reaction contact (hydrosilylation reaction) that promotes the reaction (hydrosilylation reaction) between the alkenyl group in the above-mentioned (a) components and (b) components and the hydrogen atom bonded to the silicon atom in the (c) component. The components of the function of the medium.
作為此鉑族金屬系觸媒，只要是促進氫化矽烷化反應者，則任何觸媒皆可。可列舉例如：鉑黑、銠、鈀等之鉑族金屬單質；H2 PtCl4 ・bH2 O、H2 PtCl6 ・bH2 O、NaHPtCl6 ・bH2 O、KHPtCl6 ・bH2 O、Na2 PtCl6 ・bH2 O、K2 PtCl4 ・bH2 O、PtCl4 ・bH2 O、PtCl2 、Na2 HPtCl4 ・bH2 O(式中，b為0～6之整數，較佳為0或6)等之氯化鉑、氯化鉑酸、及氯化鉑酸鹽；醇變性氯化鉑酸(參照美國專利第3,220,972號說明書)；氯化鉑酸與烯烴之錯合物(參照美國專利第3,159,601號說明書、同第3,159,662號說明書、同第3,775,452號說明書)；鉑黑、鈀等之鉑族金屬載持於氧化鋁、二氧化矽、碳等之載體者；銠-烯烴錯合物；氯參(三苯基膦)銠(威爾金森觸媒)；氯化鉑、氯化鉑酸、或氯化鉑酸鹽與含乙烯基之矽氧烷，尤其是與含乙烯基之環狀矽氧烷之錯合物等。此等當中，作為較佳者，就相溶性的觀點及氯雜質的觀點而言，可列舉將氯化鉑酸進行聚矽氧變性者，具體而言，可列舉例如：將氯化鉑酸以四甲基乙烯基二矽氧烷進行變性的鉑觸媒。As this platinum group metal-based catalyst, any catalyst may be used as long as it promotes the hydrosilylation reaction. For example, platinum group metals such as platinum black, rhodium, and palladium; H 2 PtCl 4 · bH 2 O, H 2 PtCl 6 · bH 2 O, NaHPtCl 6 · bH 2 O, KHPtCl 6 · bH 2 O, Na 2 PtCl 6 · bH 2 O, K 2 PtCl 4 · bH 2 O, PtCl 4 · bH 2 O, PtCl 2 , Na 2 HPtCl 4 · bH 2 O (wherein, b is an integer from 0 to 6, preferably 0 or 6) platinum chloride, chloroplatinic acid, and chloroplatinate; alcohol-denatured chloroplatinic acid (refer to the specification of US Pat. No. 3,220,972); complex of chloroplatinic acid and olefin (refer to U.S. Patent No. 3,159,601 specification, the same specification No. 3,159,662, the same specification No. 3,775,452); platinum group metals such as platinum black and palladium supported on alumina, silica, carbon, etc. carriers; rhodium-olefin complex Compounds; chlorosine (triphenylphosphine) rhodium (Wilkinson's catalyst); platinum chloride, chloroplatinic acid, or chloroplatinate and vinyl-containing siloxanes, especially with vinyl-containing Complexes of cyclic siloxanes, etc. Among these, preferred ones include those obtained by polysiloxane modification of chloroplatinic acid from the viewpoints of compatibility and chlorine impurities. Specifically, for example, chloroplatinic acid is exemplified by A platinum catalyst denatured with tetramethylvinyldisiloxane.
(d)成分之摻合量係作為觸媒之有效量，具體而言，相對於(a)～(c)成分之合計而言，以金屬原子之質量換算計，為1～500ppm，較佳為3～100ppm，更佳為5～40ppm之量。在1～500ppm之範圍外的情況，無法得到適當的加成反應之反應速度，而無法得到具有高強度的硬化物。The compounding amount of the component (d) is an effective amount as a catalyst. Specifically, it is preferably 1 to 500 ppm in terms of the mass of the metal atom relative to the total of the components (a) to (c). It is an amount of 3 to 100 ppm, more preferably 5 to 40 ppm. When it is outside the range of 1 to 500 ppm, an appropriate reaction rate of the addition reaction cannot be obtained, and a cured product having high strength cannot be obtained.
[(e)成分] (e)成分為含環氧基之有機矽化合物。此(e)成分係用以對本發明之加成硬化型聚矽氧組成物賦予接著性的添加劑。[Component (e)] Component (e) is an epoxy group-containing organosilicon compound. The component (e) is an additive for imparting adhesiveness to the addition-curable polysiloxane composition of the present invention.
作為(e)成分，可列舉例如：以下述組成式(4)所表示之含環氧基之有機矽化合物等。
又，作為(e)成分之具體例，可列舉以下述式所表示之含環氧基之有機矽化合物等。
(e)成分之摻合量，相對於(a)～(d)成分之合計100質量份而言，為0.01～5質量份，較佳為0.03～3質量份，更佳為0.05～2質量份。若(e)成分之摻合量超過5質量份，則恐有所得之加成硬化型聚矽氧組成物變色，或硬化物之硬度降低之虞。The compounding amount of the component (e) is 0.01 to 5 parts by mass, preferably 0.03 to 3 parts by mass, and more preferably 0.05 to 2 parts by mass with respect to 100 parts by mass of the total of the components (a) to (d). share. If the blending amount of the component (e) exceeds 5 parts by mass, the resulting addition-curing polysiloxane composition may be discolored, or the hardness of the cured product may be lowered.
[(f)成分] 本發明之加成硬化型聚矽氧組成物，亦可進一步含有作為(f)成分之含有Si-O-Ce鍵及Si-O-Ti鍵，Ce含量為50～5,000ppm，Ti含量為50～5,000ppm，且25℃時之黏度為10～10,000mPa∙s的聚有機金屬矽氧烷。此(f)成分係用以提昇本發明之加成硬化型聚矽氧組成物之耐熱性的添加劑。[Component (f)] The addition-hardening polysiloxane composition of the present invention may further contain Si-O-Ce bonds and Si-O-Ti bonds as components (f), and the Ce content is 50 to 5,000 ppm, a polyorganometallic siloxane with a Ti content of 50 to 5,000 ppm and a viscosity of 10 to 10,000 mPa∙s at 25°C. The component (f) is an additive for improving the heat resistance of the addition-hardening polysiloxane composition of the present invention.
作為(f)成分，較佳係將由下述(i)、(ii)及(iii)成分所構成之混合物以150℃以上之溫度進行熱處理所得之反應生成物。 (i)25℃時之黏度為10～10,000mPa∙s的有機聚矽氧烷：100質量份； (ii)包含以下述一般式(f-1)所表示之鈰羧酸鹽的稀土類羧酸鹽：相對於(i)成分100質量份而言，以鈰換算計，為0.05～5質量份之量，以及
作為(i)成分之聚有機矽氧烷，只要是25℃時之黏度為10～10,000mPa∙s者，則可使用以往周知者。As the polyorganosiloxane of the component (i), as long as it has a viscosity of 10 to 10,000 mPa·s at 25°C, a conventionally known one can be used.
