CN104559181B - Photosemiconductor organosilicon resin composition and its solidfied material - Google Patents
Photosemiconductor organosilicon resin composition and its solidfied material Download PDFInfo
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- CN104559181B CN104559181B CN201410563597.0A CN201410563597A CN104559181B CN 104559181 B CN104559181 B CN 104559181B CN 201410563597 A CN201410563597 A CN 201410563597A CN 104559181 B CN104559181 B CN 104559181B
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- resin composition
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- 239000000463 material Substances 0.000 title claims abstract description 79
- 239000011342 resin composition Substances 0.000 title claims abstract description 66
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 190
- 239000002245 particle Substances 0.000 claims abstract description 106
- 230000004048 modification Effects 0.000 claims abstract description 73
- 238000012986 modification Methods 0.000 claims abstract description 73
- 239000006185 dispersion Substances 0.000 claims abstract description 29
- 150000002576 ketones Chemical class 0.000 claims abstract description 18
- 150000001298 alcohols Chemical class 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims description 44
- 229910000077 silane Inorganic materials 0.000 claims description 37
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 25
- 239000004065 semiconductor Substances 0.000 claims description 11
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 8
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 abstract description 7
- 238000000576 coating method Methods 0.000 abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 33
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 33
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 33
- -1 amino, sulfydryl Chemical group 0.000 description 26
- 238000004519 manufacturing process Methods 0.000 description 14
- 238000002834 transmittance Methods 0.000 description 14
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 13
- 125000000524 functional group Chemical group 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 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
- 239000003795 chemical substances by application Substances 0.000 description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 8
- 229910052726 zirconium Inorganic materials 0.000 description 8
- 206010018612 Gonorrhoea Diseases 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 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
- KQAHMVLQCSALSX-UHFFFAOYSA-N decyl(trimethoxy)silane Chemical compound CCCCCCCCCC[Si](OC)(OC)OC KQAHMVLQCSALSX-UHFFFAOYSA-N 0.000 description 6
- 239000003822 epoxy resin Substances 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 229920000647 polyepoxide Polymers 0.000 description 6
- 239000003566 sealing material Substances 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000011859 microparticle Substances 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 4
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- 235000010716 Vigna mungo Nutrition 0.000 description 3
- 244000042295 Vigna mungo Species 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 235000013399 edible fruits Nutrition 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- WSGCRAOTEDLMFQ-UHFFFAOYSA-N nonan-5-one Chemical compound CCCCC(=O)CCCC WSGCRAOTEDLMFQ-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 3
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 3
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical class CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-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
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 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
- 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
- 238000002454 metastable transfer emission spectrometry Methods 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000009738 saturating Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 125000004665 trialkylsilyl group Chemical group 0.000 description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-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
- CXBDYQVECUFKRK-UHFFFAOYSA-N 1-methoxybutane Chemical group CCCCOC CXBDYQVECUFKRK-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
- HNVMCAHOYIOFAQ-UHFFFAOYSA-N 3-dimethoxysilylpropyl prop-2-enoate Chemical compound CO[SiH](OC)CCCOC(=O)C=C HNVMCAHOYIOFAQ-UHFFFAOYSA-N 0.000 description 1
- XDQWJFXZTAWJST-UHFFFAOYSA-N 3-triethoxysilylpropyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C=C XDQWJFXZTAWJST-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 150000007945 N-acyl ureas Chemical class 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 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
- 125000003545 alkoxy group Chemical group 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
- 229910002113 barium titanate Inorganic materials 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
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- GAURFLBIDLSLQU-UHFFFAOYSA-N diethoxy(methyl)silicon Chemical compound CCO[Si](C)OCC GAURFLBIDLSLQU-UHFFFAOYSA-N 0.000 description 1
- ZXPDYFSTVHQQOI-UHFFFAOYSA-N diethoxysilane Chemical compound CCO[SiH2]OCC ZXPDYFSTVHQQOI-UHFFFAOYSA-N 0.000 description 1
- 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 1
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-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
- 239000002612 dispersion medium Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 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
- 229940035423 ethyl ether Drugs 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 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
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000013007 heat curing 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
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 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
- 150000002513 isocyanates Chemical class 0.000 description 1
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920001558 organosilicon polymer Polymers 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-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
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002050 silicone resin Polymers 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
- 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
- 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
- JRSJRHKJPOJTMS-MDZDMXLPSA-N trimethoxy-[(e)-2-phenylethenyl]silane Chemical compound CO[Si](OC)(OC)\C=C\C1=CC=CC=C1 JRSJRHKJPOJTMS-MDZDMXLPSA-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
- 239000006097 ultraviolet radiation absorber Substances 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
Landscapes
- 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)
- Led Device Packages (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Epoxy Resins (AREA)
Abstract
The present invention provides a kind of photosemiconductor organosilicon resin composition and its solidfied material, the photosemiconductor organosilicon resin composition is characterised by, containing by the Zirconia particles after surface modification, dispersing aid and organic siliconresin, the Zirconia particles after by surface modification are dispersity, the dispersion particle diameter of the Zirconia particles after by surface modification is more than 1nm, below 50nm, as the dispersing aid, at least one containing ketone and alcohols, wherein, the photosemiconductor organosilicon resin composition can relatively increase the content of Zirconia particles in photosemiconductor organosilicon resin composition and its solidfied material, and can relatively reduce the amount of coating material, so that the refractive index of solidfied material becomes excellent.
Description
Technical field
The present invention relates to being suitable for the organosilicon resin composition in photosemiconductor field and it is had obtained from solidifying
Machine silicones solidfied material, in particular in sealing for being suitable for use in the photosemiconductors such as LED or semiconductor laser etc.
Photosemiconductor organosilicon resin composition and its solidfied material.
