WO2020043312A1 - Thermosetting silicone resin composition for reflector of led, reflector of led and semiconductor device using the same - Google Patents
Thermosetting silicone resin composition for reflector of led, reflector of led and semiconductor device using the same Download PDFInfo
- Publication number
- WO2020043312A1 WO2020043312A1 PCT/EP2018/073484 EP2018073484W WO2020043312A1 WO 2020043312 A1 WO2020043312 A1 WO 2020043312A1 EP 2018073484 W EP2018073484 W EP 2018073484W WO 2020043312 A1 WO2020043312 A1 WO 2020043312A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- component
- reflector
- resin composition
- silicone resin
- thermosetting silicone
- Prior art date
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- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 52
- 239000011342 resin composition Substances 0.000 title claims abstract description 51
- 229920002050 silicone resin Polymers 0.000 title claims abstract description 49
- 239000004065 semiconductor Substances 0.000 title claims abstract description 33
- 239000012463 white pigment Substances 0.000 claims description 52
- 239000000203 mixture Substances 0.000 claims description 40
- 125000003342 alkenyl group Chemical group 0.000 claims description 33
- 125000003118 aryl group Chemical group 0.000 claims description 27
- 229920001296 polysiloxane Polymers 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 22
- -1 siloxane units Chemical group 0.000 claims description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 12
- 238000001721 transfer moulding Methods 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 239000000049 pigment Substances 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000000748 compression moulding Methods 0.000 claims description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 5
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 229910052582 BN Inorganic materials 0.000 claims description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 2
- 125000006539 C12 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052454 barium strontium titanate Inorganic materials 0.000 claims description 2
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000003431 cross linking reagent Substances 0.000 claims description 2
- 239000003112 inhibitor Substances 0.000 claims description 2
- 239000011256 inorganic filler Substances 0.000 claims description 2
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 claims description 2
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 4
- 238000001723 curing Methods 0.000 description 20
- 238000000465 moulding Methods 0.000 description 19
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 18
- 230000008569 process Effects 0.000 description 17
- 230000003287 optical effect Effects 0.000 description 16
- 150000002430 hydrocarbons Chemical group 0.000 description 14
- 229920005989 resin Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- 229910052697 platinum Inorganic materials 0.000 description 9
- 239000000463 material Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 6
- 238000004383 yellowing Methods 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 125000005375 organosiloxane group Chemical group 0.000 description 4
- 150000003057 platinum Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- 238000005133 29Si NMR spectroscopy Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 150000004678 hydrides Chemical class 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000006038 hexenyl group Chemical group 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 229910052909 inorganic silicate Inorganic materials 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000011417 postcuring Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 230000009974 thixotropic effect Effects 0.000 description 2
- KWEKXPWNFQBJAY-UHFFFAOYSA-N (dimethyl-$l^{3}-silanyl)oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)C KWEKXPWNFQBJAY-UHFFFAOYSA-N 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 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
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000005325 aryloxy 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
- 230000005540 biological transmission Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000001444 catalytic combustion detection Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- MJSNUBOCVAKFIJ-LNTINUHCSA-N chromium;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Cr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MJSNUBOCVAKFIJ-LNTINUHCSA-N 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- DDJSWKLBKSLAAZ-UHFFFAOYSA-N cyclotetrasiloxane Chemical compound O1[SiH2]O[SiH2]O[SiH2]O[SiH2]1 DDJSWKLBKSLAAZ-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- BITPLIXHRASDQB-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound C=C[Si](C)(C)O[Si](C)(C)C=C BITPLIXHRASDQB-UHFFFAOYSA-N 0.000 description 1
- HOMYFVKFSFMSFF-UHFFFAOYSA-N ethenyl-[ethenyl(diphenyl)silyl]oxy-diphenylsilane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(C=C)O[Si](C=C)(C=1C=CC=CC=1)C1=CC=CC=C1 HOMYFVKFSFMSFF-UHFFFAOYSA-N 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 239000013627 low molecular weight specie Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000005394 methallyl group Chemical group 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 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
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001542 size-exclusion chromatography Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- ZQTYRTSKQFQYPQ-UHFFFAOYSA-N trisiloxane Chemical compound [SiH3]O[SiH2]O[SiH3] ZQTYRTSKQFQYPQ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 125000001834 xanthenyl group Chemical group C1=CC=CC=2OC3=CC=CC=C3C(C12)* 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
-
- 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
- C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
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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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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- 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
- H01L33/58—Optical field-shaping elements
- H01L33/60—Reflective elements
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2933/00—Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
- H01L2933/0008—Processes
- H01L2933/0033—Processes relating to semiconductor body packages
- H01L2933/0058—Processes relating to semiconductor body packages relating to optical field-shaping elements
Definitions
- the present invention relates to a thermosetting resin silicone composition which has high light reflectance, high heat resistance, and low yellowing properties and is used for a light-emitting diode (LED) reflector, and also relates to an LED reflector and a semiconductor device which use the thermosetting silicone composition.
- LED light-emitting diode
- optical semiconductor devices including optical semiconductor elements such as light-emitting diodes (LEDs) have been used in various applications due to their advantages such as high energy efficiency and long lifespan characteristics, and the demand therefor has increased.
- LEDs light-emitting diodes
- Such optical semiconductor devices are generally supplied in a form in which an optical semiconductor element is mounted on a substrate (optical semiconductor element-mounting substrate) and the optical semiconductor element is sealed with a transparent resin which, if necessary, contains a phosphor.
- a reflection member (reflector) for reflecting light is provided on the substrate.
- the reflector is generally manufactured by adding a white pigment to a thermosetting resin such as epoxy resin, followed by transfer molding.
- This reflector has a problem in that it is yellowed due to increased heat generation resulting from the high brightness of the optical semiconductor device and due to deterioration of the element material, and thus the light reflectance thereof is significantly reduced.
- thermosetting resin composition for an LED reflector which not only exhibits high light reflectance, but also continuously exhibits heat resistance, low yellowing, and excellent mechanical properties during the driving of an optical semiconductor element and has excellent process suitability applicable to various processes, and to also provide an LED reflector and a semiconductor device which use the thermosetting resin composition.
- thermosetting silicone resin composition for a reflector of a LED comprises:
- each R 5 can be the same or different and is independently selected from a substituted or unsubstituted monovalent hydrocarbon group, wherein at least one of R 5 per molecule is an alkenyl group, with the proviso that the ratio between alkenyl groups and silicon atoms is from 0.3 to ⁇ (as determined by 29 Si NMR spectroscopy), f, g, h, and i are independently 0 or positive, and
- the weight average molecular weight Mw of the siloxane is less than 1,000 g/mol (as measured by SEC, THF as solvent, in a concentration of 5 mg/mL, RI detector against polystyrene as standard);
- the reflector of LED according to the present invention comprises the above-described thermosetting silicone resin composition.
- the semiconductor device of the present invention comprises a reflector cured by using the above-described thermosetting silicone resin composition.
- thermosetting silicone resin composition according to the present invention not only exhibits excellent light reflectance, but also rarely undergoes changes in its weight and hardness at high temperatures, indicating that it has excellent heat resistance and mechanical properties. Furthermore, the composition may have excellent process suitability applicable to various processes as a result of suitably controlling the components and their contents in the composition.
- the present invention may provide a LED reflector stable against light emitted from an LED chip and heat generated during operation.
- the present invention may improve the reliability of a semiconductor device including the LED reflector because the LED reflector exhibits high light reflectance and hardness at high temperatures and has low yellowing properties.
- thermosetting silicone resin composition for a reflector of a LED comprising:
- each R 5 can be the same or different and is independently selected from a substituted or unsubstituted monovalent hydrocarbon group, wherein at least one of R 5 per molecule is an alkenyl group, with the proviso that the ratio between alkenyl groups and silicon atoms is from 0.3 to 1,
- f, g, h, and i are independently 0 or positive, the weight average molecular weight Mw of the siloxane is less than 1,000 g/mol; and (E) a white pigment.
- thermosetting silicone resin composition according to the present invention.
- present invention is not limited to the following exemplary embodiments, but is embodied in various different forms.
- Component (A) which is the major component of the composition according to the present composition, is used to impart strength to the cured product obtained by curing the composition.
- Component (A) represents a branched organopolysiloxane having at least one silicon-bonded alkenyl group and at least one silicon-bonded aryl group per molecule, and having siloxane units represented by the general formula: RS1O3/2 where R is a substituted or unsubstituted monovalent hydrocarbon group.
- alkenyl groups include vinyl, al!yl, methallyl, butenyl, pentenyl, and hexenyl group, preferably vinyl and allyl group, particularly preferred vinyl group.
- examples of the aryl groups include phenyl, naphthyl, anthryl, phenanthryl, indenyl, benzopheny!, fluorenyl, xanthenyl, anthronyl; aryloxyaryl groups such as 0- or p-phenoxyphenyl; alkaryl groups such as 0-, m-, p-tolyl, xylyl and ethylphenyl; aralkyl groups such as benzyl, a- and b-phenylethyl.
- the aryl group is phenyl group.
- examples of silicon-bonded organic groups of component (A) other than the alkenyl and aryl groups include substituted or unsubstituted monovalent hydrocarbon groups, examples of which include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and other alkyl groups; and halogenated alkyl groups such as chloromethyl, 3-chloropropyl, and 3,3,3-trifluoropropyl, with methyl being particularly preferable.
- R is a substituted or unsubstituted monovalent hydrocarbon group.
- Substituents of hydrocarbon groups may include the above-mentioned alkyl groups, the above- mentioned alkenyl groups, the above-mentioned aryl groups, the above-mentioned aralkyl groups, and the above-mentioned halogenated alkyl groups, particularly preferably the above-mentioned alkyl groups and the above-mentioned aryl groups.
- component (A) an organopolysiloxane represented by the average unit formula:
- each of R’, R 2 , and R 3 can be the same or different and is independently selected from a substituted or unsubstituted monovalent hydrocarbon group, wherein at least one of R 1 , R 2 or R 3 per molecule is an alkenyl group and at least one of R 1 , R 2 or R 3 per molecule is an aryl group.