作為(ii)成分之稀土類羧酸鹽，可例示2-乙基己酸、環烷酸、油酸、月桂酸、硬脂酸等之鈰鹽。As the rare earth carboxylate of the component (ii), cerium salts such as 2-ethylhexanoic acid, naphthenic acid, oleic acid, lauric acid, and stearic acid can be exemplified.
作為(iii)成分之鈦化合物，可例示：鈦酸四n-丁酯等之四烷氧基鈦，或其水解縮合物等。As the titanium compound of the component (iii), tetraalkoxytitanium such as tetran-butyl titanate, or a hydrolysis condensate thereof can be exemplified.
(f)成分之摻合量，相對於(a)～(e)成分之合計100質量份而言，較佳為0～2質量份，更佳為0.01～2質量份，再更佳為0.01～1.5質量份。只要(f)成分之摻合量為2質量份以下，則不會有所得之加成硬化型聚矽氧組成物變色，或硬化物之硬度降低的疑慮。The blending amount of the component (f) is preferably 0 to 2 parts by mass, more preferably 0.01 to 2 parts by mass, and even more preferably 0.01 with respect to 100 parts by mass of the total of the components (a) to (e). ~1.5 parts by mass. As long as the blending amount of the component (f) is 2 parts by mass or less, there is no possibility of discoloration of the obtained addition-curable polysiloxane composition or reduction in hardness of the cured product.
[其他成分] 於本發明之加成硬化型聚矽氧組成物中，除了上述(a)～(f)成分以外，亦可因應需要，而摻合以下例示之其他成分。作為其他成分，可列舉例如：氣相二氧化矽等之搖變性抑制劑；結晶性二氧化矽等之光散射劑；氣相二氧化矽、結晶性二氧化矽等之補強材；螢光體；石油系溶劑、不具有反應性官能基之非反應性聚矽氧油等之黏度調整劑；碳官能矽烷、環氧基、烷氧基、具有鍵結於矽原子的氫原子(亦即，SiH鍵)及鍵結於矽原子的乙烯基等之烯基之至少一種的(a)～(f)成分以外之聚矽氧化合物等之接著性提昇劑；銀、金等之金屬粉等之導電性賦予劑；用以著色之顏料及染料；乙炔基環己醇、四甲基四乙烯基四環矽氧烷等之反應抑制劑等。該等其他成分係可一種單獨使用亦可併用二種以上。[Other components] In addition to the above-mentioned components (a) to (f), the addition-curable polysiloxane composition of the present invention may be blended with other components exemplified below as necessary. Examples of other components include: thixotropy inhibitors such as fumed silica; light scattering agents such as crystalline silica; reinforcing materials such as fumed silica and crystalline silica; phosphors ; Viscosity modifiers for petroleum-based solvents, non-reactive polysiloxane oils without reactive functional groups, etc.; Adhesion improvers such as polysiloxanes other than components (a) to (f) other than components (a) to (f) of SiH bond) and at least one of alkenyl groups such as vinyl groups bonded to silicon atoms; metal powders such as silver, gold, etc. Conductivity imparting agents; pigments and dyes for coloring; reaction inhibitors for ethynylcyclohexanol, tetramethyltetravinyltetracyclosiloxane, etc. These other components may be used alone or in combination of two or more.
另外，本發明之加成硬化型聚矽氧組成物之硬化條件雖無特別限定，但較佳係設為120～180℃、30～180分鐘之條件。Moreover, although the hardening conditions of the addition hardening type polysiloxane composition of this invention are not specifically limited, It is preferable to set it as the conditions of 120-180 degreeC and 30-180 minutes.
又，本發明之加成硬化型聚矽氧組成物，較佳係厚度2mm之薄片狀硬化物之波長400nm的全光線透過率為80%以上，硬化物之以250℃保管500小時後的重量減少率為10%以內者。只要是如此之加成硬化型聚矽氧組成物，則可賦予具有特別適合於LED等之光學元件的密封用途之透明性及耐熱性的硬化物。In addition, the addition-curable polysiloxane composition of the present invention is preferably a sheet-like cured product with a thickness of 2 mm and a total light transmittance at a wavelength of 400 nm of 80% or more, and the weight of the cured product after being stored at 250°C for 500 hours The reduction rate is less than 10%. As long as it is such an addition-curable polysiloxane composition, a cured product having transparency and heat resistance particularly suitable for sealing applications of optical elements such as LEDs can be imparted.
如以上般，只要是本發明之加成硬化型聚矽氧組成物，則成為可賦予透明性及耐熱變色性優異，具有適度的橡膠硬度，且高溫條件下之硬度變化及重量減少小，裂縫耐性良好的硬化物之加成硬化型聚矽氧組成物。As described above, as long as it is the addition-curable polysiloxane composition of the present invention, it can impart excellent transparency and heat discoloration resistance, has moderate rubber hardness, and has little hardness change and weight loss under high temperature conditions, and cracks Addition-curable polysiloxane composition of cured products with good resistance.
＜加成硬化型聚矽氧組成物之製造方法＞ 又，於本發明中係提供製造上述之加成硬化型聚矽氧組成物的方法。 本發明之加成硬化型聚矽氧組成物，可藉由將上述之(a)～(e)成分，又，因應需要之(f)成分、其他添加劑進行混合而製造。<The manufacturing method of an addition hardening type polysiloxane composition> Moreover, this invention provides the method of manufacturing the above-mentioned addition hardening type polysiloxane composition. The addition-curable polysiloxane composition of the present invention can be produced by mixing the above-mentioned components (a) to (e), and, if necessary, the component (f) and other additives.
在加成硬化型聚矽氧組成物包含(f)成分的情況，較佳係將由上述之(i)～(iii)成分所構成之混合物以150℃以上的溫度進行熱處理，生成(f)成分之聚有機金屬矽氧烷，並將所得之(f)成分與(a)～(e)成分及任意成分進行混合。In the case where the addition-curable polysiloxane composition contains the component (f), it is preferable to heat-treat the mixture composed of the components (i) to (iii) above at a temperature of 150° C. or higher to generate the component (f). The obtained polyorganometallic siloxane is mixed with the obtained (f) component, (a) to (e) components and optional components.
只要是如此之製造方法，則由於可容易地合成具有特定之Ce含量及Ti含量的聚有機金屬矽氧烷(亦即，上述(f)成分)，因此可容易地製造本發明之加成硬化型聚矽氧組成物。According to such a production method, since polyorganometallosiloxane (that is, the above-mentioned (f) component) having a specific Ce content and Ti content can be easily synthesized, the addition hardening of the present invention can be easily produced Type polysiloxane composition.
