JP2001038215A - Modified photocatalyst and production thereof - Google Patents
Modified photocatalyst and production thereofInfo
- Publication number
- JP2001038215A JP2001038215A JP11218927A JP21892799A JP2001038215A JP 2001038215 A JP2001038215 A JP 2001038215A JP 11218927 A JP11218927 A JP 11218927A JP 21892799 A JP21892799 A JP 21892799A JP 2001038215 A JP2001038215 A JP 2001038215A
- Authority
- JP
- Japan
- Prior art keywords
- group
- photocatalyst
- platinum
- modified
- hydrosilyl group
- 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.)
- Withdrawn
Links
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 75
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 55
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- 239000000126 substance Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000007540 photo-reduction reaction Methods 0.000 claims abstract description 9
- 230000001699 photocatalysis Effects 0.000 claims description 16
- 230000004048 modification Effects 0.000 claims description 9
- 238000012986 modification Methods 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 49
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 32
- 239000002245 particle Substances 0.000 abstract description 20
- 229910052697 platinum Inorganic materials 0.000 abstract description 17
- 239000000203 mixture Substances 0.000 abstract description 15
- 229920005989 resin Polymers 0.000 abstract description 5
- 239000011347 resin Substances 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 5
- 238000004132 cross linking Methods 0.000 abstract description 3
- 150000003057 platinum Chemical class 0.000 abstract description 3
- -1 cyclic organosilane Chemical class 0.000 description 20
- 239000000243 solution Substances 0.000 description 16
- 125000004432 carbon atom Chemical group C* 0.000 description 13
- 239000002253 acid Substances 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 10
- 150000002430 hydrocarbons Chemical group 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 9
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 229920001296 polysiloxane Polymers 0.000 description 9
- 125000001424 substituent group Chemical group 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 238000006459 hydrosilylation reaction Methods 0.000 description 4
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 150000004687 hexahydrates Chemical class 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 125000000468 ketone group Chemical group 0.000 description 3
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000011163 secondary particle Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 229920001567 vinyl ester resin Polymers 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 2
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 2
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 2
- KNDQHSIWLOJIGP-UHFFFAOYSA-N 826-62-0 Chemical compound C1C2C3C(=O)OC(=O)C3C1C=C2 KNDQHSIWLOJIGP-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- CGBFEZOPOFSTTA-UHFFFAOYSA-L Cl[Pt](C1C=CC=C1)(C1C=CC=C1)Cl Chemical compound Cl[Pt](C1C=CC=C1)(C1C=CC=C1)Cl CGBFEZOPOFSTTA-UHFFFAOYSA-L 0.000 description 2
- JNJVARQLPFPYNT-UHFFFAOYSA-H Cl[Pt](Cl)(Cl)(Cl)(Cl)Cl.N Chemical compound Cl[Pt](Cl)(Cl)(Cl)(Cl)Cl.N JNJVARQLPFPYNT-UHFFFAOYSA-H 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910003089 Ti–OH Inorganic materials 0.000 description 2
- JGVLSEHAGQIPID-UHFFFAOYSA-H [K].Cl[Pt](Cl)(Cl)(Cl)(Cl)Cl Chemical compound [K].Cl[Pt](Cl)(Cl)(Cl)(Cl)Cl JGVLSEHAGQIPID-UHFFFAOYSA-H 0.000 description 2
- YKIOKAURTKXMSB-UHFFFAOYSA-N adams's catalyst Chemical compound O=[Pt]=O YKIOKAURTKXMSB-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 229940045985 antineoplastic platinum compound Drugs 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 238000004925 denaturation Methods 0.000 description 2
- 230000036425 denaturation Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 229910052762 osmium Inorganic materials 0.000 description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 150000002941 palladium compounds Chemical class 0.000 description 2
- PKELYQZIUROQSI-UHFFFAOYSA-N phosphane;platinum Chemical compound P.[Pt] PKELYQZIUROQSI-UHFFFAOYSA-N 0.000 description 2
- 150000003058 platinum compounds Chemical class 0.000 description 2
- NFOHLBHARAZXFQ-UHFFFAOYSA-L platinum(2+);dihydroxide Chemical compound O[Pt]O NFOHLBHARAZXFQ-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- BGCIWPHADHBSOS-UHFFFAOYSA-N (2,3,4,5,6-pentafluorobenzoyl) 2,3,4,5,6-pentafluorobenzoate Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1C(=O)OC(=O)C1=C(F)C(F)=C(F)C(F)=C1F BGCIWPHADHBSOS-UHFFFAOYSA-N 0.000 description 1
- SKYXLDSRLNRAPS-UHFFFAOYSA-N 1,2,4-trifluoro-5-methoxybenzene Chemical compound COC1=CC(F)=C(F)C=C1F SKYXLDSRLNRAPS-UHFFFAOYSA-N 0.000 description 1
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 1
- SNUXIIWZWKDULZ-UHFFFAOYSA-N 1-prop-2-enoxyhexane Chemical compound CCCCCCOCC=C SNUXIIWZWKDULZ-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- GCYHRYNSUGLLMA-UHFFFAOYSA-N 2-prop-2-enoxyethanol Chemical compound OCCOCC=C GCYHRYNSUGLLMA-UHFFFAOYSA-N 0.000 description 1
- FASUFOTUSHAIHG-UHFFFAOYSA-N 3-methoxyprop-1-ene Chemical compound COCC=C FASUFOTUSHAIHG-UHFFFAOYSA-N 0.000 description 1
- JSDZSLGMRRSAHD-UHFFFAOYSA-N 3-methylbutan-2-ylcyclopropane Chemical compound CC(C)C(C)C1CC1 JSDZSLGMRRSAHD-UHFFFAOYSA-N 0.000 description 1
- RNDVGJZUHCKENF-UHFFFAOYSA-N 5-hexen-2-one Chemical compound CC(=O)CCC=C RNDVGJZUHCKENF-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- LYJHVEDILOKZCG-UHFFFAOYSA-N Allyl benzoate Chemical compound C=CCOC(=O)C1=CC=CC=C1 LYJHVEDILOKZCG-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 101100422634 Postia placenta (strain ATCC 44394 / Madison 698-R) STS-02 gene Proteins 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QMYWDXMHMBXIPP-UHFFFAOYSA-N azane Chemical compound N.N.N.N.N.N QMYWDXMHMBXIPP-UHFFFAOYSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 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
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- IYNRVIKPUTZSOR-HWKANZROSA-N ethenyl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC=C IYNRVIKPUTZSOR-HWKANZROSA-N 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 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
- JFZUABNDWZQLIJ-UHFFFAOYSA-N methyl 2-[(2-chloroacetyl)amino]benzoate Chemical compound COC(=O)C1=CC=CC=C1NC(=O)CCl JFZUABNDWZQLIJ-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- JFNLZVQOOSMTJK-UHFFFAOYSA-N norbornene Chemical compound C1C2CCC1C=C2 JFNLZVQOOSMTJK-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 229920006136 organohydrogenpolysiloxane Polymers 0.000 description 1
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 1
- MYHOHFDYWMPGJY-UHFFFAOYSA-N pentafluorobenzoyl chloride Chemical compound FC1=C(F)C(F)=C(C(Cl)=O)C(F)=C1F MYHOHFDYWMPGJY-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- POSICDHOUBKJKP-UHFFFAOYSA-N prop-2-enoxybenzene Chemical compound C=CCOC1=CC=CC=C1 POSICDHOUBKJKP-UHFFFAOYSA-N 0.000 description 1
- CDXZRBLOGJXGTN-UHFFFAOYSA-N prop-2-enoxycyclohexane Chemical compound C=CCOC1CCCCC1 CDXZRBLOGJXGTN-UHFFFAOYSA-N 0.000 description 1
- ZEDLAAYLXASWJO-UHFFFAOYSA-N prop-2-enyl 2-ethylhexanoate Chemical compound CCCCC(CC)C(=O)OCC=C ZEDLAAYLXASWJO-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Silicon Polymers (AREA)
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、光触媒活性を有す
る部材及び／又は表面性状（親水性あるいは疎水性等）
が制御された部材を提供するのに有用な変性光触媒、及
びその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a member having photocatalytic activity and / or surface properties (such as hydrophilicity or hydrophobicity).
And a method for producing the same.
【０００２】[0002]
【従来の技術】酸化チタンに代表される光触媒は光エネ
ルギーによって物質の分解作用や表面の親水化作用を示
すことが知られている。ところで、光触媒表面に吸着や
配位あるいは化学結合する化合物を用いて光触媒表面を
修飾した変性光触媒は、従来の光触媒に無い種々の機能
を発現する事が期待される。例えば、和田等は酸化チタ
ンの粒子表面にペンタフルオロ塩化ベンゾイルやペンタ
フルオロ無水安息香酸を反応させることによって、酸化
チタン微粒子が通常は分散しないアセトニトリル中に安
定に分散する事を報告している（Ｊ．Ｃｈｅｍ．Ｒｅ
ｓ．（Ｓ），３２０（１９９６））。しかし、この場合
の表面修飾は酸化チタン表面水酸基とのエステル結合を
利用するものであり、水等によって容易に修飾基が脱離
するという欠点があった。2. Description of the Related Art It is known that a photocatalyst represented by titanium oxide exhibits a decomposing action of a substance and a hydrophilizing action of a surface by light energy. By the way, a modified photocatalyst in which the surface of the photocatalyst is modified by using a compound which is adsorbed, coordinated or chemically bonded to the surface of the photocatalyst is expected to exhibit various functions not found in the conventional photocatalyst. For example, Wada et al. Report that titanium oxide fine particles are stably dispersed in acetonitrile, which is not normally dispersed, by reacting pentafluorobenzoyl chloride or pentafluorobenzoic anhydride on the surface of titanium oxide particles (J Chem.Re
s. (S), 320 (1996)). However, the surface modification in this case utilizes an ester bond with the hydroxyl group on the titanium oxide surface, and has a disadvantage that the modifying group is easily eliminated by water or the like.