- the monovalent hydrocarbon group may be more specifically exemplified by the above-mentioned alkyl groups, the above-mentioned alkenyl groups, the above- mentioned aryl groups, the above-mentioned aralkyl groups, and the above-mentioned halogenated alkyl groups.
- Preferably 0.1 to 40 mol%, more preferably 5 to 25 mol%, of R 1 , R 2 , and R 3 per molecule is the above-mentioned alkenyl groups. This is due to the fact that when the content of the alkenyl groups is below the lower limit or exceeds the upper limit of the above-mentioned range, its reactivity with component (A) tends to decrease.
- R 1 , R 2 , and R 3 should be the above-mentioned aryl groups, and, in particular, in siloxane units represented by the general formula R 2 SiC>3 /2 , it is even more preferable that not less than 30 mol % of R 2 should be represented by the above-mentioned aryl groups, with R 2 other than the alkenyl and aryl groups being preferably represented by methyl groups.
- X is a hydrogen atom or alkyl group, a is 0 or a positive number, b is 0 or a positive number, c is a positive number, d is 0 or a positive number, e is 0 or a positive number, b/c is a number between 0 and 10, a/c is a number between 0 and 0.5, d/(a+b+c+d) is a number between 0 and 0.3, and e/(a+b+c+d) is a number between 0 and 0.4.
- component (A) an organopolysiloxane with the average unit formula:
- R 1 is a Ci to C12 alkyl group
- R 2 is a C 6 to C 2 o aryl group or C 7 to C20 aralkyl group
- R 3 is C 2 to C12 alkenyl group
- a is 0 or a positive number
- b is 0 or a positive number
- c is a positive number.
- component (A) when converted to standard polystyrene, its weight average molecular weight (Mw) should preferably be in the range of from 500 g/mol to 10,000 g/mol, and, especially preferably, in the range of from 700 g/mol to 7,000 g/mol, more preferably in the range from 1,000 g/mol to 5,000 g/mol, particularly from 1,500 to 3,000 g/mol.
- Component (A) is preferably present in an amount that equals or is greater than 70 %, more preferably 70 to 90 % by weight, particularly preferred, 75 to 85 % by weight, based on the sum of the amount of components (A) and (B).
- the thermosetting silicone resin composition comprises 60 to 75 parts by weight, more preferably 70 to 75 parts by weight, of Component (A), based on the 100 parts by weight of total organosiloxane which is a sum of component (A), component (B), component (C) and component (D).
- Component (A) based on the 100 parts by weight of total organosiloxane which is a sum of component (A), component (B), component (C) and component (D).
- Component (B) is the curing agent of the present composition.
- Component (B) is a linear organopolysiloxane with both terminal ends of the molecular chain blocked by silicon-bonded hydrogen atoms having at least one silicon- bonded aryl group per molecule.
- aryl groups of component (B) are the same as those described above. Phenyl group is especially preferable.
- examples of silicon -bonded organic groups of component (B) other than the aryl groups include substituted or unsubstituted monovalent hydrocarbon groups with the exception of alkenyl groups, such as the above-described alkyl groups, the above-described aralkyl groups, and the above-described halogenated alkyl groups, with methyl being particularly preferable.
- the content of the silicon-bonded aryl groups among all the silicon-bonded organic groups in component (B) should preferably be not less than 15 mol % and, particularly preferably, not less than 30 mol%.
- the viscosity of component (B) at 25 °C it is preferably in the range of from 1 to 1,000 mPa-s, and, especially preferably, in the range of from 2 to 500 mPa-s.
- component (B) is preferable as component (B).
- each R 4 can be the same or different and is independently selected from a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group with the exception of alkenyl groups.
- Examples of the monovalent hydrocarbon groups of R 4 include the above- mentioned alkyl groups, the above-mentioned aryl groups, and the above-mentioned halogenated alkyl groups.
- At least one R 4 per molecule must be one of the above-mentioned aryl groups, preferably, phenyl.
- n in the formula above is an integer of 0 or more, preferably, an integer in the range of from 0 to 20, and, especially preferably, an integer in the range of from 0 to 10. This is due to the fact that when the value of n exceeds the upper limit of the above-mentioned range, the toughness of the resultant composition, or the adhesive properties of the cured product, tend to deteriorate. It is most preferable that n is 1 to 4, particularly, 1, that is, the component (B) represents trisiloxane.
- Component (B) is preferably present in an amount of 1 to 30 % by weight, more preferably 10 to 30 % by weight, particularly prefered, 15 to 25 % by weight, based on the sum of the amount of components (A) and (B).
- the molar ratio of Si-H groups in component (B)/ alkenyl groups, for example, vinyl groups, in component (A) is 1 to 1.2 to reduce the reactive residual silicone hydride.
- the thermosetting silicone resin composition comprises 18 to 25 parts by weight, more preferably 20 to 22 parts by weight, of Component (B), based on the 100 parts by weight of total organosiloxane which is a sum of component (A), component (B), component (C) and component (D).
- Component (C) is a hydrosilylation reaction catalyst.
- the hydrosilylation reaction catalyst of component (C) is used to promote the reaction of the alkenyl groups of component (A) with the silicon-bonded hydrogen atoms of component (B).
- component (C) examples include platinum catalysts, rhodium catalysts, and palladium catalysts. Platinum catalysts are preferable because of their ability to significantly stimulate the cure of the present composition. Examples of the platinum catalysts include platinum micropowder, chloroplatinic acid, alcohol solutions of chloroplatinic acid, platinum/alkenylsiloxane complexes, platinum/olefin complexes, and platinum/carbonyl complexes, preferably, platinum/alkenylsiloxane complexes.
- alkenylsiloxanes examples include 1,3-divinyl- 1,1, 3, 3-tetramethyldisiloxane, l,3,5,7-tetramethyl-l,3,5,7-tetravinylcyclotetrasiloxane, alkenylsiloxanes obtained by substituting groups such as ethyl, phenyl etc. for some of the methyl groups of the above-mentioned alkenylsiloxanes, and alkenylsiloxanes obtained by substituting groups such as allyl, hexenyl, etc. for the vinyl groups of the above-mentioned alkenylsiloxanes.
- l ,3-divinyl-l,l,3,3-tetramethyldisiloxane is particularly preferable because of the excellent stability of the platinum/alkenylsiloxane complex. Also, due to the improvement in the stability of the complex that their addition may bring, it is desirable to add l,3-divinyl-l,l,3,3-tetramethyldisiloxane, l,3-diallyl-l, 1,3,3- tetramethyldisiloxane, l,3-divinyl-l,3-dimethyl-l,3-diphenyldisiloxane, 1,3-divinyl- 1, 1 ,3,3-tetraphenyldisiloxane, 1 ,3,5,7-tetramethyl-l ,3,5,7-tetravinylcyclotetrasiloxane and other alkenylsiloxanes and organosiloxane oligomers such as dimethylsi
- component (C) there are no limitations on the content of component (C) as long as the amount promotes curing of the present composition.
- component (C) is preferably present in an amount resulting in a platinum content of 0.05 to 100 ppm (parts per million) by weight, more preferably 0.1 to 10 ppm by weight, particularly preferred 0.1 to 5 ppm by weight, relative to 100 parts by weight of the total of components (A) and (B).
- component (C) when the content of component (C) is below the lower limit of the above-mentioned range, the present composition tends to fail to completely cure, and, on the other hand, when it exceeds the upper limit of the above-mentioned range, problems may arise in terms imparting various colors to the resultant cured product.
- Component (D1) when the content of component (C) is below the lower limit of the above-mentioned range, the present composition tends to fail to completely cure, and, on the other hand, when it exceeds the upper limit of the above-mentioned range, problems may arise in terms imparting various colors to the resultant cured product.
- Component (D) is an additive, which is a low molecular weight siloxane having at least one silicon-bonded alkenyl group per molecule, represented by the average formula
- each R 5 can be the same or different and is independently selected from a substituted or unsubstituted monovalent hydrocarbon group, wherein at least one of R 5 per molecule is an alkenyl group, with the proviso that the ratio between alkenyl groups and silicon atoms is from 0.3 to 1,
- f, g, h, and i are independently 0 or positive, and
- the weight average molecular weight Mw of the siloxane is less than 1,000 g/mol, preferably less than 800 g/mol, more preferably less than 500 g/mol.
- component (D) is selected from the group consisting of D alkenyl 4, M alkenyl 4 Q, M alkenyl 6Q2 , M alkenyl 3T.
- the alkenyl group is vinyl.
- Particularly preferred as component (D) are cyclotetrasiloxane D Vl 4, and M Vl 4Q, especially D Vl 4.
- component (D) serves to react with an unreacted site (Si-H), thereby protecting additional reaction of the unreacted site due to heat or light.
- color change and mechanical strength change to high temperature may be remarkably reduced.
- composition according to prior art which has no component (D)
- materials often show an increase in hardness after curing during storage at high temperature, which can be attributed to a post-curing reaction of remaining reactive sites and/or show a weight loss by evaporation of low molecular weight species that did not crosslink into the polymer network. Due to the change in hardness and weight loss, the materials were not stable under operating conditions.
- a reaction of component (D) with unreacted site (Si-H) leads to better stability such as less change in hardness, low weight loss, and discoloration, at high temperature.
- Component (D) also gives a filling effect, which makes it possible to lower gas and vapor transmission.
- the encapsulant further comprising component (D) provides stablity to sulfur and such effect is expected to be obtained from the filing effect.
- Component (D) is both reactive and small enough to react with residual silicone hydride. At the same time, component (D) crosslinks into the siloxane network and thus does not increase the proportion of volatile components in the cured material.
- Component (D) is preferably used in ari amount of at most 10 parts by weight, more preferably at most 7 parts by weight, and even more preferably at most 5 parts by weight relative to 100 parts by weight of the total of components (A) and (B). If component (D) is included in higher amounts, compatibility with the other components would be lower and thus, transmittance would be lower.
