CN104559181A - Silicone resin composition for optical semiconductor and cured product thereof - Google Patents
Silicone resin composition for optical semiconductor and cured product thereof Download PDFInfo
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- CN104559181A CN104559181A CN201410563597.0A CN201410563597A CN104559181A CN 104559181 A CN104559181 A CN 104559181A CN 201410563597 A CN201410563597 A CN 201410563597A CN 104559181 A CN104559181 A CN 104559181A
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- zirconia particles
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- photosemiconductor
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- 239000011342 resin composition Substances 0.000 title claims abstract description 72
- 229920002050 silicone resin Polymers 0.000 title claims abstract description 43
- 230000003287 optical effect Effects 0.000 title abstract description 12
- 239000004065 semiconductor Substances 0.000 title abstract description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 219
- 239000002245 particle Substances 0.000 claims abstract description 114
- 239000000203 mixture Substances 0.000 claims abstract description 42
- 150000001298 alcohols Chemical class 0.000 claims abstract description 16
- 150000002576 ketones Chemical class 0.000 claims abstract description 16
- 239000006185 dispersion Substances 0.000 claims description 32
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 3
- 229910052710 silicon Inorganic materials 0.000 abstract 3
- 239000010703 silicon Substances 0.000 abstract 3
- 239000003607 modifier Substances 0.000 abstract 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 42
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 38
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 38
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 38
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- -1 amino, sulfydryl Chemical group 0.000 description 20
- 238000004519 manufacturing process Methods 0.000 description 18
- 238000002834 transmittance Methods 0.000 description 16
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 14
- 125000000524 functional group Chemical group 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 229910000077 silane Inorganic materials 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 8
- 206010018612 Gonorrhoea Diseases 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- KQAHMVLQCSALSX-UHFFFAOYSA-N decyl(trimethoxy)silane Chemical compound CCCCCCCCCC[Si](OC)(OC)OC KQAHMVLQCSALSX-UHFFFAOYSA-N 0.000 description 7
- 239000003822 epoxy resin Substances 0.000 description 7
- 229920000647 polyepoxide Polymers 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 239000003566 sealing material Substances 0.000 description 7
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 6
- 230000006837 decompression Effects 0.000 description 6
- 239000011859 microparticle Substances 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 150000004756 silanes Chemical class 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 4
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000002612 dispersion medium Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 4
- 125000004665 trialkylsilyl group Chemical group 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 2
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 125000002769 thiazolinyl group Chemical group 0.000 description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- DOYKFSOCSXVQAN-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C(C)=C DOYKFSOCSXVQAN-UHFFFAOYSA-N 0.000 description 1
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 description 1
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 1
- PRKPGWQEKNEVEU-UHFFFAOYSA-N 4-methyl-n-(3-triethoxysilylpropyl)pentan-2-imine Chemical compound CCO[Si](OCC)(OCC)CCCN=C(C)CC(C)C PRKPGWQEKNEVEU-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 241000588731 Hafnia Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000005376 alkyl siloxane group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- BAAAEEDPKUHLID-UHFFFAOYSA-N decyl(triethoxy)silane Chemical compound CCCCCCCCCC[Si](OCC)(OCC)OCC BAAAEEDPKUHLID-UHFFFAOYSA-N 0.000 description 1
- GAURFLBIDLSLQU-UHFFFAOYSA-N diethoxy(methyl)silicon Chemical compound CCO[Si](C)OCC GAURFLBIDLSLQU-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 1
- CZWLNMOIEMTDJY-UHFFFAOYSA-N hexyl(trimethoxy)silane Chemical compound CCCCCC[Si](OC)(OC)OC CZWLNMOIEMTDJY-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- WSGCRAOTEDLMFQ-UHFFFAOYSA-N nonan-5-one Chemical compound CCCCC(=O)CCCC WSGCRAOTEDLMFQ-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- WUMSTCDLAYQDNO-UHFFFAOYSA-N triethoxy(hexyl)silane Chemical compound CCCCCC[Si](OCC)(OCC)OCC WUMSTCDLAYQDNO-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 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
- NESLVXDUKMNMOG-UHFFFAOYSA-N triethoxy-(propyltetrasulfanyl)silane Chemical compound CCCSSSS[Si](OCC)(OCC)OCC NESLVXDUKMNMOG-UHFFFAOYSA-N 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Epoxy Resins (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Led Device Packages (AREA)
Abstract
The invention provides a silicon resin composition for an optical semiconductor and a cured product thereof. The silicon resin composition for the optical semiconductor is characterized in that the composition includes zirconia particles modified at surfaces, dispersing auxiliaries, and organic silicone resin, the zirconia particles modified at the surfaces are in a dispersing state, the dispersing particle size of the zironia particles modified at the surfaces is more than 1 nm and less than 50 nm, and the dispersing auxiliaries contain at least one of ketones and alcohols. According to the silicon resin composition for the optical semiconductor and the cured product thereof, the content of the zironia particles can be relatively increased, the amount of surface modifiers can be relatively reduced, and the refractive index of the cured product is excellent.
Description
Technical field
The silicone resin cured article that the present invention relates to the organosilicon resin composition that is suitable for photosemiconductor field and make it solidify and obtain, particularly can be suitable for use in the photosemiconductor organosilicon resin composition in the sealing of the photosemiconductor such as LED or semiconductor laser etc. and cured article thereof.
Background technology
All the time, in photosemiconductor fields such as photodiode (LED) or laser diodes, various resin combination is used.Such as, as the sealing material of LED, there will be a known the resin combination containing epoxy resin or silicone resin etc.In addition, also known in such resin combination in order to maintain the transparency of cured article that solidification obtains and improve its specific refractory power and coordinate the metal oxide of nano-scale.
