JP5313051B2 - Zirconium oxalate sol - Google Patents
Zirconium oxalate sol Download PDFInfo
- Publication number
- JP5313051B2 JP5313051B2 JP2009130145A JP2009130145A JP5313051B2 JP 5313051 B2 JP5313051 B2 JP 5313051B2 JP 2009130145 A JP2009130145 A JP 2009130145A JP 2009130145 A JP2009130145 A JP 2009130145A JP 5313051 B2 JP5313051 B2 JP 5313051B2
- Authority
- JP
- Japan
- Prior art keywords
- photocatalyst
- dispersion
- photocatalytic
- oxide particles
- oxalic acid
- 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.)
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- DAWBXZHBYOYVLB-UHFFFAOYSA-J oxalate;zirconium(4+) Chemical compound [Zr+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O DAWBXZHBYOYVLB-UHFFFAOYSA-J 0.000 title claims abstract description 70
- 239000002245 particle Substances 0.000 claims abstract description 249
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 199
- 239000011941 photocatalyst Substances 0.000 claims abstract description 184
- 239000006185 dispersion Substances 0.000 claims abstract description 123
- 238000000576 coating method Methods 0.000 claims abstract description 100
- 239000011248 coating agent Substances 0.000 claims abstract description 99
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 65
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000001699 photocatalysis Effects 0.000 claims description 167
- 239000007788 liquid Substances 0.000 claims description 125
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 87
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 74
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 74
- 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 73
- 229910007746 Zr—O Inorganic materials 0.000 claims description 39
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 26
- 239000007787 solid Substances 0.000 claims description 25
- -1 silicon alkoxide Chemical class 0.000 claims description 22
- 239000002612 dispersion medium Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 abstract description 39
- 239000000463 material Substances 0.000 abstract description 15
- 239000000126 substance Substances 0.000 description 46
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 239000011521 glass Substances 0.000 description 24
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 20
- 239000002253 acid Substances 0.000 description 18
- 239000002243 precursor Substances 0.000 description 18
- 239000007864 aqueous solution Substances 0.000 description 13
- 239000013078 crystal Substances 0.000 description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- 239000003973 paint Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 229910017604 nitric acid Inorganic materials 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- 229910052726 zirconium Inorganic materials 0.000 description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- 238000000926 separation method Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 241000588724 Escherichia coli Species 0.000 description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 7
- 239000002609 medium Substances 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 101100258086 Postia placenta (strain ATCC 44394 / Madison 698-R) STS-01 gene Proteins 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 244000052769 pathogen Species 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 238000000108 ultra-filtration Methods 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 241000295644 Staphylococcaceae Species 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000012756 surface treatment agent Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 4
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 4
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 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
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 101150003085 Pdcl gene Proteins 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 229910002094 inorganic tetrachloropalladate Inorganic materials 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 230000002093 peripheral effect Effects 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000001384 succinic acid Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-L Oxalate Chemical compound [O-]C(=O)C([O-])=O MUBZPKHOEPUJKR-UHFFFAOYSA-L 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- KZNMRPQBBZBTSW-UHFFFAOYSA-N [Au]=O Chemical compound [Au]=O KZNMRPQBBZBTSW-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 244000052616 bacterial pathogen Species 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 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 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 2
- 229910001922 gold oxide Inorganic materials 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 229940071240 tetrachloroaurate Drugs 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 2
- 150000003755 zirconium compounds Chemical class 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
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- 238000007696 Kjeldahl method Methods 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 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
- QQUFBBAUXSERLO-UHFFFAOYSA-L [Pt](F)F.[I] Chemical compound [Pt](F)F.[I] QQUFBBAUXSERLO-UHFFFAOYSA-L 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- YKIOKAURTKXMSB-UHFFFAOYSA-N adams's catalyst Chemical compound O=[Pt]=O YKIOKAURTKXMSB-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 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
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical class [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229960004543 anhydrous citric acid Drugs 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- VUCAVCCCXQVHAN-UHFFFAOYSA-L azane dichlorocopper Chemical compound N.Cl[Cu]Cl VUCAVCCCXQVHAN-UHFFFAOYSA-L 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
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 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
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 229960004106 citric acid Drugs 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 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
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 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
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 235000019253 formic acid Nutrition 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
- 150000004820 halides Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052742 iron 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
- CYPPCCJJKNISFK-UHFFFAOYSA-J kaolinite Chemical compound [OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[O-][Si](=O)O[Si]([O-])=O CYPPCCJJKNISFK-UHFFFAOYSA-J 0.000 description 1
- 229910052622 kaolinite Inorganic materials 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
- 239000012528 membrane Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 1
- VVRQVWSVLMGPRN-UHFFFAOYSA-N oxotungsten Chemical class [W]=O VVRQVWSVLMGPRN-UHFFFAOYSA-N 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 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
- 239000000123 paper Substances 0.000 description 1
- 230000001443 photoexcitation 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
- KABWJWZACJCALW-UHFFFAOYSA-J platinum tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl.[Pt] KABWJWZACJCALW-UHFFFAOYSA-J 0.000 description 1
- KGRJUMGAEQQVFK-UHFFFAOYSA-L platinum(2+);dibromide Chemical compound Br[Pt]Br KGRJUMGAEQQVFK-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
- 229920001296 polysiloxane Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 235000019353 potassium silicate Nutrition 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
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 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
- 159000000000 sodium salts Chemical class 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
- 229910052682 stishovite Inorganic materials 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
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000009283 thermal hydrolysis Methods 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
- 238000002834 transmittance Methods 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical class [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 150000003627 tricarboxylic acid derivatives Chemical class 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Landscapes
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
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Abstract
Description
本発明は、蓚酸ジルコニウムゾルに関する。 The present invention relates to a zirconium oxalate sol.
光触媒体は、光を照射されることで活性を示す触媒であって、例えばＷＯ９８／１５６００パンフレット、特開２００３−１０５２６２号公報、特開平９−３２８３３６号公報、特開２００４−５９６８６号公報、ＷＯ０１／０２３４８３パンフレット、特開平１１−２０９６９１号公報、ＷＯ９９／０２８３９３パンフレットなどに開示されるように、バインダー成分と共に基材に塗布して、塗膜として使用されている。
しかし、従来の光触媒体コーティング液から形成される塗膜は、基材への密着強度が必ずしも十分ではなく、このため、コーティング液中の光触媒体に対するバインダー成分の使用量を多くする必要があった。バインダー成分の使用量が多いと、光触媒体が十分にその活性を発現しにくくなる。
The photocatalyst is a catalyst that shows activity when irradiated with light. For example, WO98 / 15600 pamphlet, JP-A-2003-105262, JP-A-9-328336, JP-A-2004-59686, WO01 As disclosed in / 023483 pamphlet, JP-A-11-209691 pamphlet, WO99 / 028393 pamphlet and the like, it is applied to a substrate together with a binder component and used as a coating film.
However, the coating film formed from the conventional photocatalyst coating liquid does not necessarily have sufficient adhesion strength to the base material, and therefore it is necessary to increase the amount of binder component used for the photocatalyst in the coating liquid. . If the amount of the binder component used is large, the photocatalyst will not sufficiently exhibit its activity.
金属化合物の微粒子を分散質とするゾルをバインダーとして使用する場合、ゾルは分散性が優れているため、光触媒体との均一な混合が容易であり、膜の構造を均一化でき、強力なバインダー能力を発揮して、良質の光触媒体の塗膜を与えることが期待できる。 When a sol having fine particles of a metal compound as a dispersoid is used as a binder, since the sol has excellent dispersibility, uniform mixing with a photocatalyst is easy, the structure of the film can be made uniform, and a strong binder It can be expected that the coating film of a high-quality photocatalyst body is provided by demonstrating its ability.
かかる金属化合物の微粒子のなかでも、ジルコニウム化合物微粒子はＺｒ原子同士がＯＨ基を介して重合しやすい性質をもつため、光触媒体コーティング液のバインダーとして高い適性を持つと考えられる。光触媒のバインダーとしての適性が高いと考えられるジルコニウム化合物のゾルとしては、特許文献１に開示されるゾル、すなわち、Ｘ線回折的に非晶質であり、平均粒子径が１０ｎｍのＺｒ−Ｏ系粒子を分散質とし、ｐＨ３．２、１モルのＺｒに対して０．４グラム当量の硝酸を含有するゾルが挙げられる。このＺｒ−Ｏ系粒子を分散質とするゾルは、分散質が非晶質であることや平均粒子径が１０ｎｍであることなど、光触媒体コーティング液のバインダーとして高い適正が期待できる。 Among these metal compound fine particles, zirconium compound fine particles are considered to have high suitability as a binder for a photocatalyst coating liquid because Zr atoms are easily polymerized via OH groups. Zirconium compound sol considered to be highly suitable as a binder for a photocatalyst is a sol disclosed in Patent Document 1, that is, a Zr—O system having an average particle diameter of 10 nm, which is amorphous by X-ray diffraction. A sol containing particles as a dispersoid and containing 0.4 gram equivalent of nitric acid with respect to pH 3.2 and 1 mol of Zr can be mentioned. A sol having Zr—O-based particles as a dispersoid can be expected to be highly suitable as a binder for a photocatalyst coating liquid, such as an amorphous dispersoid and an average particle diameter of 10 nm.
しかし、特許文献１に開示されるゾルは、光触媒体コーティング液のバインダーとして最適であるとは言いがたい。 However, it is difficult to say that the sol disclosed in Patent Document 1 is optimal as a binder for the photocatalyst coating liquid.
本発明は上記の問題点を鑑みなされたものであって、その目的とするところは、光触媒体塗料の優れたバインダーとして機能するゾルを提供することにある。 The present invention has been made in view of the above problems, and an object of the present invention is to provide a sol that functions as an excellent binder for a photocatalyst coating material.
本発明者等は上記の問題点について鋭意研究を重ねた結果、本発明を完成するに至った。
すなわち、本発明は、以下を提供するものである。
As a result of intensive studies on the above problems, the present inventors have completed the present invention.
That is, the present invention provides the following.
（１）蓚酸ジルコニウムを分散質とするゾルであって、蓚酸／Ｚｒモル比が１．２〜３であり、分散質の粒子径Ｄ５０が１０〜１００ｎｍであることを特徴とする蓚酸ジルコニウムゾル。
（２）水酸化ジルコニウムの分散液へ蓚酸を添加することにより、上記（１）の蓚酸ジルコニウムゾルを製造する方法であって、蓚酸の添加を２回に分けて行うことを特徴とする蓚酸ジルコニウムゾルの製造方法。
（３）水酸化ジルコニウムの分散液へ蓚酸／Ｚｒモル比が０．８〜１．０となるように蓚酸を添加し、得られた水酸化ジルコニウムと蓚酸の混合物を加熱処理した後、さらに蓚酸／Ｚｒモル比が１．２〜３．０となるように蓚酸を添加し、該混合物を再び加熱すること
を特徴とする前記（２）記載の製造方法。
（４）光触媒活性を有する被膜を形成するための光触媒体コーティング液であって、（ｉ）光触媒体、（ｉｉ）蓚酸ジルコニウム、（ｉｉｉ）非晶質Ｚｒ−Ｏ系粒子、（ｉＶ）シリコンアルコキシド、及び（Ｖ）溶媒を含み、（ｉ）が表面が互いに同じ極性に帯電してい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か、もしくは、リン酸(塩）で表面処理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、であり、（ｉ）の全固形分に対する（ｉｉ）〜（ｉＶ）の含有量が、酸化物換算（（ｉｉ）および（ｉｉｉ）はＺｒＯ２、（ｉＶ）はＳｉＯ２）で、それぞれ０．０２０〜０．２０質量倍、０．０２０〜０．４０質量倍、及び０．０４０〜０．２２質量倍である光触媒体コーティング液。
（５）基材の表面に前記（４）に記載の光触媒体コーティング液を塗布し、分散媒を揮発させることを特徴とする光触媒機能製品の製造方法。
(1) A sol having zirconium oxalate as a dispersoid, the oxalic acid / Zr molar ratio being 1.2 to 3, and the particle diameter D50 of the dispersoid being 10 to 100 nm.
(2) A method for producing the zirconium oxalate sol according to (1) above by adding oxalic acid to a dispersion of zirconium hydroxide, wherein the addition of oxalic acid is performed in two steps. A method for producing a sol.
(3) Succinic acid is added to a dispersion of zirconium hydroxide so that the oxalic acid / Zr molar ratio is 0.8 to 1.0, and the resulting mixture of zirconium hydroxide and oxalic acid is heat-treated, and further oxalic acid. The process according to (2), wherein oxalic acid is added so that the / Zr molar ratio is 1.2 to 3.0, and the mixture is heated again.
(4) A photocatalyst coating liquid for forming a film having photocatalytic activity, comprising (i) a photocatalyst, (ii) zirconium oxalate, (iii) amorphous Zr-O-based particles, and (iV) silicon alkoxide And (V) a photocatalytic titanium oxide particle and a photocatalytic titanium oxide particle having a surface charged with the same polarity as each other, or (i) a photocatalytic titanium oxide particle surface-treated with phosphoric acid (salt) And the photocatalytic tungsten oxide particles, the content of (ii) to (iV) with respect to the total solid content of (i) is converted to oxide ((ii) and (iii) are ZrO2, (iV) is SiO2) , 0.020 to 0.20 mass times, 0.020 to 0.40 mass times, and 0.040 to 0.22 mass times, respectively.