Background technology
All the time, in the photosemiconductor field such as light emitting diode (LED) or laser diode, using various
Resin combination.For example, as the sealing material of LED, it is known to the resin group containing epoxy resin or organic siliconresin etc.
Compound.In addition, it is also known that in order to maintain the transparency of solidfied material obtained from solidification and carry in such resin combination
Its refractive index high and coordinate the metal oxide of nano-scale.
For example, a kind of resin composition for encapsulating semiconductor disclosed in patent document 1, consists of：Contain resin and oxygen
Change zirconium particle, the average grain diameter of Zirconia particles is more than 1nm, below 30nm, and the surface of Zirconia particles is coated with energy
Coordination and/or the organic compound of bonding.Although as above-mentioned resin, using epoxy resin or organic siliconresin, patent
The embodiment of document 1, is all the use of the example of epoxy resin.Additionally, on the surface of Zirconia particles except above-mentioned organic
The covering of compound, and can also be processed with silane coupling agent and/or polyethers carbonic acid is processed.
Additionally, making specific organosilicon derivates that there is reaction with microparticle surfaces Patent Document 2 discloses one kind
The metal oxide microparticle of property functional group carries out Thermocurable organosilicon resin composition obtained from polymerisation.The heat cure
Property organosilicon resin composition can be used in encapsulating optical semiconductor element.Additionally, above-mentioned metal oxide microparticle can be selected from
At least one in the group be made up of titanium oxide, zirconium oxide, barium titanate, silica, aluminum oxide and hafnium oxide.And, as
The above-mentioned reactive functional groups of microparticle surfaces, illustrate hydroxyl, NCO, amino, sulfydryl, carboxyl, epoxy radicals, ethylene type
Unsaturated group, halogen radical, isocyanurate group etc..
Additionally, Patent Document 3 discloses one kind containing surface by coating material modify and more than dispersion particle diameter 1nm,
The transparent dispersion liquid such as the zirconium oxide of tetragonal zirconia particle of below 20nm and the transparent dispersion liquid is set to be dispersed in resin
And the transparent complex for being formed.The transparent complex can be used for the encapsulant of semiconductor laser or LED.Additionally, as table
Face dressing agent, can enumerate selected from by alkoxysilane compound containing trialkylsilyl group in molecular structure, silicone compounds, surfactant, titanate coupling agent
More than a kind in the group of composition, as embodiment, disclose and use the embodiment 1 of silane coupler.Additionally, modification part exists
The weight of tetragonal zirconia particle surface than reach more than 5 weight %, the 200 weight % of the tetragonal zirconia particle with
Under.
Citation
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2008-106260 publications
Patent document 2：Japanese Unexamined Patent Publication 2010-144136 publications
Patent document 3：Japanese Unexamined Patent Publication 2007-119617 publications
The content of the invention
The technical problem to be solved is intended in invention
In resin composition for encapsulating semiconductor disclosed in patent document 1, it is also possible to use organic siliconresin, but conduct
Embodiment only discloses the use of epoxy resin.In the sealing material of LED, sometimes due to ultraviolet in the light that sends of LED
The energy of line and produce free radical.The free radical aoxidizes epoxy resin, so if including ring in the sealing material of LED
Oxygen tree fat, then sealing material easily because of oxidation xanthochromia.
In the sealing material of LED, if replacing epoxy resin using organic siliconresin, xanthochromia can be avoided.
But, the sealing material containing organic siliconresin is low due to the refractive index of light, thus the extraction efficiency of the light from LED have can
Can reduce.
In Thermocurable organosilicon resin composition disclosed in patent document 2 and transparent complex disclosed in patent document 3
Organic siliconresin is all used as resinous principle.But, the Thermocurable organosilicon resin composition phase disclosed in patent document 2
For the weight portion of organosilicon derivates 100, the content of metal oxide microparticle is 1~70 weight %.Due to the metal oxide
The content of particulate is relatively few, therefore hardly can fully improve the refractive index of solidfied material.
On the other hand, after the composition of the transparent complex disclosed in patent document 3 makes to be modified by silane coupler etc.
Tetragonal zirconia particle is dispersed in organic siliconresin, and the containing ratio of tetragonal zirconia particle is more than 1 weight %, 80
Below weight %.But, the weight ratio (i.e. the amount of coating material) of the modification part of tetragonal zirconia particle is relatively more, because
This does not improve the refractive index of transparent complex fully.
The present invention is completed to solve above-mentioned problem, and oxidation can be relatively increased its object is to provide one kind
The content of zirconium particle simultaneously can relatively reduce the amount of coating material and become excellent light so as to the refractive index that makes solidfied material
Semiconductor organosilicon resin composition and its solidfied material.
Technical teaching for solving the problem was
In order to solve the above problems, photosemiconductor organosilicon resin composition of the invention contains by after surface modification
Zirconia particles, dispersing aid and organic siliconresin, by surface modification after the Zirconia particles be dispersity, by surface
The dispersion particle diameter of the Zirconia particles after modification is more than 1nm, below 50nm, as the dispersing aid, contains ketone
With alcohols at least one.
According to said structure, the dispersion particle diameter of the Zirconia particles in dispersity within the above range, and conduct
Dispersing aid contains at least one of ketone and alcohols such that it is able in photosemiconductor organosilicon resin composition relatively
Increase the content of Zirconia particles.Furthermore it is possible to relatively reduce as surface modification in the Zirconia particles of surface modification
The amount of the silane coupler of agent.Thereby, it is possible to make the solidfied material as obtained from photosemiconductor organosilicon resin composition solidifies
Refractive index become it is excellent.
In the photosemiconductor organosilicon resin composition of said structure, it is also possible to be configured to：Before surface modification
The Zirconia particles quality be 100 mass parts when, by surface modification after the Zirconia particles in surface modification portion
The quality divided is for more than 0.1 mass parts, below 10 mass parts.