Such as, in patent documentation 1, a kind of resin composition for encapsulating semiconductor is disclosed, consist of: containing resin and Zirconia particles, the median size of Zirconia particles is more than 1nm, below 30nm, and the surface coverage of Zirconia particles has the organic compound of energy coordination and/or Cheng Jian.Although as above-mentioned resin, use epoxy resin or silicone resin, the embodiment of patent documentation 1, is all the use of the example of epoxy resin.In addition, the covering on the surface of Zirconia particles except above-mentioned organic compound, can also and with silane coupling agent process and/or the process of polyethers carbonic acid.
In addition, Patent Document 2 discloses and a kind ofly make specific organosilicon derivates carry out polyreaction with the metal oxide microparticle having a reactive functional groups at microparticle surfaces and the Thermocurable organosilicon resin composition that obtains.This Thermocurable organosilicon resin composition can be used in encapsulating optical semiconductor element.In addition, above-mentioned metal oxide microparticle can be selected from least one in the group that is made up of titanium oxide, zirconium white, barium titanate, silicon-dioxide, aluminum oxide and hafnia.And, as the above-mentioned reactive functional groups of microparticle surfaces, illustrate hydroxyl, isocyanate group, amino, sulfydryl, carboxyl, epoxy group(ing), ethylene type unsaturated group, halogen radical, isocyanurate group etc.
In addition, Patent Document 3 discloses a kind of surface of containing modified by coating materials and disperse the transparent dispersion liquids such as the zirconium white of the tetragonal zirconia particle of more than particle diameter 1nm, below 20nm and make this transparent dispersion liquid be dispersed in the transparent complex formed in resin.This transparent complex can be used for the sealing material of semiconductor laser or LED.In addition, as coating materials, more than a kind in the group being selected from and being made up of alkoxysilane compound containing trialkylsilyl group in molecular structure, silicone compounds, tensio-active agent, titanate coupling agent can be enumerated, as embodiment, disclose the embodiment 1 using silane coupling agent.In addition, modification part reaches more than 5 % by weight, less than 200 % by weight of this tetragonal zirconia particle in the weight ratio of tetragonal zirconia particle surface.
At first technical literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2008-106260 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2010-144136 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2007-119617 publication
Summary of the invention
The technical problem that will solve is intended in invention
In resin composition for encapsulating semiconductor disclosed in patent documentation 1, also can use silicone resin, but only disclose the use of epoxy resin as embodiment.In the sealing material of LED, the ultraviolet energy in the light sometimes sent due to LED and produce free radical.This free radical makes epoxy resin be oxidized, if therefore comprise epoxy resin in the sealing material of LED, then and the sealing material easily xanthochromia because of oxidation.
In the sealing material of LED, if use silicone resin to replace epoxy resin, then xanthochromia can be avoided.But, the sealing material containing silicone resin due to the specific refractory power of light low, the extraction efficiency therefore from the light of LED likely reduces.
Disclosed in patent documentation 2, disclosed in Thermocurable organosilicon resin composition and patent documentation 3, transparent complex all uses silicone resin as resinous principle.But Thermocurable organosilicon resin composition disclosed in patent documentation 2 is relative to organosilicon derivates 100 weight part, and the content of metal oxide microparticle is 1 ~ 70 % by weight.Because the content of this metal oxide microparticle is relatively few, the specific refractory power of cured article therefore fully can be improved hardly.
On the other hand, the formation of transparent complex disclosed in patent documentation 3 makes the tetragonal zirconia particle dispersion after being modified by silane coupling agent etc. in silicone resin, and the containing ratio of tetragonal zirconia particle is more than 1 % by weight, less than 80 % by weight.But the weight ratio (i.e. the amount of coating materials) of the modification part of tetragonal zirconia particle is relatively many, does not therefore fully improve the specific refractory power of transparent complex.
The present invention completes to solve above-mentioned problem, and its object is to provide a kind of relatively can increase the content of Zirconia particles and relatively can reduce the amount of coating materials thus the specific refractory power of cured article can be made to become excellent photosemiconductor organosilicon resin composition and its cured article.
For the technical scheme of dealing with problems
In order to solve the problem, photosemiconductor organosilicon resin composition of the present invention contains the Zirconia particles after by finishing, dispersing auxiliary and silicone resin, be dispersion state by the described Zirconia particles after finishing, be more than 1nm, below 50nm by the dispersion particle diameter of the described Zirconia particles after finishing, as described dispersing auxiliary, at least one containing ketone and alcohols.
According to said structure, be in the dispersion particle diameter of the Zirconia particles of dispersion state in above-mentioned scope, and contain at least one of ketone and alcohols as dispersing auxiliary, thus in photosemiconductor organosilicon resin composition, relatively can increase the content of Zirconia particles.In addition, in the Zirconia particles of finishing, relatively can reduce the amount of the silane coupling agent as coating materials.Thereby, it is possible to the specific refractory power of the cured article making to be solidified by photosemiconductor organosilicon resin composition and obtain becomes excellent.
In the photosemiconductor organosilicon resin composition of said structure, also can be configured to: when the quality of the described Zirconia particles before finishing is 100 mass parts, be below more than 0.1 mass parts, 10 mass parts by the quality of finishing part in the described Zirconia particles after finishing.
In addition, in the photosemiconductor organosilicon resin composition of said structure, also can be configured to: the quality of the described Zirconia particles before finishing, when being 100 mass parts for the total amount of the quality of the described silane coupling agent of finishing and the quality of described silicone resin, being converted by the described Zirconia particles before the content finishing of the described Zirconia particles after finishing, is below more than 50 mass parts, 75 mass parts.
In the photosemiconductor organosilicon resin composition of said structure, also can be configured to: relative to composition 100 mass parts in whole compositions of described photosemiconductor organosilicon resin composition except described dispersing auxiliary, the use level of described dispersing auxiliary is below more than 50 mass parts, 2000 mass parts.
