JP2014076924A - Surface modified composite metal oxide fine particles - Google Patents
Surface modified composite metal oxide fine particles Download PDFInfo
- Publication number
- JP2014076924A JP2014076924A JP2012226366A JP2012226366A JP2014076924A JP 2014076924 A JP2014076924 A JP 2014076924A JP 2012226366 A JP2012226366 A JP 2012226366A JP 2012226366 A JP2012226366 A JP 2012226366A JP 2014076924 A JP2014076924 A JP 2014076924A
- Authority
- JP
- Japan
- Prior art keywords
- fine particles
- metal oxide
- composite metal
- group
- oxide fine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000010419 fine particle Substances 0.000 title claims abstract description 94
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 77
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 77
- 239000002131 composite material Substances 0.000 title claims abstract description 75
- 150000003377 silicon compounds Chemical class 0.000 claims abstract description 38
- 239000003960 organic solvent Substances 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims description 37
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 32
- 125000004432 carbon atom Chemical group C* 0.000 claims description 27
- 239000006185 dispersion Substances 0.000 claims description 27
- 229910002113 barium titanate Inorganic materials 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 15
- 239000011164 primary particle Substances 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000000000 cycloalkoxy group Chemical group 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims description 6
- 239000010409 thin film Substances 0.000 claims description 6
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 3
- 239000011859 microparticle Substances 0.000 claims 1
- 229920002050 silicone resin Polymers 0.000 abstract description 27
- 230000003287 optical effect Effects 0.000 abstract description 9
- 239000011256 inorganic filler Substances 0.000 abstract description 6
- 229910003475 inorganic filler Inorganic materials 0.000 abstract description 6
- 239000007970 homogeneous dispersion Substances 0.000 abstract 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- -1 n-octyl group Chemical group 0.000 description 27
- 150000002430 hydrocarbons Chemical group 0.000 description 23
- 150000001875 compounds Chemical class 0.000 description 17
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 238000006011 modification reaction Methods 0.000 description 13
- 230000004048 modification Effects 0.000 description 11
- 238000012986 modification Methods 0.000 description 11
- 238000005259 measurement Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000011324 bead Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000004817 gas chromatography Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- ZQTYRTSKQFQYPQ-UHFFFAOYSA-N trisiloxane Chemical compound [SiH3]O[SiH2]O[SiH3] ZQTYRTSKQFQYPQ-UHFFFAOYSA-N 0.000 description 5
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000006459 hydrosilylation reaction Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- SWGZAKPJNWCPRY-UHFFFAOYSA-N methyl-bis(trimethylsilyloxy)silicon Chemical compound C[Si](C)(C)O[Si](C)O[Si](C)(C)C SWGZAKPJNWCPRY-UHFFFAOYSA-N 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- QBERHIJABFXGRZ-UHFFFAOYSA-M rhodium;triphenylphosphane;chloride Chemical compound [Cl-].[Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QBERHIJABFXGRZ-UHFFFAOYSA-M 0.000 description 3
- 239000000565 sealant Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- IYTXKIXETAELAV-UHFFFAOYSA-N Nonan-3-one Chemical compound CCCCCCC(=O)CC IYTXKIXETAELAV-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 125000002015 acyclic group Chemical group 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- DSVRVHYFPPQFTI-UHFFFAOYSA-N bis(ethenyl)-methyl-trimethylsilyloxysilane;platinum Chemical compound [Pt].C[Si](C)(C)O[Si](C)(C=C)C=C DSVRVHYFPPQFTI-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
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- 150000002148 esters Chemical class 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
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- 239000005457 ice water Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000012280 lithium aluminium hydride Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
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- 230000000704 physical effect Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- OISMAZJJMNGUGL-UHFFFAOYSA-N triethoxy(2-trimethylsilylethyl)silane Chemical compound CCO[Si](OCC)(OCC)CC[Si](C)(C)C OISMAZJJMNGUGL-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
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- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 description 1
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- VPBZZPOGZPKYKX-UHFFFAOYSA-N 1,2-diethoxypropane Chemical compound CCOCC(C)OCC VPBZZPOGZPKYKX-UHFFFAOYSA-N 0.000 description 1
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- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
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- ZEQZEDMQGNNIKJ-UHFFFAOYSA-N 2,2-dimethoxyethenyl(methyl)silane Chemical compound C[SiH2]C=C(OC)OC ZEQZEDMQGNNIKJ-UHFFFAOYSA-N 0.000 description 1
- JQCWLRHNAHIIGW-UHFFFAOYSA-N 2,8-dimethylnonan-5-one Chemical compound CC(C)CCC(=O)CCC(C)C JQCWLRHNAHIIGW-UHFFFAOYSA-N 0.000 description 1
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 description 1
- 125000006179 2-methyl benzyl group Chemical group [H]C1=C([H])C(=C(C([H])=C1[H])C([H])([H])*)C([H])([H])[H] 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000006180 3-methyl benzyl group Chemical group [H]C1=C([H])C(=C([H])C(=C1[H])C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000006181 4-methyl benzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])C([H])([H])* 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- UTYJZVYEUYERNW-UHFFFAOYSA-N CC=C(C(=O)CO[Si](OC)(OC)CCC)C Chemical compound CC=C(C(=O)CO[Si](OC)(OC)CCC)C UTYJZVYEUYERNW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910013500 M-O—Si Inorganic materials 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910008423 Si—B Inorganic materials 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052454 barium strontium titanate Inorganic materials 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
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- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- XSDCTSITJJJDPY-UHFFFAOYSA-N chloro-ethenyl-dimethylsilane Chemical compound C[Si](C)(Cl)C=C XSDCTSITJJJDPY-UHFFFAOYSA-N 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
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- 238000005336 cracking Methods 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000002933 cyclohexyloxy group Chemical group C1(CCCCC1)O* 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000003493 decenyl group Chemical group [H]C([*])=C([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- KQAHMVLQCSALSX-UHFFFAOYSA-N decyl(trimethoxy)silane Chemical compound CCCCCCCCCC[Si](OC)(OC)OC KQAHMVLQCSALSX-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- XUKFPAQLGOOCNJ-UHFFFAOYSA-N dimethyl(trimethylsilyloxy)silicon Chemical compound C[Si](C)O[Si](C)(C)C XUKFPAQLGOOCNJ-UHFFFAOYSA-N 0.000 description 1
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- GCSJLQSCSDMKTP-UHFFFAOYSA-N ethenyl(trimethyl)silane Chemical compound C[Si](C)(C)C=C GCSJLQSCSDMKTP-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000005677 ethinylene group Chemical group [*:2]C#C[*:1] 0.000 description 1
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- GOKKOFHHJFGZHW-UHFFFAOYSA-N hexyl propanoate Chemical class CCCCCCOC(=O)CC GOKKOFHHJFGZHW-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 125000003136 n-heptyl 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])* 0.000 description 1
- 125000001298 n-hexoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000005187 nonenyl group Chemical group C(=CCCCCCCC)* 0.000 description 1
- RNYFPCBPUJIHRR-WCZCRHMRSA-N norbornenylethyl-poss® Chemical group C1([C@@H]2C[C@@H](C=C2)C1)CC[Si](O1)(O2)O[Si](O3)(C4CCCC4)O[Si](O4)(C5CCCC5)O[Si]1(C1CCCC1)O[Si](O1)(C5CCCC5)O[Si]2(C2CCCC2)O[Si]3(C2CCCC2)O[Si]41C1CCCC1 RNYFPCBPUJIHRR-WCZCRHMRSA-N 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- TWSRVQVEYJNFKQ-UHFFFAOYSA-N pentyl propanoate Chemical compound CCCCCOC(=O)CC TWSRVQVEYJNFKQ-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical class Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])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])[H] 0.000 description 1
- SKRWFPLZQAAQSU-UHFFFAOYSA-N stibanylidynetin;hydrate Chemical compound O.[Sn].[Sb] SKRWFPLZQAAQSU-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910019655 synthetic inorganic crystalline material Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium(IV) ethoxide Substances [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- IAORIIYGIHOPHS-UHFFFAOYSA-N trimethyl trimethylsilyl silicate Chemical compound CO[Si](OC)(OC)O[Si](C)(C)C IAORIIYGIHOPHS-UHFFFAOYSA-N 0.000 description 1
- XAASNKQYFKTYTR-UHFFFAOYSA-N tris(trimethylsilyloxy)silicon Chemical compound C[Si](C)(C)O[Si](O[Si](C)(C)C)O[Si](C)(C)C XAASNKQYFKTYTR-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000011995 wilkinson's catalyst Substances 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、特定の構造を有するケイ素化合物により表面修飾された複合金属酸化物微粒子、及びその製造方法に関する。 The present invention relates to composite metal oxide fine particles whose surface is modified with a silicon compound having a specific structure, and a method for producing the same.
従来、高い透明性が求められる光学材料の分野では、アクリル樹脂及びエポキシ樹脂が広く用いられているが、発光ダイオード（ＬＥＤ）封止材のように高温となる使用環境又は短波長の光を吸収するような使用条件では光学樹脂が徐々に劣化し、黄変又はクラックが生じることが問題となっている。そこで、高い耐久性が求められる用途では、耐熱性及び耐光性の高いシリコーン樹脂が使用されている。しかしながら、シリコーン樹脂は、従来の光学樹脂と比較して屈折率が低く、例えば、ＬＥＤ封止材又はレンズとして使用する場合には光利用効率が低下してしまうという問題があった。より屈折率の高いフェニルシリコーンも使用されているが、フェニル基の導入により耐熱性及び耐光性が低下することから、その使用範囲は限定される。 Conventionally, in the field of optical materials that require high transparency, acrylic resins and epoxy resins have been widely used. However, they absorb high-temperature environments or short-wavelength light, such as light-emitting diode (LED) sealants Under such use conditions, there is a problem that the optical resin gradually deteriorates and yellowing or cracking occurs. Therefore, silicone resins having high heat resistance and light resistance are used in applications that require high durability. However, the silicone resin has a refractive index lower than that of a conventional optical resin. For example, when it is used as an LED sealing material or a lens, there is a problem that light utilization efficiency is lowered. Phenyl silicone having a higher refractive index is also used, but since the heat resistance and light resistance are reduced by introduction of the phenyl group, the range of use is limited.
そこで、シリコーン樹脂に屈折率の高い無機フィラーを分散させて高屈折率化させる方法が検討されており、酸化チタン、酸化ジルコニウム、及び酸化亜鉛等の金属酸化物を分散させたシリコーン樹脂の開発が進められている（例えば、特許文献１〜３）。また、チタン酸バリウムに代表される複合金属酸化物は、さらに高い屈折率を有していることから、高屈折率化を目的とする無機フィラーとして好ましいと言える。
Therefore, a method of increasing the refractive index by dispersing an inorganic filler having a high refractive index in a silicone resin has been studied, and the development of a silicone resin in which metal oxides such as titanium oxide, zirconium oxide, and zinc oxide are dispersed has been developed. (For example,
しかしながら、酸化チタン、酸化ジルコニウム、酸化亜鉛等の金属酸化物は光触媒性を示すことが知られており、使用条件によっては樹脂の劣化を促進する懸念があることが知られている。一方、チタン酸バリウムに代表される複合金属酸化物の利用も検討されているが、従来の金属酸化物と比較してその微粒子の凝集性が強く、また、金属成分に由来して分散液が塩基性を示すなど、適切な表面修飾によりシリコーン樹脂への分散性を付与することが困難であった。 However, metal oxides such as titanium oxide, zirconium oxide, and zinc oxide are known to exhibit photocatalytic properties, and it is known that there is a concern of promoting deterioration of the resin depending on use conditions. On the other hand, the use of composite metal oxides typified by barium titanate has also been studied, but the fine particles are more cohesive than conventional metal oxides, and the dispersion is derived from metal components. It was difficult to impart dispersibility to the silicone resin by appropriate surface modification such as basicity.