Additionally, in the photosemiconductor organosilicon resin composition of said structure, it is also possible to be configured to：Repaiied on surface
The quality of the Zirconia particles before decorations, for surface modification the silane coupler quality and the organic siliconresin
Quality total amount be 100 mass parts when, by surface modification after the Zirconia particles content surface modification before institute
Zirconia particles conversion is stated, is more than 50 mass parts, below 75 mass parts.
In the photosemiconductor organosilicon resin composition of said structure, it is also possible to be configured to：Relative to the light
The mass parts of composition 100 in whole compositions of semiconductor organosilicon resin composition in addition to the dispersing aid, it is described
The use level of dispersing aid is more than 50 mass parts, below 2000 mass parts.
And, the present invention also includes the light for being solidified to form the photosemiconductor organosilicon resin composition of said structure
Semiconductor organic siliconresin solidfied material.
Specific embodiment
Hereinafter, the preferred embodiment of the present invention is illustrated.Photosemiconductor organosilicon resin composition of the invention contains
By the Zirconia particles after surface modification, dispersing aid and organic siliconresin, by surface modification after above-mentioned Zirconia particles at
In dispersity.Particularly, by surface modification after above-mentioned Zirconia particles dispersion particle diameter be more than 1nm, below 50nm, and
And at least one as dispersing aid, comprising ketone and alcohols.
[by the Zirconia particles after surface modification]
The Zirconia particles used in the present invention are the particles after carrying out surface modification with coating material, are repaiied as surface
Decorations agent can use silane coupler.The concrete structure of the Zirconia particles before surface modification is not particularly limited, as long as to divide
Bulk state and dispersion particle diameter have primary particle size within the above range.As long as additionally, Zirconia particles without prejudice to its light
Learn property or dispersive property, it is also possible to contain the composition beyond zirconium oxide (zirconia).In the present invention, before surface modification
Zirconia particles, for example, the zirconia dispersion that Zirconia particles are dispersed with decentralized medium can be used suitably.
The specific species that Zirconia particles are carried out with the silane coupler of surface modification is not particularly limited, used as silane idol
Connection agent can suitably use known compound.Specifically, can for example enumerate：Decyl trimethoxy silane, the second of decyl three
TMOS, hexyl trimethoxy silane, hexyl triethoxysilane, phenyltrimethoxysila,e, phenyl triethoxysilane,
The alcoxyls such as MTMS, dimethyldimethoxysil,ne, MTES, dimethyldiethoxysilane
Base silane compound；The ethene such as vinyltrimethoxy silane, VTES system silane compound；2-(3,4-
Epoxycyclohexyl) ethyl trimethoxy silane, 3- glycydoxies methyl dimethoxysilane, 3- glycidol ethers
Epoxide propyl trimethoxy silicane, 3- glycydoxies methyldiethoxysilane, 3- glycidol ethers epoxide third
The epoxy silane compound such as ethyl triethoxy silicane alkane；Dimethoxydiphenylsilane, to styryl trimethoxy silane etc.
Phenyl system silane；3- acryloxypropyls trimethoxy silane, 3- methacryloxypropyl trimethoxy silanes, 3- first
Base acryloxypropyl dimethoxysilane, 3- methacryloyloxypropyl methyls diethoxy silane, 3- methyl
(methyl) acryloyl such as acryloxypropyl triethoxysilane system silane compound；Uride MTMS, acyl
Urea MTES, 2- urides ethyl trimethoxy silane, 2- urides ethyl triethoxysilane, 3- urides propyl group three
The uride silane compounds such as methoxy silane, 3- uride propyl-triethoxysilicanes；3- isocyanates propyl-triethoxysilicane,
The isocyanates system such as 3- isocyanates propyl trimethoxy silicanes silane compound；N-2- (amino-ethyl) -3- aminopropyl first
Base dimethoxysilane, N-2- (amino-ethyl) -3- amino propyl methyls trimethoxy silane, 3- aminopropyl trimethoxy silicon
Alkane, APTES, 3- triethoxysilyls-N- (1,3- dimethyl-butylidene) propylamine, N- benzene
The amino system such as base -3- TSL 8330s silane compound；3- mercaptopropyis methyl dimethoxysilane, 3- sulfydryls
The silane chemical combination with sulfur-bearing functional group such as propyl trimethoxy silicane, double (triethoxysilylpropyltetrasulfide) tetrasulfides
Thing；Etc..These compounds can be used alone, it is also possible to which two or more is appropriately combined to use.Wherein, alkoxy is preferably used
Silane compound, phenyl system silane compound, (methyl) acryloyl system silane compound etc..
The method that Zirconia particles are carried out with surface modification using silane coupler can suitably use known method.Tool
For body, to adding silane coupler in zirconia dispersion, and under conditions of predetermined temperature, the scheduled time and predetermined pressure
It is stirred.The zirconia dispersion for now using can be commercially available product, it is also possible to use Zirconia particles and known dispersion
Medium is prepared every time.It should be noted that when manufacturing photosemiconductor organosilicon resin composition of the invention, Ke Yizhi
(former state) is connect using by the dispersion (surface modification zirconia dispersion) of the Zirconia particles after surface modification.
The Zirconia particles used in the present invention are carried out surface modification, but the oxygen before surface modification with silane coupler
When the quality for changing zirconium particle is 100 mass parts, the quality of the surface modification part (silane coupler) of the Zirconia particles can be with
For more than 0.1 mass parts, below 10 mass parts, more than preferably 0.1 mass parts, less than 5 mass parts.That is, by surface
The surface of the Zirconia particles after modification, on the basis of the quality of the Zirconia particles before surface modification, can form 0.1~10
Surface modification part in the range of quality %, preferred surface modification part is less than 0.5 mass %.
As long as by the dispersion particle diameter of the Zirconia particles after surface modification as it was previously stated, in the range of 1nm~50nm.