(5) A method for producing a photocatalytic functional product, comprising applying the photocatalyst coating liquid according to (4) above to the surface of a substrate to volatilize the dispersion medium.
本発明の蓚酸ジルコニウムゾルによれば、バインダー成分として光触媒体コーティング液に添加することにより、光触媒体の機能を阻害することなく、少ない添加量で、十分な密着力を示す塗膜を形成することができる。 According to the zirconium oxalate sol of the present invention, by adding to the photocatalyst coating liquid as a binder component, a coating film showing sufficient adhesion can be formed with a small addition amount without inhibiting the function of the photocatalyst. Can do.
本発明において、粒子径Ｄ５０とはレーザードップラー法によってゾルの粒子径測定を行ったときの体積換算累積頻度が５０％となる粒子径を意味する。 In the present invention, the particle diameter D50 means a particle diameter at which the volume conversion cumulative frequency becomes 50% when the particle diameter of the sol is measured by the laser Doppler method.
〔蓚酸ジルコニウムを分散質とするゾル〕
本発明のゾルは蓚酸ジルコニウムを分散質とする。この蓚酸ジルコニウムの蓚酸／Ｚｒモル比は特に限定されず、例えば、９５Ｚｒ−Ｚｉｒｃｏｎｉｕｍ ｏｘａｌａｔｅ（ＣＡＳ．Ｎｏ．５０２９１−６８−４）、Ｚｉｒｃｏｎｉｕｍ ｏｘａｌａｔｅ（ＣＡＳ．Ｎｏ．１４５３６−１９−７）、Ｚｉｒｃｏｎｉｕｍ ｏｘｉｄｅ ｏｘａｌａｔｅ（ＣＡＳ．Ｎｏ．３４１５６−７０−２）、Ｚｒ（Ｃ2Ｏ4）0.69（ＯＨ）2.69・ｘＨ2Ｏ（ＣＡＳ．Ｎｏ．３４１５６−７０−２）、Ｚｒ（Ｃ2Ｏ4）0.8（ＯＨ）2.4・９９Ｈ2Ｏ（ＣＡＳ．Ｎｏ．３４１５６−７０−２）、Ｚｒ（ＯＨ）（ＨＣ2Ｏ4）3・７Ｈ2Ｏ（ＣＡＳ．Ｎｏ．３４１５６−７０−２）等既知の化合物が例示される。分散質の蓚酸ジルコニウムの構造としては、ＯＨ基を介して重合されたＺｒ原子に蓚酸イオンが配位しているような構造が考えられる。その証拠に、本発明のゾルは大きくとも約−２０ｍＶの負のゼータ電位を有する。これはアニオンである蓚酸イオンの配位によって、Ｚｒ原子の重合体が負電荷を帯びていることによると推測される。
[Sol with zirconium oxalate as dispersoid]
The sol of the present invention uses zirconium oxalate as a dispersoid. The oxalic acid / Zr molar ratio of the zirconium oxalate is not particularly limited. For example, 95Zr-Zirconium oxalate (CAS. No. 50291-68-4), Zirconium oxalate (CAS. (CAS. No. 34156-70-2), Zr (C 2 O 4 ) 0.69 (OH) 2.69 · xH 2 O (CAS. No. 34156-70-2), Zr (C 2 O 4 ) 0.8 (OH ) Known compounds such as 2.4 · 99H 2 O (CAS. No. 34156-70-2) and Zr (OH) (HC 2 O 4 ) 3 · 7H 2 O (CAS. No. 34156-70-2) Is done. As the structure of the dispersoid zirconium oxalate, a structure in which oxalate ions are coordinated to Zr atoms polymerized through OH groups is conceivable. In evidence, the sol of the present invention has a negative zeta potential of at most about -20 mV. This is presumed to be because the polymer of Zr atoms is negatively charged due to the coordination of oxalate ions, which are anions.
ここで、配位した蓚酸イオンが完全に脱離して、Ｚｒ原子がＯＨ基を介した重合構造の骨格だけとなっても、光触媒体のバインダーとして機能を発揮できるため、そのような化学種がゾルに含まれていても構わない。 Here, even if the coordinated oxalate ion is completely desorbed and the Zr atom becomes only the skeleton of the polymerized structure via the OH group, it can function as a binder of the photocatalyst, so such chemical species It may be contained in the sol.
分散質の蓚酸ジルコニウムの粒子径Ｄ５０は１０〜１００ｎｍ、好ましくは１０〜８０ｎｍである。このような粒子径Ｄ５０が必要である理由は、光触媒体塗膜となったとき高い可視光透過率を確保するため、また、光触媒体の粒子径と同等の粒子径とすることで光触媒塗膜の均一化し、高い密着性や膜強度を得るためである。光触媒体コーティング液に粒子径Ｄ５０が１０ｎｍ未満の蓚酸ジルコニウムを分散質とするゾルが処方された場合、塗膜の形成過程で蓚酸ジルコニウムが結晶として析出し成長するなどして膜の不均一化の原因となるため好ましくない。また、１００ｎｍを超えると可視光の白色散乱が強くなり光触媒塗膜やその基材の外観を損ねたり、光触媒塗膜の緻密性が低下し十分な強度や密着性が得られないため好ましくない。 The particle diameter D50 of the dispersoid zirconium oxalate is 10 to 100 nm, preferably 10 to 80 nm. The reason why such a particle diameter D50 is necessary is to secure a high visible light transmittance when it becomes a photocatalyst coating film, and by setting the particle diameter to be equivalent to the particle diameter of the photocatalyst body. This is to obtain uniform adhesion and obtain high adhesion and film strength. When the photocatalyst coating liquid is formulated with a sol having a particle size D50 of less than 10 nm of zirconium oxalate as a dispersoid, the film is formed non-uniformly, such as zirconium oxalate precipitates and grows during the coating process. It is not preferable because it causes. On the other hand, when the thickness exceeds 100 nm, the white scattering of visible light becomes strong, the appearance of the photocatalyst coating film and its substrate is impaired, and the denseness of the photocatalyst coating film is lowered and sufficient strength and adhesion cannot be obtained.
本発明のゾルは蓚酸／Ｚｒモル比が１．２〜３．０の蓚酸を含有する。そのうち一部は上記のようにＯＨ基によって重合したＺｒ原子に配位していると考えられる。上記モル比が１．２未満の場合は、分散質が均一に分散せず、目的のゾルとならない。これは分散質の蓚酸ジルコニウムが分散に十分なだけの負の表面電位を持つには、蓚酸ジルコニウム中のＺｒ原子に対する蓚酸イオンの配位が一定量以上必要であるためと考えられる。ゾルに含有される蓚酸／Ｚｒモル比によってゼータ電位の制御が可能であるため、必要なゼータ電位に応じて蓚酸／Ｚｒモル比を１．２〜３．０とすればよい。蓚酸／Ｚｒモル比に伴ってゼータ電位は低下するので、分散質の蓚酸ジルコニウムの静電気的反発力は大きくなり、結果として、粘度が低下するなどの効果が得られる。 The sol of the present invention contains oxalic acid having an oxalic acid / Zr molar ratio of 1.2 to 3.0. Some of them are thought to be coordinated to Zr atoms polymerized by OH groups as described above. When the molar ratio is less than 1.2, the dispersoid is not uniformly dispersed and the intended sol is not obtained. This is presumably because the dispersoid zirconium oxalate requires a certain amount or more of coordination of oxalate ions to Zr atoms in zirconium oxalate in order to have a negative surface potential sufficient for dispersion. Since the zeta potential can be controlled by the oxalic acid / Zr molar ratio contained in the sol, the oxalic acid / Zr molar ratio may be set to 1.2 to 3.0 according to the required zeta potential. Since the zeta potential decreases with the oxalic acid / Zr molar ratio, the electrostatic repulsive force of the dispersoid zirconium oxalate increases, and as a result, effects such as a decrease in viscosity can be obtained.
蓚酸／Ｚｒモル比が３．０を超える場合、光触媒体塗膜の不純物が増大させ、光触媒機能を妨害する可能性があるため好ましくない。 When the oxalic acid / Zr molar ratio exceeds 3.0, impurities in the photocatalyst coating film increase, which may interfere with the photocatalytic function, which is not preferable.
ゾルの粒子径Ｄ５０が１０〜１００ｎｍ、好ましくは１０〜８０ｎｍとなる限り、分散媒は用途に応じて適当に選択すればよい。通常水、エタノール、メタノール等およびそれらの混合物が使用される。 As long as the particle diameter D50 of the sol is 10 to 100 nm, preferably 10 to 80 nm, the dispersion medium may be appropriately selected depending on the application. Usually water, ethanol, methanol etc. and mixtures thereof are used.
また、ゾル中に含まれるジルコニウムおよび蓚酸以外の不純物成分は極力少ないことが好ましいが、光触媒体や光触媒体塗膜の機能を阻害しない範囲内であれば含有されても問題ない。 Further, it is preferable that impurity components other than zirconium and oxalic acid contained in the sol are as small as possible.
以下に、本発明の蓚酸ジルコニウムを分散質とするゾルの製造方法、蓚酸ジルコニウムをバインダーの一成分とする光触媒体コーティング液、およびその光触媒体コーティング液を塗布した光触媒機能製品の製造方法、について、詳細に説明する。 The following is a method for producing a sol having zirconium oxalate as a dispersoid according to the present invention, a photocatalyst coating liquid containing zirconium oxalate as one component, and a method for producing a photocatalytic functional product coated with the photocatalyst coating liquid. This will be described in detail.
〔蓚酸ジルコニウムを分散質とするゾルの製造方法〕
本発明の特徴は水酸化ジルコニウムの分散液へ２回に分けて蓚酸を添加することである。本発明で使用する水酸化ジルコニウムは、通常市販されているものでも、オキシ塩化ジルコニウムの水溶液を水酸化ナトリウムなどの塩基で中和し、十分に洗浄して不純物を除去して得られるものでもよい。用いる水酸化ジルコニウムの不純物は、水酸化ジルコニウムのＺｒＯ2換算濃度に対する相対濃度として１重量％以下であることが好ましい。１重量％を超える場合、ゾル中の不純物濃度も増大し、光触媒体塗膜へ悪影響する可能性があるため好ましくない。
[Method for producing sol with zirconium oxalate as dispersoid]
A feature of the present invention is that oxalic acid is added to the zirconium hydroxide dispersion in two portions. The zirconium hydroxide used in the present invention may be a commercially available product, or may be obtained by neutralizing an aqueous solution of zirconium oxychloride with a base such as sodium hydroxide and thoroughly washing to remove impurities. . The impurity of zirconium hydroxide to be used is preferably 1% by weight or less as a relative concentration with respect to ZrO 2 equivalent concentration of zirconium hydroxide. If it exceeds 1% by weight, the impurity concentration in the sol also increases, which may be adversely affected on the photocatalyst coating film.
次に、水酸化ジルコニウムを通常は水に分散し水酸化ジルコニウムの分散液とする。この分散液のＺｒＯ2換算濃度は５〜１５重量％であることが好ましい。５％未満の場合は、非効率であり、１５％を超える場合、粒子径の制御が困難になるため不適当である。 Next, zirconium hydroxide is usually dispersed in water to obtain a zirconium hydroxide dispersion. The ZrO 2 equivalent concentration of this dispersion is preferably 5 to 15% by weight. If it is less than 5%, it is inefficient, and if it exceeds 15%, it is difficult to control the particle size, which is inappropriate.
次に、上記分散液に１回目の蓚酸添加を行う。蓚酸の供給源としては通常、蓚酸二水和物を粉末のまま使用するが、これを水に溶解したものを用いてもなんら構わない。 Next, the first oxalic acid is added to the dispersion. As the source of oxalic acid, oxalic acid dihydrate is usually used as a powder, but it is possible to use a solution obtained by dissolving this in water.
１回目に添加される蓚酸の量は蓚酸／Ｚｒモル比が０．８〜１．０であることが好ましい。この蓚酸／Ｚｒモル比が０．８未満であっても、１．０を超えても、ゾルの粒子径Ｄ５０が粗大化するため好ましくない。１回目の蓚酸添加量が上記範囲内に限定され、その範囲外において粒子径Ｄ５０が粗大化する理由は、１回目の蓚酸添加によってゾルの分散質となる蓚酸ジルコニウムの基本骨格が形成されるためと考えられる。すなわち、１回目の蓚酸添加後、上記で説明したような蓚酸イオンに配位されたＺｒ原子がＯＨ基を介した重合体が形成されるが、その大きさが１回目の蓚酸添加量によって決定されると考えられる。 The amount of oxalic acid added for the first time is preferably such that the oxalic acid / Zr molar ratio is 0.8 to 1.0. Even if this oxalic acid / Zr molar ratio is less than 0.8 or more than 1.0, the particle diameter D50 of the sol becomes coarse, which is not preferable. The reason why the first oxalic acid addition amount is limited to the above range and the particle diameter D50 is coarsened outside the above range is that the basic skeleton of zirconium oxalate which becomes the dispersoid of the sol is formed by the first oxalic acid addition. it is conceivable that. That is, after the first addition of oxalic acid, a polymer is formed in which the Zr atoms coordinated to the oxalate ions as described above are OH groups, the size of which is determined by the first oxalic acid addition amount. It is thought that it is done.