- component (D) is used in an amount of at least 1 parts by weight relative to 100 parts by weight of the total of components (A) and (B). The amount of the component (D) may be adequately selected in consideration of the specific formulation and the feature.
- the thermosetting silicone resin composition comprises 1 to 5 parts by weight, more preferably 2 to 4 parts by weight, of Component (D), based on the 100 parts by weight of total organosiloxane which is a sum of component (A), component (B), component (C) and component (D).
- Component ( ⁇ 1) based on the 100 parts by weight of total organosiloxane which is a sum of component (A), component (B), component (C) and component (D).
- Component (E) is a white pigment.
- the white pigment (E) functions to impart high light reflectance to a reflector, which is the cured product of the composition, and also to reduce the linear expansion of the reflector.
- the white pigment (E) may be any white pigment known in the art, for example, an inorganic white pigment, an organic white pigment, a hollow particle pigment, or a mixture of two or more thereof.
- Non-limiting examples of the inorganic white pigment include glass, clay, mica, talc, kaolinite (kaolin), halloysite, zeolite, acid clay, activated clay, boehmite, pseudo- boehmite, inorganic oxides; metal salts (e.g., alkaline earth metal salts, etc.), and the like.
- non-limiting examples of the organic white pigment include resin pigments, such as styrene-based resins, benzoguanamine-based resins, urea-formalin resins, melamine-formalin resins, amide-based resins, and the like.
- the white pigment (E) in the present invention may be at least one selected from the group consisting of titanium oxide, zinc oxide, silicon oxide, aluminum oxide, barium oxide, magnesium oxide, zirconium oxide, aluminum silicate, boron nitride, calcium carbonate, tantalum pentoxide, barium sulfate, magnesium carbonate, barium carbonate, and strontium titanate.
- the white pigment (E) preferably has high refractive index in order to increase the reflectance of the reflector.
- a white pigment having a refractive index of 1.5 or higher is preferable.
- a white pigment having a hollow particle structure has a very high surface reflectance due to low refractive index gas contained in the core, ands for this reason, the shell portion may also be composed of a material having a refractive index lower than 1.5.
- the pigment white (E) may be a pigment subjected to surface treatment known in the art.
- the surface treatment comprises surface treatment with a surface treatment agent, such as a metal oxide, a silane coupling agent, a titanium coupling agent, an organic acid, a polyol, silicone or the like. When this surface treatment is performed, it may improve either the compatibility of the white pigment with other components, included in the silicone resin composition according to the present invention, or the dispersibility of the white pigment.
- the shape of the white pigment (E) is not particularly limited, and may be, for example, a spherical shape, a crushed shape, a fibrous shape, a needle shape, a scaly shape, an amorphous shape, or the like. From a viewpoint of dispersibility, a spherical shape is preferably, and in particular, a spherical shape having an aspect ratio of 1.2 or less is more preferable.
- the mean particle diameter of the white pigment is not particularly limited, but may be 0.01 to 50 mm, preferably 0.1 to 50 mm, in view of increasing the light reflectance of the curing product (white reflector).
- the term “average diameter” means the diameter at 50% (median diameter, D50) of the cumulative particle size distribution measured by a laser diffraction/scattering method.
- the content of the white pigment (E) in the thermoseting silicone resin composition according to the present invention is not particularly limited and may be suitably adjusted within the range known in the art.
- the content of the white pigment (E) may be 1 to 300 parts by weight, preferably 20 to 250 parts by weight, more preferably 50 to 200 parts by weight, based on 100 parts by weight of the sum of component (A) to component (D).
- the content of the white pigment is within the above-described range, the light reflectively of a reflector, which is the curing product of the composition, can further be increased, and the reduction in flowability of the thermosetting silicone resin composition by addition of the white pigment (E) can also be inhibited, resulting in improvement in workability and moldability.
- the white pigment (E) comprises a titanium oxide-based first white pigment (E-l) having a mean particle diameter (D50) of 0.1 to 2 mm.
- This titanium oxide is preferable in view of increasing the reflectance of the curing product (white reflector) and increasing light reflectance per amount of white pigment added.
- the titanium oxide may be any titanium oxide known in the art, and may be, for example, rutile-type titanium oxide, anatase-type titanium oxide, brookite-type titanium oxide, or a mixture of two or more thereof.
- the content of the first white pigment (E-l) is not particularly limited, but may be at least 40 parts by weight, preferably 45 to 80 parts by weight, based on 100 parts by weight of the sum of component (A) to component (D).
- the composition comprises the titanium oxide-based first white pigment having the above-specified particle diameter in an amount of at least 40 parts by weight based on the total weight of component (A) to component (D), it may exhibit a light reflectance of 97% or higher, thereby maximizing the optical efficiency of the LED reflector.
- the viscosity, thixotropy, hardness after heat curing, reflectance, whiteness and the like of the composition may be suitably adjusted by using the above- described titanium oxide-based first white pigment (E-l) in combination with pigments having various sizes and components.
- the composition of the present invention may further comprise a second white pigment (E-2), a third white pigment (E- 3), and a mixture thereof, from which at least one of the mean particle diameter and component of the first white pigment (E-l) differs.
- the ratio of the content of the first white pigment (E-l) to the content of the other pigment (e.g., E-2, E-3, E-2+E-3, etc.) except the first white pigment may be 80-99.9: 0.1-20 by weight, preferably 80- 99.5: 0.5-20 by weight, based on 100 parts by weight of the total weight of the white pigment (E).
- the heat curable silicone composition of the present invention may not comprise as flexibilizing units, a linear organopolysiloxane having at least two silicon-bonded alkenyl groups and at least one silicon-bonded aryl group per molecule. It is assumed that since bulky branched organopolysiloxane such as component (A) is used as resin instead of a linear organopolysiloxane, the present curable silicone composition provides excellent hardness and toughness. That is, bulky branched organopolysiloxane is directly connected to unreacted Si-H site.
- thermosetting silicone resin composition of the present invention may further comprise a crosslinking agent, which is generally used in this field.
- thermosetting silicone resin composition of the present invention may further comprise a curing inhibitor; silica, glass, quartz, cristobalit, alumina, zinc oxide and other inorganic fillers; a catalyst; and a phosphor, which are generally used in this field.
- the present composition may also contain; micropowders of organic resins such as polymethacrylate resin; heat-stabilizers, dyes, pigments, flame retardants, solvents, etc. as optional components, so long as this does not impair the purpose of this invention.
- organic resins such as polymethacrylate resin
- heat-stabilizers, dyes, pigments, flame retardants, solvents, etc. as optional components, so long as this does not impair the purpose of this invention.
- compositions described above may be prepared by mixing the components generally used in this art, for example, by mixing all the components at ambient temperature.
- the composition may be prepared by mixing the above- described components (A, B, C, D and E) and other additives at a predetermined ratio, uniformly mixing the mixture by a Henschel mixer, a V blender, a ribbon blender, a tumbler blender or the like, followed by melt-kneading using a roll mill, a kneader, an extruder, a Banbury mixer or the like, cooling and solidifying the melt-kneaded material, and then grinding the solid material to a suitable size.
- the viscosity of a composition that may be applied to a dispensing process is 500 to 10,000 mPa-s
- the viscosity of a composition that may be applied to transfer molding and compression molding is 3,000 to 100,000 mPa-s.
- the thermosetting silicone resin composition according to the present invention has a viscosity of 100 to 2,000,000 mPa-s (at 25°C) before curing, it may be applied to all the above-described dispensing process and transfer molding and compression molding processes.
- the thermosetting silicone resin composition when the thermosetting silicone resin composition is molded by any one of transfer molding and compression molding, it may be cured rapidly at a temperature of 100 to 170°C within 30 to 600 seconds.
- thermosetting silicone resin composition of the present invention may be applied to various processes, and may be cured rapidly due to high curing rate, indicating that it has excellent workability and moldability.
- it has high mechanical strength, heat resistance and light reflectance, and thus may preferably be used for an LED reflector.
- the thermosetting silicone resin composition of the present invention may be used without limitation in various light-emitting applications which require high light reflectance and excellent heat resistance.
- it may be used as a reflection member for various light-emitting devices, including electrical/electronic parts, indoor lights, ceiling lights, outdoor lights, vehicle lights, display devices, headlights, and the like.
- the LED reflector according to the present invention includes the curing product of the above-described thermosetting silicone resin composition.
- the shape or size of the reflector is not particularly limited, and the reflector may include a conventional configuration known in the art.
- the reflector may have either a shape opened in at least side in a light emitting direction, or a non- opened planar shape.
- the reflector according to the present invention may be manufactured by a conventional molding method.
- it is obtained by shaping the above- described thermosetting silicone resin composition into a desired shape by various molding methods, such as transfer molding, compression molding, injection molding, LIM molding (injection molding), blow molding, insert molding, dam molding with a dispenser, etc.
- molding and curing of the composition may occur at the same time.
- a post-curing process may also be separately performed after the molding process.
- the transfer molding or compression molding method is preferably used.
- the transfer molding process is preferably performed using a transfer molding machine at a molding pressure of 5 to 20 N/mm 2 at a molding temperature of 120 to 190°C, particularly 120 to 180°C, for 30 to 500 seconds, particularly 30 to 300 seconds.
- the compressing molding process is preferably performed using a compression molding machine at a molding temperature of 120 to 190°C, particularly 120 to 180°C, for 30 to 600 seconds, particularly 120 to 420 seconds.
- a (post) curing process may, if necessary, be performed. Curing conditions for this process are not particularly limited, and may be suitably adjusted within the range known in the art. in one example, the curing process may be performed at a temperature of 100 to l70°C for 30 seconds to 30 minutes.
- the reflector of the present invention may exhibit high reflectance, excellent mechanical properties and low yellowing properties even at high temperature.
- the LED reflector according to the present invention may have: (i) a Shore D hardness of at least 10, preferably at least 30, more preferably at least 50; (ii) a light reflectance at 450 nm wavelength of at least 90%, preferably at least 95%, more preferably at least 97%; and (iii) a yellow index of 5 or less, preferably 3 or less.