If dispersion particle diameter is less than 1nm, particle diameter is too small, it is difficult to improve refractive index.In addition, if dispersion particle diameter is more than 50nm, then grain
Footpath is excessive, and having the tendency of dispersiveness reduces and the optical characteristics reduction in composition or solidfied material.It should be noted that this reality
In applying mode, the microtrack manufactured using Nikkiso Company Limited by the dispersion particle diameter of the Zirconia particles after surface modification
UPA-UZ152 (ProductName) is measured.
[organic siliconresin]
The organic siliconresin that the present invention is used is Thermocurable organic siliconresin, as long as have in sealing photosemiconductor neck
Optical characteristics known to domain, then its specific structure be not particularly limited.
As representational Thermocurable organic siliconresin, for example, can enumerate following structure：It is low with silane, organosilicon
Polymers, organic siliconresin, alkyl siloxanes (オ Le ガ ノ シ ロ キ サ Application), dialkyl siloxane, alkyl polysiloxanes, two hydrocarbon
The skeleton structures such as based polysiloxane, and the skeleton structure has more than one reactive functional groups.Above-mentioned skeleton structure can be
Linear chain structure, or branched structure.
Additionally, as reactive functional groups, can enumerate：The hydroxyl combined with the silicon atom contained in above-mentioned skeleton structure
Base, alkenyl, hydrogen silicyl, (methyl) acryloxy, epoxy radicals, amino, hydroxyl methyl, sulfydryl, carboxyl, phenylol etc.,
It is not particularly limited.Additionally, in above-mentioned skeleton structure, in addition to above-mentioned reactive functional groups, it is possible to have alkyl, alkenyl,
The functional groups such as aromatic series base.
The Thermocurable organic siliconresin used in the present invention, can have only a kind of skeleton structure and only a kind of reactivity
Functional group, it is possible to have various skeleton structures and various reactive functional groups.Additionally, reactive functional groups are as described above, can
To contain more than one reactive functional groups in a skeleton structure, in other words, 1 molecule organic siliconresin (has arbitrary
Skeleton structure) there are at least one reactive functional groups.It should be noted that reactive functional groups can be in skeleton structure
End, can be in side chain, it is also possible in end and the either side of side chain.
[dispersing aid]
The dispersing aid that the present invention is used can be ketone and alcohols at least any one.Used in photosemiconductor of the invention
In organosilicon resin composition, except by the Zirconia particles and organic siliconresin after surface modification, also containing ketone or alcohol
Class is used as dispersing aid such that it is able to which the Zirconia particles after making by surface modification are well dispersed into composition.
Additionally, being not particularly limited as the ketone of dispersing aid, specifically, for example, can enumerate：Acetone, first and second
Ketone, methyl iso-butyl ketone (MIBK), butyl methyl ketone, di-n-butyl ketone, cyclohexanone, dipropyl ketone, methyl amyl ketone, DIBK,
Isophorone, acetylacetone,2,4-pentanedione etc..Used as dispersing aid, these ketones can be used alone, it is also possible to which two or more is appropriately combined to make
With.
It is not particularly limited as the alcohols of dispersing aid, specifically, for example, can be enumerated：Methyl alcohol, ethanol, propyl alcohol,
Butanol, isopropanol, tetrahydrofurfuryl alcohol, ethylene glycol single methyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol list
Methyl ether, TC, propylene glycol monomethyl ether, propylene glycol monoethyl etc..As dispersing aid, these alcohols
Can be used alone, it is also possible to which two or more is appropriately combined to use.
Additionally, as dispersing aid, it is also possible to be respectively used in combination at least one ketone and alcohols.For example, aftermentioned
In embodiment, and with propylene glycol monomethyl ether and methyl iso-butyl ketone (MIBK).Additionally, simultaneously using mixing ratio when ketone and alcohols without spy
Do not limit, suitably can set mixing ratio so as to can be divided well in the composition by the Zirconia particles after surface modification
Dissipate.
It should be noted that in the present invention, as dispersing aid, it is also possible to using known outside ketone and alcohols
Other solvents, it is also possible to be used in combination other solvents and ketone or alcohols.
As ketone and the preferred compositions of alcohols, specifically, can enumerate：MEK and methyl alcohol, MEK and ethanol,
MEK and propyl alcohol, MEK and butanol, MEK and isopropanol, MEK and tetrahydrofurfuryl alcohol, MEK and ethylene glycol list first
Base ether, MEK and ethylene glycol monomethyl ether, MEK and ethylene glycol monobutyl ether, MEK and diethylene glycol monomethyl ether,
MEK and TC, MEK and propylene glycol monomethyl ether, MEK and propylene glycol monoethyl, methyl are different
Butyl ketone and methyl alcohol, methyl iso-butyl ketone (MIBK) and ethanol, methyl iso-butyl ketone (MIBK) and propyl alcohol, methyl iso-butyl ketone (MIBK) and butanol, methyl are different
Butyl ketone and isopropanol, methyl iso-butyl ketone (MIBK) and tetrahydrofurfuryl alcohol, methyl iso-butyl ketone (MIBK) and ethylene glycol single methyl ether, methyl-isobutyl
Ketone 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
With butanol, butyl methyl ketone and isopropanol, butyl methyl ketone and tetrahydrofurfuryl alcohol, butyl methyl ketone and ethylene glycol single methyl ether, fourth
Ylmethyl ketone and ethylene glycol monomethyl ether, butyl methyl ketone and ethylene glycol monobutyl ether, butyl methyl ketone and diethylene glycol list first
Base ether, butyl methyl ketone and TC, butyl methyl ketone and propylene glycol monomethyl ether, butyl methyl ketone and the third two
Alcohol list ethylether, but be not particularly limited.