前記した状況に鑑み、本発明は、シリコーン樹脂への均一分散が可能であり、シリコーン樹脂の透明性を維持し、且つ高屈折率化させる為の無機フィラーとして好適な表面修飾複合金属酸化物微粒子を提供することを課題とする。また、上記表面修飾複合金属酸化物微粒子を用いることにより、有機溶媒中に均一分散した溶液、並びにＬＥＤ封止剤及びレンズ等の光学材料として好適な硬化物の提供を課題とする。 In view of the above situation, the present invention is capable of uniform dispersion in a silicone resin, and maintains surface transparency of the silicone resin and is suitable as an inorganic filler for increasing the refractive index. It is an issue to provide. Another object of the present invention is to provide a solution uniformly dispersed in an organic solvent and a cured product suitable as an optical material such as an LED sealant and a lens by using the surface-modified composite metal oxide fine particles.
本発明者らは、上記目的を達成すべく鋭意検討を行った結果、特定の構造を有するケイ素化合物を用いて表面処理された複合金属酸化物微粒子は、シリコーン樹脂への均一分散が可能であり、かつ高屈折率化等の物性向上を目的とする無機フィラーとして有用であることを見出し、本発明を完成させた。即ち、本発明は以下の通りである。 As a result of intensive studies to achieve the above object, the present inventors have found that the composite metal oxide fine particles surface-treated with a silicon compound having a specific structure can be uniformly dispersed in a silicone resin. And it discovered that it was useful as an inorganic filler aiming at physical property improvement, such as high refractive index, and completed this invention. That is, the present invention is as follows.
［１］ 複合金属酸化物微粒子の表面に、下記一般式（１）：
Ｒ1Ｒ２Ｒ３Ｓｉ−Ａ−ＳｉＲ４ ｎＸ（３−ｎ） （１）
｛式中、Ｒ1〜Ｒ３は、各々独立に、炭素数１〜１８の炭化水素基、又は置換されていてもよいシロキシ基であり、Ｒ４は、炭素数１〜４の炭化水素基であり、Ａは、炭素数２〜６の二価の炭化水素基であり、Ｘは、水素原子、ハロゲン原子、炭素数１〜６のアルコキシ基、炭素数３〜６のシクロアルコキシ基、又はアセトキシ基であり、そしてｎは、０又は１である。｝
で表されるケイ素化合物に由来する構造部位を有する、表面修飾複合金属酸化物微粒子。
[1] On the surface of the composite metal oxide fine particles, the following general formula (1):
R 1 R 2 R 3 Si- A-SiR 4 n X (3-n) (1)
{Wherein R 1 to R 3 are each independently a hydrocarbon group having 1 to 18 carbon atoms or an optionally substituted siloxy group, and R 4 is a hydrocarbon group having 1 to 4 carbon atoms. A is a divalent hydrocarbon group having 2 to 6 carbon atoms, and X is a hydrogen atom, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a cycloalkoxy group having 3 to 6 carbon atoms, or An acetoxy group and n is 0 or 1; }
Surface-modified composite metal oxide fine particles having a structural site derived from a silicon compound represented by the formula:
［２］ 前記複合金属酸化物微粒子の平均一次粒子径が、１ｎｍ以上４０ｎｍ以下である、［１］に記載の表面修飾複合金属酸化物微粒子。 [2] The surface modified composite metal oxide fine particles according to [1], wherein the composite metal oxide fine particles have an average primary particle diameter of 1 nm or more and 40 nm or less.
［３］ 前記複合金属酸化物微粒子は、チタン酸バリウム微粒子である、［１］又は［２］に記載の表面修飾複合金属酸化物微粒子。 [3] The surface-modified composite metal oxide fine particles according to [1] or [2], wherein the composite metal oxide fine particles are barium titanate fine particles.
［４］ アルコール及び水を含む前記複合金属酸化物微粒子の均一分散液に、前記一般式（１）で表されるケイ素化合物を添加する工程を含む、［１］〜［３］のいずれか１項に記載の表面修飾複合金属酸化物微粒子の製造方法。 [4] Any one of [1] to [3], including a step of adding the silicon compound represented by the general formula (1) to the uniform dispersion of the composite metal oxide fine particles containing alcohol and water. A method for producing the surface-modified composite metal oxide fine particles according to Item.
［５］ ［１］〜［３］のいずれか１項に記載の表面修飾複合金属酸化物微粒子、及び有機溶媒を含む均一分散液。 [5] A uniform dispersion containing the surface-modified composite metal oxide fine particles according to any one of [1] to [3] and an organic solvent.
［６］ ［１］〜［３］のいずれか１項に記載の表面修飾複合金属酸化物微粒子を、溶媒を用いずに成型して得られる成形体を硬化させる工程、又は［５］に記載の均一分散液を基板上に塗布して得られる薄膜を硬化させる工程を含む、硬化物の製造方法。 [6] A step of curing a molded product obtained by molding the surface-modified composite metal oxide fine particles according to any one of [1] to [3] without using a solvent, or the method according to [5]. The manufacturing method of hardened | cured material including the process of hardening the thin film obtained by apply | coating the uniform dispersion liquid of this on a board | substrate.
［７］ ［６］に記載の製造方法により得られる硬化物。 [7] A cured product obtained by the production method according to [6].
本発明により、シリコーン樹脂への均一分散が可能であり、シリコーン樹脂の透明性を維持し、且つ高屈折率化させる為の無機フィラーとして好適な表面修飾複合金属酸化物微粒子が提供される。また、本発明の表面修飾複合金属酸化物微粒子を用いることにより、微粒子の凝集が抑制された透明性の高い均一分散液が提供される。さらに、ＬＥＤ封止剤及びレンズ等の光学材料として好適な、高透明かつ高屈折率の硬化物が提供される。 According to the present invention, surface-modified composite metal oxide fine particles that can be uniformly dispersed in a silicone resin, are suitable as an inorganic filler for maintaining the transparency of the silicone resin and increasing the refractive index are provided. Further, by using the surface-modified composite metal oxide fine particles of the present invention, a highly transparent uniform dispersion liquid in which aggregation of the fine particles is suppressed is provided. Furthermore, a highly transparent and high refractive index cured product suitable as an optical material such as an LED sealant and a lens is provided.
以下、本発明を実施するための形態（以下、「実施形態」と略記する。）について詳細に説明する。尚、本発明は、以下の実施形態に限定されるものではなく、その要旨の範囲内で種々変形して実施することができる。 Hereinafter, modes for carrying out the present invention (hereinafter abbreviated as “embodiments”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.
本実施形態の表面修飾複合金属酸化物微粒子は、複合金属酸化物微粒子の表面に、下記一般式（１）：
Ｒ1Ｒ２Ｒ３Ｓｉ−Ａ−ＳｉＲ４ ｎＸ（３−ｎ） （１）
｛式中、Ｒ1〜Ｒ３は、各々独立に、炭素数１〜１８の炭化水素基、又は置換されていてもよいシロキシ基であり、Ｒ４は、炭素数１〜４の炭化水素基であり、Ａは、炭素数２〜６の二価の炭化水素基であり、Ｘは、水素原子、ハロゲン原子、炭素数１〜６のアルコキシ基、炭素数３〜６のシクロアルコキシ基、又はアセトキシ基であり、そしてｎは、０又は１である。｝
で表されるケイ素化合物に由来する構造部位を表面に有するものである。
上記表面修飾複合金属酸化物微粒子は、上記一般式（１）で表されるケイ素化合物を用いて、複合金属酸化物微粒子を表面修飾することにより得られる。
The surface-modified composite metal oxide fine particles of the present embodiment have the following general formula (1):
R 1 R 2 R 3 Si- A-SiR 4 n X (3-n) (1)
{Wherein R 1 to R 3 are each independently a hydrocarbon group having 1 to 18 carbon atoms or an optionally substituted siloxy group, and R 4 is a hydrocarbon group having 1 to 4 carbon atoms. A is a divalent hydrocarbon group having 2 to 6 carbon atoms, and X is a hydrogen atom, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a cycloalkoxy group having 3 to 6 carbon atoms, or An acetoxy group and n is 0 or 1; }
The surface has a structural site derived from a silicon compound represented by the formula:
The surface-modified composite metal oxide fine particles can be obtained by surface-modifying the composite metal oxide fine particles using the silicon compound represented by the general formula (1).
＜ケイ素化合物＞
上記一般式（１）において、Ｒ1〜Ｒ３は、炭素数１〜１８の炭化水素基、又は置換されていてもよいシロキシ基であり、それぞれ同じでも異なっていてもよい。炭素数１〜１８の炭化水素基としては、例えば、メチル基、エチル基、ｎ−プロピル基、ｉｓо−プロピル基、ｎ−ブチル基、ｉｓо−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基、１−メチルブチル基、２−メチルブチル基、３−メチルブチル基、１−エチルプロピル基、１，１−ジメチルプロピル基、１，２−ジメチルプロピル基、２，２−ジメチルプロピル基、シクロペンチル基、ｎ−ヘキシル基、シクロヘキシル基、ｎ−ヘプチル基、２−メチルヘキシル基、ｎ−オクチル基、ｎ−ノニル基、ｎ−デシル基、オクタデシル基等の非環式又は環式の飽和炭化水素基、フェニル基、トリル基、キシリル基等の芳香族炭化水素基、ビニル基、プロペニル基、ブテニル基、ペンテニル基、ヘキセニル基、シクロヘキセニル基、シクロヘキセニルエチル基、ノルボルネニルエチル基、ヘプテニル基、オクテニル基、ノネニル基、デセニル基、スチレニル基等の非環式及び環式の不飽和炭化水素基、及びベンジル基、フェネチル基、２−メチルベンジル基、３−メチルベンジル基、４−メチルベンジル基等のアリールアルキル基等が挙げられる。また、置換されていてもよいシロキシ基としては、例えば、トリメチルシロキシ基、メチルジエチルシロキシ基、ジメチルエチルシロキシ基、ジメチルブチルシロキシ基、ジメチルシクロヘキシルシロキシ基、ジメチルフェニルシロキシ基、メチルジフェニルシロキシ基等が挙げられる。
<Silicon compound>
In the general formula (1), R 1 ~R 3 is a hydrocarbon group, or a substituted optionally may be siloxy group having 1 to 18 carbon atoms and may be the same or different. Examples of the hydrocarbon group having 1 to 18 carbon atoms include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, Acyclic or cyclic saturated carbonization such as cyclopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, 2-methylhexyl group, n-octyl group, n-nonyl group, n-decyl group, octadecyl group, etc. Aromatic hydrocarbon group such as hydrogen group, phenyl group, tolyl group, xylyl group, vinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, cyclohexenyl group An acyclic and cyclic unsaturated hydrocarbon group such as an alkyl group, a cyclohexenylethyl group, a norbornenylethyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a styryl group, and a benzyl group, a phenethyl group, Examples thereof include arylalkyl groups such as 2-methylbenzyl group, 3-methylbenzyl group, 4-methylbenzyl group and the like. Examples of the optionally substituted siloxy group include trimethylsiloxy group, methyldiethylsiloxy group, dimethylethylsiloxy group, dimethylbutylsiloxy group, dimethylcyclohexylsiloxy group, dimethylphenylsiloxy group, methyldiphenylsiloxy group and the like. Can be mentioned.