And the present invention also comprises the photosemiconductor silicone resin cured article making the photosemiconductor organosilicon resin composition of said structure be solidified to form.
Embodiment
Below, the preferred embodiment of the present invention is described.Photosemiconductor organosilicon resin composition of the present invention contains the Zirconia particles after by finishing, dispersing auxiliary and silicone resin, is in dispersion state by the above-mentioned Zirconia particles after finishing.Particularly, be more than 1nm, below 50nm by the dispersion particle diameter of the above-mentioned Zirconia particles after finishing, and as dispersing auxiliary, comprise at least one of ketone and alcohols.
[Zirconia particles by after finishing]
The Zirconia particles used in the present invention carries out the particle after finishing with coating materials, can use silane coupling agent as coating materials.The concrete structure of the Zirconia particles before finishing is not particularly limited, as long as be dispersion state and disperse particle diameter to have the primary particle size in above-mentioned scope.In addition, as long as Zirconia particles does not hinder its optical property or dispersing property, the composition beyond zirconium white (zirconia) can also be contained.In the present invention, as the Zirconia particles before finishing, such as, the zirconia dispersion being dispersed with Zirconia particles can be suitably used in dispersion medium.
The concrete kind of Zirconia particles being carried out to the silane coupling agent of finishing is not particularly limited, and can suitably use known compound as silane coupling agent.Specifically, such as can enumerate: the alkoxysilane compound containing trialkylsilyl group in molecular structure such as decyl Trimethoxy silane, decyl triethoxyl silane, hexyl Trimethoxy silane, hexyl triethoxyl silane, phenyltrimethoxysila,e, phenyl triethoxysilane, methyltrimethoxy silane, dimethyldimethoxysil,ne, Union carbide A-162, dimethyldiethoxysilane; The ethene such as vinyltrimethoxy silane, vinyltriethoxysilane system silane compound; The epoxy silane compounds such as 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 3-glycydoxy methyl dimethoxysilane, 3-glycydoxy Trimethoxy silane, 3-glycydoxy methyldiethoxysilane, 3-glycydoxy triethoxyl silane; Dimethoxydiphenylsilane, to phenyl system silane such as styryl Trimethoxy silanes; (methyl) acryloyl system silane compounds such as 3-acryloxypropyl Trimethoxy silane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloyloxypropyl methyl dimethoxysilane, 3-methacryloyloxypropyl methyl diethoxy silane, 3-methacryloxypropyl; The uride silane compounds such as uride methyltrimethoxy silane, uride Union carbide A-162,2-uride ethyl trimethoxy silane, 2-uride ethyl triethoxysilane, 3-uride propyl trimethoxy silicane, 3-uride propyl-triethoxysilicane; The isocyanate-based silane compounds such as 3-isocyanic ester propyl-triethoxysilicane, 3-isocyanic ester propyl trimethoxy silicane; The amino system silane compounds such as N-2-(amino-ethyl)-3-amino propyl methyl dimethoxysilane, N-2-(amino-ethyl)-3-amino propyl methyl Trimethoxy silane, 3-TSL 8330, APTES, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene) propylamine, N-phenyl-3-TSL 8330; 3-mercaptopropyi methyl dimethoxysilane, 3-mercaptopropyi Trimethoxy silane, two (triethoxysilylpropyltetrasulfide) tetrasulfide etc. have the silane compound of sulfur-bearing functional group; Etc..These compounds can be used alone, also can two or more appropriately combined use.Wherein, alkoxysilane compound containing trialkylsilyl group in molecular structure, phenyl system silane compound, (methyl) acryloyl system silane compound etc. is preferably used.
Silane coupling agent is used can suitably to use known method to the method that Zirconia particles carries out finishing.Specifically, in zirconia dispersion, add silane coupling agent, and stir under the condition of preset temperature, the scheduled time and predetermined pressure.The zirconia dispersion now used can be commercially available product, and Zirconia particles and known dispersion medium also can be used to be prepared at every turn.It should be noted that, when manufacturing photosemiconductor organosilicon resin composition of the present invention, can directly (former state) use by the dispersion of the Zirconia particles after finishing (finishing zirconia dispersion).
The Zirconia particles used in the present invention is carried out finishing by with silane coupling agent, but when the quality of the Zirconia particles before finishing is 100 mass parts, the quality of the finishing part (silane coupling agent) of this Zirconia particles can be below more than 0.1 mass parts, 10 mass parts, preferably more than 0.1 mass parts, is less than 5 mass parts.That is, by the surface of the Zirconia particles after finishing, with the quality of the Zirconia particles before finishing for benchmark, can form the finishing part within the scope of 0.1 ~ 10 quality %, preferred surface modification part is less than 0.5 quality %.
By the dispersion particle diameter of the Zirconia particles after finishing as previously mentioned, as long as within the scope of 1nm ~ 50nm.If dispersion particle diameter is less than 1nm, then particle diameter is too small, is difficult to improve specific refractory power.In addition, if dispersion particle diameter is more than 50nm, then particle diameter is excessive, has dispersed reduction and the tendency that reduces of optical characteristics in composition or cured article.It should be noted that, in present embodiment, measured by the microtrack UPA-UZ152 (ProductName) that the dispersion particle diameter of the Zirconia particles after finishing uses Nikkiso Company Limited to manufacture.
[silicone resin]
The silicone resin that the present invention uses is Thermocurable silicone resin, as long as have in the known optical characteristics in sealing photosemiconductor field, then its concrete structure is not particularly limited.
Representatively Thermocurable silicone resin, such as can enumerate following structure: there is the skeleton structure such as silane, silicone oligomer, silicone resin, alkyl siloxanes (オ Le ガ ノ シ ロ キ サ Application), dialkyl siloxane, alkyl polysiloxane, dialkyl polysiloxane, and this skeleton structure has more than one reactive functional groups.Above-mentioned skeleton structure can be linear chain structure, also can be branched structure.