In photosemiconductor organosilicon resin composition of the invention, as dispersing aid, it is possible to use ketone and alcohol
Class at least any one such that it is able to the surface modification part for reducing Zirconia particles (that is, can reduce making for surface conditioning agent
Consumption), and Zirconia particles content in itself can be increased.Therefore, it is possible to make the optics such as the refractive index of the solidfied material for obtaining
Characteristic is more excellent.
[organosilicon resin composition and its solidfied material]
Photosemiconductor organosilicon resin composition of the invention is as it was previously stated, containing by the zirconium oxide grain after surface modification
Son, organic siliconresin and dispersing aid, but the content of these compositions is not particularly limited.
When photosemiconductor organosilicon resin composition total amount is 100 mass parts, by the zirconium oxide grain after surface modification
The use level of son can be more than 20 mass parts, below 80 mass parts, more than preferably 50 mass parts, below 75 mass parts.Such as
Fruit is less than 20 mass parts by the Zirconia particles after surface modification, then the Zirconia particles in composition are very few, it is possible to can not
Realize good refractive index.Additionally, if Zirconia particles are more than 80 mass parts, Zirconia particles are excessive in the composition,
It is possible to disperse well or may be split because the content of Zirconia particles becomes easily to be produced in solidfied material more
Seam, it is impossible to obtain good solidfied material.
And, in the present invention, can be according to consolidating when preparing composition by the content of the Zirconia particles after surface modification
The total amount of state composition and it is specific.Specifically, the quality of the above-mentioned Zirconia particles before surface modification, in surface modification
Silane coupler quality and organic siliconresin quality total amount be 100 mass parts when, in composition by surface modification
The content of above-mentioned Zirconia particles afterwards is preferably converted with the above-mentioned Zirconia particles before surface modification, be more than 50 mass parts,
Below 75 mass parts.
That is, according to the present invention, in the solid state component of photosemiconductor organosilicon resin composition more than half (50
More than quality %) it is Zirconia particles.Thereby, it is possible to maintain the saturating of photosemiconductor organosilicon resin composition and its solidfied material
Bright property, and high concentration can be carried out to the Zirconia particles in composition, the refractive index therefore, it is possible to make solidfied material becomes excellent.
If it should be noted that the Zirconia particles in solid state component are more than 80 mass parts (80 mass %), it is likely that can not
Ensure an adequate amount of organic siliconresin and surface modification part.
Additionally, in each composition of photosemiconductor organosilicon resin composition, the use level of organic siliconresin can be solid
More than 20 mass parts in state composition, below 80 mass parts, more than preferably 25 mass parts, below 50 mass parts.If organic
Silicones is less than 20 mass parts, then the amount of organic siliconresin is very few, and good solidfied material can not be obtained sometimes.On the other hand, such as
More than 80 mass parts, then the content of the Zirconia particles in solid state component is too low for fruit organic siliconresin, therefore refractive index also step-down,
Sufficient performance can not be played in the solidfied material for obtaining.
Additionally, the use level of dispersing aid relative in whole compositions of photosemiconductor organosilicon resin composition except
The mass parts of composition 100 beyond dispersing aid, can be preferably 300 mass parts more than 50 mass parts, below 2000 mass parts
Above, below 1000 mass parts.If dispersing aid is less than 50 mass parts, by the Zirconia particles after surface modification in combination
Can not be fully dispersed in thing, composition can occur gonorrhoea cohesion sometimes.On the other hand, if dispersing aid is more than 2000 mass
Part, then relative to organic siliconresin and Zirconia particles, the dispersing aid as liquid component is excessive, can not obtain good sometimes
Solidfied material.
As long as additionally, in the purposes of photosemiconductor organosilicon resin composition without prejudice to of the invention sealing photosemiconductor
Function or physical property for seeking etc., it is also possible to contain known various additives.Specific other additives are not particularly limited, example
Can such as enumerate：Antioxidant, releasing agent, modifying agent, surfactant, prevent colour-changing agent, ultra-violet absorber, zirconium oxide grain
Inorganic filler outside son etc..It should be noted that the content of these other additives is also not particularly limited, can be with full
The mode of the respective content range of the above-mentioned Zirconia particles, organic siliconresin and dispersing aid by after surface modification of foot is carried out
Addition.
The manufacture method of photosemiconductor organosilicon resin composition of the invention is not particularly limited, can be by appropriate
Coordinate by the Zirconia particles after surface modification, organic siliconresin and dispersing aid (as needed, other additives) and mix
So as to be manufactured.Coordinate or the method for mixing is also not particularly limited, can suitably use known method.
Here, by the Zirconia particles after surface modification as it was previously stated, it is preferred that not being Zirconia particles in itself but aoxidizing
Zirconium dispersion.Here, can also zirconia dispersion and organic siliconresin and dispersing aid are carried out with merge mixing after,
The decentralized medium contained in zirconia dispersion is removed using known method.The method for removing decentralized medium is not limited especially
It is fixed, can suitably use known method.
Even if photosemiconductor organosilicon resin composition of the invention before curing in the state of also have it is good saturating
Bright property.Specifically, when film is formed with, with can hardly confirm to have muddy by range estimation or can confirm that journey reluctantly
The transparency of degree.In embodiment described later, when being formed with 20 μm of film on the glass substrate, according to 12 pounds can be distinguished
(point) Roman character evaluates the transparency, but to the photosemiconductor silicone resin composition before solidification in the present invention
The transparent evaluation not limited to this of thing.
In the present invention, except the photosemiconductor organosilicon resin composition of said structure, also comprising consolidating said composition
The organic siliconresin solidfied material of photosemiconductor obtained from change.The concrete structure of solidfied material is not particularly limited, can be with conduct
The species or use condition of the photosemiconductor of object accordingly use various structures.Photosemiconductor of the invention is with organic
Silicon resin composition is liquid or ink (ink) shape (or paste) for being dispersed with Zirconia particles, therefore according to photosemiconductor
Use condition etc. coats photosemiconductor organosilicon resin composition in necessary position, and it is heating and curing, thus, it is possible to
Obtain the solidfied material of various composition.