【０００３】また、特開昭６２−２６０７１７号公報で
は酸化チタンの表面を、酸化チタン基材表面に存在する
活性点の作用を利用してオルガノハイドロジェンポリシ
ロキサンを重合させることによって変性する方法が示唆
されている。しかし、この方法では光触媒として酸化チ
タンしか利用できないばかりか、酸化チタンを変性する
場合であっても、酸化チタンの粒子表面を選択的に変性
する場合は、粉体の状態の酸化チタンに環状オルガノシ
ロキサンの気化物を接触させる等の煩雑な方法が必須で
あった。Japanese Patent Application Laid-Open No. 62-260717 discloses a method of modifying the surface of titanium oxide by polymerizing an organohydrogenpolysiloxane utilizing the action of active sites present on the surface of a titanium oxide substrate. Is suggested. However, in this method, not only titanium oxide can be used as a photocatalyst, but even if titanium oxide is modified, when the surface of the titanium oxide particles is selectively modified, the cyclic organosilane is added to the titanium oxide in a powder state. A complicated method such as contacting a siloxane vapor is essential.
【０００４】[0004]
【発明が解決しようとする課題】本発明の課題は、光触
媒の表面を穏和な条件で修飾する方法を提供することに
より、溶媒分散性や樹脂相溶性の付与、架橋性能の付与
等、様々な機能を発現することができる変性光触媒を得
ることである。An object of the present invention is to provide a method for modifying the surface of a photocatalyst under mild conditions to provide various methods such as imparting solvent dispersibility and resin compatibility, imparting crosslinking performance, and the like. An object is to obtain a modified photocatalyst capable of exhibiting a function.
【０００５】[0005]
【課題を解決するための手段】本発明者らは上記課題を
解決すべく鋭意検討した結果、本発明に到達した。即
ち、本発明は： ヒドロシリル基を有する化合物及びヒドロシリル基
に対し脱水素縮合触媒として働く物質で変性されてなる
変性光触媒を提供する。また、 ヒドロシリル基に対し脱水素縮合触媒として働く物
質が白金族触媒である点にも特徴を有する。また、 光触媒が光触媒ゾルである点にも特徴を有する。ま
た、 ヒドロシリル基を有する化合物及びヒドロシリル基
に対し脱水素縮合触媒として働く物質で光触媒を変性さ
せる、変性光触媒の製造方法を提供する。また、 ヒドロシリル基に対し脱水素縮合触媒として働く物
質で変性された光触媒を、ヒドロシリル基を有する化合
物で変性させる変性光触媒の製造方法を提供する。ま
た、 ヒドロシリル基に対し脱水素縮合触媒として働く物
質による光触媒の変性が光還元法による点にも特徴を有
する。また、 ヒドロシリル基に対し脱水素縮合触媒として働く物
質が白金族触媒である点にも特徴を有する。また、 光触媒が光触媒ゾルである点にも特徴を有する。Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have reached the present invention. That is, the present invention provides: a compound having a hydrosilyl group and a modified photocatalyst obtained by modifying the hydrosilyl group with a substance that acts as a dehydrocondensation catalyst. Another feature is that the substance acting as a dehydrocondensation catalyst for the hydrosilyl group is a platinum group catalyst. Another feature is that the photocatalyst is a photocatalytic sol. Further, the present invention provides a method for producing a modified photocatalyst, which comprises modifying a photocatalyst with a compound having a hydrosilyl group and a substance acting as a dehydrocondensation catalyst for the hydrosilyl group. The present invention also provides a method for producing a modified photocatalyst in which a photocatalyst modified with a substance that acts as a dehydrocondensation catalyst for a hydrosilyl group is modified with a compound having a hydrosilyl group. Another feature is that the photocatalytic modification by a substance acting as a dehydrocondensation catalyst for the hydrosilyl group is performed by a photoreduction method. Another feature is that the substance acting as a dehydrocondensation catalyst for the hydrosilyl group is a platinum group catalyst. Another feature is that the photocatalyst is a photocatalytic sol.
【０００６】以下、本発明を詳細に説明する。 (i) 光触媒 本発明において使用される光触媒としては、ＴｉＯ2 、
ＺｎＯ、ＳｒＴｉＯ3、ＣｄＳ、ＧａＰ、ＩｎＰ、Ｇａ
Ａｓ、ＢａＴｉＯ3 、ＢａＴｉＯ4 、Ｋ2 ＮｂＯ3 、Ｆ
ｅ2 Ｏ3 、Ｔａ2 Ｏ5 、ＷＯ3 、ＳｎＯ2 、Ｂｉ
2 Ｏ3 、ＮｉＯ、Ｃｕ 2 Ｏ、ＳｉＣ、ＳｉＯ2 、ＭｏＳ
2 、ＩｎＰｂ、ＲｕＯ2 、ＣｅＯ2 等を挙げることがで
きる。これらの光触媒の中で、ＴｉＯ2 （酸化チタン）
は無害であり、化学的安定性にも優れるため好ましい。
酸化チタンとしては、アナターゼ、ルチル、ブルッカイ
トのいずれも使用できる。Hereinafter, the present invention will be described in detail. (i) Photocatalyst The photocatalyst used in the present invention is TiO.Two,
ZnO, SrTiOThree, CdS, GaP, InP, Ga
As, BaTiOThree, BaTiOFour, KTwoNbOThree, F
eTwoOThree, TaTwoOFive, WOThree, SnOTwo, Bi
TwoOThree, NiO, Cu TwoO, SiC, SiOTwo, MoS
Two, InPb, RuOTwo, CeOTwoEtc.
Wear. Among these photocatalysts, TiOTwo(Titanium oxide)
Is harmless and is excellent in chemical stability.
Titanium oxides include anatase, rutile and brooke
Any of these can be used.
【０００７】一般に微細な粒子からなる粉体は、複数の
粒子が強力に凝集した二次粒子を形成するため、無駄に
する表面特性が多い上、一つ一つの一次粒子にまで分散
させるのは非常に困難である。これに対し、光触媒ゾル
の場合、光触媒粒子は一次粒子に近い形で存在している
ため表面特性を有効に利用できるので好ましく使用する
ことができる。本発明に使用される光触媒としては、一
次粒子と二次粒子との混合物の体積平均分散粒子径が３
００ｎｍ以下の光触媒ゾルが変性後の光触媒の表面特性
を有効に利用できるために望ましい。より好ましくは２
００ｎｍ以下、さらに好ましくは１００ｎｍ以下１ｎｍ
以上、さらに好ましくは８０ｎｍ以下５ｎｍ以上のもの
が好適に選択される。なお、従来、二酸化チタンなどで
単に粒径として表示されている数値は、その多くは一次
粒子の径であり、凝集による二次粒子径を考慮した数値
ではない。In general, a powder composed of fine particles forms secondary particles in which a plurality of particles are strongly aggregated, so that many surface characteristics are wasted, and it is difficult to disperse the powder into individual primary particles. Very difficult. On the other hand, in the case of a photocatalyst sol, the photocatalyst particles can be preferably used because the photocatalyst particles are present in a form close to the primary particles and the surface characteristics can be effectively utilized. The photocatalyst used in the present invention has a volume average dispersed particle diameter of a mixture of primary particles and secondary particles of 3 or more.
A photocatalyst sol of 00 nm or less is desirable because the surface characteristics of the photocatalyst after modification can be effectively used. More preferably 2
00 nm or less, more preferably 100 nm or less 1 nm
Above, more preferably 80 nm or less and 5 nm or more are suitably selected. Conventionally, most of the numerical values simply indicated as particle diameters in titanium dioxide or the like are the diameters of primary particles, not numerical values in consideration of the secondary particle diameter due to aggregation.
【０００８】該光触媒ゾルとして酸化チタンのゾルを例
にとると、例えば水を分散媒とし、その中に酸化チタン
粒子が解膠された酸化チタンヒドロゾル等を挙げること
ができる。例えば、硫酸チタンや塩化チタンの水溶液を
加熱加水分解して生成したメタチタン酸をアンモニア水
で中和し、析出した含水酸化チタンを濾別、洗浄、脱水
させると酸化チタン粒子の凝集物が得られる。この凝集
物を、硝酸、塩酸、又はアンモニア等の作用の下に解膠
させると酸化チタンヒドロゾルが得られる。また、酸化
チタンヒドロゾルとしては、酸化チタン粒子を酸やアル
カリの作用の下で解膠させたり、酸やアルカリを使用せ
ず必要に応じ分散安定剤を使用し、強力なずり応力の下
で水中に分散させたゾルも用い得る。なお、酸化チタン
ヒドロゾルはチタニアゾルとして市販されている。この
ようなヒドロゾルの粘度（２０℃）は比較的低く、例え
ば、２０００ｃｐｓ〜０．５ｃｐｓ程度の範囲にあれば
よい。好ましくは１０００ｃｐｓ〜１ｃｐｓ、さらに好
ましくは５００ｃｐｓ〜１ｃｐｓである。Taking titanium oxide sol as an example of the photocatalyst sol, there may be mentioned, for example, a titanium oxide hydrosol in which water is used as a dispersion medium and titanium oxide particles are peptized therein. For example, metatitanic acid generated by heating and hydrolyzing an aqueous solution of titanium sulfate or titanium chloride is neutralized with aqueous ammonia, and precipitated hydrous titanium oxide is filtered, washed, and dehydrated to obtain an aggregate of titanium oxide particles. . This aggregate is peptized under the action of nitric acid, hydrochloric acid, ammonia, or the like, to obtain a titanium oxide hydrosol. In addition, as titanium oxide hydrosol, titanium oxide particles are peptized under the action of acid or alkali, or dispersion stabilizer is used as needed without using acid or alkali, and under strong shear stress, Sols dispersed in water may also be used. The titanium oxide hydrosol is commercially available as a titania sol. The viscosity (20 ° C.) of such a hydrosol is relatively low, for example, it may be in the range of about 2000 cps to 0.5 cps. Preferably it is 1000 cps-1 cps, more preferably 500 cps-1 cps.