In addition, as reactive functional groups, can enumerate: the hydroxyl that the Siliciumatom contained in above-mentioned skeleton structure is combined, thiazolinyl, hydrogen silyl, (methyl) acryloxy, epoxy group(ing), amino, hydroxyl methyl, sulfydryl, carboxyl, phenylol etc., be not particularly limited.In addition, in above-mentioned skeleton structure, except above-mentioned reactive functional groups, alkyl, thiazolinyl, aromatic series Ji Deng functional group can also be had.
The Thermocurable silicone resin used in the present invention, can have only a kind of skeleton structure and only a kind of reactive functional groups, also can have multiple skeleton structure and multiple reactive functional groups.In addition, reactive functional groups is described above, and can contain more than one reactive functional groups in a skeleton structure, in other words, 1 molecule silicone resin (having arbitrary skeleton structure) has at least one reactive functional groups.It should be noted that, reactive functional groups can at the end of skeleton structure, can at side chain, also can at the either side of end and side chain.
[dispersing auxiliary]
The dispersing auxiliary that the present invention uses can be ketone and alcohols at least any one.In photosemiconductor organosilicon resin composition of the present invention, except by the Zirconia particles after finishing and silicone resin, also containing ketone or alcohols as dispersing auxiliary, thus the Zirconia particles after by finishing can be made to disperse well in the composition.
In addition, ketone as dispersing auxiliary is not particularly limited, specifically, such as can enumerate: acetone, methylethylketone, methyl iso-butyl ketone (MIBK), butyl methyl ketone, di-n-butyl ketone, pimelinketone, butyrone, Methyl amyl ketone, diisobutyl ketone, isophorone, methyl ethyl diketone etc.As dispersing auxiliary, these ketones can be used alone, also can two or more appropriately combined use.
Alcohols as dispersing auxiliary is not particularly limited, specifically, such as can enumerate: methyl alcohol, ethanol, propyl alcohol, butanols, Virahol, tetrahydrofurfuryl alcohol, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, TC, propylene glycol monomethyl ether, propylene glycol monoethyl etc.As dispersing auxiliary, these alcohols can be used alone, also can two or more appropriately combined use.
In addition, as dispersing auxiliary, also can respectively at least one ketone and alcohols be carried out and use.Such as, in aftermentioned embodiment, and by propylene glycol monomethyl ether and methyl iso-butyl ketone (MIBK).In addition, and be not particularly limited by ratio of mixture when ketone and alcohols, suitably can set ratio of mixture and disperse well in the composition to enable the Zirconia particles after by finishing.
It should be noted that, in the present invention, as dispersing auxiliary, also can use other solvents known outside ketone and alcohols, also these other solvents and ketone or alcohols can be used.
As the preferably combination of ketone and alcohols, specifically, can enumerate: methylethylketone and methyl alcohol, methylethylketone and ethanol, methylethylketone and propyl alcohol, methylethylketone and butanols, methylethylketone and Virahol, methylethylketone and tetrahydrofurfuryl alcohol, methylethylketone and ethylene glycol monomethyl ether, methylethylketone and ethylene glycol monomethyl ether, methylethylketone and ethylene glycol monobutyl ether, methylethylketone and diethylene glycol monomethyl ether, methylethylketone and TC, methylethylketone and propylene glycol monomethyl ether, methylethylketone and propylene glycol monoethyl, methyl iso-butyl ketone (MIBK) and methyl alcohol, methyl iso-butyl ketone (MIBK) and ethanol, methyl iso-butyl ketone (MIBK) and propyl alcohol, methyl iso-butyl ketone (MIBK) and butanols, methyl iso-butyl ketone (MIBK) and Virahol, methyl iso-butyl ketone (MIBK) and tetrahydrofurfuryl alcohol, methyl iso-butyl ketone (MIBK) and ethylene glycol monomethyl ether, methyl iso-butyl ketone (MIBK) and ethylene glycol monomethyl ether, methyl iso-butyl ketone (MIBK) and ethylene glycol monobutyl ether, methyl iso-butyl ketone (MIBK) and diethylene glycol monomethyl ether, methyl iso-butyl ketone (MIBK) and TC, methyl iso-butyl ketone (MIBK) and propylene glycol monomethyl ether, methyl iso-butyl ketone (MIBK) and propylene glycol monoethyl, butyl methyl ketone and methyl alcohol, butyl methyl ketone and ethanol, butyl methyl ketone and propyl alcohol, butyl methyl ketone and butanols, butyl methyl ketone and Virahol, butyl methyl ketone and tetrahydrofurfuryl alcohol, butyl methyl ketone and ethylene glycol monomethyl ether, butyl methyl ketone and ethylene glycol monomethyl ether, butyl methyl ketone and ethylene glycol monobutyl ether, butyl methyl ketone and diethylene glycol monomethyl ether, butyl methyl ketone and TC, butyl methyl ketone and propylene glycol monomethyl ether, butyl methyl ketone and propylene glycol monoethyl, but be not particularly limited.
In photosemiconductor organosilicon resin composition of the present invention, as dispersing auxiliary, can use ketone and alcohols at least any one, thus the finishing part that can reduce Zirconia particles (namely, the usage quantity of surface treatment agent can be reduced), and the content of Zirconia particles itself can be increased.Therefore, it is possible to make the optical characteristics such as the specific refractory power of the cured article obtained more excellent.
[organosilicon resin composition and cured article thereof]
Photosemiconductor organosilicon resin composition of the present invention as previously mentioned, contain by the Zirconia particles after finishing, silicone resin and dispersing auxiliary, but the content of these compositions is not particularly limited.