これらの中でも、複合金属酸化物微粒子との表面修飾反応が容易に進行し、表面修飾基による屈折率の低下を抑制するという観点から、Ｒ1〜Ｒ３は、メチル基、エチル基、トリメチルシロキシ基、又はジメチルフェニルシロキシ基であることが好ましく、より好ましくはメチル基又はトリメチルシロキシ基である。 Among these, from the viewpoint that the surface modification reaction with the composite metal oxide fine particles proceeds easily and suppresses the decrease in the refractive index due to the surface modification group, R 1 to R 3 are methyl group, ethyl group, trimethylsiloxy. Or a dimethylphenylsiloxy group, more preferably a methyl group or a trimethylsiloxy group.
上記一般式（１）において、Ｒ４は炭素数１〜４の炭化水素基である。炭素数１〜４の炭化水素基としては、例えば、メチル基、エチル基、ｎ−プロピル基、ｉｓо−プロピル基、ｎ−ブチル基、ｉｓо−ブチル基、ｓｅｃ−ブチル基等が挙げられる。中でも、複合金属酸化物微粒子との表面修飾反応が容易に進行するという観点から、Ｒ４はメチル基であることが好ましい。 In the general formula (1), R 4 is a hydrocarbon group having 1 to 4 carbon atoms. Examples of the hydrocarbon group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a sec-butyl group. Among these, R 4 is preferably a methyl group from the viewpoint that the surface modification reaction with the composite metal oxide fine particles easily proceeds.
上記一般式（１）において、Ａは、炭素数２〜６の二価の炭化水素基である。炭素数２〜６の二価の炭化水素基としては、例えば、炭素数２〜６の直鎖状又は分岐状のアルキレン基などが挙げられる。これらの中でも、合成の容易さという観点から、Ａは、炭素数２又は３の直鎖状又は分岐状のアルキレン基が好ましく、より好ましくは炭素数２の直鎖状又は分岐状のアルキレン基である。 In the said General formula (1), A is a C2-C6 bivalent hydrocarbon group. As a C2-C6 bivalent hydrocarbon group, a C2-C6 linear or branched alkylene group etc. are mentioned, for example. Among these, from the viewpoint of ease of synthesis, A is preferably a linear or branched alkylene group having 2 or 3 carbon atoms, more preferably a linear or branched alkylene group having 2 carbon atoms. is there.
上記一般式（１）で表されるケイ素化合物において、上記一般式（１）におけるＡは、該ケイ素化合物の反応性及び安定性に大きく影響している。例えば、後述の複合金属酸化物微粒子との表面修飾反応において、同一ケイ素原子上に反応性の置換基｛上記一般式（１）におけるＸに相当する。｝とトリメチルシロキシ基等のシロキシ基が存在する場合、上記ケイ素化合物のみの加水分解反応及び縮合反応が優先的に進行し、目的とする表面修飾反応が進行しない。このように反応性が大きく異なる理由は定かではないが、複合金属酸化物微粒子の表面水酸基に由来する塩基性により、上記ケイ素化合物の分解反応が進行するためであると考えられる。 In the silicon compound represented by the general formula (1), A in the general formula (1) greatly affects the reactivity and stability of the silicon compound. For example, in the surface modification reaction with the composite metal oxide fine particles described later, a reactive substituent on the same silicon atom {corresponds to X in the general formula (1). } And a siloxy group such as a trimethylsiloxy group, the hydrolysis reaction and condensation reaction of only the silicon compound proceed preferentially, and the target surface modification reaction does not proceed. The reason why the reactivity is so different is not clear, but it is considered that the decomposition reaction of the silicon compound proceeds due to the basicity derived from the surface hydroxyl group of the composite metal oxide fine particles.
また、上記一般式（１）におけるＡは、二種以上が混合していてもよい。後述のように、上記一般式（１）で表されるケイ素化合物の製造方法の一例として、対応するヒドロシラン化合物とアルケニルシラン化合物のヒドロシリル化反応が挙げられる。本反応においては、一般的に、付加生成物としてシス−トランス異性体の混合物が得られるが、本実施形態においては両者を分離することなく複合金属酸化物微粒子との反応において好適に用いることができる。 Moreover, 2 or more types of A in the general formula (1) may be mixed. As will be described later, as an example of the method for producing the silicon compound represented by the general formula (1), a hydrosilylation reaction between a corresponding hydrosilane compound and an alkenylsilane compound can be mentioned. In this reaction, generally, a mixture of cis-trans isomers is obtained as an addition product, but in this embodiment, it is preferably used in the reaction with the composite metal oxide fine particles without separating them. it can.
上記一般式（１）において、Ｘは、水素原子、ハロゲン原子、炭素数１〜６のアルコキシ基、炭素数３〜６のシクロアルコキシ基、又はアセトキシ基である。ハロゲン原子としては、例えば、フッ素、塩素、臭素、ヨウ素などが挙げられる。また、炭素数１〜６のアルコキシ基としては、例えば、メトキシ基、エトキシ基、ｎ−プロポキシ基、ｉｓｏ−プロポキシ基、ｎ−ブトキシ基、ｔ−ブトキシ基、ｎ−ヘキシロキシ基等が挙げられる。また、炭素数３〜６のシクロアルコキシ基としては、例えば、シクロヘキシロキシ基等が挙げられる。
これらの中でも、反応制御の容易さという観点から、Ｘは、水素原子又はアルコキシ基であることが好ましく、より好ましくは水素原子、メトキシ基、又はエトキシ基である。
In the above general formula (1), X is a hydrogen atom, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a cycloalkoxy group having 3 to 6 carbon atoms, or an acetoxy group. Examples of the halogen atom include fluorine, chlorine, bromine, iodine and the like. Moreover, as a C1-C6 alkoxy group, a methoxy group, an ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, t-butoxy group, n-hexyloxy group etc. are mentioned, for example. Moreover, as a C3-C6 cycloalkoxy group, a cyclohexyloxy group etc. are mentioned, for example.
Among these, from the viewpoint of easy reaction control, X is preferably a hydrogen atom or an alkoxy group, more preferably a hydrogen atom, a methoxy group, or an ethoxy group.
上記一般式（１）において、ｎは０又は１である。複合金属酸化物微粒子との表面修飾反応が容易に進行するという観点から、ｎは０又は１であることが好ましい。 In the general formula (1), n is 0 or 1. From the viewpoint that the surface modification reaction with the composite metal oxide fine particles easily proceeds, n is preferably 0 or 1.
上記一般式（１）で表されるケイ素化合物は、例えば、対応するヒドロシラン化合物とアルケニルシラン化合物とのヒドロシリル化反応により製造することができる。具体的には、炭化水素系の有機溶媒中もしくは無溶媒において、ヒドロシラン化合物とアルケニルシラン化合物を等モル量又は一方の化合物がわずかに過剰になるように溶解させ、金属触媒を加えて加熱撹拌することにより製造される。 The silicon compound represented by the general formula (1) can be produced, for example, by a hydrosilylation reaction between a corresponding hydrosilane compound and an alkenylsilane compound. Specifically, in a hydrocarbon-based organic solvent or in the absence of a solvent, the hydrosilane compound and the alkenylsilane compound are dissolved so that the equimolar amount or one of the compounds is slightly excessive, and the metal catalyst is added and heated and stirred. It is manufactured by.
上記ヒドロシラン化合物及びアルケニルシラン化合物としては、上記一般式（１）で表されるケイ素化合物に対応して、下記一般式（２）：
Ｒ1Ｒ２Ｒ３Ｓｉ−Ｈ （２）
｛式中、Ｒ1〜Ｒ３は一般式（１）で定義した通りであるが、不飽和炭化水素基を除くものである。｝
で表されるヒドロシラン化合物及び下記一般式（３）：
Ｂ−ＳｉＲ４ ｎＸ（３−ｎ） （３）
｛式中、Ｒ４、Ｘ及びｎは、一般式（１）で定義した通りであるが、Ｘは水素原子を除くものであり、そしてＢは、炭素数２〜６の不飽和炭化水素基である。｝
で表されるアルケニルシラン化合物、
又は下記一般式（４）：
Ｒ1Ｒ２Ｒ３Ｓｉ−Ｂ （４）
｛式中、Ｒ1〜Ｒ３は一般式（１）で定義した通りであり、そしてＢは、炭素数２〜６の不飽和炭化水素基である。｝
で表されるアルケニルシラン化合物及び下記一般式（５）：
Ｈ−ＳｉＲ４ ｎＸ（３−ｎ） （５）
｛式中、Ｒ４、Ｘ及びｎは、一般式（１）で定義した通りである。｝
で表されるヒドロシラン化合物を組み合わせて用いることができる。
上記一般式（３）及び（４）におけるＢは、炭素数２〜６の不飽和炭化水素基である。Ｂにおいて、不飽和結合の位置、立体構造、及び分岐構造の有無については特に限定されないが、原料物質の入手、或いは合成の容易さという観点から、Ｂはビニル基及びアリル基であることが好ましい。
The hydrosilane compound and alkenylsilane compound correspond to the silicon compound represented by the general formula (1), and the following general formula (2):
R 1 R 2 R 3 Si—H (2)
{In the formula, R 1 to R 3 are as defined in the general formula (1), but exclude an unsaturated hydrocarbon group. }
And the following general formula (3):
B-SiR 4 n X (3-n) (3)
{Wherein R 4 , X and n are as defined in the general formula (1), X is a hydrogen atom and B is an unsaturated hydrocarbon group having 2 to 6 carbon atoms. It is. }
An alkenylsilane compound represented by:
Or the following general formula (4):
R 1 R 2 R 3 Si-B (4)
{Wherein R 1 to R 3 are as defined in the general formula (1), and B is an unsaturated hydrocarbon group having 2 to 6 carbon atoms. }
And an alkenylsilane compound represented by the following general formula (5):
H-SiR 4 n X (3 -n) (5)
{Wherein R 4 , X and n are as defined in the general formula (1). }
The hydrosilane compound represented by these can be used in combination.
B in the general formulas (3) and (4) is an unsaturated hydrocarbon group having 2 to 6 carbon atoms. In B, the position of the unsaturated bond, the three-dimensional structure, and the presence or absence of a branched structure are not particularly limited, but B is preferably a vinyl group or an allyl group from the viewpoint of availability of raw materials or ease of synthesis. .