＜光學半導體裝置＞ 又，於本發明中係提供一種光學半導體裝置，其係以上述之加成硬化型聚矽氧組成物之硬化物將發光二極體等之光學元件密封而成者。只要是如此之光學半導體裝置，則由於如上述般以可賦予透明性及耐熱變色性優異，且高溫條件下之硬度變化及重量減少為少的硬化物之本發明之加成硬化型聚矽氧組成物將光學元件密封，因此成為高溫條件下之可靠性優異的光學半導體裝置。<Optical semiconductor device> Further, the present invention provides an optical semiconductor device obtained by sealing optical elements such as light-emitting diodes with a cured product of the above-mentioned addition-curable polysiloxane composition. With such an optical semiconductor device, as described above, the addition-curable polysiloxane of the present invention can provide a cured product with excellent transparency and thermal discoloration resistance, and with little hardness change and weight loss under high temperature conditions. Since the composition seals the optical element, it becomes an optical semiconductor device excellent in reliability under high temperature conditions.
如此般，本發明之加成硬化型聚矽氧組成物係作為LED元件之保護・密封用材料、波長之變更・調整用材料，或者透鏡之構成材料，或其他光學裝置用或光學零件用之材料特別有用。 [實施例]In this way, the addition-curable polysiloxane composition of the present invention can be used as a protection and sealing material for LED elements, a material for wavelength change and adjustment, or a constituent material for lenses, or for other optical devices or optical parts. Materials are especially useful. [Example]
以下，雖使用合成例、實施例及比較例來具體地說明本發明，但本發明並非限定於此等者。於以下內容中，黏度係使用旋轉黏度計所測定之25℃下之值。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 the following, the viscosity is the value at 25°C measured using a rotational viscometer.
[合成例1] (f)成分之合成 於25℃時之黏度為100mPa∙s之兩末端三甲基矽氧基封鎖二甲基聚矽氧烷100質量份中，一邊充分攪拌一邊添加預先混合有以鈰作為主成分的2-乙基己酸鹽之松節油溶液(稀土類元素含量6質量%)10質量份(鈰之質量：0.55質量份)與鈦酸四n-丁酯2.1質量份(鈦之質量：1.65質量份)者，而得到黃白色之分散液。於其中一邊使氮氣少量流通一邊加熱使松節油流出，接著，以300℃進行1小時加熱，而得到深紅褐色且透明的聚有機金屬矽氧烷(f1)之均勻組成物。以如此方式合成的聚有機金屬矽氧烷(f1)之Ce含量為3,400ppm，Ti含量為3,700ppm，25℃時之黏度為104 mPa∙s。[Synthesis Example 1] (f) Synthesis of component (f) To 100 parts by mass of trimethylsiloxy-blocked dimethylpolysiloxane having a viscosity of 100 mPa·s at both ends at 25°C, it was added and mixed in advance while stirring well. There are 10 parts by mass of 2-ethylhexanoate turpentine solution containing cerium as the main component (content of rare earth elements: 6 mass %) (mass of cerium: 0.55 parts by mass) and 2.1 parts by mass of tetra-n-butyl titanate ( mass of titanium: 1.65 parts by mass) to obtain a yellow-white dispersion. The turpentine oil was heated while flowing a small amount of nitrogen gas therein, and then heated at 300° C. for 1 hour to obtain a dark reddish-brown and transparent polyorganometallic siloxane (f1) uniform composition. The polyorganometallic siloxane (f1) synthesized in this way has a Ce content of 3,400 ppm, a Ti content of 3,700 ppm, and a viscosity of 104 mPa∙s at 25°C.
[實施例1] 將兩末端被乙烯基封鎖之25℃時之黏度為5,000mPa∙s之直鏈狀之二甲基聚矽氧烷(a1)(組成式： ViMe2 SiO(Me2 SiO)450 SiMe2 Vi)，與以Me3 SiO1/2 單元、ViMe2 SiO1/2 單元、及SiO4/2 單元所構成，相對於SiO4/2 單元而言，Me3 SiO1/2 單元及ViMe2 SiO1/2 單元之莫耳比為0.8，且乙烯基量相對於固體成分為0.085莫耳/100g之固體狀的聚矽氧樹脂(b1)之甲苯溶液，以有效成分換算，並以質量比計，為二甲基聚矽氧烷(a1)：聚矽氧樹脂(b1)＝75：25之比例進行混合。在120℃、10mmHg(約1.3kPa)以下之減壓下，將甲苯從此混合物去除，而得到室溫下為透明的液體。[Example 1] Linear-chain dimethylpolysiloxane (a1) with a viscosity of 5,000 mPa·s at 25° C. with both ends blocked by vinyl groups (composition formula: ViMe 2 SiO(Me 2 SiO) 450 SiMe 2 Vi), composed of Me 3 SiO 1/2 unit, ViMe 2 SiO 1/2 unit, and SiO 4/2 unit, with respect to SiO 4/2 unit, Me 3 SiO 1/2 unit and the molar ratio of ViMe 2 SiO 1/2 unit is 0.8, and the toluene solution of the solid polysiloxane resin (b1) whose vinyl content is 0.085 mol/100g with respect to the solid content is converted in terms of active ingredient, and The ratio of dimethyl polysiloxane (a1):polysiloxane resin (b1)=75:25 is carried out in terms of mass ratio. Toluene was removed from this mixture at 120° C. under a reduced pressure of 10 mmHg (about 1.3 kPa) or less to obtain a liquid that was clear at room temperature.
接著，於此液體100質量份中，混合以下之組成式所表示之黏度為9.7mPa∙s之甲基氫聚矽氧烷(c1)4.0質量份，與作為其他成分之含環氧基之有機矽化合物之3-環氧丙氧基丙基三甲氧基矽烷(e1)0.5質量份，以及乙炔基環己醇0.05質量份，而得到透明的液體。另外，甲基氫聚矽氧烷(c1)之SiH鍵之數相對於二甲基聚矽氧烷(a1)及聚矽氧樹脂(b1)之烯基數的合計為1.50倍。
進而，添加合成例1所得之聚有機金屬矽氧烷(f1)1質量份、及具有由氯化鉑酸衍生之四甲基乙烯基二矽氧烷作為配位子的鉑觸媒(d1)，相對於二甲基聚矽氧烷(a1)、聚矽氧樹脂(b1)、及甲基氫聚矽氧烷(c1)之合計而言，以鉑原子換算計為5ppm之量，將其均勻地混合，而得到黏度為5,000mPa∙s之透明的加成硬化型聚矽氧組成物。Furthermore, 1 part by mass of the polyorganometallic siloxane (f1) obtained in Synthesis Example 1 and a platinum catalyst (d1) having tetramethylvinyldisiloxane derived from chloroplatinic acid as a ligand were added , relative to the total of dimethyl polysiloxane (a1), polysiloxane resin (b1), and methyl hydrogen polysiloxane (c1), calculated as 5 ppm in terms of platinum atoms, Mixed uniformly to obtain a transparent addition-hardening polysiloxane composition with a viscosity of 5,000 mPa∙s.