１回目の蓚酸添加後、水酸化ジルコニウムの分散液は通常、加熱されることが好ましい。
上記のように１回目の蓚酸添加後は分散質となる蓚酸ジルコニウムが形成される反応が起こると考えられるが、加熱によってその反応速度を上げることで、製造効率を高めることができる。加熱は７０〜９５℃で１０〜３０分程度行えばよい。加熱不足によって上記反応が十分進行していない場合は、最終的に得られるゾルの粒子径Ｄ５０が粗大化する原因となる。
After the first addition of oxalic acid, the zirconium hydroxide dispersion is usually preferably heated.
As described above, after the first addition of oxalic acid, it is considered that a reaction in which zirconium oxalate serving as a dispersoid is formed occurs. However, the production efficiency can be increased by increasing the reaction rate by heating. Heating may be performed at 70 to 95 ° C. for about 10 to 30 minutes. When the reaction does not proceed sufficiently due to insufficient heating, the particle diameter D50 of the sol finally obtained becomes a cause of coarsening.
上記の加熱後、２回目の蓚酸添加を行う。２回目の蓚酸添加はゾル中の蓚酸／Ｚｒモル比が１．２〜３．０になるような量を添加する。例えば、１回目の蓚酸添加において蓚酸／Ｚｒモル比で１．０の蓚酸を添加した場合は、２回目の蓚酸添加において蓚酸／Ｚｒモル比で０．２〜２．０の蓚酸を添加すればよい。この２回目の蓚酸添加によって、１回目の蓚酸添加後形成された分散質の蓚酸ジルコニウムの基本骨格から最終的にゾルの分散質となる蓚酸ジルコニウムの粒子が完成される。すなわち、ゾルの分散質となる蓚酸ジルコニウムの粒子が生成し、本発明のゾルが完成されるには最低限、蓚酸／Ｚｒモル比が１．２の蓚酸が必要である。２回目の蓚酸が添加された液の粒子径Ｄ５０を測定して１０〜１００ｎｍであれば、分散質となる蓚酸ジルコニウムの粒子が完成されたと判断できる。 After the above heating, the second addition of oxalic acid is performed. In the second addition of oxalic acid, an amount such that the oxalic acid / Zr molar ratio in the sol is 1.2 to 3.0 is added. For example, when 1.0 oxalic acid / Zr molar ratio is added in the first oxalic acid addition, 0.2-2.0 oxalic acid is added in the oxalic acid / Zr molar ratio in the second oxalic acid addition. Good. This second addition of oxalic acid completes the particles of zirconium oxalate that finally becomes the dispersoid of the sol from the basic skeleton of zirconium oxalate in the dispersoid formed after the first addition of oxalic acid. That is, at least oxalic acid having an oxalic acid / Zr molar ratio of 1.2 is required to produce zirconium oxalate particles as a dispersoid of the sol and complete the sol of the present invention. If the particle diameter D50 of the liquid to which oxalic acid is added for the second time is measured to be 10 to 100 nm, it can be determined that the particles of zirconium oxalate serving as the dispersoid have been completed.
上記の説明のように、蓚酸ジルコニウムのＺｒ原子への蓚酸イオンの配位数によって、分散質の蓚酸ジルコニウムのゼータ電位が決定されるため、最終的にゾルの分散質となる蓚酸ジルコニウムの粒子を完成させるために必要な蓚酸よりも多い量の蓚酸は必要とされるゼータ電位に応じて添加すればよい。 As described above, the zeta potential of the zirconium oxalate in the dispersoid is determined by the coordination number of the oxalate ion to the Zr atom of zirconium oxalate. A larger amount of oxalic acid than that required for completion may be added depending on the required zeta potential.
２回目の蓚酸添加後は加熱処理をすることが好ましい。加熱は７０〜９５℃で１０〜３０分程度行えばよい。加熱処理によって上記のゾルの分散質となる蓚酸ジルコニウムの粒子の完成が促進され、ゾルを効率的に製造できる。 Heat treatment is preferably performed after the second addition of oxalic acid. Heating may be performed at 70 to 95 ° C. for about 10 to 30 minutes. The heat treatment promotes the completion of the particles of zirconium oxalate that becomes the dispersoid of the sol, and the sol can be produced efficiently.
以下、本発明の光触媒体コーティング液について詳細に説明する。
本発明の光触媒体コーティング液は、（１）光触媒体、（２）蓚酸ジルコニウム、（３）非晶質Ｚｒ−Ｏ系粒子、（４）シリコンアルコキシド及び（５）溶媒を含み、（１）が表面が互いに同じ極性に帯電してい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か、もしくは、リン酸(塩）で表面処理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、であり、（１）の全固形分に対する（２）〜（４）の含有量が、酸化物換算（（２）および（３）はＺｒＯ２、（４）はＳｉＯ２）で、それぞれ０．０２０〜０．２０質量倍、０．０２０〜０．４０質量倍および０．０４０〜０．２２質量倍であることを特徴とする。
Hereinafter, the photocatalyst coating liquid of the present invention will be described in detail.
The photocatalyst coating liquid of the present invention comprises (1) a photocatalyst, (2) zirconium oxalate, (3) amorphous Zr-O-based particles, (4) silicon alkoxide, and (5) a solvent, Photocatalytic titanium oxide particles and photocatalytic tungsten oxide particles whose surfaces are charged to the same polarity, or photocatalytic titanium oxide particles and photocatalytic tungsten oxide particles surface-treated with phosphoric acid (salt), The content of (2) to (4) with respect to the total solid content is 0.020 to 0.20 times by mass in terms of oxides ((2) and (3) are ZrO 2 and (4) is SiO 2 ), respectively. 0.020 to 0.40 mass times and 0.040 to 0.22 mass times.
本発明の光触媒体は、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か、もしくは、酸化チタン粒子はリン酸(塩）で表面処理されているため、光触媒酸化チタン粒子と光触媒酸化タングステン粒子は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、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ので、本発明の光触媒体分散液を塗布することにより形成される光触媒体塗布膜は、高い光触媒活性を示す。 In the photocatalyst of the present invention, the surfaces of photocatalytic titanium oxide particles and photocatalytic tungsten oxide particles dispersed in a dispersion medium are charged to the same polarity, or the titanium oxide particles are surface-treated with phosphoric acid (salt). Therefore, the photocatalytic titanium oxide particles and the photocatalytic tungsten oxide particles do not agglomerate with each other, and therefore do not undergo solid-liquid separation. In addition, since the photocatalytic titanium oxide particles and the photocatalytic tungsten oxide particles can be applied to the base material without agglomerating each other, the photocatalyst coating film formed by applying the photocatalyst dispersion liquid of the present invention is a high photocatalyst. Shows activity.
〔光触媒体酸化チタン粒子〕
本発明の光触媒体分散液を構成する光触媒酸化チタン粒子とは、光触媒作用を示し粒子状の酸化チタンであって、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〕粒子などが挙げられる。
[Photocatalyst titanium oxide particles]
The photocatalytic titanium oxide particles constituting the photocatalyst dispersion liquid of the present invention are particulate titanium oxides exhibiting photocatalytic action, such as metatitanic acid particles, crystal forms of anatase type, brookite type, rutile type, etc. Examples include titanium [TiO 2 ] particles.
メタチタン酸粒子は、例えば以下の方法１により得ることができる。
方法１：硫酸チタニルの水溶液を加熱することにより加水分解する方法
Metatitanic acid particles can be obtained, for example, by the following method 1.
Method 1: Method of hydrolysis by heating an aqueous solution of titanyl sulfate
二酸化チタン粒子は、例えば以下の方法２−１〜方法２−３のいずれかの方法により得ることができる。
方法２−１：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
方法２−２：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
方法２−３：メタチタン酸を焼成する方法
Titanium dioxide particles can be obtained, for example, by any one of the following methods 2-1 to 2-3.
Method 2-1: A method in which a precipitate is obtained by adding a base to this solution without heating an aqueous solution of titanyl sulfate or titanium chloride, and the resulting precipitate is calcined. Method 2-2: water and acid in titanium alkoxide A method of firing a precipitate obtained by adding an aqueous solution or an aqueous solution of a base, and firing the obtained precipitate 2-3: A method of firing metatitanic acid
これらの方法２−１〜方法２−３により得られる二酸化チタン粒子は、焼成する際の焼成温度、焼成時間により、アナターゼ型、ブルッカイト型またはルチル型のものとして得る
ことができる。
The titanium dioxide particles obtained by these methods 2-1 to 2-3 can be obtained as anatase type, brookite type or rutile type depending on the firing temperature and firing time when firing.
光触媒酸化チタン粒子の粒子径は、平均分散粒子径で、光触媒作用の点で、通常２０ｎｍ〜１５０ｎｍ、好ましくは４０ｎｍ〜１００ｎｍである。 The particle diameter of the photocatalytic titanium oxide particles is an average dispersed particle diameter, and is usually 20 nm to 150 nm, preferably 40 nm to 100 nm in terms of photocatalysis.
光触媒酸化チタン粒子のＢＥＴ比表面積は、光触媒作用の点で、通常１００ｍ2／ｇ〜５００ｍ2／ｇ、好ましくは３００ｍ2／ｇ〜４００ｍ2／ｇである。 BET specific surface area of the titanium oxide photocatalyst particles in terms of photocatalytic activity is usually 100m 2 / g~500m 2 / g, preferably from 300m 2 / g~400m 2 / g.
〔光触媒体酸化タングステン粒子〕
光触媒酸化タングステン粒子とは、光触媒作用を示し、粒子状の酸化タングステンであって、通常は三酸化タングステン〔ＷＯ3〕粒子が挙げられる。三酸化タングステン粒子は、例えば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により得ることができる。また、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により得ることもできる。
[Photocatalyst tungsten oxide particles]
The photocatalytic tungsten oxide particles exhibit a photocatalytic action and are particulate tungsten oxides, and usually include tungsten trioxide [WO 3 ] particles. The tungsten trioxide particles can be obtained, for example, by adding an acid to an aqueous solution of tungstate to obtain tungstic acid as a precipitate and baking the obtained tungstic acid. Moreover, it can also obtain by the method of thermally decomposing by heating ammonium metatungstate and ammonium paratungstate.
光触媒酸化タングステン粒子の粒子径は、平均分散粒子径で、光触媒作用の点で、通常５０ｎｍ〜２００ｎｍ、好ましくは８０ｎｍ〜１３０ｎｍである。 The particle diameter of the photocatalytic tungsten oxide particles is an average dispersed particle diameter, and is usually 50 nm to 200 nm, preferably 80 nm to 130 nm in terms of photocatalysis.
光触媒酸化タングステン粒子のＢＥＴ比表面積は、光触媒作用の点で、通常５ｍ2／ｇ〜１００ｍ2／ｇ、好ましくは２０ｍ2／ｇ〜５０ｍ2／ｇである。 BET specific surface area of the tungsten oxide photocatalyst particles in terms of photocatalytic activity, typically 5m 2 / g~100m 2 / g, preferably 20m 2 / g~50m 2 / g.
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使用量比は、質量比で通常４：１〜１：８、好ましくは２：３〜３：２である。 The amount ratio of the photocatalytic titanium oxide particles and the photocatalytic tungsten oxide particles is usually 4: 1 to 1: 8, preferably 2: 3 to 3: 2 in terms of mass ratio.
〔表面の帯電〕
本発明で用いる光触媒体コーティング液において、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、具体的には共にプラスに帯電しているか、または表面が共にマイナスに帯電している。
上記の方法１により得たメタチタン酸粒子や、上記の方法２−１〜方法２−３により得た二酸化チタン粒子は通常、その表面がプラスに帯電している。
[Surface charging]
In the photocatalyst coating liquid used in the present invention, the surfaces of the photocatalytic titanium oxide particles and the photocatalytic tungsten oxide particles are charged to the same polarity, specifically, both are positively charged, or the surfaces are both negative. Charged.
The surface of the metatitanic acid particles obtained by the above-mentioned method 1 and the titanium dioxide particles obtained by the above-mentioned method 2-1 to method 2-3 are usually positively charged.
これに対して、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により得た酸化タングステン粒子や、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などを加熱することにより熱分解して得られた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記の光触媒酸化チタン粒子と、表面がマイナスに帯電した上記の光触媒酸化タングステン粒子とを用いる場合は、例えば光触媒酸化チタン粒子の表面をマイナスに帯電させて、本発明の光触媒体分散液に用いればよい。 In contrast, by adding an acid to an aqueous solution of tungstate, tungstic acid is obtained as a precipitate, and the tungsten oxide particles, ammonium metatungstate, and ammonium paratungstate obtained by baking the obtained tungstic acid are obtained. The surface of tungsten oxide particles obtained by thermal decomposition by heating or the like is negatively charged. For this reason, when using the above-mentioned photocatalytic titanium oxide particles whose surface is positively charged and the above-mentioned photocatalytic tungsten oxide particles whose surface is negatively charged, for example, the surface of the photocatalytic titanium oxide particles is negatively charged. The photocatalyst dispersion liquid of the present invention may be used.
