CN110229524B - Curable silicone composition for light-reflecting material, cured silicone resin, reflector, and LED device - Google Patents
Curable silicone composition for light-reflecting material, cured silicone resin, reflector, and LED device Download PDFInfo
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- CN110229524B CN110229524B CN201910162581.1A CN201910162581A CN110229524B CN 110229524 B CN110229524 B CN 110229524B CN 201910162581 A CN201910162581 A CN 201910162581A CN 110229524 B CN110229524 B CN 110229524B
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- silicone composition
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- 239000000463 material Substances 0.000 title claims abstract description 110
- 239000000203 mixture Substances 0.000 title claims abstract description 89
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 69
- 229920002050 silicone resin Polymers 0.000 title claims description 28
- -1 polycyclic hydrocarbon Chemical class 0.000 claims abstract description 55
- 239000000047 product Substances 0.000 claims abstract description 49
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 45
- 150000001875 compounds Chemical class 0.000 claims abstract description 30
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 30
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 16
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 15
- 238000007259 addition reaction Methods 0.000 claims abstract description 13
- 238000006459 hydrosilylation reaction Methods 0.000 claims abstract description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910021485 fumed silica Inorganic materials 0.000 claims abstract description 7
- 239000007809 chemical reaction catalyst Substances 0.000 claims abstract description 6
- 150000003961 organosilicon compounds Chemical class 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 31
- 238000002156 mixing Methods 0.000 claims description 18
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 16
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 claims description 13
- 125000003342 alkenyl group Chemical group 0.000 claims description 13
- 150000002430 hydrocarbons Chemical group 0.000 claims description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 5
- 125000005017 substituted alkenyl group Chemical group 0.000 claims description 3
- 238000002845 discoloration Methods 0.000 abstract description 13
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 10
- 229930195733 hydrocarbon Natural products 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 description 30
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 24
- 239000000126 substance Substances 0.000 description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 12
- 238000001723 curing Methods 0.000 description 11
- 230000003078 antioxidant effect Effects 0.000 description 9
- 229910052697 platinum Inorganic materials 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 8
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- 230000000052 comparative effect Effects 0.000 description 7
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- 238000000034 method Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000005024 alkenyl aryl group Chemical group 0.000 description 4
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- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 3
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 3
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- 125000003118 aryl group Chemical group 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
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- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 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
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000005843 halogen group Chemical group 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
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000004611 light stabiliser Substances 0.000 description 3
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 3
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- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 3
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 2
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 description 2
- 125000006039 1-hexenyl group Chemical group 0.000 description 2
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 description 2
- 125000006043 5-hexenyl group Chemical group 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004954 Polyphthalamide Substances 0.000 description 2
- 229910020388 SiO1/2 Inorganic materials 0.000 description 2
- 229910020447 SiO2/2 Inorganic materials 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001408 amides Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- FSIJKGMIQTVTNP-UHFFFAOYSA-N bis(ethenyl)-methyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(C=C)C=C FSIJKGMIQTVTNP-UHFFFAOYSA-N 0.000 description 2
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
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- 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
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- 238000002360 preparation method Methods 0.000 description 2
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- 229910052703 rhodium Inorganic materials 0.000 description 2
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- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- OQJPAHYVGNJBJK-UHFFFAOYSA-N (3-dimethylsilylphenyl)-dimethylsilane Chemical compound C[SiH](C)C1=CC=CC([SiH](C)C)=C1 OQJPAHYVGNJBJK-UHFFFAOYSA-N 0.000 description 1
- UHXCHUWSQRLZJS-UHFFFAOYSA-N (4-dimethylsilylidenecyclohexa-2,5-dien-1-ylidene)-dimethylsilane Chemical compound C[Si](C)C1=CC=C([Si](C)C)C=C1 UHXCHUWSQRLZJS-UHFFFAOYSA-N 0.000 description 1
- KQERVIARWMHFOS-UHFFFAOYSA-N (4-dimethylsilylphenyl)-dimethylsilane Chemical compound C[SiH](C)C1=CC=C([SiH](C)C)C=C1 KQERVIARWMHFOS-UHFFFAOYSA-N 0.000 description 1
- CZNRFEXEPBITDS-UHFFFAOYSA-N 2,5-bis(2-methylbutan-2-yl)benzene-1,4-diol Chemical compound CCC(C)(C)C1=CC(O)=C(C(C)(C)CC)C=C1O CZNRFEXEPBITDS-UHFFFAOYSA-N 0.000 description 1
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 1
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- GPNYZBKIGXGYNU-UHFFFAOYSA-N 2-tert-butyl-6-[(3-tert-butyl-5-ethyl-2-hydroxyphenyl)methyl]-4-ethylphenol Chemical compound CC(C)(C)C1=CC(CC)=CC(CC=2C(=C(C=C(CC)C=2)C(C)(C)C)O)=C1O GPNYZBKIGXGYNU-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
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 241001050985 Disco Species 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- MUUXBTFQEXVEEI-UHFFFAOYSA-N [2-(dimethyl-$l^{3}-silanyl)phenyl]-dimethylsilicon Chemical compound C[Si](C)C1=CC=CC=C1[Si](C)C MUUXBTFQEXVEEI-UHFFFAOYSA-N 0.000 description 1
- 239000002313 adhesive film Substances 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
- 150000001412 amines Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
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- 230000001588 bifunctional effect Effects 0.000 description 1
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 1
- DSVRVHYFPPQFTI-UHFFFAOYSA-N bis(ethenyl)-methyl-trimethylsilyloxysilane;platinum Chemical compound [Pt].C[Si](C)(C)O[Si](C)(C=C)C=C DSVRVHYFPPQFTI-UHFFFAOYSA-N 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 1
- 125000005708 carbonyloxy group Chemical group [*:2]OC([*:1])=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
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- 239000000470 constituent Substances 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
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- 238000006731 degradation reaction Methods 0.000 description 1
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- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 description 1
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- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
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- ZPNJBTBYIHBSIG-UHFFFAOYSA-N phenyl-(2,2,6,6-tetramethylpiperidin-4-yl)methanone Chemical compound C1C(C)(C)NC(C)(C)CC1C(=O)C1=CC=CC=C1 ZPNJBTBYIHBSIG-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—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
- C08G77/48—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
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- 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
-
- 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
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Abstract
The present invention provides a curable silicone composition for a light-reflecting material, which has high fluidity, produces a cured product that has excellent heat resistance (thermal stability), particularly excellent thermal discoloration resistance, and can achieve a high light reflectance. The curable silicone composition for light-reflecting materials is characterized by containing: 30-70 parts by mass of (A-1): (a) an addition reaction product of a compound having 2 hydrogen atoms bonded to silicon atoms in one molecule represented by the general formula (1) and (b) a polycyclic hydrocarbon having 2 addition-reactive carbon-carbon double bonds in one molecule, which has at least 2 addition-reactive carbon-carbon double bonds in one molecule; 30-70 parts by mass of (A-2): a compound represented by the general formula (3); (B) an organosilicon compound having 3 or more hydrogen atoms bonded to silicon atoms in one molecule; (C) a hydrosilylation reaction catalyst; (D) titanium oxide powder; and (E) a fumed silica powder.