When photosemiconductor organosilicon resin composition total amount is 100 mass parts, can be below more than 20 mass parts, 80 mass parts by the use level of the Zirconia particles after finishing, be preferably more than 50 mass parts, below 75 mass parts.If be less than 20 mass parts by the Zirconia particles after finishing, then the Zirconia particles in composition is very few, likely can not realize good specific refractory power.In addition, if Zirconia particles is more than 80 mass parts, then Zirconia particles is too much in the composition, likely can not disperse well or may become because the content of Zirconia particles morely easily in cured article, to produce crack, can not obtain good cured article.
And, in the present invention, can be specific for the total amount of solid state component when preparing composition by the content of the Zirconia particles after finishing.Specifically, when the total amount of the quality of the quality of the above-mentioned Zirconia particles before finishing, the quality of the silane coupling agent be used in finishing and silicone resin is 100 mass parts, preferably being converted with the above-mentioned Zirconia particles before finishing by the content of the above-mentioned Zirconia particles after finishing in composition is below more than 50 mass parts, 75 mass parts.
That is, according to the present invention, (more than 50 quality %) over half in the solid state component of photosemiconductor organosilicon resin composition are Zirconia particles.Thereby, it is possible to maintain the transparency of photosemiconductor organosilicon resin composition and cured article thereof, and high concentration can be carried out to the Zirconia particles in composition, therefore, it is possible to make the specific refractory power of cured article become excellent.It should be noted that, if the Zirconia particles in solid state component is more than 80 mass parts (80 quality %), then likely can not guarantee silicone resin and the finishing part of substantial amount.
In addition, in each composition of photosemiconductor organosilicon resin composition, the use level of silicone resin can be more than 20 mass parts in solid state component, below 80 mass parts, preferably more than 25 mass parts, below 50 mass parts.If silicone resin is less than 20 mass parts, then the amount of silicone resin is very few, sometimes can not obtain good cured article.On the other hand, if silicone resin is more than 80 mass parts, then the content of the Zirconia particles in solid state component is too low, and therefore specific refractory power also step-down, can not play sufficient performance in the cured article obtained.
In addition, the use level of dispersing auxiliary is relative to composition 100 mass parts in whole compositions of photosemiconductor organosilicon resin composition except dispersing auxiliary, can be below more than 50 mass parts, 2000 mass parts, be preferably more than 300 mass parts, below 1000 mass parts.If dispersing auxiliary is less than 50 mass parts, then can not fully be disperseed in the composition by the Zirconia particles after finishing, can there is gonorrhoea cohesion in composition sometimes.On the other hand, if dispersing auxiliary is more than 2000 mass parts, then relative to silicone resin and Zirconia particles, the dispersing auxiliary as liquid component is too much, sometimes can not obtain good cured article.
In addition, as long as photosemiconductor organosilicon resin composition of the present invention does not hinder the function of seeking or physical property etc. in the purposes of sealing photosemiconductor, also known various additive can be contained.Other concrete additives are not particularly limited, such as, can enumerate: antioxidant, releasing agent, properties-correcting agent, tensio-active agent, the inorganic filler etc. preventing outside colour-changing agent, UV light absorber, Zirconia particles.It should be noted that, the content of these other additives is also not particularly limited, and can add to meet the above-mentioned mode by the respective content range of the Zirconia particles after finishing, silicone resin and dispersing auxiliary.
The manufacture method of photosemiconductor organosilicon resin composition of the present invention is not particularly limited, can by suitably coordinating by the Zirconia particles after finishing, silicone resin and dispersing auxiliary (as required, other additives) and mixing thus manufacture.The method coordinated or mix also is not particularly limited, and can suitably use known method.
At this, by the Zirconia particles after finishing as previously mentioned, preferably not Zirconia particles itself but zirconia dispersion.At this, also can coordinate zirconia dispersion and silicone resin and dispersing auxiliary and after mixing, utilize known method to remove the dispersion medium contained in zirconia dispersion.The method of removing dispersion medium is not particularly limited, and can suitably use known method.
Even if also there is the good transparency under photosemiconductor organosilicon resin composition of the present invention state before curing.Specifically, when being formed with film, have by estimating the transparency that almost can not confirm to have muddiness or degree can be confirmed reluctantly.In embodiment described later, when being formed with the film of 20 μm on the glass substrate, according to distinguishing that the Roman character of 12 pounds (point) evaluates the transparency, but in the present invention, the evaluation of the transparency of the photosemiconductor organosilicon resin composition before solidification is not limited thereto.
In the present invention, except the photosemiconductor organosilicon resin composition of said structure, also comprise and said composition is solidified and the photosemiconductor silicone resin cured article that obtains.The concrete structure of cured article is not particularly limited, and can adopt various structure accordingly with the kind of the photosemiconductor as object or working conditions.Photosemiconductor organosilicon resin composition of the present invention is dispersed with the aqueous of Zirconia particles or ink (ink) shape (or paste), therefore photosemiconductor organosilicon resin composition is applied according to the working conditions etc. of photosemiconductor in the position of necessity, and make it be heating and curing, the cured article of various formation can be obtained thus.
At this, the optical characteristics of cured article is not particularly limited, but full light transmittance can be more than 70%, is preferably more than 80%.In addition, the specific refractory power of cured article can be more than 1.43 at wavelength 589nm place, is preferably more than 1.53.If the optical characteristics of cured article is more than above-mentioned lower value, then can be especially suitable for use as photosemiconductor purposes.It should be noted that, full light transmittance, the specific refractory power of the cured article obtained are preferably more high more preferred, and therefore higher limit is not particularly limited.
