JP5113723B2 - Photocatalyst dispersion - Google Patents
Photocatalyst dispersion Download PDFInfo
- Publication number
- JP5113723B2 JP5113723B2 JP2008283742A JP2008283742A JP5113723B2 JP 5113723 B2 JP5113723 B2 JP 5113723B2 JP 2008283742 A JP2008283742 A JP 2008283742A JP 2008283742 A JP2008283742 A JP 2008283742A JP 5113723 B2 JP5113723 B2 JP 5113723B2
- Authority
- JP
- Japan
- Prior art keywords
- oxide particles
- photocatalytic
- photocatalyst
- titanium oxide
- tungsten oxide
- 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.)
- Expired - Fee Related
Links
- 239000006185 dispersion Substances 0.000 title claims description 128
- 239000011941 photocatalyst Substances 0.000 title claims description 106
- 239000002245 particle Substances 0.000 claims description 187
- 230000001699 photocatalysis Effects 0.000 claims description 122
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 91
- 239000007788 liquid Substances 0.000 claims description 82
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 78
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 78
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 77
- 239000000126 substance Substances 0.000 claims description 47
- 239000002612 dispersion medium Substances 0.000 claims description 36
- 239000002243 precursor Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 12
- -1 alcohol compound Chemical class 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 125000004429 atom Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 42
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 239000007787 solid Substances 0.000 description 21
- 239000002253 acid Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 16
- 150000002894 organic compounds Chemical class 0.000 description 15
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 14
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 238000000926 separation method Methods 0.000 description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 241000588724 Escherichia coli Species 0.000 description 7
- 241000191967 Staphylococcus aureus Species 0.000 description 7
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 7
- 239000000654 additive Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000010931 gold Substances 0.000 description 7
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000012756 surface treatment agent Substances 0.000 description 6
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 244000052616 bacterial pathogen Species 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000002609 medium Substances 0.000 description 4
- 235000006408 oxalic acid Nutrition 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 244000052769 pathogen Species 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 101100258086 Postia placenta (strain ATCC 44394 / Madison 698-R) STS-01 gene Proteins 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000003574 free electron Substances 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 150000003627 tricarboxylic acid derivatives Chemical class 0.000 description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 description 1
- GMTXBUZKCHNBCH-UHFFFAOYSA-L [K].[Pt](Cl)Cl Chemical compound [K].[Pt](Cl)Cl GMTXBUZKCHNBCH-UHFFFAOYSA-L 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- YKIOKAURTKXMSB-UHFFFAOYSA-N adams's catalyst Chemical compound O=[Pt]=O YKIOKAURTKXMSB-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 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
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- FOSZYDNAURUMOT-UHFFFAOYSA-J azane;platinum(4+);tetrachloride Chemical compound N.N.N.N.[Cl-].[Cl-].[Cl-].[Cl-].[Pt+4] FOSZYDNAURUMOT-UHFFFAOYSA-J 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 description 1
- LLVVIWYEOKVOFV-UHFFFAOYSA-L copper;diiodate Chemical compound [Cu+2].[O-]I(=O)=O.[O-]I(=O)=O LLVVIWYEOKVOFV-UHFFFAOYSA-L 0.000 description 1
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 description 1
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 1
- FWBOFUGDKHMVPI-UHFFFAOYSA-K dicopper;2-oxidopropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[O-]C(=O)CC([O-])(C([O-])=O)CC([O-])=O FWBOFUGDKHMVPI-UHFFFAOYSA-K 0.000 description 1
- SKQUUKNCBWILCD-UHFFFAOYSA-J dicopper;chloride;trihydroxide Chemical compound [OH-].[OH-].[OH-].[Cl-].[Cu+2].[Cu+2] SKQUUKNCBWILCD-UHFFFAOYSA-J 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- ATGIETUGWDAYPU-UHFFFAOYSA-M gold monoiodide Chemical compound [Au]I ATGIETUGWDAYPU-UHFFFAOYSA-M 0.000 description 1
- PMCMJPXEJUKOAO-UHFFFAOYSA-M gold(1+);bromide Chemical compound [Au]Br PMCMJPXEJUKOAO-UHFFFAOYSA-M 0.000 description 1
- 229910021505 gold(III) hydroxide Inorganic materials 0.000 description 1
- WDZVNNYQBQRJRX-UHFFFAOYSA-K gold(iii) hydroxide Chemical compound O[Au](O)O WDZVNNYQBQRJRX-UHFFFAOYSA-K 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910002094 inorganic tetrachloropalladate Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- YWXYYJSYQOXTPL-SLPGGIOYSA-N isosorbide mononitrate Chemical compound [O-][N+](=O)O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 YWXYYJSYQOXTPL-SLPGGIOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- NXJCBFBQEVOTOW-UHFFFAOYSA-L palladium(2+);dihydroxide Chemical compound O[Pd]O NXJCBFBQEVOTOW-UHFFFAOYSA-L 0.000 description 1
- RFLFDJSIZCCYIP-UHFFFAOYSA-L palladium(2+);sulfate Chemical compound [Pd+2].[O-]S([O-])(=O)=O RFLFDJSIZCCYIP-UHFFFAOYSA-L 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- INIOZDBICVTGEO-UHFFFAOYSA-L palladium(ii) bromide Chemical compound Br[Pd]Br INIOZDBICVTGEO-UHFFFAOYSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- ZXDJCKVQKCNWEI-UHFFFAOYSA-L platinum(2+);diiodide Chemical compound [I-].[I-].[Pt+2] ZXDJCKVQKCNWEI-UHFFFAOYSA-L 0.000 description 1
- AAIMUHANAAXZIF-UHFFFAOYSA-L platinum(2+);sulfite Chemical compound [Pt+2].[O-]S([O-])=O AAIMUHANAAXZIF-UHFFFAOYSA-L 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- YLSZOZPQTCFBIR-UHFFFAOYSA-J tetrabromopalladium Chemical compound Br[Pd](Br)(Br)Br YLSZOZPQTCFBIR-UHFFFAOYSA-J 0.000 description 1
- 229940071240 tetrachloroaurate Drugs 0.000 description 1
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Description
本発明は、光触媒体として光触媒酸化チタン粒子と光触媒酸化タングステン粒子とを含む光触媒体分散液に関する。 The present invention relates to a photocatalyst dispersion liquid containing photocatalytic titanium oxide particles and photocatalytic tungsten oxide particles as a photocatalyst.
半導体にバンドギャップ以上のエネルギーを持つ光を照射すると、価電子帯の電子が伝導帯に励起され、価電子帯に正孔が、伝導帯に自由電子が、それぞれ生成する。かかる正孔および自由電子は、それぞれ強い酸化力と還元力を有することから、半導体に接触した分子種に酸化還元作用を及ぼす。この酸化還元作用は光触媒作用と呼ばれており、かかる光触媒作用を示し得る半導体は、光触媒体と呼ばれている。このような光触媒体としては、光触媒酸化チタン粒子や光触媒酸化タングステン粒子などの粒子状のものが知られている。 When a semiconductor is irradiated with light having energy greater than or equal to the band gap, electrons in the valence band are excited to the conduction band, holes are generated in the valence band, and free electrons are generated in the conduction band. Since such holes and free electrons have strong oxidizing power and reducing power, respectively, they exert a redox action on molecular species in contact with the semiconductor. This redox action is called a photocatalytic action, and a semiconductor that can exhibit such a photocatalytic action is called a photocatalyst. As such a photocatalyst, particulates such as photocatalytic titanium oxide particles and photocatalytic tungsten oxide particles are known.
光触媒酸化チタン粒子や光触媒酸化タングステン粒子は、通常、分散媒中に分散させ、光触媒体分散液として光触媒体層の形成に利用されており、例えば、光触媒酸化チタン粒子および光触媒酸化タングステン粒子を分散媒中に分散させた光触媒体分散液が開示されている（特許文献１）。かかる光触媒体分散液を基材の表面に塗布することにより、基材表面に、光触媒酸化チタン粒子および光触媒酸化タングステン粒子を含み、光触媒作用を示す光触媒体層を容易に形成することができる。 Photocatalytic titanium oxide particles and photocatalytic tungsten oxide particles are usually dispersed in a dispersion medium and used as a photocatalyst dispersion to form a photocatalyst layer. For example, photocatalytic titanium oxide particles and photocatalytic tungsten oxide particles are dispersed in a dispersion medium. A photocatalyst dispersion liquid dispersed therein is disclosed (Patent Document 1). By applying such a photocatalyst dispersion to the surface of the substrate, a photocatalyst layer that includes photocatalytic titanium oxide particles and photocatalytic tungsten oxide particles on the surface of the substrate and that exhibits a photocatalytic action can be easily formed.
しかしながら、光触媒酸化チタン粒子および光触媒酸化タングステン粒子を分散媒中に分散させた従来の光触媒体分散液は、粒子が互いに凝集して固液分離し易いという欠点があった。例えば、光触媒体分散液を輸送、保管する間に該分散液中の粒子が凝集して固液分離が生じると、分散液を基材に塗布するなどして光触媒体層を形成する際に、良好な膜を形成することができず、その結果、充分な光触媒活性を付与できない、といった問題を招くことになる。 However, the conventional photocatalyst dispersion liquid in which photocatalytic titanium oxide particles and photocatalytic tungsten oxide particles are dispersed in a dispersion medium has a drawback that the particles are aggregated with each other and easily separated into solid and liquid. For example, when the photocatalyst dispersion liquid is transported and stored, particles in the dispersion aggregate to cause solid-liquid separation. A good film cannot be formed, and as a result, a problem that sufficient photocatalytic activity cannot be imparted is caused.
そこで、本発明の課題は、分散媒中に分散された光触媒酸化チタン粒子と光触媒酸化タングステン粒子との凝集が抑制されて固液分離を起こしにくく、優れた光触媒活性を発現しうる光触媒体分散液を提供することにある。 Accordingly, an object of the present invention is to provide a photocatalyst dispersion liquid in which aggregation of the photocatalytic titanium oxide particles and the photocatalytic tungsten oxide particles dispersed in the dispersion medium is suppressed and solid-liquid separation is difficult to occur, and excellent photocatalytic activity can be expressed. Is to provide.
本発明者らは、上記課題を解決するべく鋭意研究を重ねた。その結果、光触媒酸化チタン粒子と光触媒酸化タングステン粒子とが分散媒中で凝集し易いのは、一般に、光触媒酸化チタン粒子の表面はプラスに、光触媒酸化タングステン粒子の表面はマイナスにそれぞれ帯電しているからであり、光触媒酸化チタン粒子および光触媒酸化タングステン粒子の表面を互いに同じ極性、すなわち共にプラスに帯電させるか、共にマイナスに帯電させることにより、凝集が抑制されて固液分離を起こしにくい光触媒体分散液となること、さらに、この光触媒体分散液の分散媒として炭素数が１〜４の揮発性水溶性有機化合物を特定量用いると、形成される塗膜の光触媒活性が格段に向上することを見出し、本発明に至った。 The present inventors have intensively studied to solve the above problems. As a result, the photocatalytic titanium oxide particles and the photocatalytic tungsten oxide particles are likely to aggregate in the dispersion medium. Generally, the surface of the photocatalytic titanium oxide particles is positively charged and the surface of the photocatalytic tungsten oxide particles is negatively charged. The photocatalyst dispersion is less likely to cause solid-liquid separation by suppressing the aggregation by charging the surfaces of the photocatalytic titanium oxide particles and the photocatalytic tungsten oxide particles with the same polarity, that is, both positively or negatively charged. In addition, when a specific amount of a volatile water-soluble organic compound having 1 to 4 carbon atoms is used as a dispersion medium of the photocatalyst dispersion liquid, the photocatalytic activity of the formed coating film is remarkably improved. The headline, the present invention has been reached.