上記ヒドロシラン化合物とアルケニルシラン化合物とのモル比には特に制限はないが、一般的には、ヒドロシラン化合物１モルに対して、アルケニルシラン化合物を０．９〜１．１モルの範囲で使用することが好ましい。 Although there is no restriction | limiting in particular in the molar ratio of the said hydrosilane compound and an alkenylsilane compound, Generally, an alkenylsilane compound should be used in 0.9-1.1 mol with respect to 1 mol of hydrosilane compounds. Is preferred.
上記炭化水素系の有機溶媒としては、例えば、ヘキサン、オクタン、トルエン、キシレン等の炭化水素系有機溶媒が挙げられる。また、上記有機溶媒は任意の量で使用することができる。 Examples of the hydrocarbon organic solvent include hydrocarbon organic solvents such as hexane, octane, toluene, and xylene. The organic solvent can be used in any amount.
上記金属触媒としては、例えば、白金、パラジウム、ロジウム、ルテニウム等の白金族金属、該白金族金属をカーボン、アルミナ、シリカ、ポリマー等の担体に担持した担持触媒、塩化白金酸、アルコール変性塩化白金酸、塩化白金酸のオレフィン又はアセチレン錯体、白金のビニルシロキサン錯体、テトラキス（トリフェニルホスフィン）パラジウム、クロロトリス（トリフェニルホスフィン）ロジウム等が挙げられる。これらの中でも、塩化白金酸（Ｓｐｅｉｅｒ触媒）、白金のテトラメチルジビニルジシロキサン錯体（Ｋａｒｓｔｅｄｔ触媒）、及びクロロトリス（トリフェニルホスフィン）ロジウム（Ｗｉｌｋｉｎｓｏｎ触媒）が好ましい。また、これらの金属触媒は、単独でも２種類以上を混合して用いてもよい。 Examples of the metal catalyst include platinum group metals such as platinum, palladium, rhodium, and ruthenium, supported catalysts in which the platinum group metal is supported on a carrier such as carbon, alumina, silica, and polymer, chloroplatinic acid, and alcohol-modified platinum chloride. Examples include acids, olefins or acetylene complexes of chloroplatinic acid, vinylsiloxane complexes of platinum, tetrakis (triphenylphosphine) palladium, and chlorotris (triphenylphosphine) rhodium. Among these, chloroplatinic acid (Speier catalyst), platinum tetramethyldivinyldisiloxane complex (Karsttedt catalyst), and chlorotris (triphenylphosphine) rhodium (Wilkinson catalyst) are preferable. These metal catalysts may be used alone or in combination of two or more.
上記金属触媒の使用量は、上記ヒドロシラン化合物１モルに対して、１×１０−６〜０．０１モルの範囲で使用することができる。 The usage-amount of the said metal catalyst can be used in the range of 1 * 10 < -6 > -0.01 mol with respect to 1 mol of said hydrosilane compounds.
上記ヒドロシリル化反応の反応温度は０〜１５０℃の範囲であることが好ましく、反応時間は０．５〜４８時間の範囲であることが好ましい。 The reaction temperature of the hydrosilylation reaction is preferably in the range of 0 to 150 ° C., and the reaction time is preferably in the range of 0.5 to 48 hours.
上記ヒドロシリル化反応により上記一般式（１）で表されるケイ素化合物を合成する場合、ヒドロシランがアルケニルシランの不飽和結合部位に付加する際にシス体及びトランス体が生成し、これらの異性体混合物が得られる場合がある。この異性体混合物は蒸留、カラムクロマトグラフィー等の分離操作により分離することも可能であるが、シス−トランス異性体混合物であっても後述の複合金属酸化物微粒子との表面修飾反応において好適に使用することができる。 When the silicon compound represented by the general formula (1) is synthesized by the hydrosilylation reaction, a cis isomer and a trans isomer are formed when the hydrosilane is added to the unsaturated bond site of the alkenyl silane, and a mixture of these isomers. May be obtained. This isomer mixture can be separated by a separation operation such as distillation or column chromatography. However, even if it is a cis-trans isomer mixture, it is preferably used in the surface modification reaction with the composite metal oxide fine particles described later. can do.
上記一般式（１）で表されるケイ素化合物のうち、上記一般式（１）におけるＸが水素原子であるケイ素化合物については、例えば、上記一般式（１）におけるＸがハロゲン原子、アルコキシ基、シクロアルコキシ基、又はアセトキシ基であるケイ素化合物を上述の方法により製造した後、水素化リチウムアルミニウム、水素化ホウ素ナトリウム等の還元剤を用いて還元反応を行うことにより製造することができる。 Among the silicon compounds represented by the general formula (1), for the silicon compound in which X in the general formula (1) is a hydrogen atom, for example, X in the general formula (1) is a halogen atom, an alkoxy group, A silicon compound which is a cycloalkoxy group or an acetoxy group can be produced by the above-described method and then subjected to a reduction reaction using a reducing agent such as lithium aluminum hydride or sodium borohydride.
＜複合金属酸化物微粒子＞
本実施形態では、複合金属酸化物微粒子は、２種以上の金属原子及び酸素原子を含む複合金属酸化物の微粒子から構成される。複合金属酸化物としては、例えば、チタン酸バリウム、チタン酸ストロンチウム、チタン酸鉛、珪酸ジルコニウム、ジルコン酸鉛、酸化インジウムスズ、酸化スズアンチモン、ニオブ酸リチウム、コバルト酸リチウム等が挙げられる。これらの中でも、屈折率を向上させるという観点からは、チタン酸バリウム及びチタン酸ストロンチウムが好ましい。これらは、単独で用いても、２種以上を組み合わせて用いてもよい。
<Composite metal oxide fine particles>
In the present embodiment, the composite metal oxide fine particles are composed of composite metal oxide fine particles containing two or more kinds of metal atoms and oxygen atoms. Examples of the composite metal oxide include barium titanate, strontium titanate, lead titanate, zirconium silicate, lead zirconate, indium tin oxide, antimony tin oxide, lithium niobate, and lithium cobaltate. Among these, from the viewpoint of improving the refractive index, barium titanate and strontium titanate are preferable. These may be used alone or in combination of two or more.
複合金属酸化物微粒子は、好ましくは、球状、棒状、板状若しくは繊維状又はこれらの２種類以上が合体した形状であり、より好ましくは球状である。なお、ここでいう球状とは、真球状の他、回転楕円体、卵形等も含む略球状を意味する。 The composite metal oxide fine particles are preferably spherical, rod-shaped, plate-shaped or fibrous, or a shape in which two or more of these are combined, and more preferably spherical. In addition, the spherical shape here means a substantially spherical shape including a spheroid, an oval and the like in addition to a true spherical shape.
複合金属酸化物微粒子の平均一次粒子径は、光の散乱による透明性への悪影響を避けるため、目的とする用途で使用する光の波長以下であることが好ましい。該平均一次粒子径は、１ｎｍ以上１００ｎｍ以下であることが好ましく、より好ましくは１ｎｍ以上４０ｎｍ以下である。上記平均一次粒子径が１ｎｍ以上であれば、複合金属酸化物微粒子の分散性が良好であり、１００ｎｍ以下であれば、有機溶剤又は樹脂中に分散させた際の透明性が良好である。なお本開示において、平均一次粒子径とは数平均での値を意味する。上記平均一次粒子径は、透過型電子顕微鏡（ＴＥＭ）による直接観察により求めることができる。 The average primary particle diameter of the composite metal oxide fine particles is preferably equal to or less than the wavelength of light used in the intended application in order to avoid adverse effects on transparency due to light scattering. The average primary particle diameter is preferably 1 nm or more and 100 nm or less, more preferably 1 nm or more and 40 nm or less. If the average primary particle diameter is 1 nm or more, the dispersibility of the composite metal oxide fine particles is good, and if it is 100 nm or less, the transparency when dispersed in an organic solvent or resin is good. In the present disclosure, the average primary particle diameter means a number average value. The average primary particle diameter can be determined by direct observation with a transmission electron microscope (TEM).
複合金属酸化物微粒子は、水熱法、ゾルゲル法、共沈法等により製造することが可能であり、製造条件を変更することにより、平均一次粒子径を制御することができる。
複合金属酸化物微粒子の具体的な製造方法については、例えば、チタン酸バリウムの場合には、２−メトキシエタノール中において、等モル量の金属バリウムとオルトチタン酸テトラエチルとを加熱溶解させた後、水を添加することによって加水分解反応及び縮合反応を進行させ、チタン酸バリウム微粒子の分散液を得る方法等が挙げられる。必要に応じて、スプレードライ、真空乾燥等の乾燥処理を行うことにより、粉末状のチタン酸バリウム微粒子が得られる。また、電気炉等において焼結処理を行うことにより、焼結処理時間に応じて、チタン酸バリウム微粒子の表面水酸基量を制御できる。
The composite metal oxide fine particles can be produced by a hydrothermal method, a sol-gel method, a coprecipitation method, or the like, and the average primary particle size can be controlled by changing the production conditions.
About the specific manufacturing method of the composite metal oxide fine particles, for example, in the case of barium titanate, in 2-methoxyethanol, after equimolar amounts of metal barium and tetraethyl orthotitanate are heated and dissolved, Examples thereof include a method in which a hydrolysis reaction and a condensation reaction are advanced by adding water to obtain a dispersion of barium titanate fine particles. If necessary, powdery barium titanate fine particles can be obtained by performing a drying treatment such as spray drying or vacuum drying. In addition, by performing the sintering process in an electric furnace or the like, the surface hydroxyl group amount of the barium titanate fine particles can be controlled according to the sintering process time.
＜表面処理＞
本実施形態では、上記一般式（１）で表されるケイ素化合物を上記複合金属酸化物微粒子に作用させて表面修飾反応を行い、該ケイ素化合物に由来する構造部位を表面に有する表面修飾複合金属酸化物微粒子を製造する方法が開示される。
<Surface treatment>
In the present embodiment, the surface-modified composite metal having a structure portion derived from the silicon compound on the surface by causing the silicon compound represented by the general formula (1) to act on the composite metal oxide fine particles to perform a surface modification reaction. A method for producing oxide particulates is disclosed.
具体的には、例えば、アルコール及び水を含む複合金属酸化物微粒子の均一分散液に、上記ケイ素化合物を添加する工程により製造される。使用できるアルコールとしては、水と容易に混合できるという観点から、炭素数１以上４以下のアルコールが好ましく、例えば、メタノール、エタノール、ｎ−プロパノール、２−プロパノール、ｎ−ブタノール、メトキシエタノール、エトキシエタノール等が挙げられる。 Specifically, for example, it is produced by a step of adding the silicon compound to a uniform dispersion of composite metal oxide fine particles containing alcohol and water. The alcohol that can be used is preferably an alcohol having 1 to 4 carbon atoms from the viewpoint of easy mixing with water, for example, methanol, ethanol, n-propanol, 2-propanol, n-butanol, methoxyethanol, ethoxyethanol. Etc.