Here, the optical characteristics of solidfied material is not particularly limited, but full light light transmittance can be more than 70%, preferably
More than 80%.Additionally, the refractive index of solidfied material can be more than 1.43, preferably more than 1.53 at wavelength 589nm.Solidfied material
If optical characteristics more than above-mentioned lower limit, photosemiconductor purposes can be especially suitable for use as.It should be noted that
Full light light transmittance, the refractive index of the solidfied material for arriving are preferably more high more preferred, therefore higher limit is not particularly limited.
It should be noted that the Haze that the full light light transmittance of solidfied material is made using electricity Se Industrial Co., Ltd of Japan system
Meter NDH4000 (ProductName) are measured.Additionally, the refractive index at wavelength 589nm uses METORICON
The Model 2010Prism coupler of CORPORATION manufactures are measured.Additionally, in aftermentioned embodiment, for solidification
Can the transparency of thing, in the same manner as the composition before solidification, evaluate the transparency according to the Roman character that distinguish 12 pounds, but
In the present invention, it is also possible to while the transparency is determined, the transparency is evaluated based on such range estimation.
So, photosemiconductor organosilicon resin composition of the invention is logical to the Zirconia particles in dispersity
Crossing is heated to reflux silane coupler to be obtained to carry out surface modification, and dispersion particle diameter is within the above range.Thus, in light
In semiconductor organosilicon resin composition, can relatively increase the content of Zirconia particles.Additionally, in the oxygen of surface modification
Change in zirconium particle, can relatively reduce the amount as the silane coupler of coating material.Thereby, it is possible to make to photosemiconductor
The refractive index of solidfied material obtained from being solidified with organosilicon resin composition becomes excellent.
Additionally, also include the manufacture method of photosemiconductor organosilicon resin composition in the present invention, in the method, to oxygen
Change zirconium heating particulates backflow silane coupler, so as to the Zirconia particles after obtaining by surface modification, and with this by surface modification
Zirconia particles afterwards are that dispersed and dispersion particle diameter are more than 1nm, the mode of below 50nm to by the oxidation after surface modification
Zirconium particle, dispersing aid and organic siliconresin are mixed.
In the present invention, by above structure, can relatively increase the content of Zirconia particles, and relatively reduce table
The amount of face dressing agent, so as to realize that the photosemiconductor organic siliconresin group that the refractive index that can make solidfied material becomes excellent can be provided
The effect of compound and its solidfied material.
【Embodiment】
For the present invention, further illustrated according to embodiment and comparative example, but the invention is not restricted to this.This area
Technical staff without departing from the scope of the present invention, can carry out various changes, amendment and change.It should be noted that with
Measure/the evaluation of various synthetic reactions, physical property in lower embodiment and comparative example etc. is carried out as follows.
(outward appearance of film and solidfied material film)
By the film of visual observations photosemiconductor organosilicon resin composition and obtained from making the curing of coating
The outward appearance of solidfied material film, and the transparency is evaluated based on following benchmark.
◎：12 pounds of Roman character can clearly be distinguished
○：A small amount of muddiness is produced in cured film, but 12 pounds of Roman character can be distinguished
×：There is muddiness in cured film, it is impossible to enough distinguish 12 pounds of Roman character
(refractive index of solidfied material film)
The prism coupler of Model 2010 manufactured using METORICON CORPORATION, determine solidfied material film
Refractive index at wavelength 589nm.
(the full light light transmittance of solidfied material film)
Haze Meter NDH4000 (ProductName) made using electricity Se Industrial Co., Ltd of Japan system, determine solidfied material film
Full light light transmittance.
(embodiment 1)
To the commercially available zirconia dispersion of 100 mass parts, (Sakai Chemical Industry Co., Ltd.'s manufacture, ProductName SZR-M, contain
The methyl alcohol dispersion of primary particle size 3nm, the zirconium oxide of 30 weight %) in addition as alkoxysilane compound containing trialkylsilyl group in molecular structure decyl front three
TMOS (Shin-Etsu Chemial Co., Ltd manufactures, ProductName KBM-3103) 0.3 mass parts, and it is small that 5 are carried out at 60 DEG C
When be heated to reflux in heating stirring.Thus, dispersion (the surface modification oxygen of the Zirconia particles after obtaining by surface modification
Change zirconium dispersion).
To organic siliconresin is added in the surface modification zirconia dispersion, (Shin-Etsu Chemial Co., Ltd manufactures, product
Name of an article LPS3410) 10 mass parts, the mass parts of methyl iso-butyl ketone (MIBK) 108 as dispersing aid and the matter of propylene glycol monomethyl ether 12
Amount part, and rotary evaporator is used, methyl alcohol is removed under reduced pressure.Thus, the photosemiconductor of embodiment 1 is obtained with organosilicon tree
Oil/fat composition.
And, said composition is coated on the glass substrate in the way of thickness reaches 20 μm, form film.As previously described
Is evaluated to the film (that is, photosemiconductor organosilicon resin composition) by its outward appearance for ground.The results are shown in table 1.The film is existed
After being heated 2 hours at 100 DEG C, heated 2 hours at 150 DEG C.Thus, the photosemiconductor organic siliconresin of embodiment 1 is obtained
The film (solidfied material film) of composition.For the solidfied material film for obtaining, evaluate as previously mentioned or determine its outward appearance, refractive index and
Full light light transmittance.The results are shown in table 1.