- an optical semiconductor element e.g., a light-emitting diode element having the reflector may be fabricated by mounting a conventional LED element and other components, known in the art, on the above-described reflector, and then performing sealing, joining, bonding or the like using an encapsulating resin.
- This optical semiconductor element (LED assembly) may be used in various applications. In one example, it may be used in applications, including semiconductor devices, LCD displays, backlight units (BLU), mobile phones, vehicle display lights, vehicle head lamps, flashlights, indoor lights, traffic lights, streetlights and outdoor lights.
- the present invention provides a semiconductor device including a reflector obtained by molding the above-described thermosetting silicone resin composition.
- the term“semiconductor device” includes all semiconductor devices known in the art. Specifically, the semiconductor device may comprise: the above-described reflector (or a reflector substrate); an optical semiconductor element mounted on the reflector; and a phosphor-containing transparent encapsulating resin layer sealing the optical semiconductor element.
- the optical semiconductor element may be an LED.
- Such semiconductor elements are exemplified by semiconductor elements used in diodes, transistors, thyristors, solid-state image pickup elements, monolithic ICs and in hydride ICs. In particular, it is preferable that semiconductor elements are light-emitting elements.
- Examples of such semiconductor devices included diodes, light-emitting diodes, transistors, thyristors, photocouplers, CCDs, monolithic IICs, hybrid ICs, LSIs, and VLSIs.
- the LED reflector obtained by molding the above- described thermosetting silicone resin composition exhibits high light reflectance and mechanical properties, and also exhibits excellent heat resistance and low yellowing properties during driving, and thus light-induced deterioration of the reflector surface is minimized. Accordingly, the reliability of an optical semiconductor device (LED device) comprising the LED reflector may be improved.
- Viscosity data is measured with a rheometer model MCR302 manufactured by the company Anton Paar, D-Ostfildern, according to D1N EN ISO 3219 in rotation with a cone-plate measurement system. Measurements were performed in a range where the samples behavior is newtonian. Viscosity data are given for a temperature of 25 °C and an ambient pressure of 1013 mbar.
- Molecular weight is determined as weight average molecular weight Mw and number average molecular Mn by Size Exclusion Chromatography SEC. Polystyrene is used as standard. The detector is a RI detector. THF is used as solvent. Sample concentration is 5 mg / mL.
- Ethanol was distilled at 40 °C under vacuum and 1 L ethylacetate and 50 g sodium chloride were added. The aqueous phase was removed and the organic phase was washed three times with saturated aqueous sodium chloride solution. The organic phase was dried with magnesium sulfate and was filtrated with press filter equipment. After removal of the solvent in vacuum, 470 g of a colorless, highly viscous product were obtained. Weight average molecular weight Mw is 2,546 g/mol.
- the results of 29 Si NMR are ViMe 2 SiOi /2 : 16.6 %, Me 2 Si0 2/2 : 9.7 %, Ph(0R)Si0 2/2 : 12. 8 % and PhSi0 3/2 : 60.9 %.
- Example 1 75 % by weight of the compound from synthesis example las component A, 25 % by weight of l, l,5,5-tetramethyl-3,3-diphenyltrisiloxane as component B were prepared. In addition, relative to 100 parts by weight of the total of components A and B, 0.0002 parts (with respect to Platinum) by weight of Platinum(O)- 1,3-divinyl- 1, 1 , 3,3,- tetramethyl-disiloxane complex as component C, and 4.99 parts by weight of D Vl 4 as component D were prepared.
- thermosetting silicone resin composition for an LED reflector Based on 100 parts by weight of the sum of the components (A, B, C, and D), 50 parts by weight of titanium oxide (first white pigment), having a mean particle diameter of 0.3 mm, and 0.5 parts by weight of silicon oxide (second white pigment) having a mean particle diameter of 0.02 mm were prepared as a white pigment (E) and mixed with the above components, thereby preparing a thermosetting silicone resin composition for an LED reflector according to Example 1.
- thermosetting silicone resin compositions for reflector of LED according to examples 2 to 11 were prepared in the same manner in example 1 except that component E was used in an amount as shown in following table 1.
- thermosetting silicone resin compositions for LED reflectors prepared in Examples 1 to 1 1, were measured as described below, and the results of the measurement are shown in Table 2 below. Molding of the curing products obtained by curing the compositions was performed using a transfer molding machine under the conditions of molding temperature of 165°C, molding pressure of 7 MPa and molding time of 300 seconds. The cured samples prepared by the transfer molding were post-cured at 150°C for about 4 hours.
- thermosetting silicone resin composition prepared in each of the Examples, the dynamic viscosities at shear rates of l/sec and 10/sec were measured using a 25-mm-diameter flat plate in a rheometer model MCR302 (Anton Paar) system.
- Thixotropic index was calculated as the ratio of the dynamic viscosity at a shear rate of lO/sec to the dynamic viscosity at a shear rate of l/sec.
- the hardness of a molded sample having a thickness of 6 mm was measured on a Shore Durometer Hardness (D) scale.
- the yellow index of a molded sample having a thickness of 1 mm was measured by CIE Lab colorimetry using Minolta CM5.
- the light reflectance at 450 nm of a transfer-molded sample having a thickness of 1 mm was measured using a Minolta CM 5 spectrophotometer in specular component- included mode. As shown in Table 2, it could be seen that the compositions of Examples 1 to 1 1 according to the present invention had high light reflectance, excellent mechanical properties, and low yellowing properties, which are required for a reflector.
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Abstract
Disclosed is a thermosetting silicone resin composition for a reflector of a Light Emitting Diode (LED), a reflector of a LED and a semiconductor device using the same.
Description
THERMOSETTING SILICONE RESIN COMPOSITION FOR REFLECTOR OF LED, REFLECTOR OF LED AND SEMICONDUCTOR DEVICE USING
THE SAME Technical Field
The present invention relates to a thermosetting resin silicone composition which has high light reflectance, high heat resistance, and low yellowing properties and is used for a light-emitting diode (LED) reflector, and also relates to an LED reflector and a semiconductor device which use the thermosetting silicone composition.
Background Art
In recent years, optical semiconductor devices including optical semiconductor elements such as light-emitting diodes (LEDs) have been used in various applications due to their advantages such as high energy efficiency and long lifespan characteristics, and the demand therefor has increased.
Such optical semiconductor devices are generally supplied in a form in which an optical semiconductor element is mounted on a substrate (optical semiconductor element-mounting substrate) and the optical semiconductor element is sealed with a transparent resin which, if necessary, contains a phosphor. In order to increase the efficiency of light extraction from the optical semiconductor element, a reflection member (reflector) for reflecting light is provided on the substrate.
The reflector is generally manufactured by adding a white pigment to a thermosetting resin such as epoxy resin, followed by transfer molding. This reflector has a problem in that it is yellowed due to increased heat generation resulting from the high brightness of the optical semiconductor device and due to deterioration of the
element material, and thus the light reflectance thereof is significantly reduced.
Therefore, it is an object of the present invention to provide a thermosetting resin composition for an LED reflector, which not only exhibits high light reflectance, but also continuously exhibits heat resistance, low yellowing, and excellent mechanical properties during the driving of an optical semiconductor element and has excellent process suitability applicable to various processes, and to also provide an LED reflector and a semiconductor device which use the thermosetting resin composition.
Disclosure of Invention
The thermosetting silicone resin composition for a reflector of a LED according to the present invention comprises:
(A) a branched organopolysiloxane having at least one silicon-bonded alkenyl group and at least one silicon-bonded aryl group per molecule, and having siloxane units represented by the general formula: RS1O3/2 where R is a substituted or unsubstituted monovalent hydrocarbon group;
(B) a linear organopolysiloxane with both terminal ends of the molecular chain blocked by silicon-bonded hydrogen atoms and having at least one silicon-bonded aryl group per molecule;
(C) a hydrosilylation reaction catalyst;
(D) a low molecular weight siloxane having at least one silicon-bonded alkenyl group per molecule, represented by the average formula
(R53Si0l/2)f(R52Si02/2)g(R5Si03/2)h(Si04/2)i where each R5 can be the same or different and is independently selected from a substituted or unsubstituted monovalent hydrocarbon group, wherein at least one of R5 per molecule is an alkenyl group, with the proviso that the ratio between alkenyl groups
and silicon atoms is from 0.3 to ί (as determined by 29Si NMR spectroscopy), f, g, h, and i are independently 0 or positive, and
the weight average molecular weight Mw of the siloxane is less than 1,000 g/mol (as measured by SEC, THF as solvent, in a concentration of 5 mg/mL, RI detector against polystyrene as standard); and
(E) a white pigment.
in addition, the reflector of LED according to the present invention comprises the above-described thermosetting silicone resin composition.
Furthermore, the semiconductor device of the present invention comprises a reflector cured by using the above-described thermosetting silicone resin composition.
Effects of Invention
The thermosetting silicone resin composition according to the present invention not only exhibits excellent light reflectance, but also rarely undergoes changes in its weight and hardness at high temperatures, indicating that it has excellent heat resistance and mechanical properties. Furthermore, the composition may have excellent process suitability applicable to various processes as a result of suitably controlling the components and their contents in the composition.
Accordingly, the present invention may provide a LED reflector stable against light emitted from an LED chip and heat generated during operation.
In addition, the present invention may improve the reliability of a semiconductor device including the LED reflector because the LED reflector exhibits high light reflectance and hardness at high temperatures and has low yellowing properties.
Detailed Description of the Invention
Hereinafter, an exemplary embodiment of the present invention will be described in detail. However, the exemplary embodiment of the present invention may be modified in various forms, and the scope of the present invention is not limited to an exemplary embodiment to be described below.