すなわち、本発明の光触媒体分散液は、光触媒酸化チタン粒子および光触媒酸化タングステン粒子が分散媒中に分散されてなり、光触媒酸化チタン粒子および光触媒酸化タングステン粒子は表面が互いに同じ極性に帯電しており、炭素数が１〜４のアルコール化合物と水とからなり、前記アルコール化合物を光触媒体分散液１００質量部に対して５〜５０質量部含有していることを特徴とする。
本発明の光触媒機能製品の製造方法は、基材の表面に前記本発明の光触媒体分散液を塗布し、分散媒を揮発させることを特徴とする。
That is, the photocatalyst dispersion liquid of the present invention comprises photocatalytic titanium oxide particles and photocatalytic tungsten oxide particles dispersed in a dispersion medium, and the surfaces of the photocatalytic titanium oxide particles and the photocatalytic tungsten oxide particles are charged to the same polarity. It comprises an alcohol compound having 1 to 4 carbon atoms and water, and contains 5 to 50 parts by mass of the alcohol compound with respect to 100 parts by mass of the photocatalyst dispersion liquid.
The method for producing a photocatalytic functional product of the present invention is characterized in that the photocatalyst dispersion liquid of the present invention is applied to the surface of a substrate, and the dispersion medium is volatilized.
本発明によれば、分散媒中に分散された光触媒酸化チタン粒子と光触媒酸化タングステン粒子との凝集が抑制されて固液分離を起こしにくく、優れた光触媒活性を発現しうる光触媒体分散液を提供することができる。すなわち、本発明の光触媒体分散液は、分散媒中に分散された光触媒酸化チタン粒子および光触媒酸化タングステン粒子の表面が互いに同じ極性に帯電しているので、互いに凝集することがなく、このため固液分離することがない。また、本発明の光触媒体分散液は、粒子を互いに凝集させることなく基材に塗布することができるものであり、しかも、特定炭素数の揮発性水溶性有機化合物を特定量含有するものであるので、この光触媒体分散液を用いて形成される塗膜は、高い光触媒活性を示す。 According to the present invention, there is provided a photocatalyst dispersion liquid in which aggregation of the photocatalytic titanium oxide particles and the photocatalytic tungsten oxide particles dispersed in the dispersion medium is suppressed and solid-liquid separation is hardly caused, and an excellent photocatalytic activity can be expressed. can do. That is, in the photocatalyst dispersion liquid of the present invention, the surfaces of the photocatalytic titanium oxide particles and the photocatalytic tungsten oxide particles dispersed in the dispersion medium are charged to the same polarity, so that they do not agglomerate with each other. There is no liquid separation. Moreover, the photocatalyst dispersion liquid of the present invention can be applied to a substrate without agglomerating the particles, and contains a specific amount of a volatile water-soluble organic compound having a specific carbon number. Therefore, the coating film formed using this photocatalyst dispersion liquid exhibits high photocatalytic activity.
（光触媒体分散液）
本発明の光触媒体分散液は、光触媒酸化チタン粒子（以下、単に「酸化チタン粒子」と称することもある）および光触媒酸化タングステン粒子（以下、単に「酸化タングステン粒子」と称することもある）が分散媒中に分散されたものである。
本発明の光触媒体分散液を構成する酸化チタン粒子は、光触媒作用を示す粒子状の酸化チタンであれば、特に制限はされないが、例えば、メタチタン酸粒子、結晶型がアナターゼ型、ブルッカイト型、ルチル型などである二酸化チタン〔ＴｉＯ2〕粒子等が挙げられる。なお、酸化チタン粒子は、単独で用いてもよいし、２種以上を併用してもよい。
(Photocatalyst dispersion)
In the photocatalyst dispersion liquid of the present invention, photocatalytic titanium oxide particles (hereinafter also simply referred to as “titanium oxide particles”) and photocatalytic tungsten oxide particles (hereinafter also simply referred to as “tungsten oxide particles”) are dispersed. It is dispersed in the medium.
The titanium oxide particles constituting the photocatalyst dispersion of the present invention are not particularly limited as long as they are particulate titanium oxide exhibiting a photocatalytic action. For example, metatitanic acid particles, crystal type is anatase type, brookite type, rutile type Examples thereof include titanium dioxide [TiO 2 ] particles such as molds. In addition, a titanium oxide particle may be used independently and may use 2 or more types together.
メタチタン酸粒子は、例えば、（１−ｉ）硫酸チタニルの水溶液を加熱して加水分解する方法により得ることができる。
二酸化チタン粒子は、例えば、（１−ｉｉ）硫酸チタニルまたは塩化チタンの水溶液を加熱することなく、これに塩基を加えることにより沈殿物を得、得られた沈殿物を焼成する方法、（１−ｉｉｉ）チタンアルコキシドに水、酸の水溶液または塩基の水溶液を加えて沈殿物を得、得られた沈殿物を焼成する方法、（１−ｉｖ）メタチタン酸を焼成する方法、などによって得ることができる。これらの方法で得られる二酸化チタン粒子は、焼成する際の焼成温度や焼成時間を調整することにより、アナターゼ型、ブルッカイト型またはルチル型など、所望の結晶型にすることができる。
Metatitanic acid particles can be obtained, for example, by a method of hydrolyzing an aqueous solution of (1-i) titanyl sulfate by heating.
The titanium dioxide particles can be obtained by, for example, (1-ii) a method in which a precipitate is obtained by adding a base to this without heating an aqueous solution of titanyl sulfate or titanium chloride, and the obtained precipitate is calcined. iii) It can be obtained by adding a water, an aqueous solution of an acid or an aqueous base solution to titanium alkoxide to obtain a precipitate, and firing the obtained precipitate, (1-iv) a method of firing metatitanic acid, and the like. . The titanium dioxide particles obtained by these methods can be made into a desired crystal type such as anatase type, brookite type or rutile type by adjusting the baking temperature and baking time when baking.
酸化チタン粒子の粒子径は、特に制限されないが、光触媒作用の観点からは、平均分散粒子径で、通常２０〜１５０ｎｍ、好ましくは４０〜１００ｎｍである。
酸化チタン粒子のＢＥＴ比表面積は、特に制限されないが、光触媒作用の観点からは、通常１００〜５００ｍ2／ｇ、好ましくは３００〜４００ｍ2／ｇである。
The particle size of the titanium oxide particles is not particularly limited, but from the viewpoint of photocatalysis, the average dispersed particle size is usually 20 to 150 nm, preferably 40 to 100 nm.
BET specific surface area of the titanium oxide particles is not particularly limited, from the viewpoint of photocatalytic activity, usually 100 to 500 m 2 / g, preferably from 300~400m 2 / g.
本発明の光触媒体分散液を構成する酸化タングステン粒子は、光触媒作用を示す粒子状の酸化タングステンであれば、特に制限はされないが、例えば、三酸化タングステン〔ＷＯ3〕粒子等が挙げられる。なお、酸化タングステン粒子は、単独で用いてもよいし、２種以上を併用してもよい。
三酸化タングステン粒子は、例えば、（２−ｉ）タングステン酸塩の水溶液に酸を加えることにより、沈殿物としてタングステン酸を得、得られたタングステン酸を焼成する方法、（２−ｉｉ）メタタングステン酸アンモニウム、パラタングステン酸アンモニウムを加熱することにより熱分解する方法、などによって得ることができる。
The tungsten oxide particles constituting the photocatalyst dispersion liquid of the present invention are not particularly limited as long as they are particulate tungsten oxide exhibiting a photocatalytic action, and examples thereof include tungsten trioxide [WO 3 ] particles. The tungsten oxide particles may be used alone or in combination of two or more.
The tungsten trioxide particles are obtained by, for example, (2-i) a method of adding tungstic acid as a precipitate by adding an acid to an aqueous solution of tungstate, and firing the obtained tungstic acid, (2-ii) metatungsten It can be obtained by a method of thermally decomposing by heating ammonium acid or ammonium paratungstate.
酸化タングステン粒子の粒子径は、特に制限されないが、光触媒作用の観点からは、平均分散粒子径で、通常５０〜２００ｎｍ、好ましくは８０〜１３０ｎｍである。
酸化タングステン粒子のＢＥＴ比表面積は、特に制限されないが、光触媒作用の観点からは、通常５〜１００ｍ2／ｇ、好ましくは２０〜５０ｍ2／ｇである。
The particle diameter of the tungsten oxide particles is not particularly limited, but from the viewpoint of photocatalysis, the average dispersed particle diameter is usually 50 to 200 nm, preferably 80 to 130 nm.
BET specific surface area of the tungsten oxide particles is not particularly limited, from the viewpoint of photocatalytic activity, typically 5 to 100 m 2 / g, preferably from 20 to 50 m 2 / g.
本発明の光触媒体分散液において、前記酸化チタン粒子と前記酸化タングステン粒子との比率（酸化チタン粒子：酸化タングステン粒子）は、質量比で、通常４：１〜１：８、好ましくは２：３〜３：２である。 In the photocatalyst dispersion liquid of the present invention, the ratio of the titanium oxide particles to the tungsten oxide particles (titanium oxide particles: tungsten oxide particles) is usually 4: 1 to 1: 8, preferably 2: 3 in mass ratio. ~ 3: 2.
本発明の光触媒体分散液においては、光触媒酸化チタン粒子および光触媒酸化タングステン粒子は表面が互いに同じ極性に帯電しており、具体的には、粒子表面が共にプラスに帯電しているか、または粒子表面が共にマイナスに帯電している。これにより、分散液中の酸化チタン粒子と酸化タングステン粒子との凝集が抑制され、固液分離を起こしにくくなる。 In the photocatalyst dispersion liquid of the present invention, the surfaces of the photocatalytic titanium oxide particles and the photocatalytic tungsten oxide particles are charged with the same polarity, specifically, the particle surfaces are both charged positively or the particle surface Are both negatively charged. Thereby, aggregation of the titanium oxide particles and the tungsten oxide particles in the dispersion is suppressed, and solid-liquid separation is hardly caused.