Description
Technical Field
The present invention relates to a curable silicone composition for a light-reflecting material (white thermosetting silicone composition) that produces a cured silicone resin useful as a light-reflecting material, particularly as a reflector material for a white LED (light-emitting diode), a cured product of the composition, and a reflector and an LED device using the cured product.
Background
In recent years, optical semiconductor elements such as LEDs have been widely used as indicators or light sources because of their high efficiency of light emission and their excellent driving characteristics and lighting repetition characteristics. In particular, white LEDs are widely used as backlights for display devices and flash lamps for cameras, and are expected as next-generation illumination devices. In order to improve light extraction efficiency in the irradiation direction, such a light-emitting device is equipped with a member (hereinafter referred to as a reflector) that reflects emitted light.
At present, polyphthalamide resins are widely used as materials for reflectors (hereinafter, referred to as reflector materials). However, the polyphthalamide resin is likely to undergo deterioration, particularly discoloration, peeling, a decrease in mechanical strength, and the like, due to long-term use, and is difficult to be applied to a current high-output light-emitting element.
In order to solve such problems, patent documents 1 to 4 propose a reflector material containing an epoxy resin, a silicone, a metal oxide, and the like as constituent components, and patent document 5 proposes a ceramic reflector material. However, these solid materials have excellent heat resistance and mechanical properties, but have poor fluidity at room temperature, and therefore have problems in workability and workability such as high temperature required for molding. Further, these solid materials have a problem in that they are difficult to form into fine structures or structures having a large area because they are poor in fluidity even at high temperatures.
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 2656336
Patent document 2: japanese patent laid-open No. 2008-106226
Patent document 3: japanese patent laid-open No. 2008-189833
Patent document 4: japanese laid-open patent publication No. 2013-221075
Patent document 5: japanese patent application laid-open No. 2008-117932
Disclosure of Invention
Technical problem to be solved by the invention
The present invention has been made in view of the above circumstances, and provides a curable silicone composition for a light reflective material, which has high fluidity at room temperature, produces a cured product having excellent heat resistance (thermal stability), particularly excellent thermal discoloration resistance, and can obtain a high light reflectance. That is, an object of the present invention is to provide a curable silicone composition for a light-reflecting material that produces a cured silicone resin useful as a light-reflecting material, particularly as a reflector material for a white LED, and a reflector (particularly for a white light-emitting diode) formed from a cured product of the composition.
Means for solving the problems
In order to achieve the above object, the present invention provides a curable silicone composition for a light reflective material, comprising:
30-70 parts by mass of (A-1): (a) an addition reaction product of a compound having 2 hydrogen atoms bonded to silicon atoms in one molecule represented by the following general formula (1) and (b) a polycyclic hydrocarbon having 2 addition-reactive carbon-carbon double bonds in one molecule, the addition reaction product having at least 2 addition-reactive carbon-carbon double bonds in one molecule;
30-70 parts by mass of (A-2): a compound represented by the following general formula (3) (wherein the total of the component (A-1) and the component (A-2) is 100 parts by mass);
(B) an organosilicon compound having 3 or more silicon-bonded hydrogen atoms in one molecule (the total amount of silicon-bonded hydrogen atoms in the composition is 0.5 to 3.0 in terms of a molar ratio relative to addition-reactive carbon-carbon double bonds in the composition);
(C) a hydrosilylation reaction catalyst;
(D) titanium oxide powder; and
(E) fumed silica powder.
[ chemical formula 1]
Wherein A is a divalent group selected from the group consisting of groups represented by the following general formula (2), and R is1Independently, the alkyl group is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group having 1 to 6 carbon atoms.
[ chemical formula 2]
[ chemical formula 3]
In the formula, Ph is phenyl, R2Independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, R3Is a group containing an addition reactive carbon-carbon double bond, and n is an integer of 1 to 20.
Such a curable silicone composition for a light reflective material has high fluidity at room temperature, and can produce a cured product that has excellent heat resistance (thermal stability), particularly excellent thermal discoloration resistance, and can achieve a high light reflectance.
Further, it is preferable that the (b) is represented by the following general formula (4).
[ chemical formula 4]
In the formula, R4The alkenyl group is unsubstituted or substituted alkenyl group with 2-12 carbon atoms.
Further, it is preferable that the (b) is any one of 5-vinylbicyclo [2.2.1] hept-2-ene, 6-vinylbicyclo [2.2.1] hept-2-ene and a combination thereof.
With such a raw material (b), strength can be more effectively imparted to the cured product, and high hardness can be achieved.
The component (B) is preferably a siloxane compound represented by the following general formula (5).
[ chemical formula 5]
In the formula, R5Independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms other than an alkenyl group, R6Is methyl or hydrogen atom, p is an integer of 1 to 10, and q is an integer of 0 to 7. The siloxane units denoted by p and the siloxane units denoted by q are arranged in a random manner with respect to one another.
When the component (B) is used as a reflector material, a cured product having sufficient mechanical properties can be obtained.
In this case, the viscosity at 25 ℃ is preferably 5 to 500 pas.
Such a viscosity provides high fluidity and more excellent workability and workability.
The present invention also provides a cured product of a silicone resin for a light-reflecting material, which is obtained by molding and curing the curable silicone composition for a light-reflecting material.
Such a cured silicone resin for a light-reflecting material can be suitably used as a reflector material.
In this case, it is preferable that the reflectance of light having a wavelength of 430 to 800nm immediately after curing is 95% or more, and the reflectance of light having a wavelength of 430 to 800nm after exposure to an environment at 170 ℃ for 1000 hours is 82% or more.
Such a cured silicone resin for a light-reflecting material can be suitably used as a reflector material which is less likely to suffer deterioration due to long-term use, particularly discoloration, peeling, a decrease in mechanical strength, and the like.
In this case, the shore D hardness is preferably 65 or more.
With such shore D hardness, the cured product of the reflector material has a hardness more suitable for cutting and dicing with a dicing saw.
The present invention also provides a reflector formed of the cured silicone resin for a light-reflecting material.
Further, the present invention provides an LED device equipped with the above reflector.
Such a reflector or LED device can maintain high light extraction efficiency over a long period of time.
Effects of the invention
The curable silicone composition for a light reflective material of the present invention has high fluidity at room temperature, and therefore has excellent workability and handling properties. Furthermore, the cured silicone resin for light-reflecting materials obtained by curing the above composition is excellent in light-reflecting properties and heat resistance (thermal stability), and particularly excellent in heat discoloration resistance. Therefore, the cured product is useful as a light-reflecting material, for example, a reflector material for a light-emitting device, particularly a white LED.
Detailed Description
As described above, development of a curable silicone composition for a light reflective material which has high fluidity at room temperature, produces a cured product having excellent heat resistance (thermal stability), particularly excellent thermal discoloration resistance, and can provide a high light reflectance has been demanded.