<Thermosetting silicone resin composition for a reflector of an LED>
The present invention provides a thermosetting silicone resin composition for a reflector of a LED comprising:
(A) a branched organopolysiloxane having at least one silicon-bonded alkenyl group and at least one silicon-bonded aryl group per molecule, and having siloxane units represented by the general formula: RS1O3/2 where R is a substituted or unsubstituted monovalent hydrocarbon group;
(B) a linear organopolysiloxane with both terminal ends of the molecular chain blocked by silicon-bonded hydrogen atoms and having at least one silicon-bonded aryl group per molecule;
(C) a hydrosilylation reaction catalyst;
(D) a low molecular weight siloxane having at least one silicon-bonded alkenyl group represented by the average formula
(R53Si0,/2)f(R52Si02/2)g(R5Si03/2)h(Si04/2)i
where each R5 can be the same or different and is independently selected from a substituted or unsubstituted monovalent hydrocarbon group, wherein at least one of R5 per molecule is an alkenyl group, with the proviso that the ratio between alkenyl groups and silicon atoms is from 0.3 to 1,
f, g, h, and i are independently 0 or positive,
the weight average molecular weight Mw of the siloxane is less than 1,000 g/mol; and (E) a white pigment.
Hereinafter, a chemical composition of the thermosetting silicone resin composition according to the present invention will be described in detail. However, the present invention is not limited to the following exemplary embodiments, but is embodied in various different forms.
Component (A)
Component (A), which is the major component of the composition according to the present composition, is used to impart strength to the cured product obtained by curing the composition.
Component (A) represents a branched organopolysiloxane having at least one silicon-bonded alkenyl group and at least one silicon-bonded aryl group per molecule, and having siloxane units represented by the general formula: RS1O3/2 where R is a substituted or unsubstituted monovalent hydrocarbon group.
In component (A), examples of the alkenyl groups include vinyl, al!yl, methallyl, butenyl, pentenyl, and hexenyl group, preferably vinyl and allyl group, particularly preferred vinyl group.
In component (A), examples of the aryl groups include phenyl, naphthyl, anthryl, phenanthryl, indenyl, benzopheny!, fluorenyl, xanthenyl, anthronyl; aryloxyaryl groups such as 0- or p-phenoxyphenyl; alkaryl groups such as 0-, m-, p-tolyl, xylyl and ethylphenyl; aralkyl groups such as benzyl, a- and b-phenylethyl. Preferably the aryl group is phenyl group.
In addition, examples of silicon-bonded organic groups of component (A) other than the alkenyl and aryl groups include substituted or unsubstituted monovalent
hydrocarbon groups, examples of which include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and other alkyl groups; and halogenated alkyl groups such as chloromethyl, 3-chloropropyl, and 3,3,3-trifluoropropyl, with methyl being particularly preferable.
In the siloxane units of component (A) represented by the general formula RSi03/2,
R is a substituted or unsubstituted monovalent hydrocarbon group. Substituents of hydrocarbon groups may include the above-mentioned alkyl groups, the above- mentioned alkenyl groups, the above-mentioned aryl groups, the above-mentioned aralkyl groups, and the above-mentioned halogenated alkyl groups, particularly preferably the above-mentioned alkyl groups and the above-mentioned aryl groups.
As component (A), an organopolysiloxane represented by the average unit formula:
is preferable.
In the formula above, each of R’, R2, and R3 can be the same or different and is independently selected from a substituted or unsubstituted monovalent hydrocarbon group, wherein at least one of R1, R2 or R3 per molecule is an alkenyl group and at least one of R1, R2 or R3 per molecule is an aryl group.
The monovalent hydrocarbon group may be more specifically exemplified by the above-mentioned alkyl groups, the above-mentioned alkenyl groups, the above- mentioned aryl groups, the above-mentioned aralkyl groups, and the above-mentioned halogenated alkyl groups.
Preferably 0.1 to 40 mol%, more preferably 5 to 25 mol%, of R1, R2, and R3 per molecule is the above-mentioned alkenyl groups. This is due to the fact that when the content of the alkenyl groups is below the lower limit or exceeds the upper limit of the
above-mentioned range, its reactivity with component (A) tends to decrease.
Also, in order to achieve low attenuation due to light refraction, reflection, scattering etc. in the cured product obtained by curing preferably not less than 10 mol% of R1, R2, and R3 should be the above-mentioned aryl groups, And, in particular, in siloxane units represented by the general formula R2SiC>3/2, it is even more preferable that not less than 30 mol % of R2 should be represented by the above-mentioned aryl groups, with R2 other than the alkenyl and aryl groups being preferably represented by methyl groups.
In addition, in the formula above,
X is a hydrogen atom or alkyl group, a is 0 or a positive number, b is 0 or a positive number, c is a positive number, d is 0 or a positive number, e is 0 or a positive number, b/c is a number between 0 and 10, a/c is a number between 0 and 0.5, d/(a+b+c+d) is a number between 0 and 0.3, and e/(a+b+c+d) is a number between 0 and 0.4.
As component (A), an organopolysiloxane with the average unit formula:
(R'R, R3Si0,/2)a(R'2Si02/2)b(R2Si03/2)c
is particularly preferable.
In the formula above, R1 is a Ci to C12 alkyl group, R2 is a C6 to C2o aryl group or C7 to C20 aralkyl group, R3 is C2 to C12 alkenyl group, a is 0 or a positive number, b is 0 or a positive number, and c is a positive number.
Although there are no limitations concerning the molecular weight of component (A), when converted to standard polystyrene, its weight average molecular weight (Mw) should preferably be in the range of from 500 g/mol to 10,000 g/mol, and, especially preferably, in the range of from 700 g/mol to 7,000 g/mol, more preferably in the range from 1,000 g/mol to 5,000 g/mol, particularly from 1,500 to 3,000 g/mol.
Component (A) is preferably present in an amount that equals or is greater than 70 %, more preferably 70 to 90 % by weight, particularly preferred, 75 to 85 % by weight, based on the sum of the amount of components (A) and (B).
According to an implementation of the present invention, the thermosetting silicone resin composition comprises 60 to 75 parts by weight, more preferably 70 to 75 parts by weight, of Component (A), based on the 100 parts by weight of total organosiloxane which is a sum of component (A), component (B), component (C) and component (D). Component GBΊ
Component (B) is the curing agent of the present composition.
Component (B) is a linear organopolysiloxane with both terminal ends of the molecular chain blocked by silicon-bonded hydrogen atoms having at least one silicon- bonded aryl group per molecule. By using a linear organopolysiloxane as the curing agent, instead of a branched organopolysiloxane, a good elongation performance may be obtained.
Examples of the aryl groups of component (B) are the same as those described above. Phenyl group is especially preferable.
In addition, examples of silicon -bonded organic groups of component (B) other than the aryl groups include substituted or unsubstituted monovalent hydrocarbon groups with the exception of alkenyl groups, such as the above-described alkyl groups, the above-described aralkyl groups, and the above-described halogenated alkyl groups, with methyl being particularly preferable.
In order to achieve low attenuation due to light refraction, reflection, scattering etc. in the cured product obtained by curing the content of the silicon-bonded aryl groups
among all the silicon-bonded organic groups in component (B) should preferably be not less than 15 mol % and, particularly preferably, not less than 30 mol%. Although there are no limitations concerning the viscosity of component (B) at 25 °C, it is preferably in the range of from 1 to 1,000 mPa-s, and, especially preferably, in the range of from 2 to 500 mPa-s. This is due to the fact that when the viscosity of component (B) is below the lower limit of the above-mentioned range, it may tend to volatilize and the makeup of the resultant composition may be unstable, and, on the other hand, when it exceeds the upper limit of the above-mentioned range, the handling properties of the resultant composition tend to deteriorate.
An organopolysiloxane represented by the general formula:
[Formula 2]
is preferable as component (B).
In the formula above, each R4 can be the same or different and is independently selected from a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group with the exception of alkenyl groups.
Examples of the monovalent hydrocarbon groups of R4 include the above- mentioned alkyl groups, the above-mentioned aryl groups, and the above-mentioned halogenated alkyl groups.
Here, at least one R4 per molecule must be one of the above-mentioned aryl groups, preferably, phenyl.
In addition, n in the formula above is an integer of 0 or more, preferably, an integer in the range of from 0 to 20, and, especially preferably, an integer in the range of
from 0 to 10. This is due to the fact that when the value of n exceeds the upper limit of the above-mentioned range, the toughness of the resultant composition, or the adhesive properties of the cured product, tend to deteriorate. It is most preferable that n is 1 to 4, particularly, 1, that is, the component (B) represents trisiloxane.
By having M unit as the repeating unit, instead of Q or T unit, a good elongation performance may be obtained.
Component (B) is preferably present in an amount of 1 to 30 % by weight, more preferably 10 to 30 % by weight, particularly prefered, 15 to 25 % by weight, based on the sum of the amount of components (A) and (B).
It is preferable that the molar ratio of Si-H groups in component (B)/ alkenyl groups, for example, vinyl groups, in component (A) is 1 to 1.2 to reduce the reactive residual silicone hydride.
According to an implementation of the present invention, the thermosetting silicone resin composition comprises 18 to 25 parts by weight, more preferably 20 to 22 parts by weight, of Component (B), based on the 100 parts by weight of total organosiloxane which is a sum of component (A), component (B), component (C) and component (D).
Component (Q
Component (C) is a hydrosilylation reaction catalyst.
The hydrosilylation reaction catalyst of component (C) is used to promote the reaction of the alkenyl groups of component (A) with the silicon-bonded hydrogen atoms of component (B).