表面がプラスに帯電した光触媒酸化チタン粒子の表面をマイナスに帯電させるには、該光触媒酸化チタン粒子の表面をマイナスに帯電させうる表面処理剤が分散媒に溶解された溶液中に分散させればよい。かか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、などが挙げられる。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。多価カルボン酸およびリン酸として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、好ましくは蓚酸、蓚酸アンモニウムなどが挙げられる。 In order to negatively charge the surface of the photocatalytic titanium oxide particles having a positively charged surface, a surface treatment agent capable of negatively charging the surface of the photocatalytic titanium oxide particles can be dispersed in a solution dissolved in a dispersion medium. Good. Examples of such a surface treating agent include polycarboxylic acids such as dicarboxylic acids and tricarboxylic acids. Examples of the dicarboxylic acid include succinic acid, and examples of the tricarboxylic acid include citric acid. A free acid or a salt may be used as the polyvalent carboxylic acid and phosphoric acid. Examples of the salt include ammonium salt. Preferred examples of the surface treatment agent include oxalic acid and ammonium oxalate.
上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、表面を十分に帯電させ得る点で、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。 The amount of the surface treatment agent used is usually 0.001 mol times or more, preferably 0.02 mol times or more, in that the surface can be sufficiently charged with respect to the photocatalytic titanium oxide particles in terms of TiO 2 , In terms of economy, it is usually 0.5 mol times or less, preferably 0.3 mol times or less.
上記表面処理剤が分散媒に溶解された溶液中に、表面がプラスに帯電している光触媒酸化チタン粒子を分散させることにより、表面処理溶液に溶解した表面処理剤が光触媒酸化チタン粒子の表面に吸着し、これにより、表面をマイナスに帯電させることができる。 The surface-treating agent dissolved in the surface treatment solution is dispersed on the surface of the photocatalytic titanium oxide particles by dispersing the photocatalytic titanium oxide particles whose surface is positively charged in the solution in which the surface treatment agent is dissolved in the dispersion medium. Adsorbed and thereby the surface can be negatively charged.
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の帯電は、それぞれを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、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。溶媒の使用量は、光触媒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 the photocatalytic titanium oxide particles and the photocatalytic tungsten oxide particles can be measured by the zeta potential when each is dispersed in a solvent. As a solvent used for measuring the zeta potential, an aqueous sodium chloride solution (sodium chloride concentration 0.01 mol / L) having a hydrogen ion concentration of pH 3.0 by adding hydrochloric acid is used. The amount of the solvent used is usually 10,000 to 1,000,000 times the photocatalytic titanium oxide particles or tungsten oxide particles.
〔リン酸（塩）〕
本発明の光触媒コーティング液はリン酸（塩）を含み、リン酸（塩）は光触媒酸化チタン粒子の表面近傍に存在する。リン酸（塩）としては、リン酸、もしくはそのアンモニウム塩、ナトリウム塩、カリウム塩等が挙げられるが、これらの中でも特に、リン酸二水素アンモニウム、リン酸水素二アンモニウム等のリン酸アンモニウム塩が好ましい。なお、リン酸（塩）は、単独で用いてもよいし、２種以上を併用してもよい。
[Phosphoric acid (salt)]
The photocatalyst coating solution of the present invention contains phosphoric acid (salt), and phosphoric acid (salt) is present in the vicinity of the surface of the photocatalytic titanium oxide particles. Examples of phosphoric acid (salt) include phosphoric acid or its ammonium salt, sodium salt, potassium salt, etc. Among them, ammonium phosphates such as ammonium dihydrogen phosphate and diammonium hydrogen phosphate are particularly preferable. preferable. In addition, phosphoric acid (salt) may be used independently and may use 2 or more types together.
本発明の光触媒コーティング液においては、前記リン酸（塩）の含有量は、前記酸化チタン粒子に対して０．００１〜０．２モル倍である。好ましくは、０．０１モル倍以上、０．１モル倍以下である。リン酸（塩）の含有量が０．００１モル倍未満であると、分散液中の粒子の凝集を充分に抑制することができず、一方、０．２モル倍を超えて用いても、その量に見合っただけのさらなる効果は得られないので、経済的に不利となる。 In the photocatalyst coating liquid of this invention, content of the said phosphoric acid (salt) is 0.001-0.2 mol times with respect to the said titanium oxide particle. Preferably, they are 0.01 mol times or more and 0.1 mol times or less. When the content of phosphoric acid (salt) is less than 0.001 mol times, aggregation of particles in the dispersion cannot be sufficiently suppressed. Since no further effect corresponding to the amount is obtained, it is economically disadvantageous.
〔蓚酸ジルコニウム〕
本発明の光触媒体コーティング液は、蓚酸ジルコニウムを含む。蓚酸ジルコニウムの使用量は、酸化ジルコニウム（ＺｒＯ２）換算で、光触媒酸化チタン粒子と光触媒酸化タングステン粒子の合計量に対して０．０２０〜０．２０質量倍である。蓚酸ジルコニウムの蓚酸／Ｚｒモル比は１．２〜３．０のものを用いるのが好ましい。
[Zirconium oxalate]
The photocatalyst coating liquid of the present invention contains zirconium oxalate. The amount of zirconium oxalate used is 0.020 to 0.20 mass times relative to the total amount of photocatalytic titanium oxide particles and photocatalytic tungsten oxide particles in terms of zirconium oxide (ZrO 2 ). It is preferable to use zirconium oxalate having an oxalic acid / Zr molar ratio of 1.2 to 3.0.
〔非晶質Ｚｒ−Ｏ系粒子〕
本発明の光触媒体コーティング液は、非晶質Ｚｒ−Ｏ系粒子を含有する。非晶質Ｚｒ−Ｏ系粒子としては、例えば市販のゾル（商品名：ＺＳＬ−１０Ｔ，第一稀元素化学製）などを用いることができる。非晶質Ｚｒ−Ｏ系粒子の含有量は、酸化物換算（ＺｒＯ２）で、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に対して０．０２０〜０．４０質量倍である。
[Amorphous Zr-O particles]
The photocatalyst coating liquid of the present invention contains amorphous Zr—O-based particles. As the amorphous Zr—O-based particles, for example, a commercially available sol (trade name: ZSL-10T, manufactured by Daiichi Rare Element Chemical Co., Ltd.) can be used. The content of the amorphous ZrO-based particles, in terms of oxide (ZrO 2), is 0.020 to 0.40 mass times the titanium oxide photocatalyst particles and the tungsten oxide photocatalyst particles.
〔シリコンアルコキシド〕
本発明の光触媒体コーティング液は、シリコンアルコキシドを含み、シリコンアルコキシドとしては、例えば、テトラエトキシシラン（ケイ酸エチル）、ケイ酸メチル（テトラメトキシシラン）、メチルトリエトキシシラン、メチルトリエトキシシランや、シリコンアルコキシドの加水分解物や重合物等があげられる。シリコンアルコキシドの含有量としては、酸化ケイ素(ＳｉＯ２)換算で、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に対して０．０４０〜０．２２質量倍である。
[Silicon alkoxide]
The photocatalyst coating liquid of the present invention contains a silicon alkoxide. Examples of the silicon alkoxide include tetraethoxysilane (ethyl silicate), methyl silicate (tetramethoxysilane), methyltriethoxysilane, methyltriethoxysilane, Examples thereof include hydrolysates and polymers of silicon alkoxides. The content of silicon alkoxide is 0.040 to 0.22 mass times with respect to photocatalytic titanium oxide particles and photocatalytic tungsten oxide particles in terms of silicon oxide (SiO 2 ).
〔分散媒〕
分散媒としては通常、水を主成分とする水性媒体、具体的には水の使用量が５０質量％以上で含むものが用いられ、水を単独で用いてもよいし、水と水溶性有機溶媒との混合溶媒であってもよい。水溶性有機溶媒としては、例えばメタノール、エタノール、プロパノール、ブタノールなどの水溶性アルコール溶媒、アセトン、メチルエチルケトンなどが挙げられる。
[Dispersion medium]
As the dispersion medium, an aqueous medium containing water as a main component, specifically, a medium containing water in an amount of 50% by mass or more is used. Water may be used alone, or water and a water-soluble organic substance. A mixed solvent with a solvent may be used. Examples of the water-soluble organic solvent include water-soluble alcohol solvents such as methanol, ethanol, propanol, and butanol, acetone, and methyl ethyl ketone.
分散媒の使用量は、光触媒酸化チタン粒子、光触媒酸化タングステン粒子、蓚酸ジルコニウム、およびシリコンアルコキシドの酸化物換算の合計量に対して、通常５質量倍〜２００質量倍、好ましくは１０質量倍〜１００質量倍である。分散媒の使用量が５質量倍未満では、光触媒酸化チタン粒子、光触媒酸化タングステン粒子および蓚酸ジルコニウムが沈降し易くなり、２００質量倍を超えると容積効率の点で不利である。 The amount of the dispersion medium used is usually 5 to 200 times, preferably 10 to 100 times the total amount in terms of oxides of photocatalytic titanium oxide particles, photocatalytic tungsten oxide particles, zirconium oxalate, and silicon alkoxide. Mass times. If the amount of the dispersion medium used is less than 5 mass times, the photocatalytic titanium oxide particles, photocatalytic tungsten oxide particles and zirconium oxalate are likely to settle, and if it exceeds 200 mass times, it is disadvantageous in terms of volumetric efficiency.
本発明の光触媒体コーティング液は、コーティング液から揮発成分を揮発させて得られる固形分の含有量が通常０．５重量％〜３０重量％、好ましくは１重量％〜２０重量％、より好ましくは２重量〜１０重量％程度となるように水や溶媒で希釈されて用いられる。固形分含有量が０．５重量％未満では、十分な厚さの塗膜を形成しにくくなり、また固形分含有量が３０重量％を超えると、得られる塗膜の透明性が損なわれ易くなる。 In the photocatalyst coating liquid of the present invention, the solid content obtained by volatilizing volatile components from the coating liquid is usually 0.5 wt% to 30 wt%, preferably 1 wt% to 20 wt%, more preferably It is used after being diluted with water or a solvent so as to be about 2 to 10% by weight. If the solid content is less than 0.5% by weight, it becomes difficult to form a sufficiently thick coating film. If the solid content exceeds 30% by weight, the transparency of the resulting coating film tends to be impaired. Become.
本発明の光触媒体コーティング液は、例えば光触媒体を単独で溶媒に分散させた光触媒体分散液と、蓚酸ジルコニウム、非晶質Ｚｒ−Ｏ系粒子、およびシリコンアルコキシドからなるバインダー液を混合する方法で製造することができる。 The photocatalyst coating liquid of the present invention is a method in which, for example, a photocatalyst dispersion liquid in which a photocatalyst is dispersed in a solvent is mixed with a binder liquid composed of zirconium oxalate, amorphous Zr-O-based particles, and silicon alkoxide. Can be manufactured.
〔光触媒体分散液〕
本発明の光触媒体分散液の水素イオン濃度は通常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未満では酸性が強すぎて取扱いが面倒であり、ｐＨ８．０を越えると光触媒酸化タングステン粒子が溶解するおそれがある。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、蓚酸などが使用できる。
[Photocatalyst dispersion]
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. If the hydrogen ion concentration is less than pH 0.5, the acidity is too strong and the handling is troublesome, and if it exceeds pH 8.0, the photocatalytic tungsten oxide particles may be dissolved. The hydrogen ion concentration of the photocatalyst dispersion liquid can be usually adjusted by adding an acid. Examples of the acid that can be used include nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, and succinic acid.
〔光触媒体分散液の製造〕
本発明で用いる光触媒分散体が、表面が互いに同じ極性に帯電してい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場合、例えば、表面がプラスに帯電している光触媒酸化チタン粒子を、上記表面処理剤が分散媒に溶解された溶液中に分散させたのち、表面がマイナスに帯電している光触媒酸化タングステン粒子と混合することにより、本発明出用いる光触媒体分散液を得ることができる。
[Production of photocatalyst dispersion]
When the photocatalyst dispersion used in the present invention is a photocatalytic titanium oxide particle and a photocatalytic tungsten oxide particle whose surfaces are charged to the same polarity, for example, the surface treatment is performed on the photocatalytic titanium oxide particles whose surface is positively charged. After dispersing the agent in a solution dissolved in a dispersion medium, the photocatalyst dispersion liquid used in the present invention can be obtained by mixing with the photocatalytic tungsten oxide particles whose surface is negatively charged.