【０００９】本発明において、後述するヒドロシリル基
を有する化合物を用いて上述した光触媒の表面を温和な
条件で選択的に変性するためには、予め該光触媒がヒド
ロシリル基に対し脱水素縮合触媒として働く物質で予備
変性されていることが重要である。ここで、ヒドロシリ
ル基に対し脱水素縮合触媒として働く物質とは、ヒドロ
シリル基と光触媒表面に存在する水酸基（酸化チタンの
場合はＴｉ−ＯＨ基）やチオール基、アミノ基、カルボ
キシル基等の活性水素基、さらには水等との脱水素縮合
反応を加速する物質を意味し、該脱水素縮合触媒として
働く物質で光触媒が予備変性されていることにより、温
和な条件で選択的に光触媒表面をヒドロシリル基を有す
る化合物によって変性することが可能となる。本発明に
おいて、ヒドロシリル基に対し脱水素縮合触媒として働
く物質としては、例えば白金族触媒、即ちルテニウム、
ロジウム、パラジウム、オスミウム、イリジウム、白金
の単体及びその化合物や：銀、鉄、銅、コバルト、ニッ
ケル、錫等の単体及びその化合物が挙げられる。これら
の中で白金族触媒が好ましく、白金の単体及びその化合
物が特に好ましい。In the present invention, in order to selectively modify the surface of the above-described photocatalyst under mild conditions using a compound having a hydrosilyl group described below, the photocatalyst acts as a dehydrocondensation catalyst for the hydrosilyl group in advance. It is important that the material is pre-denatured. Here, the substance which acts as a dehydrocondensation catalyst for the hydrosilyl group includes the hydrosilyl group and the active hydrogen such as a hydroxyl group (Ti-OH group in the case of titanium oxide), a thiol group, an amino group, a carboxyl group, etc. present on the surface of the photocatalyst. Group, or a substance that accelerates the dehydrocondensation reaction with water and the like.The photocatalyst is preliminarily modified with a substance that acts as a dehydrocondensation catalyst, so that the photocatalyst surface can be selectively hydrolyzed under mild conditions. It can be modified by a compound having a group. In the present invention, the substance that acts as a dehydrocondensation catalyst for the hydrosilyl group includes, for example, a platinum group catalyst, that is, ruthenium,
Simple substances of rhodium, palladium, osmium, iridium, platinum and their compounds and: simple substances of silver, iron, copper, cobalt, nickel, tin and the like and compounds thereof. Of these, platinum group catalysts are preferred, and simple platinum and its compounds are particularly preferred.
【００１０】上記脱水素縮合触媒として働く物質で光触
媒を予備変性する方法としては、物理吸着させる方法や
光還元法や熱処理によって変性する方法が挙げられる。
これらの中で、光還元法で予備変性する方法が最も好ま
しい。以下、白金、光触媒ゾルを用いて光還元法で予備
変性する方法を例にとって説明する。まず、白金溶液を
光触媒ゾル溶液に添加する。ここで白金溶液のＰＨを光
触媒ゾル溶液とほぼ同じにし、光触媒ゾルの溶液中のゼ
ータ電位をなるべく変化させないようにすることによ
り、光触媒ゾルの単分散性を維持することが好ましい。
ここで白金溶液とは白金を含む塩と溶媒からなる溶液を
いう。白金を含む塩としては、例えば塩化白金（Ｉ
Ｉ）、テトラクロロ白金酸（ＩＩ）、塩化白金（Ｉ
Ｖ）、ヘキサクロロ白金酸（ＩＶ）、ヘキサクロロ白金
（ＩＶ）アンモニウム、ヘキサクロロ白金（ＩＶ）カリ
ウム、水酸化白金（ＩＩ）、二酸化白金（ＩＶ）、ジク
ロロ−ジシクロペンタジエニル−白金（ＩＩ）、白金−
ビニルシロキサン錯体、白金−ホスフィン錯体、白金−
オレフィン錯体等を使用することができる。また溶媒と
しては、水、エタノール、プロパノール、イソプロパノ
ール、ジオキサン、テトラヒドルフラン、トルエン等が
使用できる。As a method of preliminarily denaturing the photocatalyst with the above-mentioned substance acting as a dehydrocondensation catalyst, a method of physical adsorption, a photoreduction method or a method of denaturation by heat treatment can be mentioned.
Among them, the method of preliminarily denaturing by the photoreduction method is most preferable. Hereinafter, a method of pre-denaturing by a photoreduction method using platinum and a photocatalytic sol will be described as an example. First, a platinum solution is added to the photocatalytic sol solution. Here, it is preferable to maintain the monodispersity of the photocatalytic sol by making the pH of the platinum solution substantially the same as that of the photocatalytic sol solution and keeping the zeta potential in the solution of the photocatalytic sol as small as possible.
Here, the platinum solution refers to a solution comprising a salt containing platinum and a solvent. As a salt containing platinum, for example, platinum chloride (I
I), tetrachloroplatinic acid (II), platinum chloride (I
V), hexachloroplatinic acid (IV), ammonium hexachloroplatinum (IV), potassium hexachloroplatinum (IV), platinum (II) hydroxide, platinum (IV) dioxide, dichloro-dicyclopentadienyl-platinum (II), Platinum-
Vinylsiloxane complex, platinum-phosphine complex, platinum-
An olefin complex or the like can be used. As the solvent, water, ethanol, propanol, isopropanol, dioxane, tetrahydrofuran, toluene and the like can be used.
【００１１】次に、光触媒ゾル溶液と白金塩溶液との混
合物を攪拌しながら、光触媒に電子と正孔を生成させる
ことが可能な波長の光（好ましくは紫外線を含む光）を
照射する。ここで光を照射する光源は、例えば紫外線ラ
ンプ、ＢＬＢランプ、キセノンランプ、水銀灯、蛍光灯
などが挙げられる。光の照射方法も基本的には問わない
が、第一に容器上方から照射するほうがよい。容器によ
る光の吸収がないからである。第二に光源と容器との距
離は数ｃｍ〜数１０ｃｍ程度がよい。近すぎると光源か
ら発する熱により試料溶液の上面が乾くおそれがあり、
遠すぎると照度が低下するからである。照射時間は光源
の照度により異なるが数秒〜数１０分程度照射すれば白
金が光触媒粒子に強固に付着する。Next, while stirring the mixture of the photocatalyst sol solution and the platinum salt solution, the photocatalyst is irradiated with light (preferably light containing ultraviolet rays) having a wavelength capable of generating electrons and holes. Here, examples of the light source that emits light include an ultraviolet lamp, a BLB lamp, a xenon lamp, a mercury lamp, and a fluorescent lamp. The method of irradiating light is basically not limited, but first, it is better to irradiate from above the container. This is because there is no light absorption by the container. Second, the distance between the light source and the container is preferably about several cm to several tens cm. If it is too close, the heat generated from the light source may cause the upper surface of the sample solution to dry,
This is because if the distance is too far, the illuminance decreases. The irradiation time varies depending on the illuminance of the light source, but if the irradiation is performed for several seconds to several tens of minutes, the platinum is firmly adhered to the photocatalyst particles.
【００１２】本発明においては、上記、予備変性光触媒
とヒドロシリル基を有する化合物を用いて、光触媒の変
性を行う。光触媒を変性させるのに用いるヒドロシリル
基を有する化合物としては、例えば平均組成式が下式
（1)で示されるものが挙げられる。 ＨpＲqＱrＳｉＯ(4-p-q-r)/2 ・・・（1) （式中、Ｒは一価の有機基の１種もしくは２種以上から
なる官能基を表す。Ｑは、アルコキシ基、ヒドロキシ
基、またはハロゲン原子を表す。０＜ｐ＜４、０≦ｑ＜
４、０≦ｒ＜４であり、また（ｐ＋ｑ＋ｒ）≦４であ
る。） このような化合物としては、例えば下記式（2)で表され
るヒドロシリル基含有シリコーン化合物を挙げることが
できる。 （Ｒ1ＨＳｉＯ）a（Ｒ1Ｒ2ＳｉＯ）b（Ｒ1ＸＳｉＯ）c（Ｒ1ＹＳｉＯ）d （Ｒ1ＺＳｉＯ）e（Ｒ1Ｒ1Ｒ1ＳｉＯ1/2）f ・・・（2)In the present invention, the photocatalyst is modified using the above-mentioned premodified photocatalyst and a compound having a hydrosilyl group. Examples of the compound having a hydrosilyl group used for modifying the photocatalyst include those having an average composition represented by the following formula (1). During H p R q Q r SiO ( 4-pqr) / 2 ··· (1) ( wherein, R represents one or functional groups of two or more of the monovalent organic group .Q an alkoxy group , A hydroxy group, or a halogen atom.0 <p <4, 0 ≦ q <
4, 0 ≦ r <4, and (p + q + r) ≦ 4. Examples of such a compound include a hydrosilyl group-containing silicone compound represented by the following formula (2). (R 1 HSiO) a (R 1 R 2 SiO) b (R 1 XSiO) c (R 1 YSiO) d (R 1 ZSiO) e (R 1 R 1 R 1 SiO 1/2 ) f. )
【００１３】（式中、Ｒ1はそれぞれ独立に置換基を有
しても有さなくても良い炭素数が１〜３０個の炭化水素
基を表す。Ｒ2は置換基を有しても有さなくても良い炭
素数が１〜３０個の炭化水素基を含む１価の基を表す。
Ｘは炭素数１〜３０のフルオロアルキル基を含む１価の
基を表す。Ｙは、カルボキシル基あるいはその塩を含む
１価の基、リン酸基あるいはその塩を含む１価の基、ス
ルホ基あるいはその塩を含む１価の基、ポリオキシアル
キレン基、環状無水物を含む１価の基からなる群から選
ばれた少なくとも１つの親水性基を表す。Ｚは、エポキ
シ基を含む１価の基、アクリロイル基を含む１価の基、
メタアクリロイル基を含む１価の基、環状酸無水物を含
む１価の基、ケト基を含む１価の基、ヒドロキシル基を
含む１価の基、アミノ基を含む１価の基、アルコキシ
基、ヒドロキシル基からなる群から選ばれた少なくとも
１つの反応性基を表す。ａは１以上の整数であり、ｂ、
ｃ、ｄ、ｅは０又は１以上の整数であり、ｆは０又は２
である。（ａ＋ｂ＋ｃ＋ｄ＋ｅ）≦１００００である。
また、上記シリコーン化合物は、ランダム共重合体で
も、ブロック共重合体でもよい。）(Wherein, R 1 independently represents a hydrocarbon group having 1 to 30 carbon atoms which may or may not have a substituent. R 2 may have a substituent. It represents a monovalent group containing a hydrocarbon group having 1 to 30 carbon atoms which may not be present.