[實施例2] 除了不添加合成例1所得之聚有機金屬矽氧烷(f1)以外，進行與實施例1相同的操作，而得到黏度為5,200 mPa∙s之透明的加成硬化型聚矽氧組成物。[Example 2] The same operation as in Example 1 was carried out except that the polyorganometallosiloxane (f1) obtained in Synthesis Example 1 was not added to obtain a transparent addition-hardening polysilicon with a viscosity of 5,200 mPa·s oxygen composition.
[實施例3] 將兩末端被3個乙烯基封鎖的25℃時之黏度為100,000mPa∙s之直鏈狀之二甲基聚矽氧烷(a2)(組成式：Vi3 SiO(Me2 SiO)1000 SiVi3 )，及與實施例1所使用者相同的聚矽氧樹脂(b1)之甲苯溶液，以有效成分換算，並以質量比計，為二甲基聚矽氧烷(a2)：聚矽氧樹脂(b1)＝75：25之比例進行混合。在120℃、10mmHg(約1.3kPa)以下之減壓下，將甲苯從此混合物去除，而得到室溫下為透明的液體。[Example 3] A linear dimethylpolysiloxane (a2) (composition formula: Vi 3 SiO (Me 2 SiO) 1000 SiVi 3 ), and the toluene solution of the same polysiloxane resin (b1) used in Example 1, converted into active ingredients and calculated in mass ratio, is dimethyl polysiloxane (a2) : Polysiloxane (b1) = 75:25 ratio to mix. Toluene was removed from this mixture at 120° C. under a reduced pressure of 10 mmHg (about 1.3 kPa) or less to obtain a liquid that was clear at room temperature.
接著，於此液體100質量份中，混合以下之組成式所表示之黏度為6mPa∙s之甲基氫聚矽氧烷(c2)4.1質量份，與作為其他成分之以下述式所表示之含環氧基之有機矽化合物(e2)0.5質量份，以及乙炔基環己醇0.05質量份，而得到透明的液體。另外，甲基氫聚矽氧烷(c2)與(e2)之SiH鍵之數相對於二甲基聚矽氧烷(a2)及聚矽氧樹脂(b1)之烯基數的合計為1.50倍。
進而，添加合成例1所得之聚有機金屬矽氧烷(f1)1質量份、及與實施例1所使用者相同的鉑觸媒(d1)，相對於二甲基聚矽氧烷(a2)、聚矽氧樹脂(b1)、及甲基氫聚矽氧烷(c2)之合計而言，以鉑原子換算計為5ppm之量，將其均勻地混合，而得到黏度為80,000mPa∙s之透明的加成硬化型聚矽氧組成物。Furthermore, 1 part by mass of the polyorganometallic siloxane (f1) obtained in Synthesis Example 1 and the same platinum catalyst (d1) used in Example 1 were added to the dimethylpolysiloxane (a2) , polysiloxane resin (b1), and methylhydrogen polysiloxane (c2) in total, in an amount of 5 ppm in terms of platinum atoms, and uniformly mixed to obtain a viscosity of 80,000 mPa∙s Transparent addition-hardening polysiloxane composition.
[實施例4] 將兩末端被乙烯基封鎖之25℃時之黏度為5,000mPa∙s之直鏈狀之二甲基聚矽氧烷(a1)，與以Me3 SiO1/2 單元、ViMe2 SiO1/2 單元、及SiO3/2 單元所構成，相對於SiO3/2 單元而言，Me3 SiO1/2 單元及ViMe2 SiO1/2 單元之莫耳比為1.27，且乙烯基量相對於固體成分為0.056莫耳/100g之固體狀的聚矽氧樹脂(b2)之甲苯溶液，以有效成分換算，並以質量比計，為二甲基聚矽氧烷(a1)：聚矽氧樹脂(b2)＝60：40之比例進行混合。在120℃、10mmHg(約1.3kPa)以下之減壓下，將甲苯從此混合物去除，而得到室溫下為透明的液體。[Example 4] A linear dimethylpolysiloxane (a1) with a viscosity of 5,000 mPa∙s at 25°C, whose both ends were blocked by vinyl groups, was mixed with Me 3 SiO 1/2 unit, ViMe 2 SiO 1/2 unit and SiO 3/2 unit, the molar ratio of Me 3 SiO 1/2 unit and ViMe 2 SiO 1/2 unit relative to SiO 3/2 unit is 1.27, and ethylene The base amount relative to the toluene solution of the solid polysiloxane resin (b2) with a solid content of 0.056 mol/100 g, converted to the active ingredient, and calculated as a mass ratio, is dimethyl polysiloxane (a1): Polysiloxane (b2) = 60:40 for mixing. Toluene was removed from this mixture at 120° C. under a reduced pressure of 10 mmHg (about 1.3 kPa) or less to obtain a liquid that was clear at room temperature.
接著，於此液體100質量份中，混合與實施例1所使用者相同之甲基氫聚矽氧烷(c1)4.8質量份，與作為其他成分之與實施例1所使用者相同之3-環氧丙氧基丙基三甲氧基矽烷(e1)1.0質量份，以及乙炔基環己醇0.05質量份，而得到透明的液體。另外，甲基氫聚矽氧烷(c1)之SiH鍵之數相對於二甲基聚矽氧烷(a1)及聚矽氧樹脂(b2)之烯基數的合計為1.50倍。Next, in 100 parts by mass of this liquid, 4.8 parts by mass of methylhydrogenpolysiloxane (c1), the same as that used in Example 1, was mixed with 3- 1.0 mass part of glycidoxypropyl trimethoxysilane (e1), and 0.05 mass part of ethynylcyclohexanol, and the transparent liquid was obtained. In addition, the number of SiH bonds of methylhydrogenpolysiloxane (c1) was 1.50 times the total number of alkenyl groups of dimethylpolysiloxane (a1) and polysiloxane (b2).