さらに、本発明で用いる光触媒体分散液が、酸化チタン粒子、酸化タングステン粒子、およびリン酸（塩）を含むものである場合、例えば、光触媒酸化チタン粒子を、リン酸（塩）が分散媒に溶解された溶液中に分散させたのち、光触媒酸化タングステン粒子と混合することにより、本発明で用いる光触媒体分散液を得ることができる。 Further, when the photocatalyst dispersion liquid used in the present invention contains titanium oxide particles, tungsten oxide particles, and phosphoric acid (salt), for example, the photocatalytic titanium oxide particles are dissolved in phosphoric acid (salt) in the dispersion medium. After being dispersed in the solution, the photocatalyst dispersion liquid used in the present invention can be obtained by mixing with the photocatalytic tungsten oxide particles.
分散処理は、例えば媒体撹拌式分散機を用いる通常の方法により行うことができる。光触媒酸化タングステン粒子は、そのまま混合されてもよいが、通常は分散媒中に分散させた状態で混合され、好ましくはさらに分散処理を施してから、混合される。分散処理は、例えば媒体撹拌式分散機を用いる通常の方法により行うことができる。 The dispersion treatment can be performed by a usual method using, for example, a medium stirring type disperser. The photocatalytic tungsten oxide particles may be mixed as they are, but are usually mixed in a state of being dispersed in a dispersion medium, and preferably further subjected to a dispersion treatment and then mixed. The dispersion treatment can be performed by a usual method using, for example, a medium stirring type disperser.
〔電子吸引性物質またはその前駆体〕
本発明の光触媒体コーティング液は、光触媒体の表面に担持されることにより電子吸引性を発揮しうる電子吸引性物質またはその前駆体を含んでいてもよい。電子吸引性物質が光触媒体の表面に担持されることにより、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。
[Electron-withdrawing substance or its precursor]
The photocatalyst coating liquid of the present invention may contain an electron-withdrawing substance or a precursor thereof that can exhibit electron-withdrawing properties when supported on the surface of the photocatalyst. By supporting the electron-withdrawing substance on the surface of the photocatalyst body, 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.
かかる電子吸引性物質としては、例えばＣｕ、Ｐｔ、Ａｕ、Ｐｄ、Ａｇ、Ｆｅ、Ｎｂ、Ｒｕ、Ｉｒ、Ｒｈ、Ｃｏなどの金属、好ましくはＣｕ、Ｐｔ、Ａｕ、Ｐｄなどが挙げられる。また、これらの金属の酸化物および水酸化物も挙げられる。 Examples of the electron-withdrawing substance include metals such as Cu, Pt, Au, Pd, Ag, Fe, Nb, Ru, Ir, Rh, and Co, preferably Cu, Pt, Au, and Pd. Also included are oxides and hydroxides of these metals.
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である。かかる前駆体としては、例えば上記金属の硝酸塩、硫酸塩、ハロゲン化物、有機酸塩、炭酸塩、りん酸塩などが挙げられ、具体的には、例えばＣｕの前駆体としては、硝酸銅〔Ｃｕ(ＮＯ3)2〕、硫酸銅〔ＣｕＳＯ4〕、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)〕、ジニトロジアミン白金〔Ｐｔ(ＮＯ2)2(ＮＨ3)2〕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)〕、テトラアンミンパラジウム硝酸塩〔Ｐｄ（ＮＨ３）４（ＮＯ３）２〕、テトラアンミンパラジウム塩化物〔Ｐｄ（ＮＨ３）４Ｃｌ２〕、テトラアンミンパラジウム臭化物〔Ｐｄ（ＮＨ３）４Ｂｒ２〕、テトラアンミンパラジウムテトラクロロパラジウム酸〔（Ｐｄ（ＮＨ３）４）（ＰｄＣｌ４）〕、テトラクロロパラジウム酸アンモニウム〔（ＮＨ４）２ＰｄＣｌ４〕等が、それぞれ挙げられる。 The precursor of the electron withdrawing substance is a compound that can transition to an electron withdrawing substance on the surface of the photocatalyst. Examples of the precursor include nitrates, sulfates, halides, organic acid salts, carbonates, and phosphates of the above metals. Specifically, for example, as a precursor of Cu, copper nitrate [Cu (NO 3 ) 2 ], copper sulfate [CuSO 4 ], copper chloride [CuCl 2 , CuCl], copper bromide [CuBr 2 , CuBr], copper iodide [CuI], copper iodate [CuI 2 O 6 ], Ammonium copper 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 ] and the like; as a precursor containing Pt, Platinum chloride [PtCl 2 , PtCl 4 ], platinum bromide [PtBr 2 , PtBr 4 ], iodine Platinum fluoride [PtI 2 , PtI 4 ], platinum chloride potassium [K 2 (PtCl 4 )], hexachloroplatinic acid [H 2 PtCl 6 ], platinum sulfite [H 3 Pt (SO 3 ) 2 OH], platinum oxide [PtO 2 ], tetraammineplatinum chloride [Pt (NH 3 ) 4 Cl 2 ], tetraammineplatinum hydrogen carbonate [C 2 H 14 N 4 O 6 Pt], tetraammineplatinum hydrogen phosphate [Pt (NH 3 ) 4 HPO 4 ], water Tetraammineplatinum oxide [Pt (NH 3 ) 4 (OH) 2 ], tetraammineplatinum nitrate [Pt (NO 3 ) 2 (NH 3 ) 4 ], tetraammine platinum tetrachloroplatinum [(Pt (NH 3 ) 4 ) (PtCl 4 )], Dinitrodiamine platinum [Pt (NO 2 ) 2 (NH 3 ) 2 ], etc .; as a precursor containing Au, gold chloride [AuCl], gold bromide [AuBr], gold iodide [AuI], water gold oxide [Au (OH) 2], tetrachloro aurate [ AuCl 4], potassium tetrachloro aurate [KAuCl 4], potassium tetrabromo aurate [KAuBr 4], or the like gold oxide [Au 2 O 3] is; as a precursor containing Pd, for example, palladium acetate [(CH 3 COO ) 2 Pd], palladium chloride [PdCl 2 ], palladium bromide [PdBr 2 ], palladium iodide [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 )], potassium tetrabromopalladate [K 2 (PdBr 4 )], tetraammine palladium nitrate [Pd (NH 3 ) 4 (NO 3 ) 2 ], tetraamminepalladium chloride [Pd (NH 3 ) 4 Cl 2 ], tetraammineparadiu Bromide [Pd (NH 3 ) 4 Br 2 ], tetraamminepalladium tetrachloropalladate [(Pd (NH 3 ) 4 ) (PdCl 4 )], ammonium tetrachloropalladate [(NH 4 ) 2 PdCl 4 ] and the like. , Respectively.
これらの電子吸引性物質はそれぞれ単独で、または２種以上を組合せて用いられる。かかる電子吸引性物質またはその前駆体を用いる場合、その使用量は、金属原子換算で、光触媒体粒子の合計量１００質量部に対して通常０．００５質量部〜０．６質量部、好ましくは０．０１質量部〜０．４質量部である。使用量が０．００５質量部未満では、電子吸引性物質の使用による光触媒活性の向上が十分ではなく、０．６質量部を越えると、却って光触媒作用が不十分なものとなり易い。 These electron withdrawing substances are used alone or in combination of two or more. When using such an electron-withdrawing substance or a precursor thereof, the amount used is usually 0.005 to 0.6 parts by mass, preferably 100 parts by mass of the total amount of photocatalyst particles in terms of metal atoms, preferably It is 0.01 mass part-0.4 mass part. If the amount used is less than 0.005 parts by mass, the photocatalytic activity is not sufficiently improved by using an electron-withdrawing substance, and if it exceeds 0.6 parts by mass, the photocatalytic action tends to be insufficient.
かかる電子吸引性物質またはその前駆体を含む光触媒体コーティング液は、例えば上記と同様にして光触媒体分散液を混合したのち、電子吸引性物質またはその前駆体を加える方法により得ることができる。また前駆体を加えた場合には、その後、光照射を行おこなってもよい。照射される光としては、可視光線でもよいし紫外線でもよい。光照射を行うことにより、前駆体を電子吸引性物質に変換することができる。光触媒体の光励起可能な波長の光を照射した場合、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、電子吸引性物質として光触媒体粒子表面に担持される。 Such a photocatalyst coating liquid containing an electron-withdrawing substance or a precursor thereof can be obtained, for example, by a method of adding an electron-withdrawing substance or a precursor thereof after mixing a photocatalyst dispersion in the same manner as described above. Moreover, when a precursor is added, you may perform light irradiation after that. The irradiated light may be visible light or ultraviolet light. By performing light irradiation, the precursor can be converted into an electron-withdrawing substance. When the photocatalyst is irradiated with light having a wavelength that can be photoexcited, the precursor is reduced by the electrons generated by photoexcitation and is supported on the surface of the photocatalyst particles as an electron-withdrawing substance.
〔添加剤〕
本発明の光触媒体コーティング液は、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の分散性を損なわない範囲で、添加剤を含んでいてもよい。
〔Additive〕
The photocatalyst coating liquid of the present invention may contain an additive as long as the dispersibility of the photocatalytic titanium oxide particles and the photocatalytic tungsten oxide particles is not impaired.
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、具体的には、シリカゾル、水ガラス、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度類金属水酸化物、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、アルキド樹脂などが挙げられる。これらの添加剤はそれぞれ単独で、または２種以上を組合せて用いられる。 Examples of the additive include those added for the purpose of improving the photocatalytic action, specifically, silicon compounds such as silica sol and water glass, and aluminum compounds such as amorphous alumina, alumina sol and aluminum hydroxide. Alkaline earth metal oxides or alkalinity such as aluminosilicates such as zeolite, kaolinite, magnesium oxide, calcium oxide, strontium oxide, barium oxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide Metal hydroxides, calcium phosphates, molecular sieves, activated carbon, polycondensates of organic polysiloxane compounds, phosphates, fluoropolymers, silicone polymers, acrylic resins, polyester resins, melamine resins, urethane resins, alkyd resins, etc. Cited That. These additives are used alone or in combination of two or more.
かかる添加剤を含む光触媒体コーティング液は、例えば光触媒体、蓚酸ジルコニウム、非晶質Ｚｒ−Ｏ系粒子、シリコンアルコキシド及び溶媒を混合し、そこに添加剤を加える方法により得ることができる。 A photocatalyst coating liquid containing such an additive can be obtained, for example, by mixing a photocatalyst, zirconium oxalate, amorphous Zr-O-based particles, silicon alkoxide and a solvent, and adding the additive thereto.
〔光触媒体層の形成〕
本発明の光触媒体コーティング液を基材の表面に塗布し、分散媒を揮発させることにより、基材表面に、光触媒体粒子を含み、光触媒作用を示す光触媒体層が形成された光触媒機能製品を製造することができる。
[Formation of photocatalyst layer]
By applying the photocatalyst coating liquid of the present invention to the surface of the base material and volatilizing the dispersion medium, a photocatalytic functional product including a photocatalyst particle on the surface of the base material and having a photocatalyst layer showing photocatalytic action Can be manufactured.
光触媒体コーティング液が、電子吸引性物質またはその前駆体を含む場合、電子吸引性物質またはその前駆体は、光触媒体粒子の表面に担持され、前駆体を用いた場合には、担持された前駆体は、担持されたのち、電子吸引性物質に遷移する。 When the photocatalyst coating liquid contains an electron-withdrawing substance or its precursor, the electron-withdrawing substance or its precursor is supported on the surface of the photocatalyst particles, and when a precursor is used, the supported precursor is used. After the body is supported, the body transitions to an electron-withdrawing substance.
この光触媒機能製品は、通常、その表面に光触媒体を実用に耐えうる強度で保持しているものである。ここで用いられる光触媒体には、粒子、繊維、薄片など各種形状のものが適用でき、その大きさは用途、表面性状に応じて適宜選択すればよい。また、光触媒体を、光触媒機能製品の表面に膜とする場合、その膜厚も数１００ｎｍ〜数ｍｍまで適宜選択して形成すればよい。光触媒体は、プラスチック、金属、セラミックス、木材、コンクリート、紙のような材料からなる光触媒機能製品の内表面および外表面のうち、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保持されていることが好ましい。 This photocatalytic functional product usually holds the photocatalyst on the surface with a strength that can withstand practical use. The photocatalyst used here can be of various shapes such as particles, fibers, and flakes, and the size may be appropriately selected according to the application and surface properties. In addition, when the photocatalyst is formed on the surface of the photocatalytic functional product, the film thickness may be appropriately selected from several 100 nm to several mm. The photocatalyst is a surface to which visible light is irradiated among the inner and outer surfaces of a photocatalytic functional product made of a material such as plastic, metal, ceramics, wood, concrete, and paper, and generates malodorous substances. It is preferable that the surface is held on a surface that is continuous or intermittently connected to the portion.
〔光触媒機能製品〕
光触媒機能製品の例としては、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、自動車の天井材）、衣類やカーテン等の繊維製品があげられる。
[Photocatalytic functional products]
Examples of photocatalytic functional products include ceiling materials, tiles, glass, wallpaper, wall materials, floors, building materials, automotive interior materials (automobile instrument panels, automotive seats, automotive ceiling materials), clothing, curtains, etc. Textile products.