Examples of component (C) include platinum catalysts, rhodium catalysts, and palladium catalysts. Platinum catalysts are preferable because of their ability to
significantly stimulate the cure of the present composition. Examples of the platinum catalysts include platinum micropowder, chloroplatinic acid, alcohol solutions of chloroplatinic acid, platinum/alkenylsiloxane complexes, platinum/olefin complexes, and platinum/carbonyl complexes, preferably, platinum/alkenylsiloxane complexes. Examples of the alkenylsiloxanes include 1,3-divinyl- 1,1, 3, 3-tetramethyldisiloxane, l,3,5,7-tetramethyl-l,3,5,7-tetravinylcyclotetrasiloxane, alkenylsiloxanes obtained by substituting groups such as ethyl, phenyl etc. for some of the methyl groups of the above-mentioned alkenylsiloxanes, and alkenylsiloxanes obtained by substituting groups such as allyl, hexenyl, etc. for the vinyl groups of the above-mentioned alkenylsiloxanes. l ,3-divinyl-l,l,3,3-tetramethyldisiloxane is particularly preferable because of the excellent stability of the platinum/alkenylsiloxane complex. Also, due to the improvement in the stability of the complex that their addition may bring, it is desirable to add l,3-divinyl-l,l,3,3-tetramethyldisiloxane, l,3-diallyl-l, 1,3,3- tetramethyldisiloxane, l,3-divinyl-l,3-dimethyl-l,3-diphenyldisiloxane, 1,3-divinyl- 1, 1 ,3,3-tetraphenyldisiloxane, 1 ,3,5,7-tetramethyl-l ,3,5,7-tetravinylcyclotetrasiloxane and other alkenylsiloxanes and organosiloxane oligomers such as dimethylsiloxane oligomers to the platinum/alkenylsiloxane complex, with alkenylsiloxanes being particularly preferable.
There are no limitations on the content of component (C) as long as the amount promotes curing of the present composition. Elowever, specifically, in the present composition, component (C) is preferably present in an amount resulting in a platinum content of 0.05 to 100 ppm (parts per million) by weight, more preferably 0.1 to 10 ppm by weight, particularly preferred 0.1 to 5 ppm by weight, relative to 100 parts by weight of the total of components (A) and (B). This is due to the fact that when the content of component (C) is below the lower limit of the above-mentioned range, the present
composition tends to fail to completely cure, and, on the other hand, when it exceeds the upper limit of the above-mentioned range, problems may arise in terms imparting various colors to the resultant cured product. Component (D1
Component (D) is an additive, which is a low molecular weight siloxane having at least one silicon-bonded alkenyl group per molecule, represented by the average formula
where each R5 can be the same or different and is independently selected from a substituted or unsubstituted monovalent hydrocarbon group, wherein at least one of R5 per molecule is an alkenyl group, with the proviso that the ratio between alkenyl groups and silicon atoms is from 0.3 to 1,
f, g, h, and i are independently 0 or positive, and
the weight average molecular weight Mw of the siloxane is less than 1,000 g/mol, preferably less than 800 g/mol, more preferably less than 500 g/mol.
Preferably component (D) is selected from the group consisting of Dalkenyl4, Malkenyl 4Q, Malkenyl6Q2, Malkenyl3T. Preferably the alkenyl group is vinyl. Particularly preferred as component (D) are cyclotetrasiloxane DVl4, and MVl4Q, especially DVl 4.
It is assumed that component (D) serves to react with an unreacted site (Si-H), thereby protecting additional reaction of the unreacted site due to heat or light. As a result, in the composition comprising component (D), color change and mechanical strength change to high temperature may be remarkably reduced.
In the composition according to prior art, which has no component (D), materials often show an increase in hardness after curing during storage at high temperature,
which can be attributed to a post-curing reaction of remaining reactive sites and/or show a weight loss by evaporation of low molecular weight species that did not crosslink into the polymer network. Due to the change in hardness and weight loss, the materials were not stable under operating conditions. In the present invention, a reaction of component (D) with unreacted site (Si-H) leads to better stability such as less change in hardness, low weight loss, and discoloration, at high temperature.
Component (D) also gives a filling effect, which makes it possible to lower gas and vapor transmission. The encapsulant further comprising component (D) provides stablity to sulfur and such effect is expected to be obtained from the filing effect.
As a result, an LED package with excellent reliability may be obtained.
Component (D) is both reactive and small enough to react with residual silicone hydride. At the same time, component (D) crosslinks into the siloxane network and thus does not increase the proportion of volatile components in the cured material. Component (D) is preferably used in ari amount of at most 10 parts by weight, more preferably at most 7 parts by weight, and even more preferably at most 5 parts by weight relative to 100 parts by weight of the total of components (A) and (B). If component (D) is included in higher amounts, compatibility with the other components would be lower and thus, transmittance would be lower. Preferably, component (D) is used in an amount of at least 1 parts by weight relative to 100 parts by weight of the total of components (A) and (B). The amount of the component (D) may be adequately selected in consideration of the specific formulation and the feature.
According to an implementation of the present invention, the thermosetting silicone resin composition comprises 1 to 5 parts by weight, more preferably 2 to 4 parts by weight, of Component (D), based on the 100 parts by weight of total organosiloxane which is a sum of component (A), component (B), component (C) and component (D).
Component (Έ1
Component (E) is a white pigment.
The white pigment (E) functions to impart high light reflectance to a reflector, which is the cured product of the composition, and also to reduce the linear expansion of the reflector.
The white pigment (E) may be any white pigment known in the art, for example, an inorganic white pigment, an organic white pigment, a hollow particle pigment, or a mixture of two or more thereof.
Non-limiting examples of the inorganic white pigment include glass, clay, mica, talc, kaolinite (kaolin), halloysite, zeolite, acid clay, activated clay, boehmite, pseudo- boehmite, inorganic oxides; metal salts (e.g., alkaline earth metal salts, etc.), and the like. Furthermore, non-limiting examples of the organic white pigment include resin pigments, such as styrene-based resins, benzoguanamine-based resins, urea-formalin resins, melamine-formalin resins, amide-based resins, and the like.
Preferably, the white pigment (E) in the present invention, may be at least one selected from the group consisting of titanium oxide, zinc oxide, silicon oxide, aluminum oxide, barium oxide, magnesium oxide, zirconium oxide, aluminum silicate, boron nitride, calcium carbonate, tantalum pentoxide, barium sulfate, magnesium carbonate, barium carbonate, and strontium titanate.
The white pigment (E) preferably has high refractive index in order to increase the reflectance of the reflector. In one example, a white pigment having a refractive index of 1.5 or higher is preferable. In this case, a white pigment having a hollow particle structure has a very high surface reflectance due to low refractive index gas contained in the core, ands for this reason, the shell portion may also be composed of a
material having a refractive index lower than 1.5. In addition, the pigment white (E) may be a pigment subjected to surface treatment known in the art. In one example, the surface treatment comprises surface treatment with a surface treatment agent, such as a metal oxide, a silane coupling agent, a titanium coupling agent, an organic acid, a polyol, silicone or the like. When this surface treatment is performed, it may improve either the compatibility of the white pigment with other components, included in the silicone resin composition according to the present invention, or the dispersibility of the white pigment.
In addition, the shape of the white pigment (E) is not particularly limited, and may be, for example, a spherical shape, a crushed shape, a fibrous shape, a needle shape, a scaly shape, an amorphous shape, or the like. From a viewpoint of dispersibility, a spherical shape is preferably, and in particular, a spherical shape having an aspect ratio of 1.2 or less is more preferable.
In addition, the mean particle diameter of the white pigment is not particularly limited, but may be 0.01 to 50 mm, preferably 0.1 to 50 mm, in view of increasing the light reflectance of the curing product (white reflector). As used herein, the term “average diameter” means the diameter at 50% (median diameter, D50) of the cumulative particle size distribution measured by a laser diffraction/scattering method.
The content of the white pigment (E) in the thermoseting silicone resin composition according to the present invention is not particularly limited and may be suitably adjusted within the range known in the art. In one example, the content of the white pigment (E) may be 1 to 300 parts by weight, preferably 20 to 250 parts by weight, more preferably 50 to 200 parts by weight, based on 100 parts by weight of the sum of component (A) to component (D). When the content of the white pigment is within the above-described range, the light reflectively of a reflector, which is the
curing product of the composition, can further be increased, and the reduction in flowability of the thermosetting silicone resin composition by addition of the white pigment (E) can also be inhibited, resulting in improvement in workability and moldability.
In one preferable example of the present invention, the white pigment (E) comprises a titanium oxide-based first white pigment (E-l) having a mean particle diameter (D50) of 0.1 to 2 mm. This titanium oxide is preferable in view of increasing the reflectance of the curing product (white reflector) and increasing light reflectance per amount of white pigment added. The titanium oxide may be any titanium oxide known in the art, and may be, for example, rutile-type titanium oxide, anatase-type titanium oxide, brookite-type titanium oxide, or a mixture of two or more thereof.
The content of the first white pigment (E-l) is not particularly limited, but may be at least 40 parts by weight, preferably 45 to 80 parts by weight, based on 100 parts by weight of the sum of component (A) to component (D). When the composition comprises the titanium oxide-based first white pigment having the above-specified particle diameter in an amount of at least 40 parts by weight based on the total weight of component (A) to component (D), it may exhibit a light reflectance of 97% or higher, thereby maximizing the optical efficiency of the LED reflector.
Meanwhile, in the present invention, the viscosity, thixotropy, hardness after heat curing, reflectance, whiteness and the like of the composition, which are required in various manufacturing processes, may be suitably adjusted by using the above- described titanium oxide-based first white pigment (E-l) in combination with pigments having various sizes and components. Accordingly, the composition of the present invention may further comprise a second white pigment (E-2), a third white pigment (E-
3), and a mixture thereof, from which at least one of the mean particle diameter and component of the first white pigment (E-l) differs.
In one preferable example of the present invention, the ratio of the content of the first white pigment (E-l) to the content of the other pigment (e.g., E-2, E-3, E-2+E-3, etc.) except the first white pigment may be 80-99.9: 0.1-20 by weight, preferably 80- 99.5: 0.5-20 by weight, based on 100 parts by weight of the total weight of the white pigment (E).
The heat curable silicone composition of the present invention may not comprise as flexibilizing units, a linear organopolysiloxane having at least two silicon-bonded alkenyl groups and at least one silicon-bonded aryl group per molecule. It is assumed that since bulky branched organopolysiloxane such as component (A) is used as resin instead of a linear organopolysiloxane, the present curable silicone composition provides excellent hardness and toughness. That is, bulky branched organopolysiloxane is directly connected to unreacted Si-H site.