上記均一分散液は、複合金属酸化物微粒子を製造する際の、加水分解工程において用いられる水をそのまま含んでいてもよく、その一部を除去又は水を追加することにより、水の含有量を制御することもできる。上記ケイ素化合物は、そのまま添加しても、アルコール、水又はその他の有機溶媒等で希釈してから添加してもよい。 The uniform dispersion may contain water used in the hydrolysis step when producing the composite metal oxide fine particles as it is, and by removing a part or adding water, the water content can be reduced. It can also be controlled. The silicon compound may be added as it is, or may be added after diluting with alcohol, water or other organic solvent.
上記表面修飾反応の反応温度は、０℃〜１２０℃であることが好ましく、より好ましくは３０℃〜１００℃である。また、反応時間は、０．５時間〜２４時間であることが好ましく、より好ましくは０．５時間〜３時間である。 The reaction temperature for the surface modification reaction is preferably 0 ° C to 120 ° C, more preferably 30 ° C to 100 ° C. The reaction time is preferably 0.5 hours to 24 hours, more preferably 0.5 hours to 3 hours.
表面修飾反応に用いる複合金属酸化物微粒子は、水、有機溶媒、又はこれらの混合物に分散された状態であっても、乾燥処理によって得られる粉末でもよい。粉末状の複合金属酸化物微粒子を用いて表面修飾反応を行う場合には、ビーズミル等の分散装置中で表面修飾反応を行ってもよい。 The composite metal oxide fine particles used for the surface modification reaction may be dispersed in water, an organic solvent, or a mixture thereof, or may be a powder obtained by a drying treatment. When the surface modification reaction is performed using the powdered composite metal oxide fine particles, the surface modification reaction may be performed in a dispersion apparatus such as a bead mill.
ビーズミルは、ローター、ステータ及び撹拌粒子であるビーズを分離するビーズ分離機構を備える分散装置である。撹拌粒子であるビーズは、超微小ビーズであることが必要であり、その粒子径は３μｍ〜３００μｍであることが好ましく、より好ましくは１０μｍ〜５０μｍである。粒子径が３μｍ以上であれば、分散に必要な衝撃エネルギーが得られ、３００μｍ以下であれば、過剰な衝撃エネルギーによる再凝集が抑制できる。 The bead mill is a dispersing device including a bead separation mechanism that separates beads, which are a rotor, a stator, and stirring particles. The beads that are stirring particles are required to be ultrafine beads, and the particle diameter is preferably 3 μm to 300 μm, more preferably 10 μm to 50 μm. If the particle diameter is 3 μm or more, impact energy required for dispersion can be obtained, and if it is 300 μm or less, reaggregation due to excessive impact energy can be suppressed.
上記撹拌粒子としては、例えば、ジルコニア、アルミナ、シリカ、ガラス、炭化珪素、窒化珪素等が挙げられる。これらの中でも、撹拌粒子としての強度と安定性に優れるという観点からジルコニアが好ましい。
表面修飾反応において、上記一般式（１）で表されるケイ素化合物の反応性官能基Ｘと複合金属酸化物微粒子の表面水酸基（Ｍ−ＯＨ）が縮合反応することにより、酸素原子を介した共有結合（Ｍ−Ｏ−Ｓｉ）が生成する。
酸素原子を介した共有結合（Ｍ−Ｏ−Ｓｉ）の有無については、透過型、又は拡散反射型赤外線分光装置等により、当該共有結合に由来する吸収ピークを検出することにより確認できる。
Examples of the stirring particles include zirconia, alumina, silica, glass, silicon carbide, and silicon nitride. Among these, zirconia is preferable from the viewpoint of excellent strength and stability as stirring particles.
In the surface modification reaction, the reactive functional group X of the silicon compound represented by the general formula (1) and the surface hydroxyl group (M-OH) of the composite metal oxide fine particle undergo a condensation reaction, thereby sharing via an oxygen atom. A bond (M-O-Si) is generated.
The presence or absence of a covalent bond (MO—Si) via an oxygen atom can be confirmed by detecting an absorption peak derived from the covalent bond with a transmission type or diffuse reflection type infrared spectroscopic device.
＜均一分散液＞
本実施形態の別の態様は、上記表面修飾複合金属酸化物微粒子、及び有機溶媒を含む均一分散液を提供する。上記有機溶媒は、複合金属酸化物微粒子を均一に分散できるものであることが好ましく、さらに、樹脂、分散剤、保存安定剤等を添加する場合には、それらの添加剤に対して高い溶解性を有することが好ましい。
<Uniform dispersion>
Another aspect of the present embodiment provides a uniform dispersion containing the surface-modified composite metal oxide fine particles and an organic solvent. The organic solvent is preferably one that can uniformly disperse the composite metal oxide fine particles. Further, when a resin, a dispersant, a storage stabilizer or the like is added, the organic solvent has high solubility in those additives. It is preferable to have.
上記有機溶媒としては、例えば、アルコール、ケトン、エステル、エーテル、及び炭化水素溶媒から選ばれる１種類以上の溶媒が挙げられる。
上記のアルコール、ケトン、エステル、エーテル、及び炭化水素溶媒としては、例えば、ブタノール、ペンタノール、ヘキサノール、オクタノール、メトキシエタノール、エトキシエタノール、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル等のアルコール；メチルエチルケトン、メチルイソブチルケトン、イソアミルケトン、エチルヘキシルケトン、シクロペンタノン、シクロヘキサノン、γ―ブチロラクトン等のケトン；酢酸ブチル、酢酸ペンチル、酢酸ヘキシル、プロピルプロピオネート、ブチルプロピオネート、ペンチルプロピオネート、ヘキシルプロピオネート、プロピレングリコールモノメチルエーテルアセテート、乳酸エチル等のエステル；ブチルエチルエーテル、ブチルプロピルエーテル、ジブチルエーテル、アニソール、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、プロピレングリコールジメチルエーテル、プロピレングリコールジエチルエーテル、テトラヒドロフラン等のエーテル；ヘキサン、ヘプタン、オクタン、デカン、シクロヘキサン、トルエン、キシレン等の炭化水素溶媒等が挙げられる。これらの溶媒は、単独で使用しても、複数の溶媒を組み合わせて使用してもよい。
Examples of the organic solvent include one or more solvents selected from alcohols, ketones, esters, ethers, and hydrocarbon solvents.
Examples of the alcohol, ketone, ester, ether, and hydrocarbon solvent include alcohols such as butanol, pentanol, hexanol, octanol, methoxyethanol, ethoxyethanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether; methyl ethyl ketone, Ketones such as methyl isobutyl ketone, isoamyl ketone, ethyl hexyl ketone, cyclopentanone, cyclohexanone, γ-butyrolactone; butyl acetate, pentyl acetate, hexyl acetate, propyl propionate, butyl propionate, pentyl propionate, hexyl propionate Esters, propylene glycol monomethyl ether acetate, ethyl lactate, etc .; butyl ethyl ether, butyl propyl ether Ethers such as toluene, dibutyl ether, anisole, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, and tetrahydrofuran; hydrocarbon solvents such as hexane, heptane, octane, decane, cyclohexane, toluene, xylene, etc. Can be mentioned. These solvents may be used alone or in combination of a plurality of solvents.
＜硬化物＞
本実施形態の別の態様は、上述の表面修飾された複合金属酸化物微粒子を、溶媒を用いずに成型して得られる成形体を硬化させる工程、又は上記均一分散液を基板上に塗布して得られる薄膜を硬化させる工程を含む、硬化物の製造方法を提供する。
<Hardened product>
Another aspect of the present embodiment is a step of curing a molded body obtained by molding the surface-modified composite metal oxide fine particles without using a solvent, or applying the uniform dispersion on a substrate. The manufacturing method of hardened | cured material including the process of hardening the thin film obtained by this is provided.
上記成形体は、表面処理された複合金属酸化物を、金属、樹脂、又はガラス等の金型、シート、スタンプ等を用いて成形することにより得られる。また、上記薄膜は、上記均一分散液を基板上に塗布することにより得られる。上記成形体及び薄膜の表面には、凹状、凸状、微細レンズ形状、微細周期構造などのパターン形状を付与することもできる。 The said molded object is obtained by shape | molding the composite metal oxide by which surface treatment was carried out using metal, resin, or metal mold | dies, sheets, stamps, etc .. The thin film can be obtained by applying the uniform dispersion on a substrate. A pattern shape such as a concave shape, a convex shape, a fine lens shape, and a fine periodic structure can be imparted to the surface of the molded body and the thin film.
上記表面修飾された複合金属酸化物微粒子の成型体又は上記薄膜を、熱又は光等を用いて硬化処理することにより、光学材料として好ましい透明の硬化物が得られる。 By curing the surface-modified composite metal oxide fine particles or the thin film using heat or light, a transparent cured product preferable as an optical material can be obtained.
熱による硬化処理を行う場合の硬化温度は、３０℃〜３００℃であることが好ましく、より好ましくは、７０℃〜２００℃である。また、硬化時間は１０分〜１２時間であることが好ましく、より好ましくは１０分〜３時間である。熱による硬化処理は、大気下で行っても、窒素、ヘリウム、アルゴン等の不活性ガス雰囲気下で行ってもよい。 The curing temperature in the case of performing the curing process with heat is preferably 30 ° C to 300 ° C, and more preferably 70 ° C to 200 ° C. The curing time is preferably 10 minutes to 12 hours, more preferably 10 minutes to 3 hours. The curing treatment by heat may be performed in the air or in an inert gas atmosphere such as nitrogen, helium, argon or the like.
光による硬化処理を行う場合には、例えば、可視光線、紫外線、遠紫外線等を使用できる。光源としては、例えば、低圧若しくは高圧の水銀ランプ、重水素ランプ、又はアルゴン、クリプトン、キセノン等の希ガスの放電光、ＹＡＧレーザー、アルゴンレーザー、炭酸ガスレーザー、又はＸｅＦ、ＸｅＣｌ、ＸｅＢｒ、ＫｒＦ、ＫｒＣｌ、ＡｒＦ若しくはＡｒＣｌ等のエキシマレーザー等を使用することができる。これらの光源の出力は、１０〜５，０００Ｗであることが好ましい。 In the case of performing a curing treatment with light, for example, visible light, ultraviolet light, far ultraviolet light, or the like can be used. Examples of the light source include a low-pressure or high-pressure mercury lamp, deuterium lamp, or discharge light of a rare gas such as argon, krypton, or xenon, YAG laser, argon laser, carbon dioxide laser, or XeF, XeCl, XeBr, KrF, An excimer laser such as KrCl, ArF or ArCl can be used. The output of these light sources is preferably 10 to 5,000 W.
本実施形態の更に別の態様は、上記製造方法により得られる硬化物を提供する。上記硬化物は、発光素子における封止剤、及びレンズ等の光学材料として好適に利用できる。 Yet another aspect of the present embodiment provides a cured product obtained by the above production method. The said hardened | cured material can be utilized suitably as optical materials, such as a sealing agent in a light emitting element, and a lens.
以下、実施例及び比較例により本実施形態をより詳細に説明するが、本実施形態はこれらに限定されるものではない。
なお、各製造例、実施例、比較例中の物性は以下の方法により測定した。
Hereinafter, although an embodiment and a comparative example explain this embodiment in detail, this embodiment is not limited to these.
In addition, the physical property in each manufacture example, an Example, and a comparative example was measured with the following method.