進而，添加合成例1所得之聚有機金屬矽氧烷(f1)1質量份、及與實施例1所使用者相同的鉑觸媒(d1)，相對於二甲基聚矽氧烷(a1)、聚矽氧樹脂(b2)、及甲基氫聚矽氧烷(c1)之合計而言，以鉑原子換算計為5ppm之量，將其均勻地混合，而得到黏度為4,000mPa∙s之透明的加成硬化型聚矽氧組成物。Furthermore, 1 part by mass of the polyorganometallic siloxane (f1) obtained in Synthesis Example 1 and the same platinum catalyst (d1) used in Example 1 were added to the dimethylpolysiloxane (a1) , the polysiloxane resin (b2), and the methylhydrogen polysiloxane (c1) in total, in an amount of 5 ppm in terms of platinum atoms, and uniformly mixed to obtain a viscosity of 4,000 mPa∙s. Transparent addition-hardening polysiloxane composition.
[實施例5] 將兩末端被乙烯基封鎖的25℃時之黏度為5,000mPa∙s且含有3莫耳%之二苯基矽氧基單元的直鏈狀之二甲基二苯基聚矽氧烷(a3)(組成式： ViMe2 SiO(Me2 SiO)437 (Ph2 SiO)13 SiMe2 Vi)、及與實施例4所使用者相同的聚矽氧樹脂(b2)之甲苯溶液，以有效成分換算，並以質量比計，為二甲基二苯基聚矽氧烷(a3)：聚矽氧樹脂(b2)＝60：40之比例進行混合。在120℃、10mmHg (約1.3kPa)以下之減壓下，將甲苯從此混合物去除，而得到室溫下為透明的液體。[Example 5] A linear dimethyldiphenyl polysilicon with a viscosity of 5,000 mPa·s at 25°C and containing 3 mol% of diphenylsiloxy units, which are blocked by vinyl groups at both ends Oxane (a3) (composition formula: ViMe 2 SiO(Me 2 SiO) 437 (Ph 2 SiO) 13 SiMe 2 Vi), and a toluene solution of the same polysiloxane resin (b2) used in Example 4, In terms of active ingredient conversion, and in terms of mass ratio, the mixture is mixed in a ratio of dimethyldiphenyl polysiloxane (a3):polysiloxane resin (b2)=60:40. Toluene was removed from this mixture at 120° C. under a reduced pressure of 10 mmHg (about 1.3 kPa) or less to obtain a liquid that was clear at room temperature.
接著，於此液體100質量份中，混合以下之組成式所表示之黏度為22mPa∙s之甲基氫聚矽氧烷(c3)2.6質量份，與作為其他成分之與實施例1所使用者相同之3-環氧丙氧基丙基三甲氧基矽烷(e1)1.0質量份、以及乙炔基環己醇0.05質量份，而得到透明的液體。另外，甲基氫聚矽氧烷(c3)之SiH鍵之數相對於二甲基二苯基聚矽氧烷(a3)及聚矽氧樹脂(b2)之烯基數的合計為1.50倍。
進而，添加合成例1所得之聚有機金屬矽氧烷(f1)1質量份、及與實施例1所使用者相同的鉑觸媒(d1)，相對於二甲基二苯基聚矽氧烷(a3)、聚矽氧樹脂(b2)、及甲基氫聚矽氧烷(c3)之合計而言，以鉑原子換算計為5ppm之量，將其均勻地混合，而得到黏度為4,000mPa∙s之透明的加成硬化型聚矽氧組成物。Furthermore, 1 part by mass of the polyorganometallic siloxane (f1) obtained in Synthesis Example 1 and the same platinum catalyst (d1) used in Example 1 were added to the dimethyldiphenylpolysiloxane. (a3), the polysiloxane resin (b2), and the methyl hydrogen polysiloxane (c3) in total were homogeneously mixed in an amount of 5 ppm in terms of platinum atoms to obtain a viscosity of 4,000 mPa ∙s transparent addition-hardening polysiloxane composition.
[實施例6] 除了作為(a)成分係變更成25℃時之黏度為5,000mPa∙s且直鏈狀之二甲基聚矽氧烷(a5)((組成式： ViMe2 SiO(Me2 SiO)432 (Ph2 SiO)18 SiMe2 Vi)以外，以與實施例5相同的方法，而得到黏度為4,000mPa∙s之透明的加成硬化型聚矽氧組成物。[Example 6] Except that the component (a) was changed to linear dimethylpolysiloxane (a5) ((composition formula: ViMe 2 SiO (Me 2 Except for SiO) 432 (Ph 2 SiO) 18 SiMe 2 Vi), in the same manner as in Example 5, a transparent addition-hardening polysiloxane composition with a viscosity of 4,000 mPa·s was obtained.
[實施例7] 除了作為(c)成分係變更成以下之組成式所表示之黏度為30mPa∙s之甲基氫聚矽氧烷(c4)5.4質量份以外，以與實施例1相同的方法，而得到黏度為5,200mPa∙s之透明的加成硬化型聚矽氧組成物。
[比較例1] 將兩末端被乙烯基封鎖的25℃時之黏度為5,000mPa∙s之直鏈狀之二甲基聚矽氧烷(a1)、及與實施例1所使用者相同的聚矽氧樹脂(b1)之甲苯溶液，以有效成分換算，並以質量比計，為二甲基聚矽氧烷(a2)：聚矽氧樹脂(b1)＝75：25之比例進行混合。在120℃、10mmHg(約1.3kPa)以下之減壓下，將甲苯從此混合物去除，而得到室溫下為透明的液體。[Comparative Example 1] A linear dimethylpolysiloxane (a1) having a viscosity of 5,000 mPa·s at 25°C and a viscosity of 5,000 mPa·s at both ends blocked by vinyl groups, and the same polymer as used in Example 1 were used. The toluene solution of the silicone resin (b1) is converted into an active ingredient and mixed in a ratio of dimethylpolysiloxane (a2):polysiloxane (b1)=75:25 in terms of mass ratio. Toluene was removed from this mixture at 120° C. under a reduced pressure of 10 mmHg (about 1.3 kPa) or less to obtain a liquid that was clear at room temperature.
接著，於此液體100質量份中，混合與實施例5所使用之黏度為22mPa∙s之甲基氫聚矽氧烷(c3)2.25質量份，與作為其他成分之與實施例1所使用者相同之3-環氧丙氧基丙基三甲氧基矽烷(e1)1.0質量份、以及乙炔基環己醇0.05質量份，而得到透明的液體。另外，甲基氫聚矽氧烷(c3)之SiH鍵之數相對於二甲基聚矽氧烷(a1)及聚矽氧樹脂(b1)之烯基數的合計為1.50倍。Next, in 100 parts by mass of this liquid, 2.25 parts by mass of methylhydrogen polysiloxane (c3) with a viscosity of 22 mPa·s used in Example 5 was mixed with the other components used in Example 1. The same 1.0 mass part of 3-glycidoxypropyl trimethoxysilane (e1), and 0.05 mass part of ethynylcyclohexanol, and the transparent liquid was obtained. In addition, the number of SiH bonds of methylhydrogenpolysiloxane (c3) was 1.50 times the total number of alkenyl groups of dimethylpolysiloxane (a1) and polysiloxane (b1).