The thermosetting silicone resin composition of the present invention may further comprise a crosslinking agent, which is generally used in this field.
The thermosetting silicone resin composition of the present invention may further comprise a curing inhibitor; silica, glass, quartz, cristobalit, alumina, zinc oxide and other inorganic fillers; a catalyst; and a phosphor, which are generally used in this field.
The present composition may also contain; micropowders of organic resins such as polymethacrylate resin; heat-stabilizers, dyes, pigments, flame retardants, solvents, etc. as optional components, so long as this does not impair the purpose of this invention.
The compositions described above may be prepared by mixing the components generally used in this art, for example, by mixing all the components at ambient
temperature. Specifically, the composition may be prepared by mixing the above- described components (A, B, C, D and E) and other additives at a predetermined ratio, uniformly mixing the mixture by a Henschel mixer, a V blender, a ribbon blender, a tumbler blender or the like, followed by melt-kneading using a roll mill, a kneader, an extruder, a Banbury mixer or the like, cooling and solidifying the melt-kneaded material, and then grinding the solid material to a suitable size.
In general, in a process of manufacturing an LED reflector, the viscosity of a composition that may be applied to a dispensing process is 500 to 10,000 mPa-s, and the viscosity of a composition that may be applied to transfer molding and compression molding is 3,000 to 100,000 mPa-s. Since the thermosetting silicone resin composition according to the present invention has a viscosity of 100 to 2,000,000 mPa-s (at 25°C) before curing, it may be applied to all the above-described dispensing process and transfer molding and compression molding processes. In addition, when the thermosetting silicone resin composition is molded by any one of transfer molding and compression molding, it may be cured rapidly at a temperature of 100 to 170°C within 30 to 600 seconds.
As described above, the thermosetting silicone resin composition of the present invention may be applied to various processes, and may be cured rapidly due to high curing rate, indicating that it has excellent workability and moldability. In addition, it has high mechanical strength, heat resistance and light reflectance, and thus may preferably be used for an LED reflector. In addition to its use for the LED reflector, the thermosetting silicone resin composition of the present invention may be used without limitation in various light-emitting applications which require high light reflectance and excellent heat resistance. In one example, it may be used as a reflection member for various light-emitting devices, including electrical/electronic parts, indoor lights, ceiling
lights, outdoor lights, vehicle lights, display devices, headlights, and the like.
<LED reflector>
The LED reflector according to the present invention includes the curing product of the above-described thermosetting silicone resin composition.
The shape or size of the reflector is not particularly limited, and the reflector may include a conventional configuration known in the art. In one example, the reflector may have either a shape opened in at least side in a light emitting direction, or a non- opened planar shape.
The reflector according to the present invention may be manufactured by a conventional molding method. In one example, it is obtained by shaping the above- described thermosetting silicone resin composition into a desired shape by various molding methods, such as transfer molding, compression molding, injection molding, LIM molding (injection molding), blow molding, insert molding, dam molding with a dispenser, etc. In this case, molding and curing of the composition may occur at the same time. Alternatively, a post-curing process may also be separately performed after the molding process. Among these molding methods, the transfer molding or compression molding method is preferably used.
In one specific example, the transfer molding process is preferably performed using a transfer molding machine at a molding pressure of 5 to 20 N/mm2 at a molding temperature of 120 to 190°C, particularly 120 to 180°C, for 30 to 500 seconds, particularly 30 to 300 seconds.
In one specific example, the compressing molding process is preferably performed using a compression molding machine at a molding temperature of 120 to 190°C, particularly 120 to 180°C, for 30 to 600 seconds, particularly 120 to 420 seconds.
After the above-described molding process, a (post) curing process may, if necessary, be performed. Curing conditions for this process are not particularly limited, and may be suitably adjusted within the range known in the art. in one example, the curing process may be performed at a temperature of 100 to l70°C for 30 seconds to 30 minutes.
The reflector of the present invention, manufactured as described above, may exhibit high reflectance, excellent mechanical properties and low yellowing properties even at high temperature. In one preferable example, the LED reflector according to the present invention may have: (i) a Shore D hardness of at least 10, preferably at least 30, more preferably at least 50; (ii) a light reflectance at 450 nm wavelength of at least 90%, preferably at least 95%, more preferably at least 97%; and (iii) a yellow index of 5 or less, preferably 3 or less.
In the present invention, an optical semiconductor element (e.g., a light-emitting diode element) having the reflector may be fabricated by mounting a conventional LED element and other components, known in the art, on the above-described reflector, and then performing sealing, joining, bonding or the like using an encapsulating resin. This optical semiconductor element (LED assembly) may be used in various applications. In one example, it may be used in applications, including semiconductor devices, LCD displays, backlight units (BLU), mobile phones, vehicle display lights, vehicle head lamps, flashlights, indoor lights, traffic lights, streetlights and outdoor lights.
Semiconductor device>
The present invention provides a semiconductor device including a reflector obtained by molding the above-described thermosetting silicone resin composition.
As used herein, the term“semiconductor device” includes all semiconductor
devices known in the art. Specifically, the semiconductor device may comprise: the above-described reflector (or a reflector substrate); an optical semiconductor element mounted on the reflector; and a phosphor-containing transparent encapsulating resin layer sealing the optical semiconductor element. The optical semiconductor element may be an LED.
Such semiconductor elements are exemplified by semiconductor elements used in diodes, transistors, thyristors, solid-state image pickup elements, monolithic ICs and in hydride ICs. In particular, it is preferable that semiconductor elements are light-emitting elements.
Examples of such semiconductor devices included diodes, light-emitting diodes, transistors, thyristors, photocouplers, CCDs, monolithic IICs, hybrid ICs, LSIs, and VLSIs.
In the present invention, the LED reflector obtained by molding the above- described thermosetting silicone resin composition exhibits high light reflectance and mechanical properties, and also exhibits excellent heat resistance and low yellowing properties during driving, and thus light-induced deterioration of the reflector surface is minimized. Accordingly, the reliability of an optical semiconductor device (LED device) comprising the LED reflector may be improved.
The present invention will be described in further detail below with reference to examples. However, these examples are intended to illustrate the present invention, but the scope of the present invention is not limited to these examples.
Examples
The invention will now be illustrated by examples, which are not to be construed as limiting the invention in any way.
Analytical Methods
Description of 29Si-NMR measurement:
Solvent: C6D6 99,8%d/CCl4 1: 1 v/v with 1 % w/w Cr(acac)3 as reagent for relaxation Sample concentration: ca. 2 g / 1.5 mL solvent in 10 mm NMR tube
Spectrometer: Bruker Avance 300
Sample head: 10 mm 1H/13C/l5N/29Si glassfree QNP-Head (Bruker)
Measurement parameter: Pulprog = zgig60, TD = 64k, NS = 1024, SW = 200 ppm, AQ = 2.75 s, Dl - 4 s, SFOl = 300.13 MHz, 01 = -50 ppm
Processing-Parameter: SI = 64k, WDW = EM, LB = 0.3 Hz
Viscosity:
Viscosity data is measured with a rheometer model MCR302 manufactured by the company Anton Paar, D-Ostfildern, according to D1N EN ISO 3219 in rotation with a cone-plate measurement system. Measurements were performed in a range where the samples behavior is newtonian. Viscosity data are given for a temperature of 25 °C and an ambient pressure of 1013 mbar.
Molecular weight:
Molecular weight is determined as weight average molecular weight Mw and number average molecular Mn by Size Exclusion Chromatography SEC. Polystyrene is used as standard. The detector is a RI detector. THF is used as solvent. Sample concentration is 5 mg / mL.
Synthesis example 1
700 g (2.91 mole) phenyltriethoxysilane, 61.6 g (0.415 mole) diethoxydimethylsilane and 77.6 g (0.416 mole) l,3-divinyl-l,l,3,3-tetramethyldisiloxane were mixed in a 2 L
round-botomed flask. 600 g distilled water and 3.00 g 20 % hydrochloric acid were added to the solution. The reaction mixture was refluxed for 2 hours. After cooling, 4.50 g 25 % sodium hydroxide solution were added and the reaction mixture was refluxed for 1 hour. The homogeneous mixture was neutralized with 2.00 g 20 % hydrochloric acid. Ethanol was distilled at 40 °C under vacuum and 1 L ethylacetate and 50 g sodium chloride were added. The aqueous phase was removed and the organic phase was washed three times with saturated aqueous sodium chloride solution. The organic phase was dried with magnesium sulfate and was filtrated with press filter equipment. After removal of the solvent in vacuum, 470 g of a colorless, highly viscous product were obtained. Weight average molecular weight Mw is 2,546 g/mol. The results of 29Si NMR are ViMe2SiOi/2: 16.6 %, Me2Si02/2: 9.7 %, Ph(0R)Si02/2: 12. 8 % and PhSi03/2: 60.9 %.
Example 1 75 % by weight of the compound from synthesis example las component A, 25 % by weight of l, l,5,5-tetramethyl-3,3-diphenyltrisiloxane as component B were prepared. In addition, relative to 100 parts by weight of the total of components A and B, 0.0002 parts (with respect to Platinum) by weight of Platinum(O)- 1,3-divinyl- 1, 1 , 3,3,- tetramethyl-disiloxane complex as component C, and 4.99 parts by weight of DVl 4 as component D were prepared.
Based on 100 parts by weight of the sum of the components (A, B, C, and D), 50 parts by weight of titanium oxide (first white pigment), having a mean particle diameter of 0.3 mm, and 0.5 parts by weight of silicon oxide (second white pigment) having a mean particle diameter of 0.02 mm were prepared as a white pigment (E) and mixed
with the above components, thereby preparing a thermosetting silicone resin composition for an LED reflector according to Example 1.
Examples 2 to 1 1
The thermosetting silicone resin compositions for reflector of LED according to examples 2 to 11 were prepared in the same manner in example 1 except that component E was used in an amount as shown in following table 1.