X represents a monovalent group containing a fluoroalkyl group having 1 to 30 carbon atoms. Y is a monovalent group containing a carboxyl group or a salt thereof, a monovalent group containing a phosphate group or a salt thereof, a monovalent group containing a sulfo group or a salt thereof, a polyoxyalkylene group, or a cyclic anhydride. It represents at least one hydrophilic group selected from the group consisting of monovalent groups. Z is a monovalent group containing an epoxy group, a monovalent group containing an acryloyl group,
Monovalent group containing methacryloyl group, monovalent group containing cyclic acid anhydride, monovalent group containing keto group, monovalent group containing hydroxyl group, monovalent group containing amino group, alkoxy group , At least one reactive group selected from the group consisting of a hydroxyl group. a is an integer of 1 or more, b,
c, d, and e are 0 or an integer of 1 or more, and f is 0 or 2
It is. (A + b + c + d + e) ≦ 10000.
Further, the silicone compound may be a random copolymer or a block copolymer. )
【００１４】上記(2) で表される化合物において、ｆ＝
０の場合は環状シリコーン化合物を表し、ｆ＝２の場合
は鎖状シリコーン化合物を表わす。上記式(2) で示され
るヒドロシリル基含有シリコーン化合物としては、例え
ば下記式(3) で表されるヒドロシリル基含有化合物、及
び該ヒドロシリル基含有化合物が有するヒドロシリル基
に炭素−炭素不飽和結合化合物を付加させるヒドロシリ
ル化反応により得られる化合物を挙げることができる。 （Ｒ1ＨＳｉＯ）a+c+d+e（Ｒ1Ｒ2ＳｉＯ）b（Ｒ1Ｒ1Ｒ1ＳｉＯ1/2）f ・・・(3) （式中、Ｒ1はそれぞれ独立に置換基を有しても有さな
くても良い炭素数が１〜３０個の炭化水素基を表す。Ｒ
2は置換基を有しても有さなくても良い炭素数が１〜３
０個の炭化水素基を含む１価の基を表す。ａは１以上の
整数であり、ｂ、ｃ、ｄ、ｅは０又は１以上の整数であ
り、ｆは０又は２である。（ａ＋ｂ＋ｃ＋ｄ＋ｅ）≦１
００００である。また、上記シリコーン化合物は、ラン
ダム共重合体でもブロック共重合体でもよい。）In the compound represented by the above (2), f =
0 represents a cyclic silicone compound, and f = 2 represents a chain silicone compound. As the hydrosilyl group-containing silicone compound represented by the above formula (2), for example, a hydrosilyl group-containing compound represented by the following formula (3), and a carbon-carbon unsaturated bond compound to the hydrosilyl group of the hydrosilyl group-containing compound Compounds obtained by the hydrosilylation reaction to be added can be mentioned. (R 1 HSiO) a + c + d + e (R 1 R 2 SiO) b (R 1 R 1 R 1 SiO 1/2 ) f (3) (wherein, R 1 is each independently substituted. Represents a hydrocarbon group having 1 to 30 carbon atoms which may or may not have a group.
2 has 1 to 3 carbon atoms which may or may not have a substituent.
It represents a monovalent group containing 0 hydrocarbon groups. a is an integer of 1 or more, b, c, d, and e are 0 or an integer of 1 or more, and f is 0 or 2. (A + b + c + d + e) ≦ 1
0000. Further, the silicone compound may be a random copolymer or a block copolymer. )
【００１５】上記式(3) で表されるヒドロシリル基含有
化合物に所望の官能基を導入するのに用いる炭素−炭素
不飽和結合化合物としては、例えば下記式(4) で表され
るパーフルオロアルキル基を有するオレフィン類、アリ
ルエーテル類、ビニルエーテル類、（メタ）アクリル酸
エステル類等を用いることができる。 −（ＣＦ2）gＣＦ3・・・(4) （式中、ｇは０〜５０の整数を表す。） また、置換基を有しても有さなくても良い炭素数が１〜
３０個の炭化水素基を含む１価の基を導入する場合に用
いる炭素−炭素不飽和結合化合物として、プロピレン、
１−ブテン、１−ヘキセン、１−オクテン、イソブテ
ン、５−メチル−１−ブテン、２−ヘキセン、シクロヘ
キセン、５−ノルボルネンの如きオレフィン類；酢酸ア
リル、プロピオン酸アリル、２−エチルヘキサン酸アリ
ル、安息香酸 アリル等のアリルエステル類；The carbon-carbon unsaturated bond compound used to introduce a desired functional group into the hydrosilyl group-containing compound represented by the above formula (3) is, for example, a perfluoroalkyl compound represented by the following formula (4). Olefins having a group, allyl ethers, vinyl ethers, (meth) acrylates, and the like can be used. — (CF 2 ) g CF 3 (4) (In the formula, g represents an integer of 0 to 50.) The number of carbon atoms that may or may not have a substituent is 1 to 3.
As a carbon-carbon unsaturated bond compound used when introducing a monovalent group containing 30 hydrocarbon groups, propylene,
Olefins such as 1-butene, 1-hexene, 1-octene, isobutene, 5-methyl-1-butene, 2-hexene, cyclohexene, 5-norbornene; allyl acetate, allyl propionate, allyl 2-ethylhexanoate, Allyl esters such as allyl benzoate;
【００１６】アリルメチルエーテル、アリルエチルエー
テル、アリル−ｎ−ヘキシルエーテル、アリルシクロヘ
キシルエーテル、アリル−２−エチルヘキシルエーテ
ル、アリルフェニルエーテル、アリルグリシジルエーテ
ル等のアリルエーテル類；（メタ）アクリル酸メチル、
（メタ）アクリル酸エチル、（メタ）アクリル酸ブチ
ル、（メタ）アクリル酸−２−エチルヘキシル、（メ
タ）アクリル酸シクロヘキシル、（メタ）アクリル酸フ
ェニル等の（メタ）アクリル酸エステル類；酢酸ビニ
ル、プロピオン酸ビニル、酪酸ビニル、ステアリン酸ビ
ニル、安息香酸ビニル等のカルボン酸ビニルエステル
類；メチルビニルエーテル、エチルビニルエーテル、ブ
チルビニルエーテル、イソブチルビニルエーテル、シク
ロヘキシルビニルエーテル等のビニルエーテル類；スチ
レン、（メタ）アクリロニトリル、クロトン酸エステル
類等の他の炭素−炭素不飽和結合化合物等が挙げられ
る。これらのうち、１−ヘキセン、１−オクテン等の末
端オレフィン類、アリルエステル類、アリルエーテル類
が反応性の面で好ましい。Allyl ethers such as allyl methyl ether, allyl ethyl ether, allyl-n-hexyl ether, allyl cyclohexyl ether, allyl-2-ethylhexyl ether, allyl phenyl ether and allyl glycidyl ether; methyl (meth) acrylate;
(Meth) acrylates such as ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, and phenyl (meth) acrylate; vinyl acetate; Carboxylic acid vinyl esters such as vinyl propionate, vinyl butyrate, vinyl stearate and vinyl benzoate; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether and cyclohexyl vinyl ether; styrene, (meth) acrylonitrile, crotonic acid And other carbon-carbon unsaturated bond compounds such as esters. Of these, terminal olefins such as 1-hexene and 1-octene, allyl esters, and allyl ethers are preferred in terms of reactivity.