これらの光触媒機能製品は、蛍光灯、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、例えば、この光触媒機能製品を照明のある屋内住環境に設置すれば、屋内照明による光照射により、トルエン、ホルムアルデヒドやアセトアルデヒド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、更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。 These photocatalytic functional products exhibit high catalytic action by light irradiation from a visible light source such as a fluorescent lamp and a sodium lamp. For example, if this photocatalytic functional product is installed in an indoor living environment with illumination, By irradiation with light, the concentration of volatile organic substances such as toluene, formaldehyde and acetaldehyde and the concentration of malodorous substances can be reduced, and pathogenic bacteria such as Staphylococcus aureus and Escherichia coli can be killed.
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。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by this Example.
なお、各実施例における測定法は、以下のとおりである。 In addition, the measuring method in each Example is as follows.
１．粒子径Ｄ５０（非晶質Ｚｒ−Ｏ系粒子のゾル）
粒度分布測定装置（商品名“ＵＰＡ１５０”、日機装製）を用いて、ゾルの体積換算粒度分布において累積頻度が５０％となる粒子径を測定した。
1. Particle size D50 (Amorphous Zr-O particle sol)
Using a particle size distribution measuring device (trade name “UPA150”, manufactured by Nikkiso Co., Ltd.), the particle size at which the cumulative frequency was 50% in the volume converted particle size distribution of the sol was measured.
２．ゼータ電位（非晶質Ｚｒ−Ｏ系粒子のゾル）
ゼータ電位測定装置（商品名“ＥＬＳ−Ｚ２”、大塚電子製）を用いてゾルのゼータ電位を測定した。
2. Zeta potential (amorphous Zr-O particle sol)
The zeta potential of the sol was measured using a zeta potential measuring device (trade name “ELS-Z2”, manufactured by Otsuka Electronics Co., Ltd.).
３．ＢＥＴ比表面積
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ＢＥＴ比表面積は、比表面積測定装置〔湯浅アイオニクス社製「モノソーブ」〕を用い窒素吸着法により測定した。
3. The BET specific surface area of the BET specific surface area photocatalytic titanium oxide particles and the photocatalytic tungsten oxide particles was measured by a nitrogen adsorption method using a specific surface area measuring apparatus [“Monosorb” manufactured by Yuasa Ionics Co., Ltd.].
４．平均分散粒子径（ｎｍ）（光触媒体分散液）
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で、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とした。
4). Average dispersed particle size (nm) (photocatalyst dispersion)
Measure the particle size distribution of the sample using a sub-micron particle size distribution analyzer (“N4Plus” manufactured by Coulter, Inc.), and automatically disperse the result of monodisperse mode analysis using the software provided with this device. The diameter.
５．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。
5. An X-ray diffraction spectrum was measured using a crystal type X-ray diffractometer [“RINT2000 / PC” manufactured by Rigaku Corporation], and the crystal type was determined from the spectrum.
６．ゼータ電位（光触媒体）
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および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、光触媒体の表面はプラスに帯電しており、マイナスであれば表面はマイナスに帯電している。
6). Zeta potential (photocatalyst)
Photocatalytic oxidation in a sodium chloride aqueous solution (sodium chloride concentration 0.01 mol / L) in which a hydrogen ion concentration was adjusted to pH 3.0 by adding hydrochloric acid using a laser zeta electrometer ["ELS-6000" manufactured by Otsuka Electronics Co., Ltd.] 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 each of photocatalytic titanium oxide particles and photocatalytic tungsten oxide particles used was 250,000 times the mass. If the zeta potential is positive, the surface of the photocatalyst is positively charged. If the zeta potential is negative, the surface is negatively charged.
７．耐擦れ性試験
基板との耐擦れ性は、１２枚に重ねたチーズクロス（サマーズ社製）を消しゴム摩擦試験機（三光製作所製）に固定し、試料が塗布されたガラス基板を１０往復して擦った後、塗膜の状態を目視により下記５段階で評価した。
Ａ：塗膜に全く傷がない
Ｂ：塗膜に1〜9本の傷がついている
BC：塗膜に10〜19本の浅い傷がついている
C：塗膜に10〜19本の傷がついている
D：塗膜に20〜30本の傷がついている
E：塗膜に30本以上の傷がついている
7). The rubbing resistance with the rubbing resistance test substrate was fixed to an eraser rubbing tester (manufactured by Sanko Seisakusho) with 12 pieces of cheesecloth (manufactured by Summers), and the glass substrate on which the sample was applied was reciprocated 10 times. After rubbing, the state of the coating film was visually evaluated in the following five stages.
A: No scratches on the coating film B: 1 to 9 scratches on the coating film
BC: 10-19 shallow scratches on the coating
C: 10-19 scratches on the coating
D: 20-30 scratches on the coating
E: More than 30 scratches on the coating
８．光触媒活性
〔アセトアルデヒド分解能の測定〕
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サンプルを作製した。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、得られた光触媒体コーティング液を、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コーティング層を形成した。この光触媒体コーティング層に、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サンプルとした。
得られた光触媒活性測定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、その後、酸素と窒素との体積比が１：４である混合ガス６００ｍＬを封入した。さらに１％アセトアルデヒドを含む窒素ガス３ｍＬを封入し、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〔照度計「Ｔ−１０」（ミノルタ社製）で測定〕になるようにガスバッグを設置し、アセトアルデヒドの分解反応を行った。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。蛍光灯照射後よりガスバッグ内のガスを１．５時間毎にサンプリングして、アセトアルデヒドの残存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、照射時間に対するアセトアルデヒドの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の分解能とした。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は大きい。
8). Photocatalytic activity (measurement of acetaldehyde resolution)
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 coating 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 air to form a photocatalyst coating layer on the bottom of the glass petri dish. This photocatalyst coating layer was irradiated with UV light from a black light for 16 hours so that the UV intensity was 2 mW / cm 2, and this was used as a photocatalytic activity measurement sample.
The obtained photocatalytic activity measurement sample is sealed in a gas bag (internal volume 1 L), and then the inside of the gas bag is evacuated, and then 600 mL of a mixed gas having a volume ratio of oxygen to nitrogen of 1: 4 is added. Encapsulated. Furthermore, 3 mL of nitrogen gas containing 1% acetaldehyde was sealed, and kept in the dark at room temperature for 1 hour. Then, using a commercially available white fluorescent light as a light source, a gas bag was installed so that the illuminance in the vicinity of the measurement sample was 1000 lux (measured with an illuminometer “T-10” (manufactured by Minolta)), and the decomposition reaction of acetaldehyde Went. The intensity of ultraviolet light in the vicinity of the measurement sample was 6.5 μW / cm 2 [measured by attaching a UV receiver “UD-36” manufactured by the company to a UV intensity meter “UVR-2” manufactured by Topcon Corporation]. The gas in the gas bag is sampled every 1.5 hours after irradiation with the fluorescent lamp, and the residual concentration of acetaldehyde is measured with a gas chromatograph (“GC-14A” manufactured by Shimadzu Corporation). The concentration of acetaldehyde with respect to the irradiation time From this, the first-order reaction rate constant was calculated and used as the resolution of acetaldehyde. The higher the first order rate constant, the greater the resolution of acetaldehyde.
参考例１〔光触媒酸化チタン粒子とその分散液の調製〕
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ケーク〔ＴｉＯ２換算でチタン成分を４２質量％含む〕を用いた。
蓚酸（和光純薬工業製）２．７０ｇを水６０．２ｇに溶解させて蓚酸水溶液を得た。この蓚酸水溶液に、上記のメタチタン酸ケーク５７．１ｇを加え、混合して混合物を得た。この混合物における蓚酸の使用量は、メタチタン酸１モルに対して０．１モルである。媒体攪拌式分散機〔五十嵐機械製作所社製「４ＴＳＧ−１／８」〕を用い、以下の条件で、この混合物の分散処理を行って、光触媒酸化チタン分散液を得た。
Reference Example 1 [Preparation of photocatalytic titanium oxide particles and dispersion thereof]
As the photocatalytic titanium oxide particles, an aqueous solution of titanyl sulfate hydrolyzed and collected by filtration was used a metatitanic acid cake (containing 42 mass% of titanium component in terms of TiO 2 ).
2.70 g of oxalic acid (manufactured by Wako Pure Chemical Industries) was dissolved in 60.2 g of water to obtain an aqueous oxalic acid solution. To this oxalic acid aqueous solution, 57.1 g of the above-mentioned metatitanic acid cake was added and mixed to obtain a mixture. The amount of succinic acid used in this mixture is 0.1 mole per mole of metatitanic acid. This mixture was dispersed using a medium agitating disperser [“4TSG-1 / 8” manufactured by Igarashi Machinery Co., Ltd.] to obtain a photocatalytic titanium oxide dispersion.
分散媒体：外径０．０５ｍｍのジルコニア製ビーズ ３８０ｇ
処理温度：２０℃
処理時間：３時間
回転数 ：２０００ｒｐｍ
Dispersion medium: 380 g of zirconia beads having an outer diameter of 0.05 mm
Processing temperature: 20 ° C
Processing time: 3 hours Rotational speed: 2000 rpm
得られた光触媒酸化チタン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８５ｎｍであった。水素イオン濃度はｐＨ１．６であった。こ光触媒酸化チタン分散液の一部を真空乾燥して固形分を得たところ、この固形分のＢＥＴ比表面積を測定したところ、３２５ｍ2／ｇであった。得られた光触媒酸化チタン分散液の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と、分散処理の後の光触媒酸化チタン分散液の固形分のＸ線回折スペクトルをそれぞれ測定し、比較したところ、分散処理による結晶構造の変化は見られなかった。得られた光触媒酸化チタン分散液中の光触媒酸化チタン粒子のゼータ電位は−１９．９ｍＶであった。 The average dispersed particle diameter of the photocatalytic titanium oxide particles in the obtained photocatalytic titanium oxide dispersion was 85 nm. The hydrogen ion concentration was pH 1.6. A part of this photocatalytic titanium oxide dispersion was vacuum-dried to obtain a solid content. The BET specific surface area of this solid content was measured and found to be 325 m 2 / g. The crystal form of the solid content of the obtained photocatalytic titanium oxide dispersion was anatase type. In addition, when the X-ray-diffraction spectrum of the solid part of the mixture before a dispersion process and the photocatalyst titanium oxide dispersion liquid after a dispersion process was measured and compared, respectively, the change of the crystal structure by a dispersion process was not seen. The zeta potential of the photocatalytic titanium oxide particles in the obtained photocatalytic titanium oxide dispersion was −19.9 mV.
参考例２〔光触媒酸化タングステン粒子とその分散液の調製〕
イオン交換水４ｋｇに酸化タングステン粉末〔純度９９．９９％、高純度化学社製〕１ｋｇを加えて混合して混合物を得た。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、以下の条件で、この混合物の分散処理を行って、光触媒酸化タングステン分散液を得た。
Reference Example 2 [Preparation of photocatalytic tungsten oxide particles and dispersion thereof]
1 kg of tungsten oxide powder (purity 99.99%, high purity chemical) was added to 4 kg of ion exchange water and mixed to obtain a mixture. The mixture was dispersed using a medium agitating disperser [manufactured by Kotobuki Giken, "Ultra Apex Mill UAM-1"] under the following conditions to obtain a photocatalytic tungsten oxide dispersion.
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／ｍｉｎ
処理時間：合計約５０分
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９６ｎｍであった。水素イオン濃度はｐＨ２．２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、この固形分のＢＥＴ比表面積は３７ｍ2／ｇであった。なお、分散処理の前の混合物と、分散処理の後の光触媒酸化タングステン分散液の固形分のＸ線回折装置スペクトルをそれぞれ測定し、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。光触媒酸化タングステン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、−２５．５ｍＶであった。 The average dispersed particle diameter of the photocatalytic tungsten oxide particles in the obtained photocatalytic tungsten oxide dispersion was 96 nm. The hydrogen ion concentration was pH 2.2. A part of this dispersion was vacuum-dried to obtain a solid, and the BET specific surface area of this solid was 37 m 2 / g. Incidentally, the mixture before the dispersing treatment, the X-ray diffractometer spectrum of the solid content of the tungsten oxide photocatalyst dispersion liquid after the dispersing treatment were measured respectively, were compared, both the crystal structures were WO 3, distributed processing There was no change in crystal form due to. The zeta potential of the photocatalytic tungsten oxide particles in the photocatalytic tungsten oxide dispersion was −25.5 mV.
実施例１〔蓚酸ジルコニウムの調製〕
水酸化ジルコニウム１００ｇ（ ＺｒＯ2換算で３１ｇ ）を水１００ｇに添加しよく撹拌し分散液とした。次に、１回目の蓚酸添加として、該分散液へ蓚酸二水和物３１．７ｇ（ 蓚酸／Ｚｒモル比＝１．０ ）を添加し、９０℃で１５分間加熱した。次に、２回目の蓚酸添加として該分散液へ蓚酸二水和物１５．８ｇ（蓚酸／Ｚｒモル比＝０．５）を添加し、９０℃で１５分間加熱しゾルを得た。ＺｒＯ2換算で０．５重量％に希釈した時の該ゾルのゼータ電位は−６１ｍＶで粒子径Ｄ５０は６５ｎｍであった。
Example 1 [Preparation of zirconium oxalate]
100 g of zirconium hydroxide (31 g in terms of ZrO 2 ) was added to 100 g of water and stirred well to obtain a dispersion. Next, as the first addition of oxalic acid, 31.7 g of oxalic acid dihydrate (oxalic acid / Zr molar ratio = 1.0) was added to the dispersion and heated at 90 ° C. for 15 minutes. Next, as a second addition of oxalic acid, 15.8 g of oxalic acid dihydrate (oxalic acid / Zr molar ratio = 0.5) was added to the dispersion and heated at 90 ° C. for 15 minutes to obtain a sol. When diluted to 0.5% by weight in terms of ZrO 2 , the sol had a zeta potential of −61 mV and a particle diameter D50 of 65 nm.