一般に、上述した（１−ｉ）の方法により得たメタチタン酸粒子や、（１−ｉｉ）〜（１−ｉｖ）の方法により得た二酸化チタン粒子は、その表面がプラスに帯電している。これに対して、上述した（２−ｉ）や（２−ｉｉ）の方法により得た三酸化タングステン粒子は、その表面がマイナスに帯電している。このため、表面がプラスに帯電している上述の酸化チタン粒子と、表面がマイナスに帯電している上述の酸化タングステン粒子とを用いる場合は、例えば、酸化チタン粒子の表面をマイナスに帯電させてから、酸化タングステン粒子と混合するようにすればよい。 In general, the surfaces of the metatitanic acid particles obtained by the method (1-i) and the titanium dioxide particles obtained by the methods (1-ii) to (1-iv) are positively charged. On the other hand, the surface of the tungsten trioxide particles obtained by the methods (2-i) and (2-ii) described above is negatively charged. Therefore, when using the above-mentioned titanium oxide particles whose surface is positively charged and the above-mentioned tungsten oxide particles whose surface is negatively charged, for example, the surface of the titanium oxide particles is negatively charged. Therefore, it is sufficient to mix with tungsten oxide particles.
表面がプラスに帯電した酸化チタン粒子の表面をマイナスに帯電させるには、該酸化チタン粒子を、あらかじめ、その表面をマイナスに帯電させうる表面処理剤を後述する分散媒に溶解させた溶液中に分散させればよい。これにより、溶液中に溶解した表面処理剤が酸化チタン粒子の表面に吸着し、粒子表面をマイナスに帯電させることができる。 In order to negatively charge the surface of the titanium oxide particles whose surface is positively charged, the titanium oxide particles are previously dissolved in a solution in which a surface treatment agent capable of negatively charging the surface is dissolved in a dispersion medium described later. What is necessary is just to disperse. Thereby, the surface treating agent dissolved in the solution is adsorbed on the surface of the titanium oxide particles, and the particle surface can be negatively charged.
粒子表面をマイナスに帯電させうる表面処理剤としては、例えば、ジカルボン酸、トリカルボン酸などのような多価カルボン酸、リン酸などが挙げられる。具体的には、ジカルボン酸としては例えば蓚酸などが、トリカルボン酸としては例えばクエン酸などが挙げられる。また、前記多価カルボン酸やリン酸としては、遊離酸を用いてもよいし、塩を用いてもよい。塩としては、例えばアンモニウム塩などが挙げられる。かかる表面処理剤としては、特に、蓚酸、蓚酸アンモニウムなどが好ましい。
前記表面処理剤の使用量は、ＴｉＯ2換算の光触媒酸化チタン粒子に対して、表面を充分に帯電させる点で、通常０．００１モル倍以上、好ましくは０．０２モル倍以上であり、経済性の点で、通常０．５モル倍以下、好ましくは０．３モル倍以下である。
Examples of the surface treatment agent that can negatively charge the particle surface include polyvalent carboxylic acids such as dicarboxylic acid and tricarboxylic acid, and phosphoric acid. Specifically, examples of the dicarboxylic acid include oxalic acid, and examples of the tricarboxylic acid include citric acid. Moreover, as said polyvalent carboxylic acid and phosphoric acid, a free acid may be used and a salt may be used. Examples of the salt include ammonium salt. As such a surface treatment agent, oxalic acid, ammonium oxalate and the like are particularly preferable.
The amount of the surface treatment agent used is usually 0.001 mol times or more, preferably 0.02 mol times or more, in terms of sufficiently charging the surface with respect to the TiO 2 converted photocatalytic titanium oxide particles. In view of properties, it is usually 0.5 mol times or less, preferably 0.3 mol times or less.
酸化チタン粒子および酸化タングステン粒子の表面の帯電は、それぞれ、溶媒中に分散させたときのゼータ電位により測定することができる。ゼータ電位の測定に用いられる溶媒としては、例えば、塩酸を加えて水素イオン濃度をｐＨ３．０とした塩化ナトリウム水溶液（塩化ナトリウム濃度０．０１モル／Ｌ）が用いられる。この溶媒の使用量は、酸化チタン粒子または酸化タングステン粒子に対して、通常１００００質量倍〜１００００００質量倍である。 The surface charge of titanium oxide particles and tungsten oxide particles can be measured by the zeta potential when dispersed in a solvent. As a solvent used for measuring the zeta potential, for example, a sodium chloride aqueous solution (sodium chloride concentration 0.01 mol / L) in which hydrochloric acid is added to adjust the hydrogen ion concentration to pH 3.0 is used. The amount of the solvent used is usually 10,000 to 1,000,000 times the mass of the titanium oxide particles or tungsten oxide particles.
本発明の光触媒体分散液においては、分散媒として、炭素数が１〜４の揮発性水溶性有機化合物を、光触媒体分散液１００質量部に対して５〜５０質量部、好ましくは８〜３５質量部含有する。これにより、光触媒分散液を塗布して形成される塗膜の光触媒活性を向上させることができる。炭素数が１〜４の揮発性水溶性有機化合物の含有量が前記範囲よりも少ないと、光触媒活性の向上効果が不充分となり、一方、前記範囲よりも多いと、得られる塗膜中に残留する有機物が多くなり、充分な光触媒活性が得られない。
炭素数が１〜４の揮発性水溶性有機化合物としては、例えば、メタノール、エタノール、プロパノールなどのアルコール化合物、アセトン、メチルエチルケトンなどのケトン化合物等が挙げられ、これらの中でも特にアルコール化合物が好ましい。なお、揮発性水溶性有機化合物は、単独で用いてもよいし、２種以上を併用してもよい。
In the photocatalyst dispersion liquid of the present invention, a volatile water-soluble organic compound having 1 to 4 carbon atoms is used as a dispersion medium in an amount of 5 to 50 parts by mass, preferably 8 to 35 parts per 100 parts by mass of the photocatalyst dispersion liquid. Contains part by mass. Thereby, the photocatalytic activity of the coating film formed by applying the photocatalyst dispersion liquid can be improved. If the content of the volatile water-soluble organic compound having 1 to 4 carbon atoms is less than the above range, the effect of improving the photocatalytic activity becomes insufficient. On the other hand, if it exceeds the above range, it remains in the resulting coating film. As a result, the amount of organic matter increases and sufficient photocatalytic activity cannot be obtained.
Examples of the volatile water-soluble organic compound having 1 to 4 carbon atoms include alcohol compounds such as methanol, ethanol and propanol, ketone compounds such as acetone and methyl ethyl ketone, and among these, alcohol compounds are particularly preferable. In addition, a volatile water-soluble organic compound may be used independently and may use 2 or more types together.
本発明の光触媒体分散液を構成する分散媒は、少なくとも上述した特定量の揮発性水溶性有機化合物を含有するものであれば、特に制限はなく、前記揮発性水溶性有機化合物を単独で用いてもよいし、その他の有機溶媒や水を併用してもよいが、通常、水と前記揮発性水溶性有機化合物とからなる混合溶媒が用いられる。このとき、水と前記揮発性水溶性有機化合物との混合比率については、揮発性水溶性有機化合物の量が前記範囲となる限り、適宜設定すればよい。 The dispersion medium constituting the photocatalyst dispersion liquid of the present invention is not particularly limited as long as it contains at least the above-mentioned specific amount of the volatile water-soluble organic compound, and the volatile water-soluble organic compound is used alone. Alternatively, other organic solvents or water may be used in combination, but usually a mixed solvent composed of water and the volatile water-soluble organic compound is used. At this time, the mixing ratio of water and the volatile water-soluble organic compound may be appropriately set as long as the amount of the volatile water-soluble organic compound falls within the above range.
本発明の光触媒体分散液においては、分散媒の含有量は、酸化チタン粒子および酸化タングステン粒子の合計量に対して、通常５〜２００質量倍、好ましくは１０〜１００質量倍である。分散媒が５質量倍未満であると、酸化チタン粒子および酸化タングステン粒子が沈降し易くなり、一方、２００質量倍を超えると、容積効率の点で不利となるので、いずれも好ましくない。 In the photocatalyst dispersion liquid of the present invention, the content of the dispersion medium is usually 5 to 200 times by mass, preferably 10 to 100 times by mass, with respect to the total amount of titanium oxide particles and tungsten oxide particles. If the dispersion medium is less than 5 mass times, the titanium oxide particles and the tungsten oxide particles are liable to settle, whereas if it exceeds 200 mass times, it is disadvantageous in terms of volumetric efficiency.
本発明の光触媒体分散液は、電子吸引性物質またはその前駆体をも含有していてもよい。電子吸引性物質とは、光触媒体（すなわち、酸化チタン粒子および酸化タングステン粒子）の表面に担持されて電子吸引性を発揮しうる化合物であり、電子吸引性物質の前駆体とは、光触媒体の表面で電子吸引性物質に遷移しうる化合物（例えば、光照射により電子吸引性物質に還元されうる化合物）である。電子吸引性物質が光触媒体の表面に担持されて存在すると、光の照射により伝導帯に励起された電子と価電子帯に生成した正孔との再結合が抑制され、光触媒作用をより高めることができる。 The photocatalyst dispersion liquid of the present invention may also contain an electron withdrawing substance or a precursor thereof. An electron-withdrawing substance is a compound that can be carried on the surface of a photocatalyst (that is, titanium oxide particles and tungsten oxide particles) and can exhibit electron-withdrawing properties. A compound that can transition to an electron-withdrawing substance on the surface (for example, a compound that can be reduced to an electron-withdrawing substance by light irradiation). When an electron-withdrawing substance is supported on the surface of the photocatalyst, recombination of electrons excited in the conduction band by light irradiation and holes generated in the valence band is suppressed, and the photocatalytic action is further enhanced. Can do.
前記電子吸引性物質またはその前駆体は、Ｃｕ、Ｐｔ、Ａｕ、Ｐｄ、Ａｇ、Ｆｅ、Ｎｂ、Ｒｕ、Ｉｒ、ＲｈおよびＣｏからなる群より選ばれる１種以上の金属原子を含有してなるものであることが好ましい。より好ましくは、Ｃｕ、Ｐｔ、ＡｕおよびＰｄのうちの１種以上の金属原子を含有してなるものである。例えば、前記電子吸引性物質としては、前記金属原子からなる金属、もしくは、これらの金属の酸化物や水酸化物等が挙げられ、電子吸引性物質の前駆体としては、前記金属原子からなる金属の硝酸塩、硫酸塩、ハロゲン化物、有機酸塩、炭酸塩、りん酸塩等が挙げられる。 The electron withdrawing substance or its precursor contains one or more metal atoms selected from the group consisting of Cu, Pt, Au, Pd, Ag, Fe, Nb, Ru, Ir, Rh and Co. It is preferable that More preferably, it contains one or more metal atoms of Cu, Pt, Au and Pd. For example, the electron-withdrawing substance may be a metal made of the metal atom, or an oxide or hydroxide of these metals, and the precursor of the electron-withdrawing substance may be a metal made of the metal atom. Nitrates, sulfates, halides, organic acid salts, carbonates, phosphates, and the like.