【００１７】また、親水性基を導入するのに用いる炭素
−炭素不飽和結合化合物としては、カルボキシル基ある
いはその塩、リン酸基あるいはその塩、スルホ基あるい
はその塩、ポリオキシアルキレン基、環状酸無水物から
なる群から選ばれた少なくとも１つの親水性基を有する
オレフィン類、アリルエーテル類、ビニルエーテル類、
ビニルエステル類、（メタ）アクリル酸エステル類、ス
チレン誘導体等が挙げられる。上記親水性基を有する炭
素−炭素不飽和結合化合物の好ましい具体例として、例
えば下記式(5) で表されるポリオキシエチレン基含有ア
リルエーテルや下記式(6) で表されるスルホ基を含む１
価の基を有するアリルエーテル、さらには５−ノルボル
ネン−２，３−ジカルボン酸無水物等を挙げることがで
きる。 ＣＨ2＝ＣＨＣＨ2Ｏ（ＣＨ2ＣＨ2Ｏ）ｍＲ3 ・・・(5) （式中、ｍは１〜１０００の整数を表す。Ｒ3は、置換
基を有しても有さなくても良い炭素数が１〜３０個の炭
化水素基を表す。）The carbon-carbon unsaturated bond compound used for introducing a hydrophilic group includes a carboxyl group or a salt thereof, a phosphate group or a salt thereof, a sulfo group or a salt thereof, a polyoxyalkylene group, a cyclic acid Olefins having at least one hydrophilic group selected from the group consisting of anhydrides, allyl ethers, vinyl ethers,
Examples include vinyl esters, (meth) acrylates, and styrene derivatives. Preferred specific examples of the carbon-carbon unsaturated bond compound having a hydrophilic group include, for example, a polyoxyethylene group-containing allyl ether represented by the following formula (5) and a sulfo group represented by the following formula (6). 1
Allyl ethers having a valence group, and furthermore, 5-norbornene-2,3-dicarboxylic anhydride and the like can be mentioned. CH 2 ＣＨCHCH 2 O (CH 2 CH 2 O) mR 3 (5) (wherein m represents an integer of 1 to 1000. R 3 may or may not have a substituent. Represents a hydrocarbon group having 1 to 30 carbon atoms.)
【化１】 Embedded image
【００１８】〔式中、ｎは１〜１００の整数を表す。Ｒ
4は、置換基を有しても有さなくても良い炭素数が１〜
３０個の炭化水素基を表す。Ｂは、水素原子、アルカリ
金属、アンモニウム又は式(7) で表される置換アンモニ
ウムを表す。 ＨＮＲ5Ｒ6Ｒ7 ・・・(7) （Ｒ5、Ｒ6、Ｒ7は、それぞれ独立して、水素原子、又
は置換されていないか或いはヒドロキシル基で置換され
ている直鎖状または分岐状の炭素数１〜２０のアルキル
基を表す。）〕[In the formula, n represents an integer of 1 to 100. R
4 has 1 to 1 carbon atoms which may or may not have a substituent.
Represents 30 hydrocarbon groups. B represents a hydrogen atom, an alkali metal, ammonium or a substituted ammonium represented by the formula (7). HNR 5 R 6 R 7 (7) (R 5 , R 6 , and R 7 are each independently a hydrogen atom, or a straight or branched unsubstituted or substituted hydroxyl group; Represents an alkyl group having 1 to 20 carbon atoms.)]
【００１９】また、反応性基を導入するのに用いる炭素
−炭素不飽和結合化合物としては、エポキシ基、（メ
タ）アクリロイル基、環状酸無水物、ケト基、ヒドロキ
シル基、アミノ基からなる群から選ばれた少なくとも１
つの反応性基を有するオレフィン類、アリルエーテル
類、ビニルエーテル類、ビニルエステル類、（メタ）ア
クリル酸エステル類、スチレン誘導体等が挙げられる。
上記反応性基を有する炭素−炭素不飽和結合化合物の好
ましい具体例として、例えばアリルグリシジルエーテ
ル、（メタ）アクリル酸グリシジル、（メタ）アクリル
酸アリル、ジアリルエーテル、ジアリルフタレート、
（メタ）アクリル酸ビニル、クロトン酸ビニル、エチレ
ングリコールジ（メタ）アクリル酸エステル、無水マレ
イン酸、５−ノルボルネン−２，３−ジカルボン酸無水
物、５−ヘキセン−２−オン、アリルアルコール、エチ
レングリコールモノアリルエーテル、アリルアミン等を
挙げることができる。The carbon-carbon unsaturated bond compound used to introduce the reactive group is selected from the group consisting of epoxy groups, (meth) acryloyl groups, cyclic acid anhydrides, keto groups, hydroxyl groups and amino groups. At least one chosen
Examples include olefins having two reactive groups, allyl ethers, vinyl ethers, vinyl esters, (meth) acrylates, and styrene derivatives.
Preferred specific examples of the carbon-carbon unsaturated bond compound having the reactive group include, for example, allyl glycidyl ether, glycidyl (meth) acrylate, allyl (meth) acrylate, diallyl ether, diallyl phthalate,
Vinyl (meth) acrylate, vinyl crotonate, ethylene glycol di (meth) acrylate, maleic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, 5-hexen-2-one, allyl alcohol, ethylene Glycol monoallyl ether, allylamine and the like can be mentioned.
【００２０】上記炭素−炭素不飽和化合物と上記式(3)
で表されるヒドロシリル基含有化合物のヒドロシリル化
反応は、好ましくは触媒の存在下、有機溶媒の存在下あ
るいは非存在下において０〜２００℃で炭素−炭素不飽
和化合物と式(3) で表されるヒドロシリル基含有化合物
を接触させることにより行うことができる。ヒドロシリ
ル化反応の触媒としては、白金族触媒、即ちルテニウ
ム、ロジウム、パラジウム、オスミウム、イリジウム、
白金の化合物が適しているが、特に白金の化合物とパラ
ジウムの化合物が好適である。白金の化合物としては、
例えば塩化白金（ＩＩ）、テトラクロロ白金酸（Ｉ
Ｉ）、塩化白金（ＩＶ）、ヘキサクロロ白金酸（Ｉ
Ｖ）、ヘキサクロロ白金（ＩＶ）アンモニウム、ヘキサ
クロロ白金（ＩＶ）カリウム、水酸化白金（ＩＩ）、二
酸化白金（ＩＶ）、ジクロロ−ジシクロペンタジエニル
−白金（ＩＩ）、白金−ビニルシロキサン錯体、白金−
ホスフィン錯体、白金−オレフィン錯体や白金の単体、
アルミナやシリカや活性炭に固体白金を担持させたもの
が挙げられる。The above carbon-carbon unsaturated compound and the above formula (3)
The hydrosilylation reaction of the hydrosilyl group-containing compound represented by the formula (3) is preferably carried out at 0 to 200 ° C in the presence of a catalyst, in the presence or absence of an organic solvent, at 0 to 200 ° C. By contacting the compound containing a hydrosilyl group. As the catalyst for the hydrosilylation reaction, platinum group catalysts, that is, ruthenium, rhodium, palladium, osmium, iridium,
Platinum compounds are suitable, especially platinum compounds and palladium compounds. As a compound of platinum,
For example, platinum (II) chloride, tetrachloroplatinic acid (I
I), platinum chloride (IV), hexachloroplatinic acid (I
V), ammonium hexachloroplatinum (IV), potassium hexachloroplatinum (IV), platinum (II) hydroxide, platinum (IV) dioxide, dichloro-dicyclopentadienyl-platinum (II), platinum-vinylsiloxane complex, platinum −
Phosphine complex, platinum-olefin complex or platinum simple substance,
Examples thereof include those in which solid platinum is supported on alumina, silica, or activated carbon.
【００２１】パラジウムの化合物としては、例えば塩化
パラジウム（ＩＩ）、塩化テトラアンミンパラジウム
（ＩＩ）酸アンモニウム、酸化パラジウム（ＩＩ）等が
挙げられる。また、ヒドロシリル化反応に使用できる有
機溶媒としては、例えばトルエンやキシレン等の芳香族
炭化水素類、ヘキサン、シクロヘキサン、ヘプタン等の
脂肪族炭化水素類、酢酸エチル、酢酸ｎ−ブチル等のエ
ステル類、アセトン、メチルエチルケトン、メチルイソ
ブチルケトン等のケトン類、テトラヒドロフラン、ジオ
キサン等のエーテル類、ジメチルアセトアミド、ジメチ
ルホルムアミド等のアミド類、クロロホルム、塩化メチ
レン、四塩化炭素等のハロゲン化合物類、ジメチルスル
ホキシド、ニトロベンゼン等やこれらの２種以上の混合
物が挙げられる。Examples of the palladium compound include palladium (II) chloride, ammonium ammonium tetraammonium palladium (II), and palladium (II) oxide. Examples of the organic solvent that can be used for the hydrosilylation reaction include, for example, aromatic hydrocarbons such as toluene and xylene, hexane, cyclohexane, aliphatic hydrocarbons such as heptane, ethyl acetate, esters such as n-butyl acetate, Ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ethers such as tetrahydrofuran and dioxane, amides such as dimethylacetamide and dimethylformamide, halogen compounds such as chloroform, methylene chloride and carbon tetrachloride, dimethyl sulfoxide, nitrobenzene and the like A mixture of two or more of these may be mentioned.
【００２２】本発明において、上記式（I)で表される平
均組成式を有する他の例として、分子中に下記一般式
(A) で表される繰返単位、下記一般式(B) で表される繰
返単位、末端基Ａを各々有し、該末端基Ａが１つの酸素
原子を介して繰返単位中の珪素原子に結合しているシリ
コーン化合物等も挙げることができる。In the present invention, as another example having the average composition formula represented by the above formula (I),
A repeating unit represented by (A), a repeating unit represented by the following general formula (B), and a terminal group A, wherein the terminal group A is contained in the repeating unit via one oxygen atom. Silicone compounds bonded to silicon atoms can also be mentioned.