（１）結晶構造の確認方法
複合金属酸化物微粒子の粉末、又は分散液を乾燥させたサンプルを、日本ブルカー株式会社製Ｘ線回折（ＸＲＤ）装置、Ｄ８ ＡＤＶＡＮＣＥを用いて測定し、文献記載の回折パターンと比較することにより結晶構造の確認を行った。
(1) Confirmation method of crystal structure A sample obtained by drying a powder of composite metal oxide fine particles or a dispersion liquid was measured using an X-ray diffraction (XRD) apparatus, D8 ADVANCE manufactured by Nippon Bruker Co., Ltd. The crystal structure was confirmed by comparing with the diffraction pattern.
（２）平均一次粒子径の算出方法
複合金属酸化物微粒子の分散液を微細試料捕集用の膜（コロジオン膜）に滴下して乾燥させた後、株式会社日立ハイテクノロジーズ製透過型電子顕微鏡（ＦＥ−ＴＥＭ）、ＨＦ−２０００を用いて加速電圧２００ｋＶで一次粒子径の測定を行い、５０個の粒子の数平均から平均一次粒子径を算出した。
(2) Calculation method of average primary particle diameter A dispersion liquid of composite metal oxide fine particles is dropped on a membrane for collecting a fine sample (collodion membrane) and dried, and then a transmission electron microscope manufactured by Hitachi High-Technologies Corporation ( FE-TEM) and HF-2000 were used to measure the primary particle size at an acceleration voltage of 200 kV, and the average primary particle size was calculated from the number average of 50 particles.
（３）ガスクロマトグラフィー（ＧＣ）による反応の追跡
反応混合液をガスクロマトグラフィー（ＧＣ）で測定し、原料に由来するピークの信号強度を記録した。反応混合液中に含まれる原料の量は、別途作成した検量線を用いて算出した。
［ＧＣ測定条件］
・ＧＣ装置：ＧＣ−１４Ｂ（島津製作所製）
・カラム：ＤＢ−１（３０ｍ×２５０μｍ×０．２５μｍＦ）（アジレントテクノロジー製）
・カラム温度：５０℃で５分間ホールドした後、３００℃まで毎分１０℃ずつ昇温
・キャリアガス：Ｈｅ（流量１．０ｍＬ／ｍｉｎ）
(3) Tracking reaction by gas chromatography (GC) The reaction mixture was measured by gas chromatography (GC), and the signal intensity of the peak derived from the raw material was recorded. The amount of raw material contained in the reaction mixture was calculated using a separately prepared calibration curve.
[GC measurement conditions]
-GC device: GC-14B (manufactured by Shimadzu Corporation)
Column: DB-1 (30 m × 250 μm × 0.25 μmF) (manufactured by Agilent Technologies)
Column temperature: Hold for 5 minutes at 50 ° C., then increase to 300 ° C. by 10 ° C. per minute. Carrier gas: He (flow rate: 1.0 mL / min)
（４）プロトン核磁気共鳴（１Ｈ−ＮＭＲ）スペクトルの測定
ケイ素化合物の濃度が５質量％になるように重水素化クロロホルムに溶解させ、得られた溶液のプロトン核磁気共鳴（１Ｈ−ＮＭＲ）スペクトルを、日本ブルカー株式会社製ＦＴ−ＮＭＲ装置、ＡＶＡＮＣＥ４００を用いて１６回積算することにより測定した。
(4) Measurement of proton nuclear magnetic resonance (1H-NMR) spectrum The proton nuclear magnetic resonance (1H-NMR) spectrum of the resulting solution was dissolved in deuterated chloroform so that the concentration of the silicon compound was 5% by mass. Was measured by integrating 16 times using an FT-NMR apparatus, AVANCE400 manufactured by Nippon Bruker Co., Ltd.
（５）重量平均分子量（Ｍｗ）の測定
シリコーン樹脂のイソプロピルアルコール溶液、又はプロピレングリコールメチルエーテルアセテート溶液を、シリコーン樹脂成分の濃度が１質量％になるようにテトラヒドロフランで希釈して、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定した。重量平均分子量（Ｍｗ）は、標準物質であるポリスチレン換算の値として求めた。
［ＧＰＣ測定条件］
・カラム：ＴＳＫｇｅｌ Ｇ１０００Ｈ−ＨＲ、Ｇ３０００Ｈ−ＨＲ、及びＧ５０００Ｈ−ＨＲ（いずれも東ソー製） ３本直列
・溶離液：テトラヒドロフラン（流量：１ｍＬ／ｍｉｎ）
・カラム使用温度：４０℃
(5) Measurement of weight average molecular weight (Mw) Gel permeation chromatography is obtained by diluting an isopropyl alcohol solution of a silicone resin or a propylene glycol methyl ether acetate solution with tetrahydrofuran so that the concentration of the silicone resin component becomes 1% by mass. Measured by graphic (GPC). The weight average molecular weight (Mw) was determined as a value in terms of polystyrene as a standard substance.
[GPC measurement conditions]
-Column: TSKgel G1000H-HR, G3000H-HR, and G5000H-HR (all manufactured by Tosoh Corporation) in series-Eluent: Tetrahydrofuran (flow rate: 1 mL / min)
Column operating temperature: 40 ° C
（６）表面修飾率の算出方法
表面修飾された複合金属酸化物微粒子の粉末１．０ｇと結晶セルロース（商品名：アビセル、フナコシ製）２．０ｇを混合し、自動メノウ乳鉢で３０分撹拌した。得られた粉末を２５ｍｍφの塩化ビニル製リングに充填して錠剤成形機でサンプルを作製し、リガク製走査型蛍光Ｘ線分析装置、ＺＳＸ ＰｒｉｍｕｓＩＩを用いてＦＰオーダー分析を行うことにより、バリウム原子に対するケイ素原子のモル比を測定し、複合金属酸化物微粒子の表面に存在するケイ素化合物の量を算出した。
上記平均一次粒子径から複合金属酸化物微粒子の表面積を算出し、ケイ素化合物１分子当たりの占有面積を１．３×１０−１９ｍ２とした場合に、該複合金属酸化物微粒子の表面全体が被覆される状態を表面修飾率１００％、該ケイ素化合物が全く存在しない状態を表面修飾率０％とした。
(6) Method for calculating surface modification rate 1.0 g of powder of composite metal oxide fine particles with surface modification and 2.0 g of crystalline cellulose (trade name: Avicel, manufactured by Funakoshi) were mixed and stirred in an automatic agate mortar for 30 minutes. . The obtained powder is filled into a 25 mmφ vinyl chloride ring, a sample is prepared with a tablet molding machine, and FP order analysis is performed using a Rigaku scanning X-ray fluorescence analyzer, ZSX Primus II. The molar ratio of silicon atoms was measured, and the amount of silicon compound present on the surface of the composite metal oxide fine particles was calculated.
When the surface area of the composite metal oxide fine particles is calculated from the average primary particle diameter and the occupied area per molecule of the silicon compound is 1.3 × 10 −19 m 2 , the entire surface of the composite metal oxide fine particles is The coated state was defined as a surface modification rate of 100%, and the state in which no silicon compound was present was defined as a surface modification rate of 0%.
（７）有機溶媒及びシリコーン樹脂への分散性評価
２０ｍＬサンプル管に、表面修飾された複合金属酸化物微粒子０．５ｇ、及びトルエン４．５ｇを入れ、超音波処理を行った。有機溶媒への分散性については、トルエン中に溶解して透明な均一分散液となったものを○、分散して沈降しないが濁りのあるものを△、溶解しなかったものを×とした。
また、３００ｍＬフラスコに、表面修飾された複合金属酸化物微粒子０．５ｇ、下記製造例１０で得られたシリコーン樹脂４．５ｇ、及びトルエン１００ｇを加えて撹拌し、均一分散液とした。７０℃に設定したウォーターバスで加熱しながら、エバポレータにより溶媒を留去し、複合金属酸化物微粒子の分散したシリコーン樹脂を調製した。複合金属酸化物微粒子がシリコーン樹脂中に均一分散しており、透明性が維持されているものを○、透明性は維持されているが濁りのあるものを△、相分離等により白濁して透明性を失っているものを×とした。
(7) Evaluation of dispersibility in organic solvent and silicone resin In a 20 mL sample tube, 0.5 g of surface-modified composite metal oxide fine particles and 4.5 g of toluene were placed and subjected to ultrasonic treatment. Regarding the dispersibility in an organic solvent, ○ was obtained when it was dissolved in toluene to form a transparent uniform dispersion, Δ if it was not dispersed and settled but was cloudy, and × was not dissolved.
Further, 0.5 g of surface-modified composite metal oxide fine particles, 4.5 g of the silicone resin obtained in Production Example 10 below, and 100 g of toluene were added to a 300 mL flask and stirred to obtain a uniform dispersion. While heating in a water bath set at 70 ° C., the solvent was distilled off by an evaporator to prepare a silicone resin in which composite metal oxide fine particles were dispersed. The composite metal oxide fine particles are uniformly dispersed in the silicone resin, and the transparency is maintained as ◯, the transparency is maintained but turbid as △, and the white turbidity due to phase separation is transparent. The thing which lost the property was set as x.
＜チタン酸バリウム微粒子の製造方法＞
［製造例１］
還流管、滴下ロート、及び攪拌機を備えた１Ｌセパラブルフラスコを窒素雰囲気に置換した後、２−メトキシエタノール（ＭＥ）１２０．３ｇ、金属バリウム２．７５ｇ、テトラエトキシチタン４．１９ｍＬを入れ、撹拌しながら１２０℃で２時間加熱した。ＭＥ１０２．９ｇ及びイオン交換水１８．０ｇの混合物を滴下しながら加え、１２０℃で３時間加熱撹拌を継続することにより、チタン酸バリウムの分散液（ＢＴ−１）を得た。ＸＲＤ測定において、チタン酸バリウムの回折パターンと一致することを確認した。また、ＴＥＭ測定において、ＢＴ−１の平均一次粒子径は約７ｎｍであった。
<Method for producing fine barium titanate particles>
[Production Example 1]
A 1 L separable flask equipped with a reflux tube, a dropping funnel and a stirrer was replaced with a nitrogen atmosphere, and then 120.3 g of 2-methoxyethanol (ME), 2.75 g of metal barium, and 4.19 mL of tetraethoxytitanium were added and stirred. The mixture was heated at 120 ° C. for 2 hours. A mixture of ME 102.9 g and ion-exchanged water 18.0 g was added dropwise, and heating and stirring were continued at 120 ° C. for 3 hours to obtain a barium titanate dispersion (BT-1). In the XRD measurement, it was confirmed that it coincided with the diffraction pattern of barium titanate. Moreover, in the TEM measurement, the average primary particle diameter of BT-1 was about 7 nm.
［製造例２］
イオン交換水３６．０ｇを用いる以外は上記製造例１と同様にして、チタン酸バリウム微粒子の分散液（ＢＴ−２）を得た。ＸＲＤ測定において、チタン酸バリウムの回折パターンと一致することを確認した。また、ＴＥＭ測定において、ＢＴ−２の平均一次粒子径は約１４ｎｍであった。
[Production Example 2]
A barium titanate fine particle dispersion (BT-2) was obtained in the same manner as in Production Example 1 except that 36.0 g of ion-exchanged water was used. In the XRD measurement, it was confirmed that it coincided with the diffraction pattern of barium titanate. Moreover, in the TEM measurement, the average primary particle diameter of BT-2 was about 14 nm.