電子吸引性物質の好ましい具体例としては、Ｃｕ、Ｐｔ、Ａｕ、Ｐｄ等の金属が挙げられる。また、電子吸引性物質の前駆体の好ましい具体例としては、Ｃｕを含む前駆体として、硝酸銅〔Ｃｕ(ＮＯ3)2〕、硫酸銅〔Ｃｕ(ＳＯ4)2〕、塩化銅〔ＣｕＣｌ2、ＣｕＣｌ〕、臭化銅〔ＣｕＢｒ2、ＣｕＢｒ〕、沃化銅〔ＣｕＩ〕、沃素酸銅〔ＣｕＩ2Ｏ6〕、塩化アンモニウム銅〔Ｃｕ(ＮＨ4)2Ｃｌ4〕、オキシ塩化銅〔Ｃｕ2Ｃｌ(ＯＨ)3〕、酢酸銅〔ＣＨ3ＣＯＯＣｕ、(ＣＨ3ＣＯＯ)2Ｃｕ〕、蟻酸銅〔(ＨＣＯＯ)2Ｃｕ〕、炭酸銅〔ＣｕＣＯ3）、蓚酸銅〔ＣｕＣ2Ｏ4〕、クエン酸銅〔Ｃｕ2Ｃ6Ｈ4Ｏ7〕、リン酸銅〔ＣｕＰＯ4〕等が；Ｐｔを含む前駆体として、塩化白金〔ＰｔＣｌ2、ＰｔＣｌ4〕、臭化白金〔ＰｔＢｒ2、ＰｔＢｒ4〕、沃化白金〔ＰｔＩ2、ＰｔＩ4〕、塩化白金カリウム〔Ｋ2(ＰｔＣｌ4)〕、ヘキサクロロ白金酸〔Ｈ2ＰｔＣｌ6〕、亜硫酸白金〔Ｈ3Ｐｔ(ＳＯ3)2ＯＨ〕、酸化白金〔ＰｔＯ2〕、塩化テトラアンミン白金〔Ｐｔ(ＮＨ3)4Ｃｌ2〕、炭酸水素テトラアンミン白金〔Ｃ2Ｈ14Ｎ4Ｏ6Ｐｔ〕、テトラアンミン白金リン酸水素〔Ｐｔ(ＮＨ3)4ＨＰＯ4〕、水酸化テトラアンミン白金〔Ｐｔ(ＮＨ3)4(ＯＨ)2〕、硝酸テトラアンミン白金〔Ｐｔ(ＮＯ3)2(ＮＨ3)4〕、テトラアンミン白金テトラクロロ白金〔(Ｐｔ(ＮＨ3)4)(ＰｔＣｌ4)〕等が；Ａｕを含む前駆体として、塩化金〔ＡｕＣｌ〕、臭化金〔ＡｕＢｒ〕、沃化金〔ＡｕＩ〕、水酸化金〔Ａｕ(ＯＨ)2〕、テトラクロロ金酸〔ＨＡｕＣｌ4〕、テトラクロロ金酸カリウム〔ＫＡｕＣｌ4〕、テトラブロモ金酸カリウム〔ＫＡｕＢｒ4〕、酸化金〔Ａｕ2Ｏ3〕等が；Ｐｄを含む前駆体として、例えば、酢酸パラジウム〔(ＣＨ3ＣＯＯ)2Ｐｄ〕、塩化パラジウム〔ＰｄＣｌ2〕、臭化パラジウム〔ＰｄＢｒ2〕、沃化パラジウム〔ＰｄＩ2〕、水酸化パラジウム〔Ｐｄ(ＯＨ)2〕、硝酸パラジウム〔Ｐｄ(ＮＯ3)2〕、酸化パラジウム〔ＰｄＯ〕、硫酸パラジウム〔ＰｄＳＯ4〕、テトラクロロパラジウム酸カリウム〔Ｋ2(ＰｄＣｌ4)〕、テトラブロモパラジウム酸カリウム〔Ｋ2(ＰｄＢｒ4)〕等が；それぞれ挙げられる。なお、電子吸引性物質またはその前駆体は、それぞれ単独で用いてもよいし、２種以上を併用してもよい。また、１種以上の電子吸引性物質と１種以上の前駆体とを併用してもよいことは勿論である。 Preferable specific examples of the electron withdrawing substance include metals such as Cu, Pt, Au, and Pd. Moreover, as a preferable specific example of the precursor of an electron attractive substance, as a precursor containing Cu, copper nitrate [Cu (NO 3 ) 2 ], copper sulfate [Cu (SO 4 ) 2 ], copper chloride [CuCl 2 ] , CuCl], copper bromide [CuBr 2 , CuBr], copper iodide [CuI], copper iodate [CuI 2 O 6 ], ammonium chloride [Cu (NH 4 ) 2 Cl 4 ], copper oxychloride [Cu 2 Cl (OH) 3 ], copper acetate [CH 3 COOCu, (CH 3 COO) 2 Cu], copper formate [(HCOO) 2 Cu], copper carbonate [CuCO 3 ), copper oxalate [CuC 2 O 4 ], Copper citrate [Cu 2 C 6 H 4 O 7 ], copper phosphate [CuPO 4 ], etc .; as precursors containing Pt, platinum chloride [PtCl 2 , PtCl 4 ], platinum bromide [PtBr 2 , PtBr 4] ], iodide platinum [PtI 2, PtI 4], potassium platinum chloride [K 2 (PtCl 4)], Kisakuroro chloroplatinic acid [H 2 PtCl 6], platinum sulfite [H 3 Pt (SO 3) 2 OH ], platinum oxide [PtO 2], tetraammine platinum chloride [Pt (NH 3) 4 Cl 2], bicarbonate tetraammineplatinum [ C 2 H 14 N 4 O 6 Pt], tetraammineplatinum hydrogen phosphate [Pt (NH 3 ) 4 HPO 4 ], tetraammineplatinum platinum [Pt (NH 3 ) 4 (OH) 2 ], tetraammineplatinum nitrate [Pt ( NO 3 ) 2 (NH 3 ) 4 ], tetraammineplatinum tetrachloroplatinum [(Pt (NH 3 ) 4 ) (PtCl 4 )] and the like; as a precursor containing Au, gold chloride [AuCl], gold bromide [ AuBr], gold iodide [AuI], gold hydroxide [Au (OH) 2 ], tetrachloroauric acid [HAuCl 4 ], potassium tetrachloroaurate [KAuCl 4 ], potassium tetrabromoaurate [KAuBr 4 ], oxidation gold [Au 2 O 3 Etc. is; as a precursor containing Pd, for example, palladium acetate [(CH 3 COO) 2 Pd], palladium chloride [PdCl 2], palladium bromide [PdBr 2], iodide palladium [PdI 2], palladium hydroxide [Pd (OH) 2 ], palladium nitrate [Pd (NO 3 ) 2 ], palladium oxide [PdO], palladium sulfate [PdSO 4 ], potassium tetrachloropalladate [K 2 (PdCl 4 )], tetrabromopalladium acid Potassium [K 2 (PdBr 4 )] and the like; In addition, an electron withdrawing substance or its precursor may each be used independently, and may use 2 or more types together. Needless to say, one or more electron-withdrawing substances and one or more precursors may be used in combination.
前記電子吸引性物質またはその前駆体をも含有させる場合、その含有量は、金属原子換算で、酸化チタン粒子および酸化タングステン粒子の合計量１００質量部に対して、通常０．００５〜０．６質量部、好ましくは０．０１〜０．４質量部である。電子吸引性物質またはその前駆体が０．００５質量部未満であると、電子吸引性物質による光触媒活性の向上効果が充分に得られないおそれがあり、一方、０．６質量部を超えると、却って光触媒作用が低下するおそれがある。 When the electron-withdrawing substance or its precursor is also contained, the content is usually 0.005 to 0.6 with respect to 100 parts by mass of the total amount of titanium oxide particles and tungsten oxide particles in terms of metal atoms. Part by mass, preferably 0.01 to 0.4 part by mass. If the electron-withdrawing substance or its precursor is less than 0.005 parts by mass, the effect of improving the photocatalytic activity by the electron-withdrawing substance may not be sufficiently obtained, while if it exceeds 0.6 parts by mass, On the contrary, the photocatalytic action may be reduced.
本発明の光触媒体分散液は、酸化チタン粒子および酸化タングステン粒子の表面の帯電を変更しない範囲で、従来公知の各種添加剤を含んでいてもよい。なお、添加剤は、それぞれ単独で用いてもよいし、２種以上を併用してもよい。 The photocatalyst dispersion liquid of the present invention may contain conventionally known various additives as long as the surface charge of the titanium oxide particles and the tungsten oxide particles is not changed. In addition, an additive may each be used independently and may use 2 or more types together.
前記添加剤としては、例えば、光触媒作用を向上させる目的で添加されるものが挙げられる。このような光触媒作用向上効果を目的とした添加剤としては、具体的には、非晶質シリカ、シリカゾル、水ガラス、オルガノポリシロキサンなどの珪素化合物；非晶質アルミナ、アルミナゾル、水酸化アルミニウムなどのアルミニウム化合物；ゼオライト、カオリナイトのようなアルミノ珪酸塩；酸化マグネシウム、酸化カルシウム、酸化ストロンチウム、酸化バリウム、水酸化マグネシウム、水酸化カルシウム、水酸化ストロンチウム、水酸化バリウムなどのアルカリ土類金属酸化物またはアルカリ土類金属水酸化物；リン酸カルシウム、モレキュラーシーブ、活性炭、有機ポリシロキサン化合物の重縮合物、リン酸塩、フッ素系ポリマー、シリコン系ポリマー、アクリル樹脂、ポリエステル樹脂、メラミン樹脂、ウレタン樹脂、アルキド樹脂；等が挙げられる。 Examples of the additive include those added for the purpose of improving the photocatalytic action. Specific examples of such additives for improving the photocatalytic effect include silicon compounds such as amorphous silica, silica sol, water glass, and organopolysiloxane; amorphous alumina, alumina sol, aluminum hydroxide, and the like. Aluminosilicates such as zeolite and kaolinite; alkaline earth metal oxides such as magnesium oxide, calcium oxide, strontium oxide, barium oxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide Or alkaline earth metal hydroxide; calcium phosphate, molecular sieve, activated carbon, polycondensate of organic polysiloxane compound, phosphate, fluorine polymer, silicon polymer, acrylic resin, polyester resin, melamine resin, urethane resin, alkyd Fats; and the like.
また、前記添加剤としては、光触媒体分散液を基材表面に塗布した際に光触媒体（酸化チタン粒子および酸化タングステン粒子）をより強固に基材の表面に保持させるためのバインダー等を用いることもできる（例えば、特開平８−６７８３５号公報、特開平９−２５４３７号公報、特開平１０−１８３０６１号公報、特開平１０−１８３０６２号公報、特開平１０−１６８３４９号公報、特開平１０−２２５６５８号公報、特開平１１−１６２０号公報、特開平１１−１６６１号公報、特開２００４−０５９６８６号公報、特開２００４−１０７３８１号公報、特開２００４−２５６５９０号公報、特開２００４−３５９９０２号公報、特開２００５−１１３０２８号公報、特開２００５−２３０６６１号公報、特開２００７−１６１８２４号公報など参照）。 Further, as the additive, a binder or the like for holding the photocatalyst (titanium oxide particles and tungsten oxide particles) more firmly on the surface of the substrate when the photocatalyst dispersion liquid is applied to the surface of the substrate is used. (For example, JP-A-8-67835, JP-A-9-25437, JP-A-10-183061, JP-A-10-183062, JP-A-10-168349, JP-A-10-225658. Publication No. 11-1620, No. 11-1661, No. 2004-059686, No. 2004-107381, No. 2004-256590, No. 2004-359902. JP, 2005-113028, JP, 2005-230661, JP, 2007-16182. No. see, for publication).