【化２】 〔式(A) および式(B) において、Ｒ8は下記〜の置
換基から選ばれたものであり、且つ少なくとも１個のヒ
ドロシリル基残基及び少なくとも１個の下記で表され
る置換基を有する。Ａは、水素原子、炭素数１〜３０個
の炭化水素基、−ＳｉＲ9Ｒ10Ｒ11（Ｒ9、Ｒ10、Ｒ11
は同じであっても異なっていてもよく、水素原子または
炭素数１〜３０個の炭化水素基を表す。）から選ばれた
少なくとも１つの基を表す。Embedded image [In the formulas (A) and (B), R 8 is selected from the following substituents, and at least one hydrosilyl group residue and at least one substituent represented by the following: Have. A represents a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, -SiR 9 R 10 R 11 (R 9 , R 10 , R 11
May be the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. Represents at least one group selected from
【００２３】 水素原子 置換基を有しても有さなくても良い炭素数が１〜３
０個の炭化水素基を含む１価の基、炭素数１〜３０個の
フルオロアルキル基を含む１価の基からなる群から選ば
れた少なくとも１つの疎水性基 カルボキシル基あるいはその塩を含む１価の基、リ
ン酸基あるいはその塩を含む１価の基、スルホ基あるい
はその塩を含む１価の基、ポリオキシアルキレン基から
なる群から選ばれた少なくとも１つの親水性基 エポキシ基を含む１価の基、アクリロイル基を含む
１価の基、メタアクリロイル基を含む１価の基、環状酸
無水物を含む１価の基、ケト基を含む１価の基、カルボ
ニル基を含む１価の基、ヒドロキシル基を含む１価の
基、アミノ基を含む１価の基、アルコキシ基、ヒドロキ
シル基からなる群から選ばれた少なくとも１つの反応性
基〕A hydrogen atom having 1 to 3 carbon atoms which may or may not have a substituent;
At least one hydrophobic group selected from the group consisting of a monovalent group containing 0 hydrocarbon groups and a monovalent group containing a fluoroalkyl group having 1 to 30 carbon atoms, including a carboxyl group or a salt thereof, At least one hydrophilic group selected from the group consisting of a monovalent group, a monovalent group containing a phosphate group or a salt thereof, a monovalent group containing a sulfo group or a salt thereof, and a polyoxyalkylene group containing an epoxy group Monovalent group, monovalent group containing acryloyl group, monovalent group containing methacryloyl group, monovalent group containing cyclic acid anhydride, monovalent group containing keto group, monovalent group containing carbonyl group , A monovalent group containing a hydroxyl group, a monovalent group containing an amino group, an alkoxy group, and at least one reactive group selected from the group consisting of a hydroxyl group]
【００２４】本発明においては、上記、ヒドロシリル基
を有する化合物を用いて、前述のヒドロシリル基に対し
脱水素縮合触媒として働く物質により予備変性された光
触媒の変性を実施することができる。また、光触媒の予
備変性操作をすることなく、上記ヒドロシリル基を有す
る化合物とヒドロシリル基に対し脱水素縮合触媒として
働く物質で同時に光触媒を変性することもできる。その
場合、光触媒は、物理吸着や光還元によって脱水素縮合
触媒として働く物質で変性されながら、ヒドロシリル基
を有する化合物で変性されることになる。上記いずれの
方法においても、光触媒（A)のヒドロシリル基を有する
化合物(B) による変性は、水及び／又は有機溶媒の存
在、あるいは非存在下において、固形分重量比（Ａ）／
（Ｂ）＝０．０１〜１０００、好ましくは（Ａ）／
（Ｂ）＝０．１〜１００の割合で０〜１５０℃にて混合
することにより実施できる。この変性の操作により混合
液からは水素ガスが発生する。In the present invention, using the above-mentioned compound having a hydrosilyl group, it is possible to carry out the modification of a photocatalyst which has been pre-modified with the substance acting as a dehydrocondensation catalyst for the above-mentioned hydrosilyl group. Further, the photocatalyst can be simultaneously denatured with the compound having a hydrosilyl group and the substance acting as a dehydrocondensation catalyst for the hydrosilyl group without performing a preliminary denaturation operation of the photocatalyst. In this case, the photocatalyst is modified with a compound having a hydrosilyl group while being modified with a substance that functions as a dehydrocondensation catalyst by physical adsorption or photoreduction. In any of the above methods, the modification of the photocatalyst (A) with the compound (B) having a hydrosilyl group is carried out in the presence or absence of water and / or an organic solvent in the solid content weight ratio (A) /
(B) = 0.01 to 1000, preferably (A) /
It can be carried out by mixing at a rate of (B) = 0.1 to 100 at 0 to 150 ° C. Hydrogen gas is generated from the mixed solution by this denaturing operation.
【００２５】また、例えばヒドロシリル基に対し脱水素
縮合触媒として働く物質で変性された光触媒として白金
を担持した酸化チタンを用いた場合、上記変性の操作に
より、Ｔｉ−ＯＨ基の減少がＩＲスペクトルにおける３
６３０〜３６４０ｃｍ−１の吸収の減少として観測され
る。これらのことより本発明の変性光触媒は、上記ヒド
ロシリル基を有する化合物と光触媒との単なる混合物で
はなく、化学結合等の何らかの相互作用をもったもので
あることが予測できる。また、有機溶媒を使用して上記
変性を行う場合、使用できる有機溶媒としては、例えば
ジオキサン、テトラヒドロフラン、ジメチルアセトアミ
ド、アセトン、メチルエチルケトン、エチレングリコー
ル、ブチルセロソルブ、エタノール、メタノール等の親
水性有機溶媒、及びトルエン、キシレン、ヘキサン等の
疎水性有機溶媒が挙げられる。When, for example, titanium oxide carrying platinum is used as a photocatalyst modified with a substance acting as a dehydrocondensation catalyst for a hydrosilyl group, the decrease of the Ti—OH group in the IR spectrum is caused by the above modification operation. 3
It is observed as a decrease in absorption at 630-3640 cm-1. From these facts, it can be predicted that the modified photocatalyst of the present invention is not a simple mixture of the compound having a hydrosilyl group and the photocatalyst, but has any interaction such as a chemical bond. When the above modification is performed using an organic solvent, examples of usable organic solvents include, for example, dioxane, tetrahydrofuran, dimethylacetamide, acetone, methyl ethyl ketone, ethylene glycol, butyl cellosolve, ethanol, a hydrophilic organic solvent such as methanol, and toluene. , Xylene, hexane and the like.
【００２６】本発明において光触媒の形態として光触媒
ヒドロゾルを選択すると水系の変性光触媒ゾルを得るこ
とができる。この場合、該光触媒ヒドロゾルに対する変
性の容易性、及び得られる変性光触媒ゾルの分散安定性
の面からヒドロシリル基を有する化合物として親水性基
を有するもの（例えば、ヒドロシリル基を有する化合物
が上記式（2)で表されるヒドロシリル基含有シリコーン
化合物の場合は、式（2)におけるｄが１以上の整数であ
るもの）の使用が好ましい。また、光触媒粒子と上記ヒ
ドロシリル基含有シリコーン化合物との接触を補助する
目的で上述した親水性有機溶媒を使用しても良い。In the present invention, when a photocatalyst hydrosol is selected as the form of the photocatalyst, an aqueous modified photocatalyst sol can be obtained. In this case, a compound having a hydrophilic group as a compound having a hydrosilyl group (for example, a compound having a hydrosilyl group is represented by the above formula (2)) in view of easiness of modification of the photocatalytic hydrosol and dispersion stability of the resulting modified photocatalytic sol. In the case of the hydrosilyl group-containing silicone compound represented by the formula (2), the use of a compound wherein d in the formula (2) is an integer of 1 or more is preferable. Further, the above-mentioned hydrophilic organic solvent may be used for the purpose of assisting the contact between the photocatalyst particles and the above-mentioned hydrosilyl group-containing silicone compound.
【００２７】本発明の製造方法によって得られた変性光
触媒は、溶媒分散性や樹脂相溶性の発現、架橋性能の発
現等、様々な機能を発現するとともに、光触媒のバンド
ギャップエネルギーよりも高いエネルギーの光を照射す
ることにより親水性及び／又は光触媒活性を示す。よっ
て、本発明によって得られる変性触媒は、光触媒活性を
有する部材及び／又は表面性状（親水性あるいは疎水性
等）が制御された部材を提供するのに非常に有用であ
る。The modified photocatalyst obtained by the production method of the present invention not only exhibits various functions such as expression of solvent dispersibility, resin compatibility, expression of crosslinking performance, etc., but also has an energy higher than the band gap energy of the photocatalyst. It exhibits hydrophilicity and / or photocatalytic activity when irradiated with light. Therefore, the modified catalyst obtained by the present invention is very useful for providing a member having photocatalytic activity and / or a member whose surface properties (hydrophilicity, hydrophobicity, etc.) are controlled.
【００２８】[0028]
【発明の実施の形態】本発明を下記の参考例及び実施例
により説明するが、これらは本発明の範囲を制限するも
のではない。実施例中の部は重量部を意味する。実施例
中に用いられる各種物性の測定方法は、下記の通りであ
る。 体積平均分散粒子径 体積平均分散粒子径は、湿式粒度分析計（日機装（株）
製 マイクロトラックＵＰＡ−９２３０）を使用して測
定した。 粘度 光触媒ヒドロゾルの粘度はＢ型粘度計を用いて、ロータ
Ｎｏ．２、回転数６０ｒｐｍ、２０℃の条件で測定し
た。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described with reference to the following Reference Examples and Examples, which do not limit the scope of the present invention. Parts in the examples mean parts by weight. The methods for measuring various physical properties used in the examples are as follows. Volume average dispersed particle size The volume average dispersed particle size is calculated using a wet particle size analyzer (Nikkiso Co., Ltd.)
Manufactured by Microtrac UPA-9230). Viscosity The viscosity of the photocatalyst hydrosol was measured using a B-type viscometer, using a rotor No. 2. Measured under the conditions of a rotation speed of 60 rpm and 20 ° C.