The present inventors have conducted extensive studies to solve the above-mentioned problems, and as a result, have found that a curable silicone composition for a light-reflecting material, which has high fluidity at room temperature, produces a cured product having excellent heat resistance (thermal stability), particularly excellent thermal discoloration resistance, and can achieve a high light reflectance, can be obtained by blending titanium oxide powder into a thermosetting silicone composition containing a reaction addition product generated by a hydrosilylation reaction having a specific structure and an organopolysiloxane having a specific structure, and have completed the present invention.
That is, the present invention is a curable silicone composition for a light reflective material, comprising:
30-70 parts by mass of (A-1): (a) an addition reaction product of a compound having 2 hydrogen atoms bonded to silicon atoms in one molecule represented by the above general formula (1) and (b) a polycyclic hydrocarbon having 2 addition-reactive carbon-carbon double bonds in one molecule, the addition reaction product having at least 2 addition-reactive carbon-carbon double bonds in one molecule;
30-70 parts by mass of (A-2): a compound represented by the general formula (3) (wherein the total of the component (A-1) and the component (A-2) is 100 parts by mass);
(B) an organosilicon compound having 3 or more silicon-bonded hydrogen atoms in one molecule (the total amount of silicon-bonded hydrogen atoms in the composition is 0.5 to 3.0 in terms of a molar ratio relative to addition-reactive carbon-carbon double bonds in the composition);
(C) a hydrosilylation reaction catalyst;
(D) titanium oxide powder; and
(E) fumed silica powder.
The present invention will be described in detail below, but the present invention is not limited thereto. In the present specification, Me and Ph represent methyl and phenyl groups, respectively, and the viscosity is a value measured by a rotational viscometer.
[ (A-1) component ]
The component (a-1) of the curable silicone composition for a light-reflecting material of the present invention is a component that imparts strength to a cured product after curing to achieve high hardness.
The component (A-1) is an addition reaction product of (a) a compound represented by the following general formula (1) and having 2 hydrogen atoms bonded to silicon atoms in one molecule and (b) a polycyclic hydrocarbon having 2 addition-reactive carbon-carbon double bonds in one molecule, and has at least 2 addition-reactive carbon-carbon double bonds in one molecule. The following will describe the raw material (a) and the raw material (b) as the raw material of the component (A-1).
[ chemical formula 1]
Wherein A is a divalent group selected from the group consisting of groups represented by the following general formula (2), and R is1Independently, the alkyl group is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group having 1 to 6 carbon atoms.
[ chemical formula 2]
< raw Material (a) >)
In the (a) compound (raw material (a)) having 2 hydrogen atoms (hereinafter, sometimes referred to as "SiH") bonded to silicon atoms in one molecule represented by the above general formula (1) as a reaction raw material of the component (a-1), a in the above general formula (1) is a divalent group represented by the above general formula (2), and thus is a compound represented by the following general formula (6),
[ chemical formula 6]
R1Independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, preferably an unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms.
In the above general formula (6), when R is1Examples of the monovalent hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, isopentyl, hexyl, and sec-hexyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; aryl groups such as phenyl, o-tolyl, m-tolyl, and p-tolyl; aralkyl groups such as benzyl and 2-phenylethyl; alkenyl groups such as vinyl, allyl, 1-butenyl, 1-hexenyl and the like; alkenylaryl such as p-vinylphenyl; and halogenated alkyl groups such as chloromethyl, 3-chloropropyl, 3,3, 3-trifluoropropyl, etc., wherein 1 or more hydrogen atoms bonded to carbon atoms in these groups are substituted with a halogen atom, cyano, an epoxy ring-containing group, etc.; 2-cyanoethyl; 3-glycidoxypropyl and the like.
In addition, when R is1Examples of the alkoxy group include methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy and tert-butoxy.
Among the above, R1Groups other than alkenyl and alkenylaryl groups are preferred because all R in one molecule1The methyl group is particularly preferred because it is industrially easy to prepare and easily available.
Examples of the compound represented by the above general formula (6) include the structural formula: HMe2Si-p-C6H4-SiMe21, 4-bis (dimethylsilyl) benzene represented by H, structural formula: HMe2Si-m-C6H4-SiMe21, 3-bis (dimethylsilyl) benzene represented by H, structural formula: HMe2Si-o-C6H4-SiMe2And silylene compounds such as 1, 2-bis (dimethylsilyl) benzene represented by H.
The compound represented by the above general formula (6) (the above raw material (a) as a reaction raw material of the component (a-1)) may be used singly or in combination of two or more.
< raw Material (b) >)
In the polycyclic hydrocarbon (raw material (b)) having 2 addition-reactive carbon-carbon double bonds in one molecule of (b) which is the reaction raw material of the component (a-1), "addition reactivity" means a property of being able to accept addition of a hydrogen atom bonded to a silicon atom (well known as a hydrosilylation reaction).
The raw material (b) may be any of: (i) a compound having an addition-reactive carbon-carbon double bond formed between 2 adjacent carbon atoms among the carbon atoms forming the polycyclic skeleton of the polycyclic hydrocarbon; (ii) a compound in which a hydrogen atom bonded to a carbon atom forming a polycyclic skeleton of a polycyclic hydrocarbon is substituted with a group having an addition-reactive carbon-carbon double bond; or (iii) a compound in which an addition-reactive carbon-carbon double bond is formed between 2 adjacent carbon atoms among the carbon atoms forming the polycyclic skeleton of the polycyclic hydrocarbon, and a hydrogen atom bonded to a carbon atom forming the polycyclic skeleton of the polycyclic hydrocarbon is substituted with a group containing an addition-reactive carbon-carbon double bond. Examples of the group having an addition-reactive carbon-carbon double bond include alkenyl groups such as a vinyl group, an allyl group, a propenyl group, a butenyl group, a hexenyl group, and a norbornyl group, and particularly a group having 2 to 12 carbon atoms.
Examples of the component (b) include alkenyl norbornene compounds represented by the following general formula (4). Further, specific examples of the compound represented by the following general formula (4) include 5-vinylbicyclo [2.2.1] hept-2-ene represented by the following structural formula (7), 6-vinylbicyclo [2.2.1] hept-2-ene represented by the following structural formula (8), and a combination of both (hereinafter, when it is not necessary to distinguish between the three, they may be collectively referred to as "vinylnorbornene").
[ chemical formula 4]
In the formula, R4The alkenyl group is unsubstituted or substituted alkenyl group with 2-12 carbon atoms.
[ chemical formula 7]
[ chemical formula 8]
The substitution position of the vinyl group of the vinyl norbornene may be either cis configuration (exo configuration) or trans configuration (endo configuration), and the difference in such configuration does not cause a particular difference in reactivity of the raw material (b), and therefore, a combination of isomers of both configurations may be used.