実施例２〔蓚酸ジルコニウムの調製〕
実施例１で得られたゾル１００ｇ（ ＺｒＯ２換算で約１２ｇ ）に５００ｇの水を加え、５００ｇの分散媒を除去するまで限外ろ過膜（ 分画分子量：６０００ ）を用いて限外ろ過を行う操作を４回繰り返して１００ｇのゾルを得た。限外ろ過によって除去した分散媒の蓚酸濃度から計算した該ゾル中の蓚酸／Ｚｒモル比は１．３であった。また、ＺｒＯ２換算で０．５重量％に希釈した時の該ゾルのゼータ電位は−４８ｍＶで粒子径Ｄ５０は７０ｎｍであった。
Example 2 [Preparation of zirconium oxalate]
500 g of water was added to 100 g of the sol obtained in Example 1 (about 12 g in terms of ZrO 2 ), and ultrafiltration was performed using an ultrafiltration membrane (fractionated molecular weight: 6000) until 500 g of the dispersion medium was removed. The operation to be performed was repeated 4 times to obtain 100 g of sol. The oxalic acid / Zr molar ratio in the sol calculated from the oxalic acid concentration of the dispersion medium removed by ultrafiltration was 1.3. The sol had a zeta potential of −48 mV and a particle diameter D50 of 70 nm when diluted to 0.5% by weight in terms of ZrO 2 .
実施例３
〔光触媒体分散液の調製〕
参考例１で得た光触媒酸化チタン分散液と、参考例２で得た光触媒酸化タングステン分散液とを、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使用量比が１：１（質量比）で、光触媒酸化チタン粒子と光触媒酸化タングステン粒子の合計量が、分散液に対して５重量％となるように混合した。この光触媒体分散液に固液分離は見られなかった。
Example 3
(Preparation of photocatalyst dispersion)
The photocatalytic titanium oxide dispersion obtained in Reference Example 1 and the photocatalytic tungsten oxide dispersion obtained in Reference Example 2 were used at a 1: 1 ratio (mass ratio) of photocatalytic titanium oxide particles and photocatalytic tungsten oxide particles. The total amount of the photocatalytic titanium oxide particles and the photocatalytic tungsten oxide particles was mixed so as to be 5% by weight with respect to the dispersion. Solid-liquid separation was not observed in this photocatalyst dispersion.
〔光触媒体コーティング液の調製〕
実施例２で得られた蓚酸ジルコニウム（ＺｒＯ２換算濃度：１１．２重量％）０．０６７ｇを水０．８１５ｇに分散し、非晶質Ｚｒ−Ｏ系粒子の分散液（商品名：ＺＳＬ−１０Ｔ，第一稀元素化学製，濃度１０．５重量％）０．２１４ｇを添加した。その後、更にそこに高純度正ケイ酸エチル（多摩化学製）０．１０４ｇを添加した。こうして得られたバインダーに、上の光触媒体分散液（濃度５重量％）４．８ｇ加え、光触媒体コーティング液を得た。光触媒酸化チタン粒子と光触媒酸化タングステン粒子の合計量に対し、蓚酸ジルコニウム、非晶質Ｚｒ−Ｏ系粒子、及びケイ酸エチルの重量は、酸化物換算でそれぞれ０．０３１質量倍、０．０９４質量倍、及び０．１３質量倍であった。
[Preparation of photocatalyst coating liquid]
0.067 g of zirconium oxalate (ZrO 2 conversion concentration: 11.2 wt%) obtained in Example 2 was dispersed in 0.815 g of water, and a dispersion of amorphous Zr—O-based particles (trade name: ZSL— 10T, manufactured by Daiichi Rare Elemental Chemical Co., Ltd., concentration 10.5% by weight) 0.214 g was added. Thereafter, 0.104 g of high-purity ethyl silicate (manufactured by Tama Chemical) was further added thereto. To the binder thus obtained, 4.8 g of the above photocatalyst dispersion (concentration: 5% by weight) was added to obtain a photocatalyst coating liquid. The weight of zirconium oxalate, amorphous Zr-O-based particles, and ethyl silicate is 0.031 mass times and 0.094 mass in terms of oxide, respectively, with respect to the total amount of photocatalytic titanium oxide particles and photocatalytic tungsten oxide particles. It was double and 0.13 mass times.
上で得られた光触媒体コーティング液を、十分に脱脂したスライド硝子に塗布した後、スピンコーター（商品名“１Ｈ−Ｄ７”、ミカサ製）を用いて、３００ｒｐｍで３分間回転させて、過剰の分散液を取り除いた後、この硝子板を１１０℃で乾燥して、スライド硝子の片面全体にバインダー含有光触媒体膜を形成した。その後塗膜の密着性を調べたところ、塗膜の状態はＢCであった。 After the photocatalyst coating liquid obtained above was applied to a sufficiently degreased slide glass, it was rotated at 300 rpm for 3 minutes using a spin coater (trade name “1H-D7”, manufactured by Mikasa). After removing the dispersion, the glass plate was dried at 110 ° C. to form a binder-containing photocatalyst film on one side of the slide glass. Thereafter, when the adhesion of the coating film was examined, the state of the coating film was BC.
実施例４
実施例２で得られた蓚酸ジルコニウム（ＺｒＯ２換算濃度：１１．２重量％）０．１１４ｇを水０．７１３ｇに分散し、非晶質Ｚｒ−Ｏ系粒子の分散液（商品名：ＺＳＬ−１０Ｔ，第一稀元素化学製，濃度１０．５重量％）０．３２２ｇを添加した。その後、更にそこに高純度正ケイ酸エチル（多摩化学製）０．０５２ｇを添加した。こうして得られたバインダーに、実施例３の光触媒体分散液（濃度５重量％）４．８ｇ加え、光触媒体コーティング液を得た。光触媒酸化チタン粒子と光触媒酸化タングステン粒子の合計量に対し、蓚酸ジルコニウム、非晶質Ｚｒ−Ｏ系粒子、及びケイ酸エチルの重量は、酸化物換算でそれぞれ０．０５３質量倍、０．１４質量倍、及び０．０６３質量倍であった。
Example 4
0.114 g of zirconium oxalate (ZrO 2 equivalent concentration: 11.2 wt%) obtained in Example 2 was dispersed in 0.713 g of water, and a dispersion of amorphous Zr—O-based particles (trade name: ZSL— 10T, manufactured by Daiichi Rare Elemental Chemical Co., Ltd., concentration of 10.5% by weight) was added in an amount of 0.322 g. Thereafter, 0.052 g of highly pure ethyl silicate (manufactured by Tama Chemical) was further added thereto. To the binder thus obtained, 4.8 g of the photocatalyst dispersion liquid (concentration: 5% by weight) of Example 3 was added to obtain a photocatalyst coating liquid. With respect to the total amount of the photocatalytic titanium oxide particles and the photocatalytic tungsten oxide particles, the weights of zirconium oxalate, amorphous Zr-O-based particles, and ethyl silicate are 0.053 times by mass and 0.14 mass in terms of oxide, respectively. Double and 0.063 mass times.
上で得られた光触媒体コーティング液を用いて、実施例３と同様にしてスライド硝子の片面全体にバインダー含有光触媒体膜を形成し、その後塗膜の密着性を調べたところ、塗膜の状態はBCであった。 Using the photocatalyst coating liquid obtained above, a binder-containing photocatalyst film was formed on one entire surface of the slide glass in the same manner as in Example 3, and then the adhesion of the paint film was examined. Was BC.
実施例５
実施例２で得られた蓚酸ジルコニウム（ＺｒＯ２換算濃度：１１．２重量％）０．２０１ｇを水０．８２４ｇに分散し、非晶質Ｚｒ−Ｏ系粒子の分散液（商品名：ＺＳＬ−１０Ｔ，第一稀元素化学製，濃度１０．５重量％）０．０７２ｇを添加した。その後、更にそこに高純度正ケイ酸エチル（多摩化学製）０．１０４ｇを添加した。こうして得られたバインダーに、実施例３の光触媒体分散液（濃度５重量％）４．８ｇ加え、光触媒体コーティング液を得た。光触媒酸化チタン粒子と光触媒酸化タングステン粒子の合計量に対し、蓚酸ジルコニウム、非晶質Ｚｒ−Ｏ系粒子、及びケイ酸エチルの重量は、酸化物換算でそれぞれ、０．０９４質量倍、０．０３２質量倍、及び０．１３質量倍であった。
Example 5
0.201 g of zirconium oxalate (ZrO 2 equivalent concentration: 11.2 wt%) obtained in Example 2 was dispersed in 0.824 g of water, and a dispersion of amorphous Zr—O-based particles (trade name: ZSL— 10T, manufactured by Daiichi Rare Elemental Chemical Co., Ltd., concentration of 10.5% by weight) was added. Thereafter, 0.104 g of high-purity ethyl silicate (manufactured by Tama Chemical) was further added thereto. To the binder thus obtained, 4.8 g of the photocatalyst dispersion liquid (concentration: 5% by weight) of Example 3 was added to obtain a photocatalyst coating liquid. With respect to the total amount of the photocatalytic titanium oxide particles and the photocatalytic tungsten oxide particles, the weights of zirconium oxalate, amorphous Zr—O-based particles, and ethyl silicate are 0.094 times by mass and 0.032 times in terms of oxide, respectively. The mass was 0.13 and the mass was 0.13.
上で得られた光触媒体コーティング液を用いて、実施例３と同様にしてスライド硝子の片面全体にバインダー含有光触媒体膜を形成し、その後塗膜の密着性を調べたところ、塗膜の状態はCであった。 Using the photocatalyst coating liquid obtained above, a binder-containing photocatalyst film was formed on one entire surface of the slide glass in the same manner as in Example 3, and then the adhesion of the paint film was examined. Was C.
実施例６
実施例２で得られた蓚酸ジルコニウム（ＺｒＯ２換算濃度：１１．２重量％）０．２２７ｇを水０．７０６ｇに分散し、非晶質Ｚｒ−Ｏ系粒子の分散液（商品名：ＺＳＬ−１０Ｔ，第一稀元素化学製，濃度１０．５重量％）０．２１５ｇを添加した。その後、更にそこに高純度正ケイ酸エチル（多摩化学製）０．０５２ｇを添加した。こうして得られたバインダーに、実施例３の光触媒体分散液（濃度５重量％）４．８ｇ加え、光触媒体コーティング液を得た。光触媒酸化チタン粒子と光触媒酸化タングステン粒子の合計量に対し、蓚酸ジルコニウム、非晶質Ｚｒ−Ｏ系粒子、及びケイ酸エチルの重量は、酸化物換算でそれぞれ、０．１０６質量倍、０．０９４質量倍、及び０．０６３質量倍であった。
Example 6
0.227 g of zirconium oxalate (ZrO 2 equivalent concentration: 11.2 wt%) obtained in Example 2 was dispersed in 0.706 g of water, and a dispersion of amorphous Zr—O-based particles (trade name: ZSL— 1015, manufactured by Daiichi Rare Elemental Chemical Co., Ltd., concentration 10.5% by weight) was added. Thereafter, 0.052 g of highly pure ethyl silicate (manufactured by Tama Chemical) was further added thereto. To the binder thus obtained, 4.8 g of the photocatalyst dispersion liquid (concentration 5% by weight) of Example 3 was added to obtain a photocatalyst coating liquid. With respect to the total amount of the photocatalytic titanium oxide particles and the photocatalytic tungsten oxide particles, the weights of zirconium oxalate, amorphous Zr-O-based particles, and ethyl silicate are 0.106 mass times and 0.094, respectively, in terms of oxide. They were mass times and 0.063 times mass.
上で得られた光触媒体コーティング液を用いて、実施例３と同様にしてスライド硝子の片面全体にバインダー含有光触媒体膜を形成し、その後塗膜の密着性を調べたところ、塗膜の状態はBCであった。 Using the photocatalyst coating liquid obtained above, a binder-containing photocatalyst film was formed on one entire surface of the slide glass in the same manner as in Example 3, and then the adhesion of the paint film was examined. Was BC.