(embodiment 2)
In addition to the addition of organic siliconresin (ProductName LPS3410) is changed into 30 mass parts, with above-described embodiment 1
Similarly, the photosemiconductor organosilicon resin composition and its solidfied material film of embodiment 2 are obtained.For these compositions and admittedly
Compound film, evaluates its outward appearance, and determine refractive index and full light light transmittance to solidfied material film as previously mentioned.Result is shown in table 1.
(embodiment 3)
It is and upper in addition to the addition of decyl trimethoxy silane (ProductName KBM-3103) is changed into 0.03 mass parts
State embodiment 1 similarly, obtain the photosemiconductor organosilicon resin composition and its solidfied material film of embodiment 3.For these
Composition and solidfied material film, evaluate its outward appearance, and determine refractive index and full light light transmittance to solidfied material film as previously mentioned.Knot
Fruit is shown in table 1.
(embodiment 4)
It is and above-mentioned in addition to the addition of decyl trimethoxy silane (ProductName KBM-3103) is changed into 3 mass parts
Embodiment 1 similarly, obtains the photosemiconductor organosilicon resin composition and its solidfied material film of embodiment 4.For these groups
Compound and solidfied material film, evaluate its outward appearance, and determine refractive index and full light light transmittance to solidfied material film as previously mentioned.As a result
It is shown in table 1.
(embodiment 5)
Except the diphenyl diformazan as phenyl system silane compound as silane coupler addition equivalent (0.3 mass parts)
TMOS (Shin-Etsu Chemial Co., Ltd manufacture, ProductName KBM-202SS) come beyond replacing decyl trimethoxy silane,
In the same manner as above-described embodiment 1, the photosemiconductor organosilicon resin composition and its solidfied material film of embodiment 5 are obtained.For
These compositions and solidfied material film, evaluate its outward appearance, and determine refractive index and full light printing opacity to solidfied material film as previously mentioned
Rate.Result is shown in table 1.
(embodiment 6)
Except conduct (methyl) the acryloyl-oxy base system silane compound as silane coupler addition equivalent (0.3 mass parts)
3- acryloxypropyls trimethoxy silane (Shin-Etsu Chemial Co., Ltd manufacture, ProductName KBM-5103) replace
Beyond decyl trimethoxy silane, in the same manner as above-described embodiment 1, the photosemiconductor organic siliconresin group of embodiment 6 is obtained
Compound and its solidfied material film.For these compositions and solidfied material film, its outward appearance is evaluated as previously mentioned, and to solidfied material film
Determine refractive index and full light light transmittance.Result is shown in table 1.
(embodiment 7)
Except the 3- as (methyl) acryloyl system silane compound as silane coupler addition equivalent (0.3 mass parts)
Methacryloxypropyl trimethoxy silane (Shin-Etsu Chemial Co., Ltd manufacture, ProductName KBM-5103) replaces
Beyond decyl trimethoxy silane, in the same manner as above-described embodiment 1, the photosemiconductor organic siliconresin group of embodiment 7 is obtained
Compound and its solidfied material film.For these compositions and solidfied material film, its outward appearance is evaluated as previously mentioned, and to solidfied material film
Determine refractive index and full light light transmittance.Result is shown in table 1.
(embodiment 8)
Replace letter except the ProductName KER-6020F that Shin-Etsu Chemial Co., Ltd manufactures is used as organic siliconresin
Beyond the more ProductName LPS3410 of chemical industry Co., Ltd. manufacture, in the same manner as above-described embodiment 1, the light of embodiment 8 is obtained
Semiconductor organosilicon resin composition and its solidfied material film.For these compositions and solidfied material film, evaluate as previously mentioned
Its outward appearance, and refractive index and full light light transmittance are determined to solidfied material film.Result is shown in table 1.
(embodiment 9)
In addition to dispersing aid is using only 120 mass parts methyl iso-butyl ketone (MIBK)s, in the same manner as above-described embodiment 1, reality is obtained
Apply the photosemiconductor organosilicon resin composition and its solidfied material film of example 9.For these compositions and solidfied material film, such as preceding institute
Evaluate its outward appearance with stating, and refractive index and full light light transmittance are determined to solidfied material film.Result is shown in table 1.
(embodiment 10)
In addition to dispersing aid is using only 120 mass parts propylene glycol monomethyl ethers, in the same manner as above-described embodiment 1, obtain
The photosemiconductor organosilicon resin composition and its solidfied material film of embodiment 10.For these compositions and solidfied material film, such as
It is preceding to evaluate its outward appearance describedly, and refractive index and full light light transmittance are determined to solidfied material film.Result is shown in table 1.
(embodiment 11)
In addition to 360 mass parts methyl iso-butyl ketone (MIBK)s and 40 mass parts propylene glycol monomethyl ethers are used as dispersing aid,
In the same manner as above-described embodiment 1, the photosemiconductor organosilicon resin composition and its solidfied material film of embodiment 11 are obtained.For
These compositions and solidfied material film, evaluate its outward appearance, and determine refractive index and full light printing opacity to solidfied material film as previously mentioned
Rate.Result is shown in table 1.
(comparative example 1)
Only do not add to dispersing aid is added in the surface modification zirconia dispersion obtained in the same manner as above-described embodiment 1
Plus organic siliconresin (ProductName LPS3410), and in the same manner as above-described embodiment 1, using rotary evaporator, methyl alcohol is subtracted
Pressure is removed, and attempts the manufacture of manufacture organosilicon resin composition.It can only obtaining the composition of gonorrhoea cohesion.
(comparative example 2)
In addition to using the Zirconia particles that silane coupler is also surface-treated are not added with, with above-described embodiment 1
Similarly, using rotary evaporator, methyl alcohol is removed under reduced pressure, attempts manufacture organosilicon resin composition.It can only
To the composition of gonorrhoea cohesion.
(comparative example 3)
In addition to the Zirconia particles that with the addition of silane coupler but be heated to reflux are used, with above-described embodiment 1
Similarly, using rotary evaporator, methyl alcohol is removed under reduced pressure, attempts manufacture organosilicon resin composition.It can only
To the composition of gonorrhoea cohesion.