進而，添加合成例1所得之聚有機金屬矽氧烷(f1)1質量份、及與實施例1所使用者相同的鉑觸媒(d1)，相對於二甲基聚矽氧烷(a1)、聚矽氧樹脂(b1)、及甲基氫聚矽氧烷(c3)之合計而言，以鉑原子換算計為5ppm之量，將其均勻地混合，而得到黏度為5,000mPa∙s之透明的加成硬化型聚矽氧組成物。Furthermore, 1 part by mass of the polyorganometallic siloxane (f1) obtained in Synthesis Example 1 and the same platinum catalyst (d1) used in Example 1 were added to the dimethylpolysiloxane (a1) , the polysiloxane resin (b1), and the methylhydrogen polysiloxane (c3) in total, in an amount of 5 ppm in terms of platinum atoms, and uniformly mixed to obtain a viscosity of 5,000 mPa∙s. Transparent addition-hardening polysiloxane composition.
[比較例2] 除了不添加合成例1所得之聚有機金屬矽氧烷(f1)以外，進行與比較例1相同的操作，而得到黏度為5,200 mPa∙s之透明的加成硬化型聚矽氧組成物。[Comparative Example 2] The same operation as in Comparative Example 1 was performed except that the polyorganometallosiloxane (f1) obtained in Synthesis Example 1 was not added to obtain a transparent addition-hardening polysilicon with a viscosity of 5,200 mPa·s oxygen composition.
[比較例3] 將兩末端被乙烯基封鎖的25℃時之黏度為5,000mPa∙s之直鏈狀之二甲基聚矽氧烷(a1)、及與實施例4所使用者相同的聚矽氧樹脂(b2)之甲苯溶液，以有效成分換算，並以質量比計，為二甲基聚矽氧烷(a1)：聚矽氧樹脂(b2)＝60：40之比例進行混合。在120℃、10mmHg(約1.3kPa)以下之減壓下，將甲苯從此混合物去除，而得到室溫下為透明的液體。[Comparative Example 3] A linear dimethylpolysiloxane (a1) with a viscosity of 5,000 mPa·s at 25°C blocked at both ends by vinyl groups, and the same polymer as used in Example 4 were used. The toluene solution of the silicone resin (b2) is converted into an active ingredient and is mixed in a ratio of dimethylpolysiloxane (a1):polysiloxane (b2)=60:40 in terms of mass ratio. Toluene was removed from this mixture at 120° C. under a reduced pressure of 10 mmHg (about 1.3 kPa) or less to obtain a liquid that was clear at room temperature.
接著，於此液體100質量份中，混合與實施例5所使用之黏度為22mPa∙s之甲基氫聚矽氧烷(c3)2.6質量份，與作為其他成分之3-環氧丙氧基丙基三甲氧基矽烷(e1)0.5質量份、以及乙炔基環己醇0.05質量份，而得到透明的液體。另外，甲基氫聚矽氧烷(c3)之SiH鍵之數相對於二甲基聚矽氧烷(a1)及聚矽氧樹脂(b2)之烯基數的合計為1.50倍。Next, 2.6 parts by mass of methylhydrogen polysiloxane (c3) with a viscosity of 22 mPa·s used in Example 5 was mixed with 100 parts by mass of this liquid, and 3-glycidoxyl as another component 0.5 mass part of propyltrimethoxysilane (e1), and 0.05 mass part of ethynylcyclohexanol, and the transparent liquid was obtained. In addition, the number of SiH bonds of methylhydrogenpolysiloxane (c3) is 1.50 times the total number of alkenyl groups of dimethylpolysiloxane (a1) and polysiloxane (b2).
進而，添加合成例1所得之聚有機金屬矽氧烷(f1)1質量份、及與實施例1所使用者相同的鉑觸媒(d1)，相對於二甲基聚矽氧烷(a1)、聚矽氧樹脂(b2)、及甲基氫聚矽氧烷(c3)之合計而言，以鉑原子換算計為5ppm之量，將其均勻地混合，而得到黏度為5,000mPa∙s之透明的加成硬化型聚矽氧組成物。Furthermore, 1 part by mass of the polyorganometallic siloxane (f1) obtained in Synthesis Example 1 and the same platinum catalyst (d1) used in Example 1 were added to the dimethylpolysiloxane (a1) , polysiloxane resin (b2), and methylhydrogen polysiloxane (c3) in total, in an amount of 5 ppm in terms of platinum atoms, and uniformly mixed to obtain a viscosity of 5,000 mPa∙s Transparent addition-hardening polysiloxane composition.
[比較例4] 將兩末端被乙烯基封鎖的25℃時之黏度為5,000mPa∙s且含有10莫耳%之二苯基矽氧基單元的直鏈狀之二甲基二苯基聚矽氧烷(a4)(組成式： ViMe2 SiO(Me2 SiO)198 (Ph2 SiO)22 SiMe2 Vi)，及與實施例4所使用者相同的聚矽氧樹脂(b2)之甲苯溶液，以有效成分換算，並以質量比計，為二甲基二苯基聚矽氧烷(a4)：聚矽氧樹脂(b2)＝60：40之比例進行混合。在120℃、10mmHg (約1.3kPa)以下之減壓下，將甲苯從此混合物去除，而得到室溫下為透明的液體。[Comparative Example 4] A linear dimethyldiphenyl polysilicon with a viscosity of 5,000 mPa∙s at 25°C and containing 10 mol% of diphenylsiloxy units, which are blocked by vinyl groups at both ends Oxane (a4) (composition formula: ViMe 2 SiO(Me 2 SiO) 198 (Ph 2 SiO) 22 SiMe 2 Vi), and a toluene solution of the same polysiloxane resin (b2) used in Example 4, In terms of the active ingredient conversion and the mass ratio, the mixture is mixed in the ratio of dimethyldiphenyl polysiloxane (a4):polysiloxane resin (b2)=60:40. Toluene was removed from this mixture at 120° C. under a reduced pressure of 10 mmHg (about 1.3 kPa) or less to obtain a liquid that was clear at room temperature.