【００２９】（参考例１） ＜光触媒への白金の光還元
法による固定＞ ビーカーに入れた体積平均分散粒子径１８ｎｍのアナタ
ーゼ型酸化チタンゾル〔商品名：ＳＴＳ−０２、石原産
業（株）製、塩酸解膠型、ＴｉＯ２濃度３０重量％、平
均結晶子径７ｎｍ（カタログ値）のもの。粘度は１７５
ｃｐｓであった。〕１００部に塩化白金（ＩＶ）酸六水
和物の５重量％イソプロパノール溶液１．６部を添加
し、撹拌子で撹拌しながら溶液上方約８ｃｍの位置から
ブラックライト（東芝ライテック（株）製 ＦＬ２０Ｓ
ＢＬＢ）の光を３時間照射することにより、白金が担
持された酸化チタンゾルを得た。Reference Example 1 <Fixation of Platinum on Photocatalyst by Photoreduction Method> An anatase-type titanium oxide sol having a volume average dispersed particle diameter of 18 nm in a beaker [trade name: STS-02, manufactured by Ishihara Sangyo Co., Ltd.] Hydrochloric acid peptized, TiO2 concentration 30% by weight, average crystallite diameter 7nm (catalog value). Viscosity is 175
cps. 1.6 parts of a 5% by weight isopropanol solution of chloroplatinic (IV) acid hexahydrate is added to 100 parts, and a black light (manufactured by Toshiba Lighting & Technology Corporation) is placed at a position about 8 cm above the solution while stirring with a stirrer. FL20S
By irradiating the light of BLB) for 3 hours, a titanium oxide sol carrying platinum was obtained.
【００３０】（実施例１）還流冷却器、温度計および撹
拌装置を有する反応器に、参考例１で調整した白金担持
酸化チタンゾルを１００部と水５０部を添加し、撹拌下
５０℃に昇温した。これにメチルハイドロジェンシロキ
サン−ジメチルシロキサンコポリマー（商品名：ＫＦ９
９０１、信越化学（株）製、ヒドロシリル基７．１４ｍ
ｍｏｌ／ｇ（カタログ値）のもの）７．５部をジオキサ
ン６７．５部に溶解した溶液を５０℃にて撹拌下約３０
分かけて添加し、さらに５０℃にて６時間撹拌を続けた
後冷却することにより均一に分散した変性酸化チタンゾ
ルを得た。この時、ヒドロシリル基を有する化合物（メ
チルハイドロジェンシロキサン−ジメチルシロキサンコ
ポリマー）の反応に伴い生成した水素ガス量は２４℃に
おいて８４０ｍｌであった。得られた変性酸化チタンゾ
ルをガラス板上に膜厚が２μとなるようにキャスティン
グした後、室温で１日乾燥することによりコーティング
膜を有するガラス板を得た。得られたコーティング膜は
著しい疎水性を示した。また、得られたコーティング膜
にブラックライト（東芝ライテック（株）製 ＦＬ２０
Ｓ ＢＬＢ）の光を２４時間照射することにより、コー
ティング膜は著しい親水性に変化した。Example 1 100 parts of the platinum-supported titanium oxide sol prepared in Reference Example 1 and 50 parts of water were added to a reactor having a reflux condenser, a thermometer and a stirrer, and the mixture was heated to 50 ° C. with stirring. Warmed. A methyl hydrogen siloxane-dimethyl siloxane copolymer (trade name: KF9)
901, manufactured by Shin-Etsu Chemical Co., Ltd., 7.14 m hydrosilyl group
mol / g (catalog value) 7.5 parts of a solution prepared by dissolving 7.5 parts of dioxane at 50 ° C. under stirring for about 30 minutes.
Then, the mixture was further stirred for 6 hours at 50 ° C., and then cooled to obtain a uniformly dispersed modified titanium oxide sol. At this time, the amount of hydrogen gas generated by the reaction of the compound having a hydrosilyl group (methylhydrogensiloxane-dimethylsiloxane copolymer) was 840 ml at 24 ° C. The resulting modified titanium oxide sol was cast on a glass plate so as to have a thickness of 2 μm, and then dried at room temperature for one day to obtain a glass plate having a coating film. The obtained coating film showed remarkable hydrophobicity. Also, the obtained coating film was coated with a black light (FL20 manufactured by Toshiba Lighting & Technology Corporation).
By irradiating (BLBL) light for 24 hours, the coating film changed to a remarkably hydrophilic property.
【００３１】（実施例２）還流冷却器、温度計および撹
拌装置を有する反応器に、体積平均分散粒子径１８ｎｍ
のアナターゼ型酸化チタンゾル（商品名：ＳＴＳ−０
２、石原産業（株）製、塩酸解膠型、ＴｉＯ２濃度３０
重量％、平均結晶子径７ｎｍ（カタログ値）のもの。粘
度は１７５ｃｐｓであった。）を１００部と水５０部を
添加し、撹拌下５０℃に昇温した。これにメチルハイド
ロジェンシロキサン−ジメチルシロキサンコポリマー
（商品名：ＫＦ９９０１、信越化学（株）製、ヒドロシ
リル基７．１４ｍｍｏｌ／ｇ（カタログ値）のもの）
７．５部と塩化白金（ＩＶ）酸六水和物の５重量％イソ
プロパノール溶液１．６部をジオキサン６７．５部に溶
解した溶液を５０℃にて撹拌下約３０分かけて添加し、
さらに５０℃にて６時間撹拌を続けた後冷却することに
より均一に分散した変性酸化チタンゾルを得た。この
時、ヒドロシリル基を有する化合物（メチルハイドロジ
ェンシロキサン−ジメチルシロキサンコポリマー）の反
応に伴い生成した水素ガス量は２４℃において１１８０
ｍｌであった。また、この反応によって若干量の白金黒
と思われる黒色沈殿も生成した。得られた変性酸化チタ
ンゾルをガラス板上に膜厚が２μとなるようにキャステ
ィングした後、室温で１日乾燥することによりコーティ
ング膜を有するガラス板を得た。得られたコーティング
膜は、若干の相分離は見られるものの、著しい疎水性を
示した。また、得られたコーティング膜にブラックライ
ト（東芝ライテック（株）製 ＦＬ２０Ｓ ＢＬＢ）の
光を２４時間照射することにより、コーティング膜は著
しい親水性に変化した。Example 2 A reactor having a reflux condenser, a thermometer and a stirrer was charged with a volume average dispersed particle diameter of 18 nm.
Anatase type titanium oxide sol (trade name: STS-0)
2. Ishihara Sangyo Co., Ltd., peptized hydrochloric acid, TiO2 concentration 30
% By weight, average crystallite diameter 7 nm (catalog value). The viscosity was 175 cps. ) And 50 parts of water were added, and the temperature was raised to 50 ° C. with stirring. Methyl hydrogen siloxane-dimethyl siloxane copolymer (product name: KF9901, manufactured by Shin-Etsu Chemical Co., Ltd., with hydrosilyl group 7.14 mmol / g (catalog value))
A solution obtained by dissolving 7.5 parts and 1.6 parts of a 5% by weight isopropanol solution of chloroplatinic acid (IV) hexahydrate in 67.5 parts of dioxane was added at 50 ° C. with stirring over about 30 minutes.
After further stirring at 50 ° C. for 6 hours, the mixture was cooled to obtain a uniformly dispersed modified titanium oxide sol. At this time, the amount of hydrogen gas generated by the reaction of the compound having a hydrosilyl group (methylhydrogensiloxane-dimethylsiloxane copolymer) is 1180 at 24 ° C.
ml. This reaction also produced some amount of black precipitate, which was probably platinum black. The resulting modified titanium oxide sol was cast on a glass plate so as to have a thickness of 2 μm, and then dried at room temperature for one day to obtain a glass plate having a coating film. The obtained coating film showed remarkable hydrophobicity, though some phase separation was observed. When the obtained coating film was irradiated with light of a black light (FL20S BLB manufactured by Toshiba Lighting & Technology Corp.) for 24 hours, the coating film changed to remarkable hydrophilicity.
【００３２】（比較例１）還流冷却器、温度計および撹
拌装置を有する反応器に、体積平均分散粒子径１８ｎｍ
のアナターゼ型酸化チタンゾル〔商品名：ＳＴＳ−０
２、石原産業（株）製、塩酸解膠型、ＴｉＯ２濃度３０
重量％、平均結晶子径７ｎｍ（カタログ値）のもの。粘
度は１７５ｃｐｓであった。〕を１００部と水５０部を
添加し、撹拌下５０℃に昇温した。これにメチルハイド
ロジェンシロキサン−ジメチルシロキサンコポリマー
〔商品名：ＫＦ９９０１、信越化学（株）製、ヒドロシ
リル基７．１４ｍｍｏｌ／ｇ（カタログ値）のもの〕
７．５部をジオキサン６７．５部に溶解した溶液を５０
℃にて撹拌下約３０分かけて添加し、さらに５０℃にて
６時間撹拌を続けた後冷却した。この時、ヒドロシリル
基を有する化合物（メチルハイドロジェンシロキサン−
ジメチルシロキサンコポリマー）の反応に伴い生成する
水素ガスの発生はほとんど観測できなかった。得られた
混合物をガラス板上に膜厚が２μとなるようにキャステ
ィングしたが、酸化チタンとメチルハイドロジェンシロ
キサン−ジメチルシロキサンコポリマーは完全に相分離
し、コーティング膜を得ることはできなかった。Comparative Example 1 A reactor having a reflux condenser, a thermometer and a stirrer was charged with a volume average dispersed particle diameter of 18 nm.
Anatase type titanium oxide sol [trade name: STS-0]
2. Ishihara Sangyo Co., Ltd., peptized hydrochloric acid, TiO2 concentration 30
% By weight, average crystallite diameter 7 nm (catalog value). The viscosity was 175 cps. ] And 50 parts of water were added, and the mixture was heated to 50 ° C. with stirring. Methyl hydrogen siloxane-dimethyl siloxane copolymer [product name: KF9901, manufactured by Shin-Etsu Chemical Co., Ltd., with a hydrosilyl group of 7.14 mmol / g (catalog value)]
A solution obtained by dissolving 7.5 parts in 67.5 parts of dioxane was added to 50 parts.