本発明の光触媒体分散液は、その水素イオン濃度が、通常ｐＨ０．５〜ｐＨ８．０、好ましくはｐＨ１．０〜ｐＨ７．０である。水素イオン濃度がｐＨ０．５未満であると、酸性が強すぎて取扱いが面倒であり、一方、ｐＨ８．０を超えると、酸化タングステン粒子が溶解するおそれがあるので、いずれも好ましくない。光触媒体分散液の水素イオン濃度は、通常、酸を加えることにより調整すればよい。水素イオン濃度の調整に用いることのできる酸としては、例えば、硝酸、塩酸、硫酸、リン酸、ギ酸、酢酸、蓚酸等が挙げられる。 The hydrogen ion concentration of the photocatalyst dispersion liquid of the present invention is usually pH 0.5 to pH 8.0, preferably pH 1.0 to pH 7.0. When the hydrogen ion concentration is less than pH 0.5, the acidity is too strong and the handling is troublesome. On the other hand, when the pH exceeds 8.0, the tungsten oxide particles may be dissolved. The hydrogen ion concentration of the photocatalyst dispersion liquid may be usually adjusted by adding an acid. Examples of the acid that can be used for adjusting the hydrogen ion concentration include nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, oxalic acid, and the like.
本発明の光触媒体分散液の製造方法は、上述した各含有成分（表面が互いに同じ極性に帯電した酸化チタン粒子および酸化タングステン粒子、前記揮発性水溶性有機化合物を必須とする分散媒等）を混合し、分散させうる方法であればよく、各含有成分の混合順序などに特に制限はない。 The production method of the photocatalyst dispersion liquid of the present invention includes the above-described components (titanium oxide particles and tungsten oxide particles whose surfaces are charged with the same polarity as each other, a dispersion medium that essentially includes the volatile water-soluble organic compound, etc.). Any method can be used as long as it can be mixed and dispersed, and there is no particular limitation on the order of mixing the components.
酸化チタン粒子と酸化タングステン粒子とは、それぞれ、そのまま（粒子の状態で）混合してもよいが、通常は、両方または一方を、あらかじめ分散媒（分散媒に表面処理剤等を溶解させた溶液であってもよい）中に分散させて、酸化チタン粒子分散液または酸化タングステン粒子分散液としたのちに混合する。酸化チタン粒子分散液や酸化タングステン粒子分散液には、例えば媒体撹拌式分散機を用いるなど通常の方法により分散処理を施すことが好ましい。 Titanium oxide particles and tungsten oxide particles may be mixed as they are (in the form of particles), but usually both or one of them is a dispersion medium (a solution obtained by dissolving a surface treatment agent or the like in a dispersion medium). Or a titanium oxide particle dispersion or a tungsten oxide particle dispersion, and then mixed. The titanium oxide particle dispersion or tungsten oxide particle dispersion is preferably subjected to a dispersion treatment by a usual method such as using a medium stirring type disperser.
前記揮発性水溶性有機化合物は、どの段階で添加してもよく、例えば、酸化チタン粒子分散液や酸化タングステン粒子分散液を得る際の分散媒として用いてもよいし、酸化チタン粒子（または酸化チタン粒子分散液）と酸化タングステン粒子（または酸化タングステン粒子分散液）とを混合したのちに、別に添加するようにしてもよい。
なお、酸化チタン粒子および酸化タングステン粒子の少なくとも一方を分散液とする場合、各分散液に用いる分散媒の種類や使用量は、最終的に得られる光触媒体分散液における揮発性水溶性有機化合物の含有量や分散媒の含有量が上述した範囲となる限り、特に制限されない。
The volatile water-soluble organic compound may be added at any stage. For example, the volatile water-soluble organic compound may be used as a dispersion medium when obtaining a titanium oxide particle dispersion or a tungsten oxide particle dispersion, or titanium oxide particles (or oxidation). The titanium particle dispersion) and the tungsten oxide particles (or tungsten oxide particle dispersion) may be mixed and then added separately.
When at least one of titanium oxide particles and tungsten oxide particles is used as a dispersion, the type and amount of the dispersion medium used in each dispersion are determined according to the volatile water-soluble organic compound in the finally obtained photocatalyst dispersion. There is no particular limitation as long as the content and the content of the dispersion medium are within the above-described ranges.
例えば、表面がプラスに帯電している酸化チタン粒子を、適当な分散媒（例えば、水等）に前記表面処理剤を溶解させた溶液中に分散させることにより粒子表面をマイナスに帯電させた後、必要に応じて分散処理を施し、これに、表面がマイナスに帯電している酸化タングステン粒子を適当な分散媒（例えば、水等）中に分散させた分散液と、前記揮発性水溶性有機化合物とを順次混合することにより、本発明の光触媒体分散液を得ることができる。 For example, after the surface of the titanium oxide particles having a positive charge is dispersed in a solution in which the surface treatment agent is dissolved in an appropriate dispersion medium (for example, water), the particle surface is negatively charged. The dispersion process is performed as necessary, and a dispersion liquid in which tungsten oxide particles whose surface is negatively charged is dispersed in an appropriate dispersion medium (for example, water), and the volatile water-soluble organic substance. The photocatalyst dispersion liquid of the present invention can be obtained by sequentially mixing the compound.
本発明の光触媒体分散液に前記電子吸引性物質またはその前駆体を含有させる場合には、電子吸引性物質またはその前駆体の添加は、どの段階で行なってもよく、例えば、酸化チタン粒子分散液に対して行ってもよいし、酸化タングステン粒子分散液に対して行ってもよいし、酸化チタン粒子（酸化チタン粒子分散液）と酸化タングステン粒子（酸化タングステン粒子分散液）とを混合した後の分散液に対して行ってもよいが、高い光触媒活性を得る観点からは、電子吸引性物質またはその前駆体は酸化タングステン粒子分散液に添加するのが好ましい。 When the photocatalyst dispersion liquid of the present invention contains the electron-withdrawing substance or its precursor, the addition of the electron-withdrawing substance or its precursor may be performed at any stage, for example, titanium oxide particle dispersion May be performed on the liquid, may be performed on the tungsten oxide particle dispersion, or after mixing the titanium oxide particles (titanium oxide particle dispersion) and the tungsten oxide particles (tungsten oxide particle dispersion). However, from the viewpoint of obtaining high photocatalytic activity, it is preferable to add the electron-withdrawing substance or its precursor to the tungsten oxide particle dispersion.
前記電子吸引性物質の前駆体を添加した場合には、その添加後に光照射を行ってもよい。光照射を行うことにより、光励起によって生成した電子によって前駆体が還元されて電子吸引性物質となり、光触媒体粒子（酸化チタン粒子および酸化タングステン粒子）の表面に担持される。なお、前記前駆体を添加した場合に、たとえ光照射を行なわなくても、得られた光触媒体分散液により形成された光触媒体層に光が照射された時点で電子吸引性物質へ変換されることになるので、その光触媒能が損なわれることはない。
前記光照射で照射する光としては、特に制限はなく、可視光線でもよいし、紫外線でもよい。また、前記光照射は、前記前駆体の添加後であれば、どの段階で行なってもよい。
When a precursor of the electron withdrawing substance is added, light irradiation may be performed after the addition. By performing light irradiation, the precursor is reduced by electrons generated by photoexcitation to become an electron-withdrawing substance, and is supported on the surface of the photocatalyst particles (titanium oxide particles and tungsten oxide particles). When the precursor is added, the photocatalyst layer formed from the obtained photocatalyst dispersion liquid is converted into an electron-withdrawing substance when light is irradiated to the photocatalyst layer formed by the obtained photocatalyst dispersion liquid. As a result, the photocatalytic ability is not impaired.
There is no restriction | limiting in particular as light irradiated by the said light irradiation, A visible ray may be sufficient and an ultraviolet-ray may be sufficient. The light irradiation may be performed at any stage as long as the precursor is added.
本発明の光触媒体分散液に上述した各種添加剤を含有させる場合には、各種添加剤の添加はどの段階で行なってもよいが、例えば、酸化チタン粒子（酸化チタン粒子分散液）と酸化タングステン粒子（酸化タングステン粒子分散液）とを混合した後に行なうことが好ましい。 When the above-mentioned various additives are contained in the photocatalyst dispersion liquid of the present invention, the various additives may be added at any stage. For example, titanium oxide particles (titanium oxide particle dispersion liquid) and tungsten oxide are added. It is preferable to carry out after mixing the particles (tungsten oxide particle dispersion).
（光触媒機能製品の製造方法）
本発明の光触媒機能製品の製造方法は、上述した本発明の光触媒体分散液を基材の表面に塗布し、分散媒を揮発させるものである。この方法により、光触媒酸化チタン粒子および光触媒酸化タングステン粒子を含み光触媒作用を示す光触媒体層を、表面に備えた光触媒機能製品を製造できる。ここで、前記光触媒体分散液が電子吸引性物質またはその前駆体を含む場合には、光触媒体層を構成する光触媒酸化チタン粒子および光触媒酸化タングステン粒子の表面に電子吸引性物質またはその前駆体が担持される。担持された電子吸引性物質の前駆体は、担持されたのち、例えば光が照射されることなどによって電子吸引性物質に遷移する。
(Production method of photocatalytic functional products)
In the method for producing a photocatalytic functional product of the present invention, the above-described photocatalyst dispersion liquid of the present invention is applied to the surface of a substrate to volatilize the dispersion medium. By this method, a photocatalytic product having a photocatalyst layer containing photocatalytic titanium oxide particles and photocatalytic tungsten oxide particles and having a photocatalytic action on the surface can be produced. Here, when the photocatalyst dispersion liquid contains an electron-withdrawing substance or a precursor thereof, the electron-withdrawing substance or a precursor thereof is formed on the surface of the photocatalytic titanium oxide particles and the photocatalytic tungsten oxide particles constituting the photocatalyst layer. Supported. The precursor of the supported electron-withdrawing substance is transferred to the electron-withdrawing substance, for example, when irradiated with light.
基材（製品）の表面に光触媒体層を形成するにあたり、光触媒体分散液の塗布は、従来公知の方法を適宜採用して行えばよい。光触媒体層の膜厚は、特に制限されるものではなく、通常、その用途等に応じて、数百ｎｍ〜数ｍｍまで適宜設定すればよい。また、塗布後に分散媒を揮発させる方法についても、特に制限はなく、従来公知の方法を適宜採用することができる。 In forming the photocatalyst layer on the surface of the substrate (product), the photocatalyst dispersion liquid may be applied by appropriately employing a conventionally known method. The film thickness of the photocatalyst body layer is not particularly limited, and usually may be appropriately set from several hundred nm to several mm according to the application. Moreover, there is no restriction | limiting in particular also about the method of volatilizing a dispersion medium after application | coating, A conventionally well-known method can be employ | adopted suitably.