［製造例３］
還流管、滴下ロート、及び攪拌機を備えた２Ｌセパラブルフラスコを窒素雰囲気に置換した後、エタノール８５５ｍＬ、金属バリウム２４．７ｇ、テトラエトキシチタン３７．７ｍＬを入れ、撹拌しながら７０℃で２時間加熱した。エタノール５７６ｍＬとイオン交換水３２４ｍＬの混合物を滴下しながら加え、７０℃で３時間加熱を継続することにより、チタン酸バリウム微粒子のエタノール懸濁液を得た。
上記懸濁液を遠心分離器を用いて８，０００ｒｐｍで３０分処理することによりエタノール及び水を除去し、固形分を分離した。この固形分をエタノールで洗浄した後、７０℃の真空乾燥機で８時間減圧乾燥させることにより、チタン酸バリウム微粒子の粉末（ＢＴ−３）を得た。ＸＲＤ測定において、チタン酸バリウムの回折パターンと一致することを確認した。また、ＴＥＭ測定において、ＢＴ−３の平均一次粒子径は約７ｎｍであった。
[Production Example 3]
A 2 L separable flask equipped with a reflux tube, a dropping funnel and a stirrer was replaced with a nitrogen atmosphere, and then 855 mL of ethanol, 24.7 g of barium metal and 37.7 mL of tetraethoxytitanium were added and heated at 70 ° C. for 2 hours with stirring. did. A mixture of 576 mL of ethanol and 324 mL of ion exchange water was added dropwise, and heating was continued at 70 ° C. for 3 hours to obtain an ethanol suspension of barium titanate fine particles.
The suspension was treated at 8,000 rpm for 30 minutes using a centrifuge to remove ethanol and water and separate the solids. This solid content was washed with ethanol and then dried under reduced pressure for 8 hours with a 70 ° C. vacuum dryer to obtain barium titanate fine particle powder (BT-3). In the XRD measurement, it was confirmed that it coincided with the diffraction pattern of barium titanate. Moreover, in the TEM measurement, the average primary particle diameter of BT-3 was about 7 nm.
＜ケイ素化合物の製造方法＞
［製造例４］
還流管、及び攪拌機を備えた２Ｌセパラブルフラスコを窒素雰囲気に置換した後、脱水トルエン８００ｇ、１，１，１，３，５，５，５−ヘプタメチルトリシロキサン１２８．６ｇ、トリメトキシビニルシラン７１．４ｇ、及び白金のテトラメチルジビニルジシロキサン錯体（Ｋａｒｓｔｅｄｔ触媒）の２質量％キシレン溶液１１０μＬを入れ、ガスクロマトグラフィーにおいて、原料のトリメトキシビニルシランのピークが消失するまで６０℃で８時間加熱撹拌した。エバポレータでトルエンを減圧留去した後、減圧蒸留により目的とする１，１，１，３，５，５，５−ヘプタメチル−２−（２−トリメトキシシリルエチル）トリシロキサン（Ｓ−１）を得た。Ｓ−１の沸点は、０．５７ｋＰａにおいて１０３℃であった。Ｓ−１の１Ｈ−ＮＭＲチャートを図１に示す。
<Method for producing silicon compound>
[Production Example 4]
After replacing a 2 L separable flask equipped with a reflux tube and a stirrer with a nitrogen atmosphere, 800 g of dehydrated toluene, 128.6 g of 1,1,1,3,5,5,5-heptamethyltrisiloxane, trimethoxyvinylsilane 71 .4 g and 110 μL of a 2% by mass xylene solution of platinum tetramethyldivinyldisiloxane complex (Karstedt catalyst) were added, and the mixture was heated and stirred at 60 ° C. for 8 hours until the peak of the starting material trimethoxyvinylsilane disappeared in gas chromatography. . After evaporating toluene under reduced pressure with an evaporator, the desired 1,1,1,3,5,5,5-heptamethyl-2- (2-trimethoxysilylethyl) trisiloxane (S-1) was obtained by distillation under reduced pressure. Obtained. The boiling point of S-1 was 103 ° C. at 0.57 kPa. A 1H-NMR chart of S-1 is shown in FIG.
［製造例５］
原料として、トリメチルビニルシラン及びトリエトキシシランを用いる以外は上記製造例４と同様にして、目的とする（２−トリメチルシリルエチル）トリエトキシシラン（Ｓ−２）を得た。
[Production Example 5]
The target (2-trimethylsilylethyl) triethoxysilane (S-2) was obtained in the same manner as in Production Example 4 except that trimethylvinylsilane and triethoxysilane were used as raw materials.
［製造例６］
１，１，１，３，５，５，５−ヘプタメチルトリシロキサンの代わりにペンタメチルジシロキサンを用いる以外は上記製造例４と同様にして、目的とするペンタメチル（２−トリメトキシシリルエチル）ジシロキサン（Ｓ−３）を得た。
[Production Example 6]
The target pentamethyl (2-trimethoxysilylethyl) is prepared in the same manner as in Production Example 4 except that pentamethyldisiloxane is used instead of 1,1,1,3,5,5,5-heptamethyltrisiloxane. Disiloxane (S-3) was obtained.
［製造例７］
１，１，１，３，５，５，５−ヘプタメチルトリシロキサンの代わりにトリス（トリメチルシロキシ）シランを用いる以外は上記製造例４と同様にして、目的とするトリス（トリメチルシロキシ）（２−トリメトキシシリルエチル）シラン（Ｓ−４）を得た。
[Production Example 7]
The target tris (trimethylsiloxy) (2) was prepared in the same manner as in Production Example 4 except that tris (trimethylsiloxy) silane was used instead of 1,1,1,3,5,5,5-heptamethyltrisiloxane. -Trimethoxysilylethyl) silane (S-4) was obtained.
［製造例８］
トリメトキシビニルシランの代わりにメチルジメトキシビニルシランを用いる以外は上記製造例４と同様にして、目的とする，１，１，３，５，５，５−ヘプタメチル−２−（２−メチルジメトキシシリルエチル）トリシロキサン（Ｓ−５）を得た。
[Production Example 8]
The desired 1,1,3,5,5,5-heptamethyl-2- (2-methyldimethoxysilylethyl) is prepared in the same manner as in Production Example 4 except that methyldimethoxyvinylsilane is used instead of trimethoxyvinylsilane. Trisiloxane (S-5) was obtained.
［製造例９］
還流管、滴下ロート、及び攪拌機を備えた１Ｌフラスコを窒素雰囲気に置換した後、氷水で冷却しながら水素化リチウムアルミニウム３．８ｇ、及び超脱水ジエチルエーテル２００ｍＬを入れた。この溶液に、上記製造例４で合成したケイ素化合物（Ｓ−１）２６．４ｇ及び超脱水ジエチルエーテル５０ｍＬの混合物を、フラスコの内温が１５℃を超えないように滴下した後、室温で１時間撹拌した。ガスクロマトグラフィーにおいて、原料であるＳ−１のピークが消失したことを確認した後、再度氷水で冷却し、酢酸エチル１７．６ｇをフラスコの内温が１５℃を超えないように滴下した後、室温で８時間撹拌した。この反応液をセライト５４５を用いて減圧濾過した後、ジエチルエーテル及び過剰の酢酸エチルをエバポレータで減圧留去した。減圧蒸留により、目的とする１，１，１，３，５，５，５−ヘプタメチル−２−（２−トリヒドロシリルエチル）トリシロキサン（Ｓ−６）を得た。Ｓ−６の沸点は、０．５ｋＰａにおいて５８℃であった。Ｓ−６の１Ｈ−ＮＭＲチャートを図２に示す。
[Production Example 9]
A 1 L flask equipped with a reflux tube, a dropping funnel and a stirrer was replaced with a nitrogen atmosphere, and then 3.8 g of lithium aluminum hydride and 200 mL of ultra-dehydrated diethyl ether were added while cooling with ice water. To this solution, a mixture of 26.4 g of the silicon compound (S-1) synthesized in Production Example 4 above and 50 mL of ultra-dehydrated diethyl ether was added dropwise so that the internal temperature of the flask did not exceed 15 ° C. Stir for hours. In gas chromatography, after confirming that the peak of S-1 as a raw material had disappeared, it was cooled again with ice water, and 17.6 g of ethyl acetate was added dropwise so that the internal temperature of the flask did not exceed 15 ° C. Stir at room temperature for 8 hours. The reaction solution was filtered under reduced pressure using Celite 545, and then diethyl ether and excess ethyl acetate were distilled off under reduced pressure using an evaporator. The desired 1,1,1,3,5,5,5-heptamethyl-2- (2-trihydrosilylethyl) trisiloxane (S-6) was obtained by distillation under reduced pressure. The boiling point of S-6 was 58 ° C. at 0.5 kPa. A 1H-NMR chart of S-6 is shown in FIG.
＜シリコーン樹脂の製造方法＞
［製造例１０］
還流管、滴下ロート、及び攪拌機を備えた１Ｌセパラブルフラスコに、メチルトリメトキシシラン１４９．９ｇ、エトキシトリメチルシラン３２．５ｇ、及びイソプロピルアルコール（ＩＰＡ）１２０ｇを入れて撹拌し、さらに１Ｍ塩酸５８ｍｇとイオン交換水１２８．７ｇとの混合物を滴下しながら加え、８０℃に設定したオイルバスで２時間加熱して反応混合物を得た。
上記反応混合物を１Ｌフラスコに移し、プロピレングリコールメチルエーテルアセテート（ＰＧＭＥＡ）を３６０ｇ加え、エバポレータでＩＰＡ及び水を留去した。さらに、シリコーン樹脂成分が３３．３質量％になるまで濃縮し、シリコーン樹脂のＰＧＭＥＡ溶液を得た。得られたシリコーン樹脂の重量平均分子量（Ｍｗ）は９５７であった。
別に準備した還流管、滴下ロート、及び攪拌機を備えた１Ｌセパラブルフラスコに、上記シリコーン樹脂のＰＧＭＥＡ溶液２８８ｇ、ピリジン９０．１ｇ、及びＰＧＭＥＡ１００ｇを入れて撹拌し、さらにビニルジメチルクロロシラン６８．８ｇ及びトリメチルクロロシラン６２．０ｇの混合物を滴下しながら加え、室温で１時間撹拌した。
シクロヘキサン１００ｇ、及びイオン交換水１００ｇを加えたのち、分液操作により水層を除去し、得られた有機層をイオン交換水１００ｇで２度洗浄した。エバポレータで有機溶媒を留去し、目的とするシリコーン樹脂１４６ｇを得た。得られたシリコーン樹脂の重量平均分子量（Ｍｗ）は２，０９２であった。
<Manufacturing method of silicone resin>
[Production Example 10]
In a 1 L separable flask equipped with a reflux tube, a dropping funnel, and a stirrer, 149.9 g of methyltrimethoxysilane, 32.5 g of ethoxytrimethylsilane, and 120 g of isopropyl alcohol (IPA) were added and stirred. A mixture with 128.7 g of ion-exchanged water was added dropwise and heated in an oil bath set at 80 ° C. for 2 hours to obtain a reaction mixture.