接著，於此液體100質量份中，混合與實施例5所使用之黏度為22mPa∙s之甲基氫聚矽氧烷(c3)2.6質量份，與作為其他成分之與實施例1所使用者相同之3-環氧丙氧基丙基三甲氧基矽烷(e1)1.0質量份、以及乙炔基環己醇0.05質量份，而得到透明的液體。另外，甲基氫聚矽氧烷(c3)之SiH鍵之數相對於二甲基二苯基聚矽氧烷(a4)及聚矽氧樹脂(b2)之烯基數的合計為1.50倍。Next, in 100 parts by mass of this liquid, 2.6 parts by mass of methyl hydrogen polysiloxane (c3) with a viscosity of 22 mPa·s used in Example 5 was mixed with the other components used in Example 1. The same 1.0 mass part of 3-glycidoxypropyl trimethoxysilane (e1), and 0.05 mass part of ethynylcyclohexanol, and the transparent liquid was obtained. In addition, the number of SiH bonds of methylhydrogenpolysiloxane (c3) was 1.50 times the total number of alkenyl groups of dimethyldiphenylpolysiloxane (a4) and polysiloxane (b2).
進而，添加合成例1所得之聚有機金屬矽氧烷(f1)1質量份、及與實施例1所使用者相同的鉑觸媒(d1)，相對於二甲基二苯基聚矽氧烷(a4)、聚矽氧樹脂(b2)、及甲基氫聚矽氧烷(c3)之合計而言，以鉑原子換算計為5ppm之量，將其均勻地混合，而得到黏度為4,000 mPa∙s之透明的加成硬化型聚矽氧組成物。Furthermore, 1 part by mass of the polyorganometallic siloxane (f1) obtained in Synthesis Example 1 and the same platinum catalyst (d1) used in Example 1 were added to the dimethyldiphenylpolysiloxane. (a4), the polysiloxane resin (b2), and the methyl hydrogen polysiloxane (c3) in total were homogeneously mixed in an amount of 5 ppm in terms of platinum atoms to obtain a viscosity of 4,000 mPa ∙s transparent addition-hardening polysiloxane composition.
[比較例5] 除了作為(a)成分係變更成25℃時之黏度為5,000mPa∙s且直鏈狀之二甲基聚矽氧烷(a6)((組成式： ViMe2 SiO(Me2 SiO)380 (Ph2 SiO)20 SiMe2 Vi)以外，以與實施例5相同的方法，而得到黏度為4,000mPa∙s之透明的加成硬化型聚矽氧組成物。[Comparative Example 5] Except that the component (a) was changed to linear dimethylpolysiloxane (a6) ((composition formula: ViMe 2 SiO (Me 2 ) with a viscosity of 5,000 mPa∙s at 25°C Except for SiO) 380 (Ph 2 SiO) 20 SiMe 2 Vi), in the same manner as in Example 5, a transparent addition-hardening polysiloxane composition with a viscosity of 4,000 mPa·s was obtained.
[比較例6] 除了作為(c)成分係變更成以下之組成式所表示之黏度為30mPa∙s之甲基氫聚矽氧烷(c5)6.1質量份以外，以與實施例1相同的方法，而得到黏度為5,300mPa∙s之透明的加成硬化型聚矽氧組成物。
將實施例1～7及比較例1～6所調製之加成硬化型聚矽氧組成物之組成彙整於表1及表2。下述表中，(d)成分以外之各成分之摻合量係以質量份表示。
接著，針對以上述方式所調製之加成硬化型聚矽氧組成物，進行如以下般之試驗。將試驗的結果顯示於表3及表4。Next, with respect to the addition-curable polysiloxane composition prepared as described above, the following tests were performed. The results of the test are shown in Table 3 and Table 4.
(硬化物之光透過率之測定) 藉由使用於各實施例及各比較例中所得之加成硬化型聚矽氧組成物，以150℃進行1小時加熱而硬化，而製作厚度2mm之薄片狀之硬化物。以日立分光光度計U-3310(股份有限公司日立製作所製)測定所得之硬化物之波長400nm的全光線透過率(光路徑長2mm)。另外，將此時點之值設為「初期」。(Measurement of light transmittance of cured product) A sheet of 2 mm in thickness was produced by using the addition-curable polysiloxane composition obtained in each example and each comparative example, and heating at 150° C. for 1 hour to harden it. shaped hardening. The total light transmittance (optical path length 2 mm) of the wavelength 400nm of the obtained hardened|cured material was measured with the Hitachi spectrophotometer U-3310 (made by Hitachi, Ltd.). In addition, the value at this point is set to "initial stage".
(耐熱性試驗後之光透過率之測定) 將上述之光透過率之測定中使用的硬化物在260℃、500小時之環境下保管後，再度測定波長400nm的全光線透過率。(Measurement of light transmittance after heat resistance test) After storing the cured product used in the measurement of light transmittance above at 260°C for 500 hours, the total light transmittance at a wavelength of 400 nm was measured again.
(硬化物之硬度之測定) 測定藉由使用於各實施例及各比較例中所得之加成硬化型聚矽氧組成物，以150℃進行3小時加熱所得之硬化物之TypeA硬度。將此時點之硬度設為「初期」。(Measurement of Hardness of Hardened Product) The Type A hardness of the hardened product obtained by heating at 150° C. for 3 hours by using the addition-hardening polysiloxane composition obtained in each Example and each Comparative Example was measured. The hardness at this point was set to "initial stage".
(耐熱性試驗後之硬度之測定) 將上述之硬度之測定中使用的硬化物在260℃、500小時之環境下保管後，再度測定硬化物之TypeA硬度。硬度之變化率係依據下述之式而求出。 (變化率)=((耐熱性試驗後之硬度)÷(初期之硬度)× 100)-100(%)(Measurement of hardness after heat resistance test) After storing the cured product used in the above-mentioned hardness measurement at 260°C for 500 hours, the Type A hardness of the cured product was measured again. The change rate of hardness was calculated|required according to the following formula. (change rate)=((hardness after heat resistance test)÷(hardness at initial stage)×100)-100(%)
(以耐熱性試驗進行之重量減少率之測定) 將相對於以與上述之光透過率之測定相同的條件所製作之硬化物之初期重量設為100的情況之在260℃之環境下保管500小時後之重量進行比較。(Measurement of weight loss rate by heat resistance test) When the initial weight of the cured product produced under the same conditions as the above-mentioned measurement of light transmittance is 100, it is stored in an environment of 260°C for 500 The weights were compared after hours.