< preparation of component (A-1) >
The component (a-1) of the curable silicone composition for light-reflecting materials of the present invention is obtained as an addition reaction product having at least 2 addition-reactive carbon-carbon double bonds in one molecule and no SiH, and is obtained by subjecting 1 mole of the raw material (a) having 2 SiH in one molecule to an addition reaction with an excess of the raw material (b) having 2 addition-reactive carbon-carbon double bonds in one molecule, which is more than 1 mole and 10 moles or less, preferably more than 1 mole and 5 moles or less, in the presence of a hydrosilylation reaction catalyst.
The component (A-1) obtained in the above manner may contain, in addition to the addition-reactive carbon-carbon double bond derived from the raw material (b), R derived from the raw material (a) (specifically, R in the general formula (1))1) Is a carbon-carbon double bond of addition reactivity, and thus contains in one moleculeThere are at least 2 addition-reactive carbon-carbon double bonds, the number of which is preferably 2 to 6, more preferably 2. When the addition-reactive carbon-carbon double bond is in such an amount, a cured product obtained by curing the curable silicone composition for a light-reflecting material of the present invention will not become brittle.
As the hydrosilylation catalyst, any conventionally known catalyst can be used. Examples thereof include carbon powder carrying platinum metal, platinum black, platinum chloride, chloroplatinic acid, reaction products of chloroplatinic acid and monohydric alcohols, and complexes of platinum and vinylsiloxanes such as divinyltetramethyldisiloxane; platinum catalysts such as chloroplatinic acid-olefin complexes and platinum bis (acetoacetate); platinum group metal catalysts such as palladium catalysts and rhodium catalysts. The conditions for addition reaction, the use of a solvent, and the like are not particularly limited, and may be the same as usual.
As described above, since the raw material (b) is used in an excess molar amount relative to the raw material (a) in the production of the component (a-1), the component (a-1) has 2 addition-reactive carbon-carbon double bonds derived from the structure of the raw material (b) in one molecule. The component (A-1) may have a structure in which a residue derived from the raw material (a) is bonded to a divalent residue derived from the raw material (b) but not having an addition-reactive carbon-carbon double bond.
That is, examples of the component (A-1) include compounds represented by the following general formula (9).
[ chemical formula 9]
Y-X-(Y′-X)m-Y (9)
Wherein X is a divalent residue of the compound of the raw material (a), Y is a monovalent residue of the polycyclic hydrocarbon of the raw material (b), Y' is a divalent residue of the raw material (b), and m is an integer of 0 to 10, preferably 0 to 5.
The value of m, which is the number of repeating units represented by (Y' -X), can be set by adjusting the molar excess of the raw material (a) that reacts with 1 mole of the raw material (b).
Specific examples of Y in the general formula (9) include monovalent residues represented by the following structural formula (hereinafter, when there is no need to distinguish between the following 6 types of residues, these are collectively referred to as "NB group", and the structures of the 6 types of residues may not be distinguished and may be abbreviated as "NB").
Specific examples of Y' in the general formula (9) include divalent residues represented by the following structural formulae.
The structure of the asymmetric divalent residue represented by the above structural formula is not limited to the above description, and the structure includes substantially all of the structures rotated by 180 degrees on the paper surface.
Preferred specific examples of the component (A-1) represented by the above general formula (9) are shown below, but the present invention is not limited thereto (the meaning of "NB" is as described above).
Wherein r is an integer of 0 to 10.
Further, the component (a-1) of the curable silicone composition for a light-reflecting material of the present invention may be used singly or in combination of two or more.
[ (A-2) component ]
The component (A-2) has high compatibility with the component (A-1), and is a component that imparts heat resistance (thermal stability), particularly resistance to thermal discoloration, without lowering the strength of the cured product after curing.
The component (A-2) is a linear diorganopolysiloxane having a main chain composed of repeating diphenylsiloxane units and having both molecular chain terminals capped with triorganosiloxy groups having groups containing addition-reactive carbon-carbon double bonds. The organopolysiloxane of component (A-2) may be used alone, or two or more organopolysiloxanes different in molecular weight, type of organic group bonded to a silicon atom, and the like may be used together.
As R in the above general formula (3)3The addition-reactive carbon-carbon double bond-containing group (b) is a group containing a carbon-carbon double bond having a property of accepting addition of a hydrogen atom bonded to a silicon atom (well known as a hydrosilylation reaction), as described in the above description of < raw material (b) >.
The addition-reactive carbon-carbon double bond-containing group may be used singly or in combination of two or more.
Specific examples of the group having an addition-reactive carbon-carbon double bond include alkenyl groups having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms such as vinyl group, allyl group, 5-hexenyl group, propenyl group, butenyl group, and the like; an alkadienyl group having 4 to 10 carbon atoms such as 1, 3-butadienyl group; acryloyloxy (-o (o) CCH ═ CH2) Methacryloxy (-O) (O) CC (CH)3)＝CH2) Combinations of the above alkenyl groups and carbonyloxy groups; acrylamido (-NH (O) CCH ═ CH2) And combinations of the above alkenyl groups and carbonylamino groups.
Among these, vinyl groups, allyl groups and 5-hexenyl groups are preferable as the groups containing an addition-reactive carbon-carbon double bond, and vinyl groups are particularly preferable from the viewpoints of productivity and cost in obtaining a raw material of the component (A-2), and reactivity of the component (A-2).
R in the above general formula (3)2Independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and examples thereof include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, isopentyl, hexyl, and sec-hexyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; aryl groups such as phenyl, o-tolyl, m-tolyl, and p-tolyl; aralkyl groups such as benzyl and 2-phenylethyl; alkenyl groups such as vinyl, allyl, 1-butenyl, 1-hexenyl and the like; alkenylaryl such as p-vinylphenyl; and 1 or more hydrogen atoms bonded to carbon atoms in these groups are substituted with halogen atoms, cyano groups, or epoxy ring-containing groupsHalogenated alkyl groups such as chloromethyl, 3-chloropropyl, and 3,3, 3-trifluoropropyl; 2-cyanoethyl; 3-glycidoxypropyl and the like.
Among the above, due to R2The compound which is a methyl group or a phenyl group is particularly preferable because it can be industrially easily produced and obtained.
In the component (A-2), the degree of polymerization n of the diphenylsiloxane unit is 1 to 20, preferably 1 to 15, and more preferably 2 to 10. If n is more than 20, the fluidity or the compatibility with the component (A-1) may be lowered, which is not preferable.
The amount of the component (A-2) to be incorporated is 30 to 70 parts by mass, preferably 35 to 65 parts by mass, and more preferably 40 to 60 parts by mass, based on 100 parts by mass of the total of the components (A-1) and (A-2). If the amount of the component (A-2) is less than 30 parts by mass, the thermal discoloration resistance is lowered, and if it exceeds 70 parts by mass, the strength, particularly the hardness, of the cured product is lowered.
The component (A-2) can be obtained, for example, by: after or simultaneously with hydrolysis and condensation of a bifunctional silane such as dichlorodiphenylsilane or dialkoxydiphenylsilane, the terminal is capped with a capping agent having a group containing an addition-reactive carbon-carbon double bond.