The mixture was added with stirring at about 30 ° C. over about 30 minutes, and further stirred at 50 ° C. for 6 hours, and then cooled. At this time, the compound having a hydrosilyl group (methylhydrogensiloxane-
The generation of hydrogen gas generated by the reaction of dimethylsiloxane copolymer) was hardly observed. The obtained mixture was cast on a glass plate so as to have a thickness of 2 μm. However, the titanium oxide and the methylhydrogensiloxane-dimethylsiloxane copolymer completely separated in phase, and a coating film could not be obtained.
【００３３】（参考例２）還流冷却器、温度計および撹
拌装置を有する反応器に水１５０部を添加し、撹拌下５
０℃に昇温した。これにメチルハイドロジェンシロキサ
ン−ジメチルシロキサンコポリマー〔商品名：ＫＦ９９
０１、信越化学（株）製、ヒドロシリル基７．１４ｍｍ
ｏｌ／ｇ（カタログ値）のもの〕７．５部と塩化白金
（ＩＶ）酸六水和物の５重量％イソプロパノール溶液
１．６部をジオキサン６７．５部に溶解した溶液を５０
℃にて撹拌下約３０分かけて添加し、さらに５０℃にて
６時間撹拌を続けた後冷却することにより、多量の白金
黒と思われる黒色沈殿、及び透明シリコン樹脂の沈殿が
生成した。この時、ヒドロシリル基を有する化合物（メ
チルハイドロジェンシロキサン−ジメチルシロキサンコ
ポリマー）の反応に伴い生成した水素ガス量は２４℃に
おいて１０５０ｍｌであった。実施例１及び実施例２で
は透明シリコン樹脂の沈殿は生成せず、均一に分散した
変性酸化チタンゾルが得られていることより、本発明の
方法によるとヒドロシリル基を有する化合物は光触媒酸
化チタンの粒子表面で反応していることが推測される。Reference Example 2 150 parts of water was added to a reactor having a reflux condenser, a thermometer, and a stirring device, and the mixture was stirred for 5 minutes.
The temperature was raised to 0 ° C. Methyl hydrogen siloxane-dimethyl siloxane copolymer [trade name: KF99]
01, manufactured by Shin-Etsu Chemical Co., Ltd., hydrosilyl group 7.14 mm
ol / g (catalog value)], and a solution prepared by dissolving 7.5 parts and 1.6 parts of a 5% by weight isopropanol solution of chloroplatinic acid (IV) hexahydrate in 67.5 parts of dioxane was used.
The mixture was added with stirring at about 30 ° C. over about 30 minutes, and further stirred for 6 hours at 50 ° C., followed by cooling, thereby producing a large amount of black precipitate, which is considered to be platinum black, and a precipitate of transparent silicon resin. At this time, the amount of hydrogen gas generated by the reaction of the compound having a hydrosilyl group (methylhydrogensiloxane-dimethylsiloxane copolymer) was 1,050 ml at 24 ° C. According to the method of the present invention, according to the method of the present invention, the compound having a hydrosilyl group is a photocatalytic titanium oxide particle, since a transparent silicon resin precipitate is not formed in Examples 1 and 2 and a uniformly dispersed modified titanium oxide sol is obtained. It is presumed that the reaction occurs on the surface.
【００３４】[0034]
【発明の効果】本発明の製造方法により、非常に穏和な
条件でヒドロシリル基を有する化合物で変性された変性
光触媒を得ることができる。According to the production method of the present invention, a modified photocatalyst modified with a compound having a hydrosilyl group can be obtained under very mild conditions.
フロントページの続き Ｆターム(参考） 4G069 AA03 AA08 BA04B BA37 BA48A BC69A BC69B CB80 EA08 4J035 BA14 CA021 CA03M CA032 CA06M CA062 CA082 CA09M CA092 CA11M CA112 CA13M CA132 CA16M CA162 CA19M CA192 CA26M CA262 FB01 GA01 LA05 LB15 LB20 Continued on the front page F-term (reference) 4G069 AA03 AA08 BA04B BA37 BA48A BC69A BC69B CB80 EA08 4J035 BA14 CA021 CA03M CA032 CA06M CA062 CA082 CA09M CA092 CA11M CA112 CA13M CA132 CA16M CA162 CA19M CA192 CA26M CA05 CB01
Claims (8)
ロシリル基に対し脱水素縮合触媒として働く物質で変性
されてなる変性光触媒。1. A modified photocatalyst obtained by modifying a compound having a hydrosilyl group and a substance acting as a dehydrocondensation catalyst on the hydrosilyl group.
して働く物質が白金族触媒であることを特徴とする、請
求項１記載の変性光触媒。2. The modified photocatalyst according to claim 1, wherein the substance acting as a dehydrocondensation catalyst for the hydrosilyl group is a platinum group catalyst.
する請求項１又は２記載の変性光触媒。3. The modified photocatalyst according to claim 1, wherein the photocatalyst is a photocatalytic sol.
ロシリル基に対し脱水素縮合触媒として働く物質で光触
媒を変性させることを特徴とする、変性光触媒の製造方
法。4. A method for producing a modified photocatalyst, comprising modifying a photocatalyst with a compound having a hydrosilyl group and a substance acting as a dehydrocondensation catalyst for the hydrosilyl group.
して働く物質で変性された光触媒を、ヒドロシリル基を
有する化合物で変性させることを特徴とする変性光触媒
の製造方法。5. A method for producing a modified photocatalyst, comprising modifying a photocatalyst modified with a substance acting as a dehydrocondensation catalyst for a hydrosilyl group with a compound having a hydrosilyl group.
して働く物質による光触媒の変性が、光還元法によるこ
とを特徴とする、請求項４又は５記載の変性光触媒の製
造方法。6. The method for producing a modified photocatalyst according to claim 4, wherein the modification of the photocatalyst with a substance acting as a dehydrocondensation catalyst for the hydrosilyl group is performed by a photoreduction method.
して働く物質が白金族触媒であることを特徴とする、請
求項４〜６のいずれかに記載の変性光触媒の製造方法。7. The method for producing a modified photocatalyst according to claim 4, wherein the substance acting as a dehydrocondensation catalyst for the hydrosilyl group is a platinum group catalyst.
する請求項４〜６のいずれかに記載の変性光触媒の製造
方法。8. The method for producing a modified photocatalyst according to claim 4, wherein the photocatalyst is a photocatalytic sol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11218927A JP2001038215A (en) | 1999-08-02 | 1999-08-02 | Modified photocatalyst and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11218927A JP2001038215A (en) | 1999-08-02 | 1999-08-02 | Modified photocatalyst and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001038215A true JP2001038215A (en) | 2001-02-13 |
Family
ID=16727509
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11218927A Withdrawn JP2001038215A (en) | 1999-08-02 | 1999-08-02 | Modified photocatalyst and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001038215A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008104996A (en) * | 2006-10-27 | 2008-05-08 | Central Japan Railway Co | Photocatalyst, coating liquid for forming photocatalyst and method for manufacturing photocatalyst |
-
1999
- 1999-08-02 JP JP11218927A patent/JP2001038215A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008104996A (en) * | 2006-10-27 | 2008-05-08 | Central Japan Railway Co | Photocatalyst, coating liquid for forming photocatalyst and method for manufacturing photocatalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100393925B1 (en) | Modified photocatalyst sol | |
| US20100190643A1 (en) | Deactivation resistant photocatalyst and method of preparation | |
| JP2001329189A (en) | Photocatalyst composition | |
| JP4540971B2 (en) | Neutral titanium oxide sol and method for producing the same | |
| JP7088082B2 (en) | A method for producing a titanium oxide fine particle mixture, a dispersion thereof, a photocatalyst thin film, a member having a photocatalyst thin film on the surface, and a titanium oxide fine particle dispersion. | |
| JP7070474B2 (en) | Titanium oxide fine particles, their dispersion, and a method for producing the dispersion. | |
| JP4737972B2 (en) | Self-grading photocatalytic composition | |
| JP2001038215A (en) | Modified photocatalyst and production thereof | |
| JP4454476B2 (en) | Dye-sensitized photocatalyst and photocatalyst composition using the same | |
| JP4454477B2 (en) | Modified photocatalyst particles | |
| JP2009101287A (en) | Modified photocatalyst sol and its manufacturing method | |
| JP2006136758A (en) | Photocatalyst composition and photocatalyst member | |
| JP3806998B2 (en) | PHOTOCATALYST COMPOSITION, FORMING AGENT THEREOF, AND SUBSTRATE WITH PHOTOCATALYST COMPOSITION | |
| JP2001029785A (en) | Production of surface modified photocatalyst sol | |
| JP2006136782A (en) | Photocatalyst aluminum member | |
| JP2003071296A (en) | Silicone-modified photocatalyst and silica-modified photocatalyst derived therefrom | |
| JP7077550B2 (en) | Titanium oxide airgel particles, method for producing titanium oxide airgel particles, composition for forming a photocatalyst, photocatalyst, and structure. | |
| JP2019048263A (en) | Titanium oxide aerogel particle, method for producing titanium oxide aerogel particle, photocatalyst-forming composition, photocatalyst and structure | |
| JP2010120805A (en) | Photocatalytic body dispersion | |
| JP2001059064A (en) | Coating composition and coated article having hydrophobic film | |
| JP2005224727A (en) | Modified photocatalyst | |
| JP2022156818A (en) | Composite nanoparticle | |
| JP2001049180A (en) | Coating composition, hydrophilic coating film coated article having hydrophilic coating film | |
| JP2023147700A (en) | Titania nanoparticle and production method thereof | |
| JP2001059063A (en) | Coating composition, hydrophobic coating film and coated article having hydrophobic coating film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20060725 |
|
| A761 | Written withdrawal of application |
Free format text: JAPANESE INTERMEDIATE CODE: A761 Effective date: 20080612 |