[Table 1]
*unit: parts by weight relative to the 100 parts by weight of a sum of components
(A), (B), (C) and (D)
[Evaluation Example]
The physical properties of the thermosetting silicone resin compositions for LED
reflectors, prepared in Examples 1 to 1 1, were measured as described below, and the results of the measurement are shown in Table 2 below. Molding of the curing products obtained by curing the compositions was performed using a transfer molding machine under the conditions of molding temperature of 165°C, molding pressure of 7 MPa and molding time of 300 seconds. The cured samples prepared by the transfer molding were post-cured at 150°C for about 4 hours.
<Results of evaluation of physical properties>
(1) Measurement of viscosity
For the thermosetting silicone resin composition prepared in each of the Examples, the dynamic viscosities at shear rates of l/sec and 10/sec were measured using a 25-mm-diameter flat plate in a rheometer model MCR302 (Anton Paar) system.
(2) Thixotropic index
Thixotropic index was calculated as the ratio of the dynamic viscosity at a shear rate of lO/sec to the dynamic viscosity at a shear rate of l/sec.
(3) Shore hardness (D)
The hardness of a molded sample having a thickness of 6 mm was measured on a Shore Durometer Hardness (D) scale.
(4) Yellow index (b*)
The yellow index of a molded sample having a thickness of 1 mm was measured by CIE Lab colorimetry using Minolta CM5.
(5) Light reflectance
The light reflectance at 450 nm of a transfer-molded sample having a thickness of 1 mm was measured using a Minolta CM 5 spectrophotometer in specular component- included mode.
As shown in Table 2, it could be seen that the compositions of Examples 1 to 1 1 according to the present invention had high light reflectance, excellent mechanical properties, and low yellowing properties, which are required for a reflector.
Claims
1. A thermosetting silicone resin composition for reflector of LED comprising:
(A) a branched organopolysiloxane having at least one silicon-bonded alkenyl group and at least one silicon-bonded aryl group per molecule, and having siloxane units represented by the general formula: RS1O3/2 where R is a substituted or unsubstituted monovalent hydrocarbon group;
(B) a linear organopolysiloxane with both terminal ends of the molecular chain blocked by silicon-bonded hydrogen atoms and having at least one silicon-bonded aryl group per molecule;
(C) a hydrosilylation reaction catalyst;
(D) a low molecular weight siloxane having at least one silicon-bonded alkenyl group represented by the average formula
where each Rs can be the same or different and is independently selected from a substituted or unsubstituted monovalent hydrocarbon group, wherein at least one of R5 per molecule is an alkenyl group, with the proviso that the ratio between alkenyl groups and silicon atoms is from 0.3 to 1,
f, g, h, and i are independently 0 or positive,
the weight average molecular weight Mw of the siloxane is less than 1,000 g/mol; and
(E) a white pigment,
wherein the white pigment (E) is contained in an amount of 1 to 300 parts by weight based on 100 parts by weight of a sum of component (A) to component (D).
2. The thermosetting silicone resin composition of claim 1, wherein the composition has a viscosity of 100 to 2,000,000 mPa s (at 25°C) before curing, and is cured rapidly at a temperature of 100 to 170°C within 30 to 600 seconds when being molded by any one method selected from among transfer molding and compression molding.
3. The thermosetting silicone resin composition of claim 1, wherein the white pigment (E) is at least one selected from the group consisting of titanium oxide, zinc oxide, silicon oxide, aluminum oxide, barium oxide, magnesium oxide, zirconium oxide, aluminum silicate, boron nitride, calcium carbonate, tantalum pentoxide, barium sulfate, magnesium carbonate, barium carbonate, and strontium titanate.
4. The thermosetting silicone resin composition of claim 1, wherein the white pigment (E) has a mean particle diameter (D50) of 0.01 to 50 mm.
5. The thermosetting silicone resin composition of claim 1, wherein the white pigment (E) comprises a titanium oxide-based first white pigment (E-l) having a mean particle diameter of 0.1 to 2 mm.
6. The thermosetting silicone resin composition of claim 5, wherein the first white pigment (E-l) is contained in an amount of at least 40 parts by weight based on 100 parts by weight of a sum of component (A) to component (D).
7. The thermosetting silicone resin composition of claim 5, wherein the white pigment further comprises a second white pigment (E-2), a third white pigment (E-3), or
a mixture thereof, in which at least one of the mean particle diameter and component of the first white pigment (E-l) differs.
8. The thermosetting silicone resin composition of claim 7, wherein a ratio of a content of the first white pigment (E-l) to a content of the remaining pigment exclusive of the first white pigment is 80-99.9: 0.1-20 by weight, based on 100 parts by weight of a total weight of the white pigment (E).
9. The thermosetting silicone resin composition for reflector of LED according to claim 1, in which component (A) is an organopolysiloxane represented by the average unit formula:
where each of R1, R2, and R3 can be the same or different, and is independently selected from a substituted or unsubstituted monovalent hydrocarbon group, wherein at least one of R1, R2, or R3 per molecule is an alkenyl group and at least one of R1, R2, or R3 per molecule is an aryl group,
X is a hydrogen atom or alkyl group,
a is 0 or a positive number,
b is 0 or a positive number,
c is a positive number,
d is 0 or a positive number,
e is 0 or a positive number,
b/c is a number between 0 and 10,
a/c is a number between 0 and 0.5,
d/(a+b+c+d) is a number between 0 and 0.3, and
e/(a+b+c+d) is a number between 0 and 0.4.
10. The thermosetting silicone resin composition for reflector of LED according to claim 1, in which component (A) is an organopolysiloxane with the average unit formula:
(R1R1 R3Si0!/2)a(R12Si02/2)b(R2Si03/2)c
where R1 is a Ci to C12 alkyl group,
R2 is a C6 to C20 aryl group or C7 to C20 aralkyl group,
R3 is C2 to C12 alkenyl group,
a is 0 or a positive number,
b is 0 or a positive number, and
c is a positive number.
1 1. The thermosetting silicone resin composition for reflector of LED according to claim 1, in which component (B) is an organopolysiloxane represented by the general formula:
[Formula 2] where each R4 can be the same or different and is independently selected from a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group with the exception of alkenyl groups, wherein at least one R4 per molecule is an aryl group, and n is an integer of 0 or more.
12. The thermosetting silicone resin composition for reflector of LED according to claim 1, wherein a weight ratio of component (A) to component (B) is 70:30 to 90: 10.
13. The thermosetting silicone resin composition for reflector of LED according to claim 12, wherein a weight ratio of component (A) to component (B) is 75:25 to 85: 15.
14. The thermosetting silicone resin composition for reflector of LED according to claim 1, in which component (D) is selected from the group consisting of Dvi 4, Mvi 4Q, MVi 6Q2, and Mvi 3T.
15. The thermosetting silicone resin composition for reflector of LED according to claim 14, in which component (D) comprises DV 4.
16. The thermosetting silicone resin composition for reflector of LED according to claim 1, wherein component (D) is comprised in an amount of at most 10 parts by weight, relative to 100 parts by weight of the total of components (A) and (B).
17. The thermosetting silicone resin composition for reflector of LED according to claim 1, wherein the molar ratio of the hydrosilyl group in component (B) with respect to the alkenyl group in component (A) is 1 to 1. 2.
18. The thermosetting silicone resin composition for reflector of LED according to claim 1, further comprising at least one selected from the group consisting of crosslinking agent, inorganic filler, a curing inhibitor, a catalyst, and a phosphor.
19. An LED reflector comprising a cured product formed by curing the thermosetting silicone resin composition claimed in any one of claims 1 to 18.
20. The LED reflector of claim 17, which has:
a Shore D hardness of 10 or more;
a light reflectance of 90% or higher at a wavelength of 450 nm; and a yellow index of 5 or less.
21. A semiconductor device comprising the reflector of claim 18.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/EP2018/073484 WO2020043312A1 (en) | 2018-08-31 | 2018-08-31 | Thermosetting silicone resin composition for reflector of led, reflector of led and semiconductor device using the same |
| TW108128939A TW202010793A (en) | 2018-08-31 | 2019-08-14 | Thermosetting silicone resin composition for reflector of LED, reflector of LED and semiconductor device using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/EP2018/073484 WO2020043312A1 (en) | 2018-08-31 | 2018-08-31 | Thermosetting silicone resin composition for reflector of led, reflector of led and semiconductor device using the same |
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| Publication Number | Publication Date |
|---|---|
| WO2020043312A1 true WO2020043312A1 (en) | 2020-03-05 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022202592A1 (en) * | 2021-03-26 | 2022-09-29 | デンカ株式会社 | Inorganic oxide powder, resin composition, and compression molded product |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2075280A1 (en) * | 2007-12-26 | 2009-07-01 | Shin-Etsu Chemical Co., Ltd. | White heat-curable silicone resin composition, optoelectric part case, and molding method |
| WO2013115415A1 (en) * | 2012-02-02 | 2013-08-08 | Dow Corning Toray Co., Ltd. | Curable silicone composition, cured product thereof, and optical semiconductor device |
| WO2018028792A1 (en) * | 2016-08-12 | 2018-02-15 | Wacker Chemie Ag | Curable organopolysiloxane composition, encapsulant and semiconductor device |
-
2018
- 2018-08-31 WO PCT/EP2018/073484 patent/WO2020043312A1/en unknown
-
2019
- 2019-08-14 TW TW108128939A patent/TW202010793A/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2075280A1 (en) * | 2007-12-26 | 2009-07-01 | Shin-Etsu Chemical Co., Ltd. | White heat-curable silicone resin composition, optoelectric part case, and molding method |
| WO2013115415A1 (en) * | 2012-02-02 | 2013-08-08 | Dow Corning Toray Co., Ltd. | Curable silicone composition, cured product thereof, and optical semiconductor device |
| WO2018028792A1 (en) * | 2016-08-12 | 2018-02-15 | Wacker Chemie Ag | Curable organopolysiloxane composition, encapsulant and semiconductor device |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022202592A1 (en) * | 2021-03-26 | 2022-09-29 | デンカ株式会社 | Inorganic oxide powder, resin composition, and compression molded product |
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