It should be noted that, the Haze Meter NDH4000 (ProductName) that the full light transmittance of cured article uses Japanese electricity Se Industrial Co., Ltd to manufacture measures.In addition, the Model 2010Prism coupler that the specific refractory power at wavelength 589nm place uses METORICON CORPORATION to manufacture measures.In addition, in aftermentioned embodiment, for the transparency of cured article, in the same manner as the composition before solidification, according to distinguishing that the Roman character of 12 pounds evaluates the transparency, but in the present invention, also while the mensuration transparency, the transparency can be evaluated based on such range estimation.
Like this, photosemiconductor organosilicon resin composition of the present invention obtains by making silane coupling agent reflux carry out finishing the Zirconia particles being in dispersion state, and disperse particle diameter in above-mentioned scope.Thus, in photosemiconductor organosilicon resin composition, relatively can increase the content of Zirconia particles.In addition, in the Zirconia particles of finishing, the amount of the silane coupling agent as coating materials can relatively be reduced.Thereby, it is possible to the specific refractory power of the cured article making to be cured photosemiconductor organosilicon resin composition and obtain becomes excellent.
In addition, also the manufacture method of photosemiconductor organosilicon resin composition is comprised in the present invention, in the method, to Zirconia particles reflux silane coupling agent, thus obtain the Zirconia particles after by finishing, and with this by the Zirconia particles after finishing for dispersed and dispersion particle diameter be more than 1nm, the mode of below 50nm mixes by the Zirconia particles after finishing, dispersing auxiliary and silicone resin.
In the present invention, by above structure, relatively can increase the content of Zirconia particles, and relatively reduce the amount of coating materials, thus realization can provide the specific refractory power that can make cured article to become excellent photosemiconductor organosilicon resin composition and the effect of cured article thereof.
[embodiment]
For the present invention, further illustrate according to embodiment and comparative example, but the present invention is not limited thereto.Those skilled in the art without departing from the scope of the present invention, can carry out various change, correction and change.It should be noted that, the mensuration/evaluation of various building-up reactionss, physical property etc. in following examples and comparative example is carried out as follows.
(outward appearance of film and cured article film)
By the film of visual observations photosemiconductor organosilicon resin composition and the outward appearance of cured article film that makes this curing of coating and obtain, and evaluate the transparency based on following benchmark.
◎: the Roman character that clearly can distinguish 12 pounds
Zero: cured film produces a small amount of muddiness, but the Roman character of 12 pounds can be distinguished
×: cured film there is muddiness, the Roman character of 12 pounds can not be distinguished
(specific refractory power of cured article film)
Use the Model 2010 prism coupler that METORICON CORPORATION manufactures, measure the specific refractory power of cured article film at wavelength 589nm place.
(the full light transmittance of cured article film)
Use the Haze Meter NDH4000 (ProductName) that Japanese electricity Se Industrial Co., Ltd manufactures, measure the full light transmittance of cured article film.
(embodiment 1)
(Sakai Chemical Industry Co., Ltd. manufactures the zirconia dispersion commercially available to 100 mass parts, ProductName SZR-M, containing primary particle size 3nm, 30 % by weight zirconic methyl alcohol dispersion) in add as alkoxysilane compound containing trialkylsilyl group in molecular structure decyl Trimethoxy silane (Shin-Etsu Chemial Co., Ltd manufacture, ProductName KBM-3103) 0.3 mass parts, and at 60 DEG C, carry out heated and stirred limit, the limit reflux of 5 hours.Thus, the dispersion (finishing zirconia dispersion) of the Zirconia particles after by finishing is obtained.
Silicone resin (Shin-Etsu Chemial Co., Ltd manufacture, ProductName LPS3410) 10 mass parts are added, as methyl iso-butyl ketone (MIBK) 108 mass parts of dispersing auxiliary and propylene glycol monomethyl ether 12 mass parts in this finishing zirconia dispersion, and use rotatory evaporator, decompression removing is carried out to methyl alcohol.Thus, the photosemiconductor organosilicon resin composition of embodiment 1 is obtained.
And, the mode that said composition reaches 20 μm with thickness is applied on the glass substrate, forms film.As previously mentioned its outward appearance is evaluated to this film (that is, photosemiconductor organosilicon resin composition).The results are shown in table 1.After this film is heated 2 hours at 100 DEG C, heat 2 hours at 150 DEG C.Thus, the film (cured article film) of the photosemiconductor organosilicon resin composition of embodiment 1 is obtained.For the cured article film obtained, evaluate or measure its outward appearance, specific refractory power and full light transmittance as previously mentioned.The results are shown in table 1.
(embodiment 2)
Except changing to except 30 mass parts by the addition of silicone resin (ProductName LPS3410), in the same manner as above-described embodiment 1, obtain photosemiconductor organosilicon resin composition and the cured article film thereof of embodiment 2.For these compositions and cured article film, evaluate its outward appearance as previously mentioned, and specific refractory power and full light transmittance are measured to cured article film.Result is shown in table 1.
(embodiment 3)
Except changing to except 0.03 mass parts by the addition of decyl Trimethoxy silane (ProductName KBM-3103), in the same manner as above-described embodiment 1, obtain photosemiconductor organosilicon resin composition and the cured article film thereof of embodiment 3.For these compositions and cured article film, evaluate its outward appearance as previously mentioned, and specific refractory power and full light transmittance are measured to cured article film.Result is shown in table 1.
(embodiment 4)
Except changing to except 3 mass parts by the addition of decyl Trimethoxy silane (ProductName KBM-3103), in the same manner as above-described embodiment 1, obtain photosemiconductor organosilicon resin composition and the cured article film thereof of embodiment 4.For these compositions and cured article film, evaluate its outward appearance as previously mentioned, and specific refractory power and full light transmittance are measured to cured article film.Result is shown in table 1.