[ (B) component ]
The component (B) of the curable silicone composition for a light-reflecting material of the present invention is an organosilicon compound having 3 or more SiH in one molecule. The SiH in the component (B) is added to at least 2 addition-reactive carbon-carbon double bonds in one molecule of the components (A-1) and (A-2) by a hydrosilylation reaction, thereby producing a cured product having a three-dimensional network structure.
Examples of the component (B) include siloxane compounds represented by the following general formula (5).
[ chemical formula 5]
In the formula, R5Independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms other than an alkenyl group, R6Is methyl or hydrogen atom, p is an integer of 1 to 10, and q is an integer of 0 to 7. The siloxane units denoted by p and the siloxane units denoted by q are arranged in a random manner with respect to one another.
As R in the above general formula (5)5Examples thereof include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, isopentyl, hexyl, and sec-hexyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; aryl groups such as phenyl, o-tolyl, m-tolyl, and p-tolyl; aralkyl groups such as benzyl and 2-phenylethyl; alkenylaryl such as p-vinylphenyl; and halogenated alkyl groups such as chloromethyl, 3-chloropropyl, 3,3, 3-trifluoropropyl, etc., wherein 1 or more hydrogen atoms bonded to carbon atoms in these groups are substituted with a halogen atom, cyano, an epoxy ring-containing group, etc.; 2-cyanoethyl; 3-glycidoxypropyl and the like.
Among the above, due to R5The compound which is a methyl group or a phenyl group is particularly preferable because it can be industrially easily produced and obtained.
Preferred specific examples of the component (B) are shown below, but the present invention is not limited thereto.
HMe2SiO(HMeSiO)2(Ph2SiO)2SiMe2H
HMe2SiO(HMeSiO)2(Ph2SiO)2(Me2SiO)2SiMe2H
HMe2SiO(HMeSiO)1(Ph2SiO)1(Me2SiO)4SiMe2H
HMe2SiO(HMeSiO)3(Me2SiO)5SiMe2H
The curable silicone composition for light-reflecting materials of the present invention may be used as component (B) alone or in combination of two or more.
(B) The blending amount of the components is preferably set as follows. The curable silicone composition for a light-reflecting material of the present invention may contain one or both of a component having SiH other than the component (B) (for example, the component (G) described below) and a component having an addition-reactive carbon-carbon double bond bonded to a silicon atom other than the component (a-1) or (a-2) (for example, a vinylsiloxane which may be contained in the present composition as the component (C) described below in a state where a complex with platinum is formed). Therefore, the amount of the silicon atom-bonded hydrogen atoms in the present composition is preferably 0.5 to 3.0 mol, and more preferably 0.8 to 2.0 mol, based on 1 mol of the silicon atom-bonded addition-reactive carbon-carbon double bonds in the present composition. When the blending amount of the component (B) is an amount satisfying such a condition, a cured product having sufficient mechanical properties can be obtained from the curable silicone composition for a light-reflecting material of the present invention when used as a reflector material.
When only the components (a-1) and (a-2) have addition-reactive carbon-carbon double bonds bonded to silicon atoms and only the component (B) has SiH, the amount of the component (B) in the curable silicone composition for a light-reflecting material of the present invention is preferably 0.5 to 3.0 moles of SiH in the component (B) relative to 1 mole of the addition-reactive carbon-carbon double bonds in the component (a), and more preferably 0.8 to 2.0 moles of SiH in the component (B) relative to 1 mole of the addition-reactive carbon-carbon double bonds in the component (a).
[ (C) ingredient ]
As the hydrosilylation reaction catalyst of the component (C) of the curable silicone composition for a light-reflecting material of the present invention, any conventionally known catalyst can be used. Examples thereof include carbon powder carrying platinum metal, platinum black, platinum chloride, chloroplatinic acid, reaction products of chloroplatinic acid and monohydric alcohols, and complexes of platinum and vinylsiloxanes such as divinyltetramethyldisiloxane; platinum catalysts such as chloroplatinic acid-olefin complexes and platinum bis (acetoacetate); platinum group metal catalysts such as palladium catalysts and rhodium catalysts.
(C) The amount of the component (C) to be blended in the curable silicone composition for a light-reflecting material of the present invention is not particularly limited as long as it is an effective amount as a catalyst, and is preferably 1 to 500ppm, particularly preferably about 2 to 100ppm, based on the mass of the platinum group metal atom, relative to the total amount of the components (A-1), (A-2) and (B). By setting the blending amount within such a range, the time required for the curing reaction can be made appropriate, and problems such as coloring of the cured product do not occur.
(C) The components can be used singly or in combination of two or more.
[ (D) component ]
The component (D) of the curable silicone composition for a light-reflecting material of the present invention is titanium oxide powder. Since the titanium oxide powder (metal compound powder) of the component (D) is white, the cured silicone resin for a light-reflecting material of the present invention exhibits a good light reflectance by blending the component (D).
(D) The particle size of the component (D) is not particularly limited, but generally, a commercially available material having an average particle size in the range of 0.1 to 200 μm is often used and easy to handle, and a material having an average particle size in the range of 0.5 to 100 μm is more preferable. When the average particle diameter of the component (D) is in the range of 0.1 to 200 μm, the curable silicone composition for a light-reflecting material of the present invention is likely to have good fluidity, and the surface of the cured product of the composition is less likely to be roughened, so that the light-reflecting performance is effectively improved. In the present specification, the average particle diameter refers to a volume-based average particle diameter corresponding to 50% of the cumulative distribution, which is obtained by a particle size distribution measuring apparatus using a laser diffraction method.
The amount of the component (D) is preferably 50 to 1000 parts by mass, more preferably 60 to 900 parts by mass, and still more preferably 100 to 800 parts by mass, based on 100 parts by mass of the total of the components (A-1), (A-2), and (B). When the blending amount is in the range of 50 to 1000 parts by mass, the flowability of the curable silicone composition for a light-reflecting material of the present invention is likely to be good, and the light-reflecting performance of a cured product of the composition is likely to be sufficient.
(D) Two or more of the components may be used in combination.
[ (E) ingredient ]
The component (E) of the curable silicone composition for a light-reflecting material of the present invention is a fumed silica powder. By including the component (E) in the composition, precipitation and aggregation of the component (D) having a specific gravity higher than those of the components (A-1), (A-2) and (B) can be prevented, and a cured product free from unevenness can be obtained.
(E) The particle size of the component (E) is not particularly limited, and generally, a commercially available material having an average particle size of 1 to 100nm is usually used for the component (E) and the handling thereof is easy, and a material having a particle size of 5 to 50nm is more preferable. When the average particle diameter of the component (E) is in the range of 1 to 100nm, precipitation and aggregation of the component (D) can be more effectively prevented, and a cured product free from unevenness can be obtained.