光触媒体層は、基材（製品）の内表面または外表面であれば、どの部分に形成されていてもよいが、例えば、光（可視光線）が照射される面であって、かつ悪臭物質が発生する箇所と連続または断続して空間的につながる面に形成されていることが好ましい。なお、基材（製品）の材質は、形成される光触媒体層を実用に耐えうる強度で保持できる限り、特に制限されるものではなく、例えば、プラスチック、金属、セラミックス、木材、コンクリート、紙など、あらゆる材料からなる製品を対象にすることができる。 The photocatalyst layer may be formed on any part as long as it is an inner surface or an outer surface of the base material (product). For example, the photocatalyst layer is a surface irradiated with light (visible light), and a malodorous substance. It is preferably formed on a surface that is continuously or intermittently connected to a place where the occurrence occurs. The material of the base material (product) is not particularly limited as long as the formed photocatalyst layer can be held at a strength that can be practically used. For example, plastic, metal, ceramics, wood, concrete, paper, etc. , Products made of any material can be targeted.
本発明にかかる光触媒機能製品の具体例としては、例えば、天井材、タイル、ガラス、壁紙、壁材、床等の建築資材、自動車内装材（自動車用インストルメントパネル、自動車用シート、自動車用天井材）、衣類やカーテン等の繊維製品などが挙げられる。 Specific examples of the photocatalytic functional product according to the present invention include, for example, building materials such as ceiling materials, tiles, glass, wallpaper, wall materials, floors, automobile interior materials (automobile instrument panels, automobile seats, automobile ceilings). Material), textile products such as clothing and curtains.
本発明にかかる光触媒機能製品は、蛍光灯やナトリウムランプのような可視光源からの光照射により高い触媒作用を示すものであり、有機物の分解や窒素酸化物の分解に好適に用いることができる。例えば、この光触媒機能製品を、照明設備を備えた屋内住環境に設置すれば、屋内照明による光照射によって、アルデヒド類（ホルムアルデヒド、アセトアルデヒド等）、メルカプタン類、ケトン類、芳香族有機化合物類（トルエン等）、アンモニアのような、環境中の揮発性有機物や悪臭物質を簡易に分解、除去することができる。さらには、黄色ブドウ球菌や大腸菌等の病原菌を死滅させることも可能である。 The photocatalytic functional product according to the present invention exhibits high catalytic action when irradiated with light from a visible light source such as a fluorescent lamp or a sodium lamp, and can be suitably used for the decomposition of organic substances and the decomposition of nitrogen oxides. For example, if this photocatalytic functional product is installed in an indoor living environment equipped with lighting equipment, aldehydes (formaldehyde, acetaldehyde, etc.), mercaptans, ketones, aromatic organic compounds (toluene) are irradiated by light from indoor lighting. Etc.), volatile organic substances and malodorous substances in the environment such as ammonia can be easily decomposed and removed. Furthermore, it is possible to kill pathogenic bacteria such as Staphylococcus aureus and Escherichia coli.
以下、実施例によって本発明をより詳細に説明するが、本発明は、かかる実施例によって限定されるものではない。
なお、実施例および比較例における各物性の測定およびその光触媒活性の評価については、以下の方法で行った。
EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by this Example.
In addition, about the measurement of each physical property in an Example and a comparative example, and the evaluation of the photocatalytic activity, it performed with the following method.
＜結晶型＞
Ｘ線回折装置（リガク社製「ＲＩＮＴ２０００／ＰＣ」）を用いてＸ線回折スペクトルを測定し、そのスペクトルから結晶型を決定した。
<Crystal type>
An X-ray diffraction spectrum was measured using an X-ray diffractometer (“RINT2000 / PC” manufactured by Rigaku Corporation), and a crystal type was determined from the spectrum.
＜ＢＥＴ比表面積＞
比表面積測定装置（湯浅アイオニクス社製「モノソーブ」）を用いて窒素吸着法により測定した。
<BET specific surface area>
It measured by the nitrogen adsorption method using the specific surface area measuring apparatus ("Monosorb" by Yuasa Ionics Co., Ltd.).
＜平均分散粒子径＞
サブミクロン粒度分布測定装置（コールター社製「Ｎ４Ｐｌｕｓ」）を用いて試料の粒度分布を測定し、この装置に付属のソフトにより自動的に単分散モード解析して得られた結果を、平均分散粒子径（ｎｍ）とした。
<Average dispersed particle size>
Measure the particle size distribution of the sample using a submicron particle size distribution analyzer (Coulter's “N4Plus”), and use the software attached to this device to automatically analyze the monodisperse mode. The diameter (nm) was used.
＜ゼータ電位＞
レーザーゼータ電位計（大塚電子社製「ＥＬＳ−６０００」）を用い、塩酸を加えて水素イオン濃度をｐＨ３．０に調整した塩化ナトリウム水溶液（塩化ナトリウム濃度０．０１モル／Ｌ）中に光触媒酸化チタン粒子または光触媒酸化タングステン粒子を分散させて、ゼータ電位を測定した。光触媒酸化チタン粒子または光触媒酸化タングステン粒子のそれぞれの使用量に対する塩化ナトリウム水溶液の使用量は、２５００００質量倍とした。このゼータ電位がプラスであれば、粒子の表面はプラスに帯電しており、マイナスであれば、粒子の表面はマイナスに帯電している。
<Zeta potential>
Photocatalytic oxidation in a sodium chloride aqueous solution (sodium chloride concentration 0.01 mol / L) using a laser zeta electrometer (ELS-6000, manufactured by Otsuka Electronics Co., Ltd.) adjusted to pH 3.0 by adding hydrochloric acid. Titanium particles or photocatalytic tungsten oxide particles were dispersed, and the zeta potential was measured. The amount of sodium chloride aqueous solution used relative to the amount of photocatalytic titanium oxide particles or photocatalytic tungsten oxide particles used was 250,000 times the mass. If the zeta potential is positive, the particle surface is positively charged. If the zeta potential is negative, the particle surface is negatively charged.
＜光触媒活性の評価＞
光触媒活性は、蛍光灯の光の照射下でのアセトアルデヒドの分解反応における一次反応速度定数を測定することにより評価した。
まず、光触媒活性測定用の試料を作製した。すなわち、ガラス製シャーレ（外径７０ｍｍ、内径６６ｍｍ、高さ１４ｍｍ、容量約４８ｍＬ）に、得られた光触媒体分散液を、底面の単位面積あたりの固形分換算の滴下量が１ｇ／ｍ2となるように滴下し、シャーレの底面全体に均一となるように展開した。次いで、このシャーレを１１０℃の乾燥機内で大気中１時間保持することにより乾燥させて、ガラス製シャーレの底面に光触媒体層を形成した。この光触媒体層に、紫外線強度が２ｍＷ／ｃｍ2となるようにブラックライトからの紫外線を１６時間照射して、これを光触媒活性測定用サンプルとした。
<Evaluation of photocatalytic activity>
The photocatalytic activity was evaluated by measuring a first-order reaction rate constant in the decomposition reaction of acetaldehyde under irradiation of light from a fluorescent lamp.
First, a sample for measuring photocatalytic activity was prepared. That is, in a glass petri dish (outer diameter: 70 mm, inner diameter: 66 mm, height: 14 mm, capacity: about 48 mL), the obtained photocatalyst dispersion liquid has a dripping amount in terms of solid content per unit area of the bottom surface of 1 g / m 2 . It dripped so that it might become, and it developed so that it might become uniform to the whole bottom face of a petri dish. Next, this petri dish was dried by holding it in the air at 110 ° C. for 1 hour in the atmosphere to form a photocatalyst layer on the bottom of the glass petri dish. This photocatalyst layer was irradiated with ultraviolet light from black light for 16 hours so that the ultraviolet intensity was 2 mW / cm 2, and this was used as a sample for photocatalytic activity measurement.
次に、この光触媒活性測定用サンプルをガスバッグ（内容積１Ｌ）に入れて密閉し、次いで、このガスバッグ内を真空にした後、酸素と窒素との体積比が１：４である混合ガス６００ｍＬを封入し、さらにその中に、１容量％でアセトアルデヒドを含む窒素ガス３ｍＬを封入して、暗所で室温下、１時間保持した。その後、市販の白色蛍光灯を光源とし、測定サンプル近傍での照度が１０００ルクス（ミノルタ社製照度計「Ｔ−１０」で測定）となるようにガスバッグの外から蛍光灯の光を照射し、アセトアルデヒドの分解反応を行った。このとき、測定サンプル近傍の紫外光の強度は６．５μＷ／ｃｍ2（トプコン社製紫外線強度計「ＵＶＲ−２」に、同社製受光部「ＵＤ−３６」を取り付けて測定）であった。蛍光灯の光照射を開始してから１．５時間毎にガスバッグ内のガスをサンプリングし、アセトアルデヒドの濃度をガスクロマトグラフ（島津製作所社製「ＧＣ−１４Ａ」）にて測定した。そして、照射時間に対するアセトアルデヒドの残存濃度から一次反応速度定数を算出し、これをアセトアルデヒド分解能として評価した。この一次反応速度定数が大きいほど、アセトアルデヒドの分解能（すなわち光触媒活性）は高い。 Next, this sample for photocatalytic activity measurement is sealed in a gas bag (internal volume 1 L), and then the inside of the gas bag is evacuated, and then a mixed gas in which the volume ratio of oxygen to nitrogen is 1: 4. 600 mL was sealed, and 3 mL of nitrogen gas containing acetaldehyde at 1% by volume was sealed therein, and kept in the dark at room temperature for 1 hour. Then, using a commercially available white fluorescent lamp as the light source, irradiate the fluorescent lamp light from the outside of the gas bag so that the illuminance near the measurement sample is 1000 lux (measured with the illuminometer “T-10” manufactured by Minolta). Then, acetaldehyde was decomposed. At this time, the intensity of the ultraviolet light in the vicinity of the measurement sample was 6.5 μW / cm 2 (measured by attaching the light receiving unit “UD-36” manufactured by the company to the UV intensity meter “UVR-2” manufactured by Topcon Corporation). The gas in the gas bag was sampled every 1.5 hours after the light irradiation of the fluorescent lamp was started, and the concentration of acetaldehyde was measured with a gas chromatograph (“GC-14A” manufactured by Shimadzu Corporation). Then, a first-order reaction rate constant was calculated from the residual concentration of acetaldehyde with respect to the irradiation time, and this was evaluated as acetaldehyde resolution. The larger the first-order rate constant, the higher the resolution (ie photocatalytic activity) of acetaldehyde.