(comparative example 4)
It is and above-mentioned in addition to the mass parts of propylene glycol monomethyl ether 120 as esters are used as dispersing aid
Embodiment 1 similarly, using rotary evaporator, is removed under reduced pressure to methyl alcohol, attempts manufacture organosilicon resin composition.But
It is the composition that can only obtain gonorrhoea cohesion.
(comparative example 5)
It is and upper in addition to the mass parts of methyl iso-butyl ketone (MIBK) 27, the mass parts of propylene glycol monomethyl ether 3 are used as dispersing aid
State embodiment 1 similarly, using rotary evaporator, methyl alcohol is removed under reduced pressure, attempt manufacture organosilicon resin composition.But
It is the composition that can only obtain gonorrhoea cohesion.
Table 1
So, photosemiconductor organosilicon resin composition of the invention and its solidfied material (embodiment 1~12) are respectively provided with
Good optical characteristics, but it is surface-treated (comparative example in no addition dispersing aid (comparative example 1), not to Zirconia particles
2), at least one in Zirconia particles surface does not form the chemical bond (comparative example 3) of silane coupler, ketone and alcohols is not used
In the case that person is as dispersing aid (comparative example 4) or dispersing aid amount few (comparative example 5), the group of gonorrhoea cohesion is can only obtain
Compound.
It should be noted that the invention is not restricted to the record of above-mentioned implementation method, can be in scope of the claims
Various changes can be carried out, for disclosed technical method is combined respectively by different embodiments or in multiple variations
Implementation method obtained from use is also contained in technical scope of the invention.
Industrial applicibility
The present invention for example can be widely applied to be used in the photosemiconductor such as light emitting diode (LED) or laser diode
Resin combination field.
Although in detail or with reference to particular implementation ground, the present invention is described, and those skilled in the art should
This is understood, can make various changes and modifications without departing from the spirit and scope of the present invention.
The application is based on the Japanese patent application (Patent 2013-219081) for proposing on October 22nd, 2013, and its is complete
Portion's content is hereby incorporated by, used as reference.
Claims (4)
1. a kind of photosemiconductor organosilicon resin composition, it is characterised in that containing by the Zirconia particles after surface modification,
Dispersing aid and organic siliconresin, by surface modification after the Zirconia particles be dispersity,
The dispersion particle diameter of the Zirconia particles after by surface modification be more than 1nm, below 50nm,
The Zirconia particles before surface modification quality be 100 mass parts when, by surface modification after the zirconium oxide
In particle the quality of surface modification part be 0.1 mass parts more than, below 10 mass parts,
At least one as the dispersing aid, containing ketone and alcohols.
2. photosemiconductor organosilicon resin composition as claimed in claim 1, it is characterised in that the institute before surface modification
State Zirconia particles quality, for surface modification silane coupler quality and the organic siliconresin quality total amount
During for 100 mass parts,
Zirconia particles conversion before the content surface modification of the Zirconia particles after by surface modification, is 50 matter
More than amount part, below 75 mass parts.
3. photosemiconductor organosilicon resin composition as claimed in claim 1 or 2, it is characterised in that relative to the light
The mass parts of composition 100 in whole compositions of semiconductor organosilicon resin composition in addition to the dispersing aid, it is described
The use level of dispersing aid is more than 50 mass parts, below 2000 mass parts.
4. a kind of photosemiconductor organic siliconresin solidfied material, it is characterised in that make any one of claims 1 to 3
Photosemiconductor is solidified to form with organosilicon resin composition.
Applications Claiming Priority (2)
| 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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| Publication Number | Publication Date |
|---|---|
| CN104559181A CN104559181A (en) | 2015-04-29 |
| CN104559181B true CN104559181B (en) | 2017-07-07 |
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| JP (1) | JP2015081275A (en) |
| KR (1) | KR20150046761A (en) |
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| US11692080B2 (en) | 2017-08-04 | 2023-07-04 | Sumitomo Osaka Cement Co., Ltd. | Dispersion liquid, composition, sealing member, light-emitting device, illumination tool, display device, and method for producing light-emitting device |
| JP6656606B2 (en) * | 2017-08-04 | 2020-03-04 | 住友大阪セメント株式会社 | Dispersion, composition, sealing member, light emitting device, lighting fixture, display device, and method for manufacturing light emitting device |
| 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 |
| CN112789323B (en) * | 2018-10-02 | 2024-02-02 | 株式会社力森诺科 | Resin composition, cured product, and semiconductor device |
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| JP5034314B2 (en) * | 2006-05-19 | 2012-09-26 | 住友大阪セメント株式会社 | High refractive index transparent particle manufacturing method, high refractive index transparent particle, high refractive index transparent composite, and light emitting device |
| JP5445140B2 (en) * | 2008-01-09 | 2014-03-19 | 旭硝子株式会社 | Surface-modified zirconia particles, method for producing the same, and resin composition |
| CA2778761A1 (en) * | 2009-10-29 | 2011-05-05 | Sakai Chemical Industry Co., Ltd. | Method for producing dispersion of microparticles of inorganic oxide in organic solvent |
| JP2014077117A (en) * | 2012-09-21 | 2014-05-01 | Dow Corning Toray Co Ltd | Highly refractive surface treatment agent, and fine member and optical material surface-treated by using the same |
| 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 |
| CN103131189B (en) * | 2013-01-05 | 2014-11-05 | 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 |
| JP2015017195A (en) * | 2013-07-11 | 2015-01-29 | 日産化学工業株式会社 | Composition for forming reflow-type high refractive index film for solid-state imaging device |
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| TWI496827B (en) | 2015-08-21 |
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| CN104559181A (en) | 2015-04-29 |
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