The amount of the component (E) is preferably 1 to 50 parts by mass, more preferably 1 to 20 parts by mass, and still more preferably 1 to 10 parts by mass, based on 100 parts by mass of the total of the components (A-1), (A-2), and (B). When the blending amount is 50 parts by mass or less, the curable silicone composition for a light reflective material of the present invention exhibits more favorable fluidity, and when the blending amount is 1 part by mass or more, precipitation or aggregation of the component (D) is not caused.
(E) Two or more of the components may be used in combination.
In addition, the curable silicone composition for a light-reflecting material of the present invention is preferably blended with an adhesion improver. Examples of the adhesion improver include a silane coupling agent or an oligomer thereof, and a silicone having the same reactive group as the silane coupling agent, and among them, the following components (F) and (G) are preferable.
(F) The component (A) is a compound represented by the following general formula (10), and the component (G) is a compound represented by the following general formula (11).
[ chemical formula 10]
Wherein s is an integer of 1 to 3, t is an integer of 0 to 2, and s + t is 3. The amide units denoted by s and the amide units denoted by t are arranged in a random manner with respect to one another.
[ chemical formula 11]
Wherein u is an integer of 1 to 2, v is an integer of 2 to 4, and u + v is an integer of 4 to 5. The siloxane units denoted by u and the siloxane units denoted by v are arranged in a random manner with respect to one another.
(F) The component (c) and the component (G) are optional components blended in the curable silicone composition for a light reflective material of the present invention for improving the adhesion of the cured product thereof to a substrate. The base material here refers to a metal material such as gold, silver, copper, or nickel, a ceramic material such as alumina, aluminum nitride, or titanium oxide, or a polymer material such as silicone resin or epoxy resin. (F) The component (C) and the component (G) may be used singly or in combination of two or more.
The amount of each of the components (F) and (G) is preferably 1 to 30 parts by mass, more preferably 5 to 20 parts by mass, based on 100 parts by mass of the total of the components (A-1), (A-2) and (B). When the amount of the curable silicone composition for a light reflective material of the present invention is 1 to 30 parts by mass, the adhesion of the curable silicone composition for a light reflective material and a cured product thereof to a substrate is effectively improved, and the composition is less likely to be colored.
Preferred specific examples of the component (F) include, but are not limited to, compounds represented by the following formulae.
Preferred specific examples of the component (G) include, but are not limited to, compounds represented by the following formulae.
[ other blending Components ]
In addition to the above components, it is optional whether or not other components are blended in the curable silicone composition for a light reflective material of the present invention. Examples of the other components include those described below.
< antioxidant >
In the case where the addition-reactive carbon-carbon double bond in the component (a-1) remains unreacted in the cured product of the curable silicone composition for a light-reflecting material of the present invention, for example, the following cases may occur: contains a carbon-carbon double bond existing in either one or both of a 2- (bicyclo [2.2.1] hept-2-en-5-yl) ethyl group represented by the following structural formula and a 2- (bicyclo [2.2.1] hept-2-en-6-yl) ethyl group represented by the following structural formula. When such a carbon-carbon double bond is contained, it is oxidized by oxygen in the atmosphere, which causes coloring of the cured product. Therefore, in the curable silicone composition for a light-reflecting material of the present invention, coloration can be prevented in advance by adding an antioxidant, if necessary.
2- (bicyclo [2.2.1] hept-2-en-5-yl) ethyl
2- (bicyclo [2.2.1] hept-2-en-6-yl) ethyl
As the antioxidant, any conventionally known antioxidant can be used, and examples thereof include hindered amine compounds and hindered phenol compounds, and specific examples thereof include 2, 6-di-tert-butyl-4-methylphenol, 2, 5-di-tert-amylhydroquinone, 2, 5-di-tert-butylhydroquinone, 4 ' -butylidenebis (3-methyl-6-tert-butylphenol), 2 ' -methylenebis (4-methyl-6-tert-butylphenol), and 2,2 ' -methylenebis (4-ethyl-6-tert-butylphenol). These may be used alone or in combination of two or more.
When the antioxidant is used, the amount thereof is not particularly limited as long as it is an effective amount as an antioxidant, and may be preferably about 10 to 10,000ppm, particularly preferably about 100 to 1,000ppm, based on the total of the above components (A-1), (A-2) and (B). By setting the blending amount within such a range, the antioxidant ability can be sufficiently exhibited, and a cured product having excellent light reflectance without causing coloration, oxidation degradation, or the like can be obtained.
< Others >
In addition, in order to secure pot life (pot life), an addition reaction control agent such as 1-ethynylcyclohexanol, 3, 5-dimethyl-1-hexyn-3-ol, or the like may be blended.
Further, a light stabilizer for imparting resistance to light deterioration caused by light energy such as light from the light-emitting element and sunlight may be used. As the light stabilizer, a hindered amine-based stabilizer that traps radicals generated by photooxidative deterioration is suitable, and the antioxidant effect is further improved by using an antioxidant in combination. Specific examples of the light stabilizer include bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate, 4-benzoyl-2, 2,6, 6-tetramethylpiperidine and the like.
[ curable Silicone composition for light-reflecting Material ]
The curable silicone composition for a light reflective material (white thermosetting silicone composition) of the present invention is in a liquid state before curing, and the viscosity at 25 ℃ is preferably 5 to 500Pa · s, and more preferably 10 to 400Pa · s. When the viscosity is within the range of 5 to 500 pas, the workability and handling of the resulting composition are easily improved, and bubbles or air mixing is less likely to occur during molding and curing.
The viscosity of the curable silicone composition for a light-reflecting material of the present invention can be adjusted by the blending ratio of the components (a-1) (a-2) to (E) and other blending components, the viscosity of the liquid substance in these components, the average particle diameter of the components (D) and (E), and the like.
[ cured Silicone resin for light-reflecting Material ]
The curable silicone composition for a light-reflecting material of the present invention is molded and cured to obtain a cured silicone resin for a light-reflecting material. The curable silicone composition for a light reflective material of the present invention can be applied to a conventionally used molding method such as an injection molding method or a transfer molding method. Further, since the curable silicone composition for a light reflective material of the present invention has high fluidity at 25 ℃, it can be molded by a dispensing method or a pouring method (which cannot be applied to conventional solid reflector materials). The curing conditions of the curable silicone composition for a light-reflecting material of the present invention are not particularly limited, and vary depending on the shape of the molded product, the curing method, and the like, but it is generally preferable to set the conditions as follows: at 80 to 200 ℃, preferably 100 to 180 ℃, for 1 minute to 24 hours, preferably 5 minutes to 5 hours.