（製造例１−光触媒酸化チタン粒子分散液の調製）
光触媒酸化チタン粒子として、硫酸チタニルの水溶液を加水分解し、濾取して得られたメタチタン酸の固形物（ケーキ）（ＴｉＯ2換算でチタン成分を４５質量％含有）を用いた。このメタチタン酸の固形物（ケーキ）２．２ｋｇを、蓚酸二水和物（和光純薬工業製）１５８ｇを水１．８８ｋｇに溶解させることにより調製した蓚酸水溶液中に加え、混合して混合物を得た。この混合物における蓚酸の含有量は、メタチタン酸１モルに対して０．１モルである。
(Production Example 1-Preparation of photocatalytic titanium oxide particle dispersion)
As the photocatalytic titanium oxide particles, a solid solution (cake) of metatitanic acid (containing 45 mass% of titanium component in terms of TiO 2 ) obtained by hydrolyzing an aqueous solution of titanyl sulfate and collecting by filtration was used. This metatitanic acid solid (cake) (2.2 kg) was added to an aqueous oxalic acid solution prepared by dissolving 158 g of oxalic acid dihydrate (manufactured by Wako Pure Chemical Industries, Ltd.) in 1.88 kg of water. Obtained. The content of succinic acid in this mixture is 0.1 mol with respect to 1 mol of metatitanic acid.
上記で得られた混合物を、媒体攪拌式分散機（コトブキ技研社製「ウルトラアペックスミル ＵＡＭ−１」）を用いて下記の条件で分散処理して、光触媒酸化チタン粒子分散液を得た。
分散媒体：直径０．０５ｍｍのジルコニア製ビーズ１．８５ｋｇ
攪拌速度：周速１２．６ｍ／秒
流速：０．２５Ｌ／分
水の添加：処理開始１７分後に水５ｋｇを追加添加
処理時間：合計約９０分
The mixture obtained above was subjected to a dispersion treatment under the following conditions using a medium stirring type disperser (“Ultra Apex Mill UAM- 1 ” manufactured by Kotobuki Giken Co., Ltd.) to obtain a photocatalytic titanium oxide particle dispersion.
Dispersion medium: 1.85 kg of zirconia beads having a diameter of 0.05 mm
Stirring speed: peripheral speed 12.6 m / sec Flow rate: 0.25 L / min Water addition: 5 kg of water added after 17 minutes of treatment Treatment time: about 90 minutes in total
得られた光触媒酸化チタン粒子分散液における光触媒酸化チタン粒子の平均分散粒子径は５５ｎｍであり、分散液中の光触媒酸化チタン粒子のゼータ電位は−１０．５ｍＶであった。また、得られた分散液の水素イオン濃度はｐＨ１．５であった。この光触媒酸化チタン粒子分散液の一部を真空乾燥して固形分を得たところ、該固形分のＢＥＴ比表面積は３０１ｍ2／ｇであり、該固形分の結晶型はアナターゼ型であった。なお、分散処理の前の混合物中の固形分と、分散処理の後の分散液中の固形分とについて、Ｘ線回折スペクトルをそれぞれ測定して比較したところ、分散処理による結晶型の変化は見られなかった。 The average dispersed particle size of the photocatalytic titanium oxide particles in the obtained photocatalytic titanium oxide particle dispersion was 55 nm, and the zeta potential of the photocatalytic titanium oxide particles in the dispersion was −10.5 mV. Further, the hydrogen ion concentration of the obtained dispersion was pH 1.5. A part of this photocatalytic titanium oxide particle dispersion was vacuum dried to obtain a solid content. As a result, the BET specific surface area of the solid content was 301 m 2 / g, and the crystal form of the solid content was anatase type. Note that when the solid content in the mixture before the dispersion treatment and the solid content in the dispersion after the dispersion treatment were measured and compared, respectively, changes in the crystal form due to the dispersion treatment were observed. I couldn't.
（製造例２−光触媒酸化タングステン粒子分散液の調製）
光触媒酸化タングステン粒子である酸化タングステン粉末（日本無機化学製）１ｋｇをイオン交換水４ｋｇ中に加え、混合して混合物を得た。
上記で得られた混合物を、媒体攪拌式分散機（コトブキ技研社製「ウルトラアペックスミル ＵＡＭ−１」）を用いて下記の条件で分散処理して、光触媒酸化タングステン粒子分散液を得た。
分散媒体：直径０．０５ｍｍのジルコニア製ビーズ１．８５ｋｇ
攪拌速度：周速１２．６ｍ／秒
流速：０．２５Ｌ／分
処理時間：合計約５０分
(Production Example 2-Preparation of photocatalytic tungsten oxide particle dispersion)
1 kg of tungsten oxide powder (manufactured by Nippon Inorganic Chemical), which is photocatalytic tungsten oxide particles, was added to 4 kg of ion-exchanged water and mixed to obtain a mixture.
The mixture obtained above was subjected to a dispersion treatment under the following conditions using a medium stirring type disperser (“Ultra Apex Mill UAM- 1 ” manufactured by Kotobuki Giken Co., Ltd.) to obtain a photocatalytic tungsten oxide particle dispersion.
Dispersion medium: 1.85 kg of zirconia beads having a diameter of 0.05 mm
Stirring speed: peripheral speed 12.6 m / sec Flow rate: 0.25 L / min Processing time: about 50 minutes in total
得られた光触媒酸化タングステン粒子分散液における光触媒酸化タングステン粒子の平均分散粒子径は１１８ｎｍであった。この分散液の一部を真空乾燥して固形分を得たところ、該固形分のＢＥＴ比表面積は４０ｍ2／ｇであった。なお、分散処理の前の混合物中の固形分と、分散処理の後の分散液中の固形分とについて、Ｘ線回折スペクトルをそれぞれ測定して比較したところ、どちらも結晶型はＷＯ3であり、分散処理による結晶型の変化は見られなかった。 The average dispersed particle diameter of the photocatalytic tungsten oxide particles in the obtained photocatalytic tungsten oxide particle dispersion was 118 nm. A part of this dispersion was vacuum-dried to obtain a solid content. The BET specific surface area of the solid content was 40 m 2 / g. Incidentally, the solid content in the mixture before the dispersing treatment, for the solids in the dispersion liquid after the dispersing treatment were compared by measuring the X-ray diffraction spectrum, respectively, both the crystal structures is an WO 3 The crystal form was not changed by the dispersion treatment.
次に、上記で得た光触媒酸化タングステン粒子分散液に、ヘキサクロロ白金酸（Ｈ2ＰｔＣｌ6）の水溶液を加え、さらにメタノールを加えて、光触媒体酸化タングステン粒子分散液とした。このとき、ヘキサクロロ白金酸の使用量は、白金原子換算で光触媒酸化タングステン粒子の使用量１００質量部に対して０．１２質量部とし、メタノールの使用量は、得られる光触媒酸化タングステン粒子分散液におけるメタノール濃度が６．２５質量％となるようにした。
得られた光触媒体酸化タングステン粒子分散液１００質量部中の固形分は１１．４質量部であった（固形分濃度１１．４質量％）。また、この分散液中の光触媒酸化タングステン粒子のゼータ電位は−２．８ｍＶであった。
Next, an aqueous solution of hexachloroplatinic acid (H 2 PtCl 6 ) was added to the photocatalyst tungsten oxide particle dispersion obtained above, and methanol was further added to obtain a photocatalyst tungsten oxide particle dispersion. At this time, the amount of hexachloroplatinic acid used is 0.12 parts by mass with respect to 100 parts by mass of photocatalytic tungsten oxide particles in terms of platinum atoms, and the amount of methanol used is in the resulting photocatalytic tungsten oxide particle dispersion. The methanol concentration was adjusted to 6.25% by mass.
The solid content in 100 parts by mass of the obtained photocatalyst tungsten oxide particle dispersion was 11.4 parts by mass (solid content concentration 11.4% by mass). Further, the zeta potential of the photocatalytic tungsten oxide particles in this dispersion was −2.8 mV.
（実施例１）
製造例１で得た光触媒酸化チタン粒子分散液と、製造例２で得た光触媒酸化タングステン粒子分散液とを、光触媒酸化チタン粒子と光触媒酸化タングステン粒子との比率が１：１（質量比）となるように混合し、その中にさらに、所定の濃度（含有量）となる量のエタノールと、適量の水とを添加して、光触媒体分散液を得た。この光触媒体分散液１００質量部中、光触媒酸化チタン粒子と光触媒酸化タングステン粒子との合計含有量は５質量部であり、メタノールの含有量は１．４質量部であり、エタノールの含有量は１０質量部であった（固形分濃度５質量％）。
得られた光触媒体分散液を２０℃で３時間保管したところ、保管中に固液分離は見られなかった。また、得られた光触媒体分散液を用いて形成した光触媒体層の光触媒活性を評価したところ、一次反応速度定数は０．４１７ｈ-1であった。
Example 1
The photocatalytic titanium oxide particle dispersion liquid obtained in Production Example 1 and the photocatalytic tungsten oxide particle dispersion liquid obtained in Production Example 2 have a 1: 1 ratio (mass ratio) of photocatalytic titanium oxide particles and photocatalytic tungsten oxide particles. Then, an amount of ethanol having a predetermined concentration (content) and an appropriate amount of water were added to obtain a photocatalyst dispersion liquid. In 100 parts by mass of the photocatalyst dispersion, the total content of the photocatalytic titanium oxide particles and the photocatalytic tungsten oxide particles is 5 parts by mass, the methanol content is 1.4 parts by mass, and the ethanol content is 10 parts. It was a mass part (solid content concentration 5 mass%).
When the obtained photocatalyst dispersion liquid was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage. Moreover, when the photocatalytic activity of the photocatalyst layer formed using the obtained photocatalyst dispersion liquid was evaluated, the first-order rate constant was 0.417 h −1 .
（実施例２）
エタノールの濃度（含有量）が２倍になるようにエタノールと水の添加量を変更したこと以外は、実施例１と同様に操作して、光触媒体分散液を得た。すなわち、この光触媒体分散液１００質量部中、光触媒酸化チタン粒子と光触媒酸化タングステン粒子との合計含有量は５質量部であり、メタノールの含有量は１．４質量部であり、エタノールの含有量は２０質量部であった（固形分濃度５質量％）。
得られた光触媒体分散液を２０℃で３時間保管したところ、保管中に固液分離は見られなかった。また、得られた光触媒体分散液を用いて形成した光触媒体層の光触媒活性を評価したところ、一次反応速度定数は０．４０１ｈ-1であった。
(Example 2)
A photocatalyst dispersion liquid was obtained in the same manner as in Example 1 except that the addition amounts of ethanol and water were changed so that the ethanol concentration (content) was doubled. That is, in 100 parts by mass of the photocatalyst dispersion, the total content of the photocatalytic titanium oxide particles and the photocatalytic tungsten oxide particles is 5 parts by mass, the methanol content is 1.4 parts by mass, and the ethanol content Was 20 parts by mass (solid content concentration 5% by mass).
When the obtained photocatalyst dispersion liquid was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage. When the photocatalytic activity of the photocatalyst layer formed using the photocatalyst dispersion liquid was evaluated, the first-order reaction rate constant was 0.401 h −1 .