The reaction mixture was transferred to a 1 L flask, 360 g of propylene glycol methyl ether acetate (PGMEA) was added, and IPA and water were distilled off with an evaporator. Furthermore, it concentrated until the silicone resin component became 33.3 mass%, and the PGMEA solution of silicone resin was obtained. The weight average molecular weight (Mw) of the obtained silicone resin was 957.
Into a 1 L separable flask equipped with a reflux tube, a dropping funnel, and a stirrer prepared separately, 288 g of the above PGMEA solution of silicone resin, 90.1 g of pyridine, and 100 g of PGMEA were stirred, and further 68.8 g of vinyldimethylchlorosilane and trimethyl were added. A mixture of 62.0 g of chlorosilane was added dropwise and stirred at room temperature for 1 hour.
After adding 100 g of cyclohexane and 100 g of ion-exchanged water, the aqueous layer was removed by a liquid separation operation, and the obtained organic layer was washed twice with 100 g of ion-exchanged water. The organic solvent was distilled off with an evaporator to obtain 146 g of the desired silicone resin. The weight average molecular weight (Mw) of the obtained silicone resin was 2,092.
＜表面修飾反応＞
［実施例１］
上記製造例１で得られたチタン酸バリウム微粒子の分散液（ＢＴ−１）に、ケイ素化合物（Ｓ−１）３．３１ｇを加え、７０℃で１時間加熱することにより、白色の懸濁液が得られた。遠心分離機を用いて７，０００ｒｐｍで３０分処理することにより溶媒を除去し、得られた固形成分をアセトン及びエタノールで洗浄した後、４０℃で真空乾燥することにより目的とする表面修飾されたチタン酸バリウム微粒子（Ｐ−１）を得た。Ｐ−１の表面修飾率は２９％であった。
<Surface modification reaction>
[Example 1]
A white suspension is obtained by adding 3.31 g of the silicon compound (S-1) to the dispersion (BT-1) of the barium titanate fine particles obtained in Production Example 1 and heating at 70 ° C. for 1 hour. was gotten. The solvent was removed by treating at 7,000 rpm for 30 minutes using a centrifuge, and the resulting solid component was washed with acetone and ethanol, and then vacuum-dried at 40 ° C. to achieve the desired surface modification. Barium titanate fine particles (P-1) were obtained. The surface modification rate of P-1 was 29%.
［実施例２］
Ｓ−１の代わりにＳ−２を用いる以外は上記実施例１と同様にして、目的とする表面修飾されたチタン酸バリウム微粒子（Ｐ−２）を得た。
[Example 2]
The target surface-modified barium titanate fine particles (P-2) were obtained in the same manner as in Example 1 except that S-2 was used instead of S-1.
［実施例３］
Ｓ−１の代わりにＳ−３を用いる以外は上記実施例１と同様にして、目的とする表面修飾されたチタン酸バリウム微粒子（Ｐ−３）を得た。
[Example 3]
The target surface-modified barium titanate fine particles (P-3) were obtained in the same manner as in Example 1 except that S-3 was used instead of S-1.
［実施例４］
Ｓ−１の代わりにＳ−４を用いる以外は上記実施例１と同様にして、目的とする表面修飾されたチタン酸バリウム微粒子（Ｐ−４）を得た。
[Example 4]
The target surface-modified barium titanate fine particles (P-4) were obtained in the same manner as in Example 1 except that S-4 was used instead of S-1.
［実施例５］
Ｓ−１の代わりにＳ−５を用いる以外は上記実施例１と同様にして、目的とする表面修飾されたチタン酸バリウム微粒子（Ｐ−５）を得た。
[Example 5]
The target surface-modified barium titanate fine particles (P-5) were obtained in the same manner as in Example 1 except that S-5 was used instead of S-1.
［実施例６］
Ｓ−１の代わりにＳ−６を用いる以外は上記実施例１と同様にして、目的とする表面修飾されたチタン酸バリウム微粒子（Ｐ−６）を得た。
[Example 6]
The target surface-modified barium titanate fine particles (P-6) were obtained in the same manner as in Example 1 except that S-6 was used instead of S-1.
［実施例７］
ＢＴ−１の代わりにＢＴ−２を用いた以外は上記実施例１と同様にして、目的とする表面修飾されたチタン酸バリウム微粒子（Ｐ−７）を得た。
[Example 7]
The target surface-modified barium titanate fine particles (P-7) were obtained in the same manner as in Example 1 except that BT-2 was used instead of BT-1.
［実施例８］
還流管及び攪拌機を備えた１Ｌセパラブルフラスコに上記製造例３で得られたチタン酸バリウム微粒子の粉末（ＢＴ−３）１０ｇ、トルエン３２３ｇ、及びケイ素化合物（Ｓ−６）８．０２ｇを入れ、４０℃に設定したオイルバス中で１時間加熱撹拌した。
この反応液をビーズミル（ＵＡＭ−０１５、寿工業株式会社製）のタンクに入れ、トルエン１００ｇを追加した。粒子径１５μｍのジルコニアビーズ（ＤＺＢ、型番φ１５、大研化学工業株式会社製）３５０ｇを用いて、ローター回転数１２ｍ／秒、流速７０ｍＬ／分の条件で分散処理することにより、目的とする表面修飾されたチタン酸バリウム微粒子のトルエン分散液（Ｐ−８）を得た。Ｐ−８の表面修飾率は９０％であった。
[Example 8]
A 1 L separable flask equipped with a reflux tube and a stirrer was charged with 10 g of the barium titanate fine particle powder (BT-3) obtained in Production Example 3 above, 323 g of toluene, and 8.02 g of a silicon compound (S-6). The mixture was heated and stirred for 1 hour in an oil bath set to 40 ° C.
This reaction liquid was put into a tank of a bead mill (UAM-015, manufactured by Kotobuki Industries Co., Ltd.), and 100 g of toluene was added. By subjecting 350 g of zirconia beads having a particle size of 15 μm (DZB, model number φ15, manufactured by Daiken Chemical Industry Co., Ltd.) to dispersion treatment under conditions of a rotor rotation speed of 12 m / sec and a flow rate of 70 mL / min, the desired surface modification A toluene dispersion (P-8) of the barium titanate fine particles thus obtained was obtained. The surface modification rate of P-8 was 90%.
［比較例１］
上記製造例３で得られたチタン酸バリウム微粒子の粉末（ＢＴ−３）を表面修飾することなく、そのままＰ−９とした。
[Comparative Example 1]
The barium titanate fine particle powder (BT-3) obtained in Production Example 3 was directly used as P-9 without surface modification.
［比較例２］
Ｓ−１の代わりにデシルトリメトキシシランを用いる以外は上記実施例１と同様にして、目的とする表面修飾されたチタン酸バリウム微粒子（Ｐ−１０）を得た。
[Comparative Example 2]
The target surface-modified barium titanate fine particles (P-10) were obtained in the same manner as in Example 1 except that decyltrimethoxysilane was used instead of S-1.
［比較例３］
Ｓ−１の代わりにビニルトリメトキシシランを用いる以外は上記実施例１と同様にして、目的とする表面修飾されたチタン酸バリウム微粒子（Ｐ−１１）を得た。
[Comparative Example 3]
The target surface-modified barium titanate fine particles (P-11) were obtained in the same manner as in Example 1 except that vinyltrimethoxysilane was used instead of S-1.
［比較例４］
Ｓ−１の代わりに（３−メチルメタクリル）プロピルトリメトキシシランを用いる以外は上記実施例１と同様にして、目的とする表面修飾されたチタン酸バリウム微粒子（Ｐ−１２）を得た。
[Comparative Example 4]
The target surface-modified barium titanate fine particles (P-12) were obtained in the same manner as in Example 1 except that (3-methylmethacryl) propyltrimethoxysilane was used instead of S-1.
［比較例５］
Ｓ−１の代わりにメチルトリメトキシシランを用いる以外は上記実施例１と同様にして実施したが、不溶性のゲル状生成物が得られた。
[Comparative Example 5]
An insoluble gel-like product was obtained in the same manner as in Example 1 except that methyltrimethoxysilane was used instead of S-1.
［比較例６］
Ｓ−１の代わりに１，１，１−トリメチル−３，３，３−トリメトキシジシロキサン（表１では「トリメチルシロキシトリメトキシシラン」と略記する）を用いる以外は上記実施例１と同様にして実施したが、不溶性のゲル状生成物が得られた。
[Comparative Example 6]
Example 1 was used except that 1,1,1-trimethyl-3,3,3-trimethoxydisiloxane (abbreviated as “trimethylsiloxytrimethoxysilane” in Table 1) was used instead of S-1. An insoluble gel product was obtained.
＜有機溶媒及びシリコーン樹脂への分散性評価＞
上記実施例１〜８及び比較例１〜６で得られた複合金属酸化物微粒子Ｐ−１〜１４について、有機溶媒及びシリコーン樹脂への分散性評価を行った結果を表１に示す。
<Evaluation of dispersibility in organic solvent and silicone resin>
Table 1 shows the results of evaluation of dispersibility in organic solvents and silicone resins for the composite metal oxide fine particles P-1 to P-14 obtained in Examples 1 to 8 and Comparative Examples 1 to 6.
本発明の複合金属酸化物微粒子は、レンズ、封止材、及びコーティング剤等の光学材料として利用可能な、高透明かつ高屈折率な有機無機複合樹脂の原料として好適に使用できる。 The composite metal oxide fine particles of the present invention can be suitably used as a raw material for a highly transparent and high refractive index organic-inorganic composite resin that can be used as an optical material such as a lens, a sealing material, and a coating agent.
Claims (7)
Ｒ1Ｒ２Ｒ３Ｓｉ−Ａ−ＳｉＲ４ ｎＸ（３−ｎ） （１）
｛式中、Ｒ1〜Ｒ３は、各々独立に、炭素数１〜１８の炭化水素基、又は置換されていてもよいシロキシ基であり、Ｒ４は、炭素数１〜４の炭化水素基であり、Ａは、炭素数２〜６の二価の炭化水素基であり、Ｘは、水素原子、ハロゲン原子、炭素数１〜６のアルコキシ基、炭素数３〜６のシクロアルコキシ基、又はアセトキシ基であり、そしてｎは、０又は１である。｝
で表されるケイ素化合物に由来する構造部位を有する、表面修飾複合金属酸化物微粒子。 On the surface of the composite metal oxide fine particles, the following general formula (1):
R 1 R 2 R 3 Si- A-SiR 4 n X (3-n) (1)
{Wherein R 1 to R 3 are each independently a hydrocarbon group having 1 to 18 carbon atoms or an optionally substituted siloxy group, and R 4 is a hydrocarbon group having 1 to 4 carbon atoms. A is a divalent hydrocarbon group having 2 to 6 carbon atoms, and X is a hydrogen atom, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a cycloalkoxy group having 3 to 6 carbon atoms, or An acetoxy group and n is 0 or 1; }
Surface-modified composite metal oxide fine particles having a structural site derived from a silicon compound represented by the formula:
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