In general, the initial reflectance of visible light (wavelength: 430 to 800nm) is preferably 95% or more (i.e., 95 to 100%), and more preferably 97% or more (i.e., 97 to 100%), in order to function as a reflector material. When the reflectance is 95% or more, the light extraction efficiency becomes higher when the cured product is used as a reflector material for a light-emitting device such as a lighting fixture, and sufficient luminance can be easily ensured. The reflectance is preferably 82% or more, more preferably 84% or more, not only in the initial stage of production of the cured product but also after a heat resistance test (performed by leaving the cured product at 170 ℃ for 1,000 hours). The cured silicone resin for light-reflecting materials obtained from the curable silicone composition for light-reflecting materials of the present invention can provide a cured product having a reflectance of visible light (wavelength: 430 to 800nm) of 95% or more and a reflectance of light after standing at 170 ℃ for 1,000 hours of 82% or more, and can provide a sufficient reflectance as a reflector material. In the present specification, the reflectance of light is a value measured by a spectrophotometer device equipped with an integrating sphere.
The reflector material may be diced through a cutting process using a dicing saw or the like. In this step, since the cutting is difficult if the hardness is not sufficient, the shore D hardness of the cured silicone resin for a light-reflecting material of the present invention used as a reflector material is preferably 65 or more, and more preferably 70 or more.
[ Reflector and LED device ]
The curable silicone composition for a light-reflecting material (white heat-curable silicone resin composition) of the present invention is for a light-reflecting material, and the use of the light-reflecting material is not particularly limited, and for example, the light-reflecting material can be suitably used as a reflector material for a light-emitting device such as an LED, particularly for a white LED (white light-emitting diode). A light-emitting device (particularly, an LED device, a white LED device, or the like) provided with a reflector made of a cured silicone resin material for a light-reflecting material of the present invention can maintain high light extraction efficiency over a long period of time. Further, since the composition of the present invention has high fluidity and is therefore easily molded, the light-reflecting material of the present invention used as a reflector material can be easily molded into a desired shape with a cured silicone resin in accordance with these light-emitting devices including white LEDs.
Examples
The present invention will be specifically described below by way of examples and comparative examples, but the present invention is not limited to the following examples. In the following examples, the viscosity was measured at 25 ℃ using a screw viscometer (model PC-1T, manufactured by Malcom Co., Ltd.) as a rotational viscometer.
The following examples show symbols representing the compositions of silicone oils and silicone resins. The number of moles of each silicone oil or each silicone resin represents the number of moles of vinyl groups or silicon atom-bonded hydrogen atoms contained in each component.
MH：(CH3)2HSiO1/2
MVi：(CH2＝CH)(CH3)2SiO1/2
MViΦ：(CH2＝CH)(C6H5)(CH3)SiO1/2
DH：(CH3)HSiO2/2
DΦ：(C6H5)(CH3)SiO2/2
D2Φ：(C6H5)2SiO2/2
[ Synthesis example 1] (A-1) preparation of component
1785g (14.88 moles) of vinylnorbornene (trade name: V0062, manufactured by Tokyo Chemical Industry Co., Ltd.; an approximately equimolar amount of an isomer mixture of 5-vinylbicyclo [2.2.1] hept-2-ene and 6-vinylbicyclo [2.2.1] hept-2-ene) and 455g of toluene were charged in a 5L four-necked flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer, and heated to 85 ℃ using an oil bath. To this was added 3.6g of carbon powder supporting 5 mass% of platinum, and 1698g (8.75 moles) of 1, 4-bis (dimethylsilyl) benzene was added dropwise over 180 minutes with stirring. After the completion of the dropwise addition, the mixture was further heated and stirred at 110 ℃ for 24 hours, and then cooled to room temperature. Then, the platinum-carrying carbon was removed by filtration, and toluene and excess vinylnorbornene were distilled off under reduced pressure to obtain 3362g of a colorless transparent oily reaction product (viscosity at 25 ℃ C.: 12820 mPas).
The reaction product was analyzed by FT-IR, NMR, GPC, etc., and as a result, it was found that the reaction product was a mixture of:
(1) a compound having 2 p-phenylenes (one example of a representative structural formula is shown below): about 41 mole%;
(2) a compound having 3 p-phenylene groups (one example of a representative structural formula is shown below): about 32 mole%;
(3) a compound having 4 or more p-phenylene groups: about 27 mole%.
The content of the addition-reactive carbon-carbon double bonds in the whole mixture was 0.36 mol/100 g.
Examples 1 to 4 and comparative examples 1 to 4
The following components (A-1) to (H) were blended in the blending amounts (unit: parts by mass) shown in Table 1 to obtain compositions of examples 1 to 4 and comparative examples 1 to 4, respectively. That is, first, the components (A), (D), (E) and (H) were charged into a 5-liter gate mixer (INOUE MFG., INC., product name: 5-liter planetary mixer) in the blending amounts shown in Table 1, and mixed at room temperature for 1 hour, then the components (B), (F) and (G) were added in the blending amounts shown in Table 1, and mixed at room temperature for 30 minutes to homogeneity, and finally the component (C) was added in the blending amount shown in Table 1, and mixed at room temperature under reduced pressure for 30 minutes to homogeneity to obtain a white curable silicone composition. The viscosity of the resulting composition was measured. The results are shown in Table 1.
(A-1) the reaction product obtained in Synthesis example 1,
(A-2-1) average molecular formula: mViΦ 2D2Φ 3The organopolysiloxane(s) represented by (a) is (a),
(A-2-2) average molecular formula: mVi 2D2Φ 4The organopolysiloxane(s) represented by (a) is (a),
(A-3) average molecular formula: mVi 2DΦ 6The organopolysiloxane(s) represented by (a) is (a),
(B) average molecular formula: mH 2DH 2D2Φ 2The organopolysiloxane(s) represented by (a) is (a),
(C) platinum-divinyltetramethyldisiloxane Complex toluene solution (containing 1 mass% of platinum atoms),
(D) titanium oxide powder having an average particle diameter of 0.5 μm,
(E) a fumed silica powder having an average particle diameter of 14nm,
(F) a compound represented by the following formula (I),
(G) a compound represented by the following formula (I),
(H) 1-ethynyl-1-cyclohexanol in 50 mass% toluene (addition reaction control agent).
[ Table 1]
Then, the compositions of examples 1 to 4 and comparative examples 1 to 4 were injected into a mold, cured under pressure at 150 ℃ and 100MPa for 15 minutes, and then cured in an oven at 150 ℃ and atmospheric pressure for 3 hours to obtain cured products (H1 to H4, H5 to H8 in Table 2) having a thickness of 2 mm. The properties of the resulting cured product are shown in table 2. The properties of the cured product were observed or measured in the following manner.
Appearance: the surface of each cured product was observed with a microscope. The results are shown in table 2 according to the following criteria.
Uniform in appearance (∘); unevenness due to coagulation of Filler (X)
Hardness (shore D): the hardness (Shore D) of each cured product was measured in accordance with ASTM D2240.
Cutting property: each composition was applied to a 0.2mm thick copper plate and cured under the above conditions to prepare a 1mm thick cured product. After standing at room temperature, an adhesive film was attached to the substrate, and cut into a size of 5mm × 5mm using a dicing apparatus (model DAD 341) manufactured by DISCO Corporation. The results are shown in table 2 according to the following criteria.