（実施例３）
エタノールの濃度（含有量）が３倍になるようにエタノールと水の添加量を変更したこと以外は、実施例１と同様に操作して、光触媒体分散液を得た。すなわち、この光触媒体分散液１００質量部中、光触媒酸化チタン粒子と光触媒酸化タングステン粒子との合計含有量は５質量部であり、メタノールの含有量は１．４質量部であり、エタノールの含有量は３０質量部であった（固形分濃度５質量％）。
得られた光触媒体分散液を２０℃で３時間保管したところ、保管中に固液分離は見られなかった。また、得られた光触媒体分散液を用いて形成した光触媒体層の光触媒活性を評価したところ、一次反応速度定数は０．４１８ｈ-1であった。
(Example 3)
A photocatalyst dispersion liquid was obtained in the same manner as in Example 1 except that the addition amounts of ethanol and water were changed so that the ethanol concentration (content) was tripled. That is, in 100 parts by mass of the photocatalyst dispersion, the total content of the photocatalytic titanium oxide particles and the photocatalytic tungsten oxide particles is 5 parts by mass, the methanol content is 1.4 parts by mass, and the ethanol content Was 30 parts by mass (solid content concentration 5% by mass).
When the obtained photocatalyst dispersion liquid was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage. Moreover, when the photocatalytic activity of the photocatalyst layer formed using the photocatalyst dispersion liquid was evaluated, the first-order rate constant was 0.418 h −1 .
（実施例４）
エタノールの濃度（含有量）が４倍になるようにエタノールと水の添加量を変更したこと以外は、実施例１と同様に操作して、光触媒体分散液を得た。すなわち、この光触媒体分散液１００質量部中、光触媒酸化チタン粒子と光触媒酸化タングステン粒子との合計含有量は５質量部であり、メタノールの含有量は１．４質量部であり、エタノールの含有量は４０質量部であった（固形分濃度５質量％）。
得られた光触媒体分散液を２０℃で３時間保管したところ、保管中に固液分離は見られなかった。また、得られた光触媒体分散液を用いて形成した光触媒体層の光触媒活性を評価したところ、一次反応速度定数は０．３８４ｈ-1であった。
Example 4
A photocatalyst dispersion liquid was obtained in the same manner as in Example 1 except that the addition amount of ethanol and water was changed so that the concentration (content) of ethanol was 4 times. That is, in 100 parts by mass of the photocatalyst dispersion, the total content of the photocatalytic titanium oxide particles and the photocatalytic tungsten oxide particles is 5 parts by mass, the methanol content is 1.4 parts by mass, and the ethanol content Was 40 parts by mass (solid content concentration 5% by mass).
When the obtained photocatalyst dispersion liquid was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage. Moreover, when the photocatalytic activity of the photocatalyst body layer formed using the obtained photocatalyst body dispersion liquid was evaluated, the first-order rate constant was 0.384 h −1 .
（比較例１）
製造例１で得た光触媒酸化チタン粒子分散液に代えて、市販の酸化チタン粒子分散液（石原産業社製「ＳＴＳ−０１」；硝酸含有、平均分散粒径：５０ｎｍ、固形分濃度：３０質量％）を用いた以外は、実施例１と同様に操作して、光触媒体分散液を調製した。すなわち、この光触媒体分散液１００質量部中、光触媒酸化チタン粒子と光触媒酸化タングステン粒子との合計含有量は５質量部であり、メタノールの含有量は１．４質量部であり、エタノールの含有量は１０質量部であった（固形分濃度５質量％）。なお、ここで用いた酸化チタン粒子分散液（ＳＴＳ−０１）に含まれる酸化チタン粒子のゼータ電位は＋４０．１ｍＶであった。
得られた光触媒体分散液は、調製後、直ちに凝集粒子が生成し、固液分離が起こった。
(Comparative Example 1)
Instead of the photocatalytic titanium oxide particle dispersion obtained in Production Example 1, a commercially available titanium oxide particle dispersion (“STS-01” manufactured by Ishihara Sangyo Co., Ltd .; nitric acid-containing, average dispersed particle size: 50 nm, solid content concentration: 30 mass) %) Was used in the same manner as in Example 1 to prepare a photocatalyst dispersion. That is, in 100 parts by mass of the photocatalyst dispersion, the total content of the photocatalytic titanium oxide particles and the photocatalytic tungsten oxide particles is 5 parts by mass, the methanol content is 1.4 parts by mass, and the ethanol content Was 10 parts by mass (solid content concentration 5% by mass). In addition, the zeta potential of the titanium oxide particles contained in the titanium oxide particle dispersion (STS-01) used here was +40.1 mV.
The obtained photocatalyst dispersion liquid produced aggregated particles immediately after preparation, and solid-liquid separation occurred.
（比較例２）
エタノールを添加せず、代わりに水の添加量を増やしたこと以外は、実施例１と同様に操作して、光触媒体分散液を得た。すなわち、この光触媒体分散液１００質量部中、光触媒酸化チタン粒子と光触媒酸化タングステン粒子との合計含有量は５質量部であり、メタノールの含有量は１．４質量部であった（固形分濃度５質量％）。
得られた光触媒体分散液を２０℃で３時間保管したところ、保管中に固液分離は見られなかった。また、得られた光触媒体分散液を用いて形成した光触媒体層の光触媒活性を評価したところ、一次反応速度定数は０．２５１ｈ-1であった。
(Comparative Example 2)
A photocatalyst dispersion liquid was obtained in the same manner as in Example 1 except that ethanol was not added and the amount of water added was increased instead. That is, in 100 parts by mass of the photocatalyst dispersion, the total content of the photocatalytic titanium oxide particles and the photocatalytic tungsten oxide particles was 5 parts by mass, and the methanol content was 1.4 parts by mass (solid content concentration). 5% by mass).
When the obtained photocatalyst dispersion liquid was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage. Moreover, when the photocatalytic activity of the photocatalyst body layer formed using the obtained photocatalyst body dispersion liquid was evaluated, the first-order rate constant was 0.251 h −1 .
（参考例１）
実施例１〜４で得た光触媒体分散液を、それぞれ、天井材に塗布し、その後、乾燥して分散媒を揮発させると、屋内照明による光照射により、屋内空間におけるホルムアルデヒド、アセトアルデヒド、アセトン、トルエン等の揮発性有機物濃度や悪臭物質の濃度を低減することができ、さらに、黄色ブドウ球菌や大腸菌等の病原菌を死滅させることができる。
(Reference Example 1)
When the photocatalyst dispersion liquid obtained in each of Examples 1 to 4 was applied to a ceiling material and then dried to volatilize the dispersion medium, formaldehyde, acetaldehyde, acetone, The concentration of volatile organic substances such as toluene and the concentration of malodorous substances can be reduced, and pathogenic bacteria such as Staphylococcus aureus and Escherichia coli can be killed.
（参考例２）
実施例１〜４で得た光触媒体分散液を、それぞれ、タイルに塗布し、その後、乾燥して分散媒を揮発させると、屋内照明による光照射により、屋内空間におけるホルムアルデヒド、アセトアルデヒド、トルエン、アセトン等の揮発性有機物濃度や悪臭物質の濃度を低減することができ、さらに、黄色ブドウ球菌や大腸菌等の病原菌を死滅させることができる。
(Reference Example 2)
When the photocatalyst dispersion liquid obtained in each of Examples 1 to 4 was applied to a tile and then dried to volatilize the dispersion medium, formaldehyde, acetaldehyde, toluene, and acetone in an indoor space were irradiated with light by indoor lighting. The concentration of volatile organic substances such as odorous substances and malodorous substances can be reduced, and pathogenic bacteria such as Staphylococcus aureus and Escherichia coli can be killed.
（参考例３）
実施例１〜４で得た光触媒体分散液をそれぞれガラスに塗布し、その後、乾燥して分散媒を揮発させると、屋内照明による光照射により、屋内空間におけるホルムアルデヒド、アセトアルデヒド、トルエン、アセトン等の揮発性有機物濃度や悪臭物質の濃度を低減することができ、さらに、黄色ブドウ球菌や大腸菌等の病原菌を死滅させることができる。
(Reference Example 3)
When each of the photocatalyst dispersions obtained in Examples 1 to 4 was applied to glass and then dried to volatilize the dispersion medium, formaldehyde, acetaldehyde, toluene, acetone, etc. The concentration of volatile organic substances and malodorous substances can be reduced, and pathogens such as Staphylococcus aureus and Escherichia coli can be killed.
（参考例４）
実施例１〜４で得た光触媒体分散液をそれぞれ壁紙に塗布し、その後、乾燥して分散媒を揮発させると、屋内照明による光照射により、屋内空間におけるホルムアルデヒド、アセトアルデヒド、トルエン、アセトン等の揮発性有機物濃度や悪臭物質の濃度を低減することができ、さらに、黄色ブドウ球菌や大腸菌等の病原菌を死滅させることができる。
(Reference Example 4)
Each of the photocatalyst dispersion liquids obtained in Examples 1 to 4 was applied to wallpaper, and then dried to volatilize the dispersion medium. By light irradiation with indoor lighting, formaldehyde, acetaldehyde, toluene, acetone, etc. in the indoor space The concentration of volatile organic substances and malodorous substances can be reduced, and pathogens such as Staphylococcus aureus and Escherichia coli can be killed.
（参考例５）
実施例１〜４で得た光触媒体分散液をそれぞれ床に塗布し、その後、乾燥して分散媒を揮発させると、屋内照明による光照射により、屋内空間におけるホルムアルデヒド、アセトアルデヒド、トルエン、アセトン等の揮発性有機物濃度や悪臭物質の濃度を低減することができ、さらに、黄色ブドウ球菌や大腸菌等の病原菌を死滅させることができる。
(Reference Example 5)
When the photocatalyst dispersion liquid obtained in Examples 1 to 4 was applied to the floor and then dried to volatilize the dispersion medium, formaldehyde, acetaldehyde, toluene, acetone, etc. in the indoor space were irradiated by light irradiation with indoor lighting. The concentration of volatile organic substances and malodorous substances can be reduced, and pathogens such as Staphylococcus aureus and Escherichia coli can be killed.
（参考例６）
実施例１〜４で得た光触媒体分散液を自動車用インストルメントパネル、自動車用シート、自動車天井材などの自動車内装材の表面に塗布し、その後、乾燥して分散媒を揮発させると、車内照明による光照射により、車内空間におけるホルムアルデヒド、アセトアルデヒド、トルエン、アセトン等の揮発性有機物濃度や悪臭物質の濃度を低減することができ、さらに、黄色ブドウ球菌や大腸菌等の病原菌を死滅させることができる。
(Reference Example 6)
When the photocatalyst dispersion liquid obtained in Examples 1 to 4 is applied to the surface of an automotive interior material such as an automotive instrument panel, an automotive seat, or an automotive ceiling material, and then dried to volatilize the dispersion medium, Light irradiation can reduce the concentration of volatile organic substances such as formaldehyde, acetaldehyde, toluene, and acetone and malodorous substances in the interior of the vehicle, and can kill pathogenic bacteria such as Staphylococcus aureus and Escherichia coli. .
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