如表3及表4所示般，於加成硬化型聚矽氧組成物之(a)成分或(c)成分之至少一者以特定的範圍內導入有苯基之實施例1～7中，可得到透明性優異，又，耐熱性試驗後光透過率及硬度之變化小，且重量減少為少的硬化物。另一方面，於加成硬化型聚矽氧組成物之(a)成分及(c)成分之任一者皆不具有苯基之比較例1～3中，於耐熱性試驗中發生硬化物之破裂，而無法測定光透過率及硬度。又，於(a)成分中之苯基之量大幅超過本發明之範圍之比較例4中，耐熱試驗後之光透過率明顯降低。進而，於(a)成分中之苯基之量超過本發明之範圍之比較例5、(c)成分中之苯基之量超過本發明之範圍之比較例6中，耐熱試驗後之光透過率降低。As shown in Tables 3 and 4, in Examples 1 to 7 in which a phenyl group was introduced into at least one of (a) component or (c) component of the addition-curable polysiloxane composition within a specific range , it is possible to obtain a cured product with excellent transparency, little change in light transmittance and hardness after the heat resistance test, and little weight loss. On the other hand, in Comparative Examples 1 to 3 in which neither of the components (a) and (c) of the addition-curable polysiloxane composition has a phenyl group, in the heat resistance test, the difference of the cured product occurred. cracked, and the light transmittance and hardness could not be measured. In addition, in Comparative Example 4 in which the amount of the phenyl group in the component (a) greatly exceeded the scope of the present invention, the light transmittance after the heat resistance test was significantly lowered. Furthermore, in Comparative Example 5 in which the amount of the phenyl group in the component (a) exceeds the scope of the present invention, and Comparative Example 6 in which the amount of the phenyl group in the component (c) exceeds the scope of the present invention, the light transmits after the heat resistance test. rate decreased.
由以上內容，明瞭只要是本發明之加成硬化型聚矽氧組成物，則可賦予高溫條件下之光透過性、硬度、及重量之變化小的硬化物。From the above, it is clear that the addition-curable polysiloxane composition of the present invention can provide a cured product with little change in light transmittance, hardness, and weight under high temperature conditions.
如以上般，只要是於組成中導入有特定範圍之苯基的加成硬化型聚矽氧組成物，則可賦予透明性及耐熱變色性優異，具有適度的橡膠硬度，且高溫條件下之硬度變化及重量減少為少，裂縫耐性良好的硬化物。因而，本發明之加成硬化型聚矽氧組成物係作為LED元件之保護・密封用材料、波長之變更・調整用材料，或者透鏡之構成材料，或其他光學裝置用或光學零件用之材料特別有用。As described above, as long as it is an addition-curable polysiloxane composition in which a specific range of phenyl groups is introduced into the composition, it can impart excellent transparency and thermal discoloration resistance, and has moderate rubber hardness and hardness under high temperature conditions. Hardened product with little change and weight loss and good crack resistance. Therefore, the addition-curable polysiloxane composition of the present invention can be used as a material for protecting and sealing LED elements, a material for changing and adjusting wavelengths, a material for constituting a lens, or a material for other optical devices or optical parts. Especially useful.
另外，本發明並非限定於上述實施形態者。上述實施形態係為例示，具有與記載於本發明之申請專利範圍中的技術性思想實質上相同的構造，且達成相同的作用效果者，任一者皆包含於本發明之技術範圍內。In addition, this invention is not limited to the above-mentioned embodiment. The above-described embodiments are merely examples, and those having substantially the same structure as the technical idea described in the scope of the claims of the present invention and achieving the same effects are included in the technical scope of the present invention.
Claims (7)
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| JP7103974B2 (en) * | 2019-02-25 | 2022-07-20 | 信越化学工業株式会社 | Additive-curable silicone composition, cured silicone for light-reflecting material, light-reflecting material and optical semiconductor device |
| JP7360910B2 (en) * | 2019-11-18 | 2023-10-13 | 株式会社カネカ | A curable composition and a semiconductor device using the composition as a sealant. |
| CN113652194B (en) * | 2021-08-19 | 2023-05-05 | 广东万木新材料科技有限公司 | Phenyl polysiloxane adhesive and preparation method thereof |
| CN113930157B (en) * | 2021-10-29 | 2022-05-06 | 上海宜瓷龙新材料股份有限公司 | Preservative-free water-based building coating and preparation method thereof |
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| JP2008291148A (en) * | 2007-05-25 | 2008-12-04 | Shin Etsu Chem Co Ltd | Silicone gel composition excellent in heat resistance |
| JP2014189789A (en) * | 2013-03-28 | 2014-10-06 | Sekisui Chem Co Ltd | Curable composition for optical semiconductor device, and optical semiconductor device using the same |
| JP2016169331A (en) * | 2015-03-13 | 2016-09-23 | 信越化学工業株式会社 | Method for producing laminate and curable silicone gel composition for use in the method |
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| JPS60163966A (en) | 1984-02-06 | 1985-08-26 | Shin Etsu Chem Co Ltd | Heat-resistant organopolysiloxane composition |
| JP3344286B2 (en) | 1997-06-12 | 2002-11-11 | 信越化学工業株式会社 | Addition-curable silicone resin composition |
| JP2002060719A (en) * | 2000-08-21 | 2002-02-26 | Shin Etsu Chem Co Ltd | Adhesive silicone rubber composition and semiconductor device |
| JP4009067B2 (en) | 2001-03-06 | 2007-11-14 | 信越化学工業株式会社 | Addition-curing silicone resin composition |
| JP2004186168A (en) | 2002-11-29 | 2004-07-02 | Shin Etsu Chem Co Ltd | Silicone resin composition for light emitting diode element |
| TW200427111A (en) * | 2003-03-12 | 2004-12-01 | Shinetsu Chemical Co | Material for coating/protecting light-emitting semiconductor and the light-emitting semiconductor device |
| EP2752459B1 (en) | 2011-12-08 | 2017-11-15 | Momentive Performance Materials Japan LLC | Hydrosilylation-curable silicone rubber composition |
| US20150346601A1 (en) * | 2013-04-26 | 2015-12-03 | Chi Mei Corporation | Photosensitive polysiloxane composition, protective film and element having the protective film |
| WO2015034821A1 (en) * | 2013-09-03 | 2015-03-12 | Dow Corning Corporation | Additive for a silicone encapsulant |
| KR102338110B1 (en) * | 2013-12-16 | 2021-12-09 | 모멘티브 파포만스 마테리아루즈 쟈판 고도가이샤 | Addition-curable silicone composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2008291148A (en) * | 2007-05-25 | 2008-12-04 | Shin Etsu Chem Co Ltd | Silicone gel composition excellent in heat resistance |
| JP2014189789A (en) * | 2013-03-28 | 2014-10-06 | Sekisui Chem Co Ltd | Curable composition for optical semiconductor device, and optical semiconductor device using the same |
| JP2016169331A (en) * | 2015-03-13 | 2016-09-23 | 信越化学工業株式会社 | Method for producing laminate and curable silicone gel composition for use in the method |
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| JP2018184580A (en) | 2018-11-22 |
| KR20180120595A (en) | 2018-11-06 |
| CN108795049A (en) | 2018-11-13 |
| TW201843240A (en) | 2018-12-16 |
| CN108795049B (en) | 2021-05-18 |
| KR102482134B1 (en) | 2022-12-29 |
| JP6751368B2 (en) | 2020-09-02 |
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