The cut surface was good (o); burr generation (X)
Light reflectance: the measurement was carried out at 25 ℃ in a wavelength region of 430 to 800nm using a spectrophotometer device U-3310 manufactured by Hitachi Corporation equipped with an integrating sphere.
[ Table 2]
Then, the cured products H1 to H8 were left at 170 ℃ for 1,000 hours to conduct a heat resistance test. The heat resistance was evaluated by calculating the difference between the initial (before test) light reflectance and the post test light reflectance. The evaluation results are shown in table 3. The evaluation was: the smaller the difference in light reflectance, the higher the heat resistance. All cured products were white in the initial stage as a result of visual observation, but only H5 was clearly changed to brown after the heat resistance test.
[ Table 3]
As shown in tables 1 to 3, in examples 1 to 4 using the curable silicone composition for a light reflective material of the present invention, the composition had excellent fluidity because of its low viscosity. In addition, a high light reflectance was obtained in the initial stage, and the light reflectance was only slightly decreased after the heat resistance test. That is, it is found that the composition is also excellent in heat resistance (particularly, heat discoloration resistance).
On the other hand, in comparative example 1, the light reflectance after the heat resistance test was significantly reduced, and the heat resistance (particularly, heat discoloration resistance) was poor. In comparative examples 2 and 3, the cured product had low hardness and therefore had poor cuttability. In comparative example 4, a good appearance of the cured product was not obtained.
The above results show that the curable silicone composition for a light reflective material of the present invention has high fluidity at room temperature, and the cured product thereof has high hardness, and is suitable for use not only in a dicing process, but also excellent in initial light reflectance and heat discoloration resistance. Therefore, the cured product of the curable silicone composition for a light-reflecting material of the present invention is useful as a light-reflecting material, particularly as a reflector material for a white LED.
The present invention is not limited to the above embodiments. The above-described embodiments are illustrative, and any embodiments having substantially the same configuration as the technical idea described in the claims of the present invention and exhibiting the same operational effects are included in the technical scope of the present invention.
Claims (15)
1. A curable silicone composition for a light-reflecting material, characterized by comprising:
30-70 parts by mass of (A-1): (a) an addition reaction product of a compound having 2 hydrogen atoms bonded to silicon atoms in one molecule represented by the following general formula (1) and (b) an alkenyl norbornene compound represented by the following general formula (4), the addition reaction product having at least 2 addition-reactive carbon-carbon double bonds in one molecule;
30-70 parts by mass of (A-2): a compound represented by the following general formula (3), wherein the total of the component (A-1) and the component (A-2) is 100 parts by mass;
(B) an organosilicon compound having 3 or more silicon atom-bonded hydrogen atoms in one molecule, wherein the total amount of silicon atom-bonded hydrogen atoms in the composition is in an amount of 0.5 to 3.0 in terms of a molar ratio relative to addition-reactive carbon-carbon double bonds in the composition;
(C) a hydrosilylation reaction catalyst;
(D) titanium oxide powder; and
(E) a fumed silica powder, which is obtained by grinding a fumed silica powder,
the component (D) has an average particle diameter of 0.1 to 200 μm, and is incorporated in an amount of 50 to 1000 parts by mass based on 100 parts by mass of the total of the components (A-1), (A-2) and (B),
the average particle diameter of the component (E) is 1-100 nm, and the mixing amount of the component (E) is 1-50 parts by mass relative to 100 parts by mass of the total of the components (A-1), (A-2) and (B),
wherein A is a divalent group selected from the group consisting of groups represented by the following general formula (2), and R is1Independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group having 1 to 6 carbon atoms,
in the formula, Ph is phenyl, R2Independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, R3To contain additionA reactive carbon-carbon double bond group, n is an integer of 1 to 20,
in the formula, R4The alkenyl group is unsubstituted or substituted alkenyl group with 2-12 carbon atoms.
2. The curable silicone composition for light-reflecting materials according to claim 1, wherein (b) is any one of 5-vinylbicyclo [2.2.1] hept-2-ene, 6-vinylbicyclo [2.2.1] hept-2-ene, and a combination thereof.
3. The curable silicone composition for light-reflecting materials according to claim 1, wherein the component (B) is a siloxane compound represented by the following general formula (5),
in the formula, R5Independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms other than an alkenyl group, R6Is methyl or hydrogen atom, p is an integer of 1 to 10, q is an integer of 0 to 7; the siloxane units denoted by p and the siloxane units denoted by q are arranged in a random manner with respect to one another.
4. The curable silicone composition for light-reflecting materials according to claim 2, wherein the component (B) is a siloxane compound represented by the following general formula (5),
in the formula, R5Independently a hydrogen atom or an unsubstituted or substituted number of carbon atoms other than alkenylA monovalent hydrocarbon group of 1 to 12, R6Is methyl or hydrogen atom, p is an integer of 1 to 10, q is an integer of 0 to 7; the siloxane units denoted by p and the siloxane units denoted by q are arranged in a random manner with respect to one another.
5. The curable silicone composition for light-reflecting materials according to any one of claims 1 to 4, characterized in that the viscosity at 25 ℃ is 5 to 500 Pa-s.
6. A cured silicone resin for light-reflecting materials, which is obtained by molding and curing the curable silicone composition for light-reflecting materials according to any one of claims 1 to 4.
7. A cured product of a silicone resin for a light-reflecting material, which is obtained by molding and curing the curable silicone composition for a light-reflecting material according to claim 5.
8. The cured silicone resin for light-reflecting materials according to claim 6, wherein the reflectance of light having a wavelength of 430 to 800nm immediately after curing is 95% or more, and the reflectance of light having a wavelength of 430 to 800nm after exposure to an environment at 170 ℃ for 1000 hours is 82% or more.
9. The cured silicone resin for light-reflecting materials according to claim 7, wherein the reflectance of light having a wavelength of 430 to 800nm immediately after curing is 95% or more, and the reflectance of light having a wavelength of 430 to 800nm after exposure to an environment at 170 ℃ for 1000 hours is 82% or more.
10. The cured silicone resin for light-reflecting materials according to claim 6, characterized by having a Shore D hardness of 65 or more.
11. The cured silicone resin for light-reflecting materials according to claim 7, characterized by having a Shore D hardness of 65 or more.
12. A reflector comprising the cured silicone resin for light-reflecting material according to claim 6.
13. A reflector comprising the cured silicone resin for light-reflecting material according to claim 7.
14. An LED device equipped with the reflector according to claim 12.
15. An LED device loaded with the reflector of claim 13.
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| US20230055125A1 (en) * | 2019-12-19 | 2023-02-23 | Momentive Performance Materials Japan Llc | Curable composition |
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| KR20190105509A (en) | 2019-09-17 |
| KR102634630B1 (en) | 2024-02-08 |
| JP6908546B2 (en) | 2021-07-28 |
| TW201938687A (en) | 2019-10-01 |
| CN110229524A (en) | 2019-09-13 |
| JP2019151768A (en) | 2019-09-12 |
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