(embodiment 5)
Except the dimethoxydiphenylsilane as phenyl system silane compound (Shin-Etsu Chemial Co., Ltd's manufacture, ProductName KBM-202SS) adding equivalent (0.3 mass parts) as silane coupling agent replaces except decyl Trimethoxy silane, in the same manner as above-described embodiment 1, obtain photosemiconductor organosilicon resin composition and the cured article film thereof of embodiment 5.For these compositions and cured article film, evaluate its outward appearance as previously mentioned, and specific refractory power and full light transmittance are measured to cured article film.Result is shown in table 1.
(embodiment 6)
Except the 3-acryloxypropyl Trimethoxy silane as (methyl) acryloyl-oxy base system silane compound adding equivalent (0.3 mass parts) as silane coupling agent, (Shin-Etsu Chemial Co., Ltd manufactures, ProductName KBM-5103) replace beyond decyl Trimethoxy silane, in the same manner as above-described embodiment 1, obtain photosemiconductor organosilicon resin composition and the cured article film thereof of embodiment 6.For these compositions and cured article film, evaluate its outward appearance as previously mentioned, and specific refractory power and full light transmittance are measured to cured article film.Result is shown in table 1.
(embodiment 7)
Except the 3-methacryloxypropyl trimethoxy silane as (methyl) acryloyl system silane compound of adding equivalent (0.3 mass parts) as silane coupling agent, (Shin-Etsu Chemial Co., Ltd manufactures, ProductName KBM-5103) replace beyond decyl Trimethoxy silane, in the same manner as above-described embodiment 1, obtain photosemiconductor organosilicon resin composition and the cured article film thereof of embodiment 7.For these compositions and cured article film, evaluate its outward appearance as previously mentioned, and specific refractory power and full light transmittance are measured to cured article film.Result is shown in table 1.
(embodiment 8)
Except the ProductName LPS3410 that the ProductName KER-6020F using Shin-Etsu Chemial Co., Ltd to manufacture as silicone resin replaces Shin-Etsu Chemial Co., Ltd to manufacture, in the same manner as above-described embodiment 1, obtain photosemiconductor organosilicon resin composition and the cured article film thereof of embodiment 8.For these compositions and cured article film, evaluate its outward appearance as previously mentioned, and specific refractory power and full light transmittance are measured to cured article film.Result is shown in table 1.
(embodiment 9)
Except dispersing auxiliary only uses 120 mass parts methyl iso-butyl ketone (MIBK), in the same manner as above-described embodiment 1, obtain photosemiconductor organosilicon resin composition and the cured article film thereof of embodiment 9.For these compositions and cured article film, evaluate its outward appearance as previously mentioned, and specific refractory power and full light transmittance are measured to cured article film.Result is shown in table 1.
(embodiment 10)
Except dispersing auxiliary only uses 120 mass parts propylene glycol monomethyl ether, in the same manner as above-described embodiment 1, obtain photosemiconductor organosilicon resin composition and the cured article film thereof of embodiment 10.For these compositions and cured article film, evaluate its outward appearance as previously mentioned, and specific refractory power and full light transmittance are measured to cured article film.Result is shown in table 1.
(embodiment 11)
Except use 360 mass parts methyl iso-butyl ketone (MIBK) and 40 mass parts propylene glycol monomethyl ether as dispersing auxiliary except, in the same manner as above-described embodiment 1, obtain photosemiconductor organosilicon resin composition and the cured article film thereof of embodiment 11.For these compositions and cured article film, evaluate its outward appearance as previously mentioned, and specific refractory power and full light transmittance are measured to cured article film.Result is shown in table 1.
(comparative example 1)
In the finishing zirconia dispersion obtained in the same manner as above-described embodiment 1, do not add dispersing auxiliary and only add silicone resin (ProductName LPS3410), and in the same manner as above-described embodiment 1, use rotatory evaporator, decompression removing is carried out to methyl alcohol, attempts the manufacture manufacturing organosilicon resin composition.But, the composition of gonorrhoea cohesion can only be obtained.
(comparative example 2)
Do not add silane coupling agent except use not carry out except surface-treated Zirconia particles yet, in the same manner as above-described embodiment 1, use rotatory evaporator, decompression removing is carried out to methyl alcohol, attempt manufacturing organosilicon resin composition.But, the composition of gonorrhoea cohesion can only be obtained.
(comparative example 3)
With the addition of silane coupling agent except use but do not carry out except the Zirconia particles of reflux, in the same manner as above-described embodiment 1, using rotatory evaporator, decompression removing is carried out to methyl alcohol, attempting manufacturing organosilicon resin composition.But, the composition of gonorrhoea cohesion can only be obtained.
(comparative example 4)
Except propylene glycol monomethyl ether 120 mass parts being used as ester class as dispersing auxiliary, in the same manner as above-described embodiment 1, use rotatory evaporator, decompression removing is carried out to methyl alcohol, attempt manufacturing organosilicon resin composition.But, the composition of gonorrhoea cohesion can only be obtained.
(comparative example 5)
Use except methyl iso-butyl ketone (MIBK) 27 mass parts, propylene glycol monomethyl ether 3 mass parts except as dispersing auxiliary, in the same manner as above-described embodiment 1, use rotatory evaporator, decompression removing is carried out to methyl alcohol, attempt manufacturing organosilicon resin composition.But, the composition of gonorrhoea cohesion can only be obtained.
Table 1
Like this, photosemiconductor organosilicon resin composition of the present invention and cured article (embodiment 1 ~ 12) thereof all have good optical characteristics, but when not adding dispersing auxiliary (comparative example 1), surface treatment (comparative example 2) do not carried out to Zirconia particles, do not form the chemical bond (comparative example 3) of silane coupling agent on Zirconia particles surface, when not using that in ketone and alcohols, at least one is as dispersing auxiliary (comparative example 4) or dispersing auxiliary amount few (comparative example 5), the composition of gonorrhoea cohesion can only be obtained.
It should be noted that; the invention is not restricted to the record of above-mentioned embodiment; can can carry out various change in the protection domain of claim, for by different embodiment or in multiple variation respectively disclosed technological method carry out combinationally using and the embodiment that obtains also is contained in technical scope of the present invention.
Industrial applicibility
The present invention such as can be widely used in the field of the resin combination used in the photosemiconductors such as photodiode (LED) or laser diode.
Although describe the present invention in detail or with reference to particular implementation, it is apparent to those skilled in the art that and can make various changes and modifications without departing from the spirit and scope of the present invention.
The Japanese patent application (Patent 2013-219081) that the application proposed based on October 22nd, 2013, and its full content is incorporated into this, as a reference.
Claims (6)
1. a photosemiconductor organosilicon resin composition, is characterized in that, containing by the Zirconia particles after finishing, dispersing auxiliary and silicone resin, is dispersion state by the described Zirconia particles after finishing,
Be more than 1nm, below 50nm by the dispersion particle diameter of the described Zirconia particles after finishing,
As described dispersing auxiliary, at least one containing ketone and alcohols.
2. photosemiconductor organosilicon resin composition as claimed in claim 1, it is characterized in that, when the quality of the described Zirconia particles before finishing is 100 mass parts, be below more than 0.1 mass parts, 10 mass parts by the quality of finishing part in the described Zirconia particles after finishing.
3. photosemiconductor organosilicon resin composition as claimed in claim 1, it is characterized in that, the quality of the described Zirconia particles before finishing, when being 100 mass parts for the total amount of the quality of the silane coupling agent of finishing and the quality of described silicone resin
Being converted by the described Zirconia particles before the content finishing of the described Zirconia particles after finishing, is below more than 50 mass parts, 75 mass parts.
4. photosemiconductor organosilicon resin composition as claimed in claim 2, it is characterized in that, the quality of the described Zirconia particles before finishing, when being 100 mass parts for the total amount of the quality of the silane coupling agent of finishing and the quality of described silicone resin
Being converted by the described Zirconia particles before the content finishing of the described Zirconia particles after finishing, is below more than 50 mass parts, 75 mass parts.
5. the photosemiconductor organosilicon resin composition according to any one of Claims 1 to 4, it is characterized in that, relative to composition 100 mass parts in whole compositions of described photosemiconductor organosilicon resin composition except described dispersing auxiliary, the use level of described dispersing auxiliary is below more than 50 mass parts, 2000 mass parts.
6. a photosemiconductor silicone resin cured article, is characterized in that, the photosemiconductor organosilicon resin composition according to any one of Claims 1 to 5 is solidified to form.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-219081 | 2013-10-22 | ||
| JP2013219081A JP2015081275A (en) | 2013-10-22 | 2013-10-22 | Silicone resin composition for optical semiconductor, and cured product of the same |
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| CN104559181A true CN104559181A (en) | 2015-04-29 |
| CN104559181B CN104559181B (en) | 2017-07-07 |
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| JP (1) | JP2015081275A (en) |
| KR (1) | KR20150046761A (en) |
| CN (1) | CN104559181B (en) |
| TW (1) | TWI496827B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110785860A (en) * | 2017-08-04 | 2020-02-11 | 住友大阪水泥株式会社 | Dispersion, composition, sealing member, light-emitting device, lighting fixture, display device, and method for producing light-emitting device |
| CN110785859A (en) * | 2017-08-04 | 2020-02-11 | 住友大阪水泥株式会社 | Dispersion, composition, sealing member, light-emitting device, lighting fixture, display device, and method for producing light-emitting device |
| CN112789323A (en) * | 2018-10-02 | 2021-05-11 | 昭和电工材料株式会社 | Resin composition, cured product, and semiconductor device |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2020002306A (en) * | 2018-06-29 | 2020-01-09 | 住友大阪セメント株式会社 | Dispersion liquid, composition, sealing member, light-emitting device, lighting apparatus and display device |
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- 2014-10-16 TW TW103135853A patent/TWI496827B/en active
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| CN103031006A (en) * | 2012-09-29 | 2013-04-10 | 复旦大学 | Surface treatment method of inorganic nano-microparticle and preparation method of composite material |
| CN103131189A (en) * | 2013-01-05 | 2013-06-05 | 中科院广州化学有限公司 | Inorganic or organic hybridization nanocomposite for packaging light emitting diode (LED) and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110785860A (en) * | 2017-08-04 | 2020-02-11 | 住友大阪水泥株式会社 | Dispersion, composition, sealing member, light-emitting device, lighting fixture, display device, and method for producing light-emitting device |
| CN110785859A (en) * | 2017-08-04 | 2020-02-11 | 住友大阪水泥株式会社 | Dispersion, composition, sealing member, light-emitting device, lighting fixture, display device, and method for producing light-emitting device |
| CN110785860B (en) * | 2017-08-04 | 2021-03-26 | 住友大阪水泥株式会社 | Dispersion, composition, sealing member, light-emitting device, lighting fixture, display device, and method for producing light-emitting device |
| CN110785859B (en) * | 2017-08-04 | 2021-04-13 | 住友大阪水泥株式会社 | Dispersion, composition, sealing member, light-emitting device, lighting fixture, display device, and method for producing light-emitting device |
| CN112789323A (en) * | 2018-10-02 | 2021-05-11 | 昭和电工材料株式会社 | Resin composition, cured product, and semiconductor device |
| CN112789323B (en) * | 2018-10-02 | 2024-02-02 | 株式会社力森诺科 | Resin composition, cured product, and semiconductor device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104559181B (en) | 2017-07-07 |
| TWI496827B (en) | 2015-08-21 |
| KR20150046761A (en) | 2015-04-30 |
| JP2015081275A (en) | 2015-04-27 |
| TW201516082A (en) | 2015-05-01 |
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