参考例３〔光触媒酸化チタン粒子とその分散液の調製〕
リン酸二水素アンモニウム（和光特級試薬）２０．７ｇを水５．３９ｋｇに溶解させ、得られたリン酸二水素アンモニウム水溶液に、硫酸チタニルの加熱加水分解により得られたメタチタン酸の固形物（ケーキ）（ＴｉＯ2として固形分濃度４６．２質量％）１．４９ｋｇを混合した。このとき、リン酸二水素アンモニウムの量は、メタチタン酸１モルに対して０．０２モルであった。得られた混合物を、媒体攪拌式分散機（寿工業（株）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、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８．１ｍ／秒
流速：０．２５Ｌ／分
処理温度：２０℃
合計処理時間：約７６分
Reference Example 3 [Preparation of photocatalytic titanium oxide particles and dispersion thereof]
20.7 g of ammonium dihydrogen phosphate (Wako Special Grade Reagent) was dissolved in 5.39 kg of water, and the resulting aqueous solution of ammonium dihydrogen phosphate in the solid solution of metatitanic acid (cake) obtained by thermal hydrolysis of titanyl sulfate. ) (Solid content concentration of 46.2 mass% as TiO 2 ) 1.49 kg was mixed. At this time, the amount of ammonium dihydrogen phosphate was 0.02 mol with respect to 1 mol of metatitanic acid. The obtained mixture was subjected to a dispersion treatment under the following conditions using a medium stirring type disperser (“Ultra Apex Mill UAM-1” manufactured by Kotobuki Industries Co., Ltd.) to obtain a titanium oxide particle dispersion.
Dispersion medium: 1.85 kg of zirconia beads having a diameter of 0.05 mm
Stirring speed: peripheral speed 8.1 m / sec Flow rate: 0.25 L / min Processing temperature: 20 ° C.
Total processing time: about 76 minutes
得られた酸化チタン粒子分散液中の酸化チタン粒子の平均分散粒子径は９６ｎｍであり、分散液のｐＨは８．２であった。また、この分散液の一部を真空乾燥して固形分を得たところ、得られた固形分のＢＥＴ比表面積は３３０ｍ2／ｇであった。なお、分散処理の前の混合物についても同様に真空乾燥して固形分を得、分散処理前の混合物の固形分と分散処理後の分散液の固形分について、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、どちらも結晶型はアナターゼ型であり、分散処理による結晶型の変化は見られなかった。この時点で、得られた分散液を２０℃で１２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。 The average dispersed particle diameter of the titanium oxide particles in the obtained titanium oxide particle dispersion was 96 nm, and the pH of the dispersion was 8.2. Moreover, when a part of this dispersion was vacuum-dried to obtain a solid content, the BET specific surface area of the obtained solid content was 330 m 2 / g. Similarly, the mixture before the dispersion treatment is also vacuum-dried to obtain a solid content, and X-ray diffraction spectra are respectively measured for the solid content of the mixture before the dispersion treatment and the solid content of the dispersion after the dispersion treatment. As a result of comparison, in both cases, the crystal form was anatase, and no change in the crystal form due to the dispersion treatment was observed. At this time, when the obtained dispersion was stored at 20 ° C. for 12 hours, no solid-liquid separation was observed during storage.
参考例４〔光触媒酸化タングステン粒子とその分散液の調製〕
イオン交換水４ｋｇに、粒子状の光触媒体である酸化タングステン粉末（日本無機化学製）１ｋｇを加えて混合して混合物を得た。この混合物を、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、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
合計処理時間：約５０分
Reference Example 4 [Preparation of photocatalytic tungsten oxide particles and dispersion thereof]
1 kg of tungsten oxide powder (manufactured by Nippon Inorganic Chemical Co., Ltd.), which is a particulate photocatalyst, was added to 4 kg of ion exchange water and mixed to obtain a mixture. This mixture was subjected to dispersion treatment under the following conditions using a medium agitating disperser (“Ultra Apex Mill UAM-1” manufactured by Kotobuki Giken Co., Ltd.) to obtain a 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 Total processing time: about 50 minutes
得られた酸化タングステン粒子分散液における酸化タングステン粒子の平均分散粒子径は１１８ｎｍであった。また、この分散液の一部を真空乾燥して固形分を得たところ、得られた固形分のＢＥＴ比表面積は４０ｍ2／ｇであった。なお、分散処理の前の混合物についても同様に真空乾燥して固形分を得、分散処理前の混合物の固形分と分散処理後の分散液の固形分について、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。この時点で、得られた分散液を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。 The average dispersed particle diameter of the tungsten oxide particles in the obtained tungsten oxide particle dispersion was 118 nm. Moreover, when a part of this dispersion was vacuum-dried to obtain a solid content, the BET specific surface area of the obtained solid content was 40 m 2 / g. Similarly, the mixture before the dispersion treatment is also vacuum-dried to obtain a solid content, and X-ray diffraction spectra are respectively measured for the solid content of the mixture before the dispersion treatment and the solid content of the dispersion after the dispersion treatment. As a result of comparison, the crystal form of both was WO 3 , and no change in crystal form due to dispersion treatment was observed. At this time, when the obtained dispersion was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage.
参考例５〔非晶質Ｚｒ−Ｏ系粒子の調製〕
水酸化ジルコニウム（ＺｒＯ２換算で３０重量％含有）３００ｇを純水１０７０ｇに分散し、適度に攪拌しながらそこへ６７．５重量％硝酸１２６ｇを添加し反応分散液を調製した。このとき反応分散液のジルコニウム濃度はＺｒＯ２換算で６重量％であり、１モルのＺｒに対する硝酸（ＨＮＯ３）のグラム当量数は１．８５であった。次に、該分散液を９５℃まで加熱し、２４時間保持した後静置して自然冷却し、非晶質のゾルを得た。さらに、該ゾルの限外ろ過処理によって該ゾル中の硝酸を除去し、ジルコニウム濃度を濃縮することで、ジルコニウム濃度がＺｒＯ２換算で１０重量％であり、ｐＨが３．２、ケルダール法によって測定された１モルのＺｒに対する硝酸（ＨＮＯ３）のグラム当量数が０．４のゾルを得た。該ゾルの粒度分布測定より、ゾルの粒子径Ｄ５０は１５ｎｍであった。また、該ゾルを１００℃で恒量まで乾燥したもののＸ線回折パターンは特定の結晶系に帰属されなかった。
Reference Example 5 (Preparation of amorphous Zr-O-based particles)
300 g of zirconium hydroxide (containing 30% by weight in terms of ZrO 2 ) was dispersed in 1070 g of pure water, and 126 g of 67.5% by weight nitric acid was added thereto with proper stirring to prepare a reaction dispersion. At this time, the zirconium concentration of the reaction dispersion was 6% by weight in terms of ZrO 2 , and the number of gram equivalents of nitric acid (HNO 3 ) with respect to 1 mol of Zr was 1.85. Next, the dispersion was heated to 95 ° C., held for 24 hours, and then allowed to stand to cool naturally to obtain an amorphous sol. Furthermore, by removing nitric acid in the sol by ultrafiltration treatment of the sol and concentrating the zirconium concentration, the zirconium concentration is 10% by weight in terms of ZrO 2 , pH is 3.2, measured by Kjeldahl method A sol having a gram equivalent number of nitric acid (HNO 3 ) per 0.4 mol of Zr was 0.4. From the particle size distribution measurement of the sol, the particle size D50 of the sol was 15 nm. Further, the X-ray diffraction pattern of the sol dried to a constant weight at 100 ° C. was not assigned to a specific crystal system.
上記の非晶質Ｚｒ−Ｏ系粒子を分散質とするゾル１０００ｇに対して、６４ｇの無水クエン酸を添加し、次に、１２０ｇの２５重量％アンモニア水を添加することで塩基性ゾルを得た。さらに、該ゾルへ水を添加して限外ろ過処理によって該ゾルを精製、濃縮する操作を繰り返すことでジルコニウム濃度がＺｒＯ２換算で１５重量％であり、ｐＨが８．６のゾルを得た。
該ゾルの粒子系分布は、上記非晶質Ｚｒ−Ｏ系粒子を分散質とするゾルとほぼ同じで、粒子径Ｄ５０は１２ｎｍであり、また、該ゾルを１００℃で恒量まで乾燥したもののＸ線回折パターンは、上記非晶質Ｚｒ−Ｏ系粒子を分散質とするゾルとほぼ同様であり、特定の結晶系に帰属されなかった。
64 g of anhydrous citric acid is added to 1000 g of the sol having the above amorphous Zr—O-based particles as a dispersoid, and then 120 g of 25 wt% aqueous ammonia is added to obtain a basic sol. It was. Furthermore, by repeating the operation of adding water to the sol and purifying and concentrating the sol by ultrafiltration, a sol having a zirconium concentration of 15% by weight in terms of ZrO 2 and a pH of 8.6 was obtained. .
The particle system distribution of the sol is almost the same as that of the sol using the amorphous Zr—O-based particles as a dispersoid, the particle diameter D50 is 12 nm, and the sol is dried to a constant weight at 100 ° C. The line diffraction pattern was almost the same as that of the sol using the amorphous Zr—O-based particles as a dispersoid, and was not assigned to a specific crystal system.
実施例7
〔光触媒体分散液の調製〕
参考例３で得た光触媒酸化チタン分散液と、参考例４で得た光触媒酸化タングステン分散液とを、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使用量比が１：１（質量比）で、光触媒酸化チタン粒子と光触媒酸化タングステン粒子の合計量が、分散液に対して５重量％となるように混合した。尚、この際、分散液中の濃度が４０重量％となるようにエタノールを添加した。この光触媒体分散液に固液分離は見られなかった。
Example 7
(Preparation of photocatalyst dispersion)
The photocatalytic titanium oxide dispersion obtained in Reference Example 3 and the photocatalytic tungsten oxide dispersion obtained in Reference Example 4 were used at a 1: 1 ratio (mass ratio) of photocatalytic titanium oxide particles and photocatalytic tungsten oxide particles. The total amount of the photocatalytic titanium oxide particles and the photocatalytic tungsten oxide particles was mixed so as to be 5% by weight with respect to the dispersion. At this time, ethanol was added so that the concentration in the dispersion was 40% by weight. Solid-liquid separation was not observed in this photocatalyst dispersion.
〔光触媒体コーティング液の調製〕
実施例１で得られた蓚酸ジルコニウム（ＺｒＯ２換算濃度：１２．５重量％）０．０７２ｇを蓚酸二水和物水溶液（蓚酸二水和物として５重量％）０．００７４ｇと水０．６０４ｇの混合液に分散し、参考例５の非晶質Ｚｒ−Ｏ系粒子の分散液（濃度１４．６重量％）０．１８５ｇを添加した。その後、更にそこに高純度正ケイ酸エチル（多摩化学製）０．０３１ｇを添加した。こうして得られたバインダーに、上記の光触媒体分散液（濃度５重量％）２．１ｇ加え、光触媒体コーティング液を得た。光触媒酸化チタン粒子と光触媒酸化タングステン粒子の合計量に対し、蓚酸ジルコニウム、非晶質Ｚｒ−Ｏ系粒子、及びケイ酸エチルの重量は、酸化物換算でそれぞれ、０．０８６質量倍、０．２５７質量倍、及び０．０８６質量倍であった。
[Preparation of photocatalyst coating liquid]
0.072 g of zirconium oxalate (ZrO 2 equivalent concentration: 12.5% by weight) obtained in Example 1 was added to 0.0074 g of oxalic acid dihydrate aqueous solution (5% by weight as oxalic acid dihydrate) and 0.604 g of water. Then, 0.185 g of a dispersion (concentration: 14.6 wt%) of amorphous Zr—O-based particles of Reference Example 5 was added. Thereafter, 0.031 g of highly pure ethyl silicate (manufactured by Tama Chemical) was further added thereto. To the binder thus obtained, 2.1 g of the above photocatalyst dispersion (concentration 5% by weight) was added to obtain a photocatalyst coating liquid. With respect to the total amount of the photocatalytic titanium oxide particles and the photocatalytic tungsten oxide particles, the weights of zirconium oxalate, amorphous Zr-O-based particles, and ethyl silicate are 0.086 mass times and 0.257, respectively, in terms of oxide. The mass was 0.086 mass times.
上で得られた光触媒体コーティング液を、十分に脱脂したスライド硝子に塗布した後、スピンコーター（商品名“１Ｈ−Ｄ７”、ミカサ製）を用いて、１０００ｒｐｍで１０秒間回転させ、引き続き３０００ｒｐｍで１０秒間回転させて、過剰の分散液を取り除いた後、この硝子板を１１０℃で乾燥して、スライド硝子の片面全体にバインダー含有光触媒体膜を形成した。その後塗膜の密着性を調べたところ、塗膜の状態はCであった。 The photocatalyst coating liquid obtained above was applied to a sufficiently degreased slide glass and then rotated at 1000 rpm for 10 seconds using a spin coater (trade name “1H-D7”, manufactured by Mikasa). After rotating for 10 seconds to remove excess dispersion, this glass plate was dried at 110 ° C. to form a binder-containing photocatalyst film on one side of the slide glass. Thereafter, when the adhesion of the coating film was examined, the state of the coating film was C.
比較例１
参考例１で得た光触媒酸化チタン分散液に代えて、市販の酸化チタン分散液〔石原産業社製、「ＳＴＳ−０１」、硝酸含有、平均分散粒径５０ｎｍ〕を用いた以外は、実施例３と同様に操作して、光触媒体分散液を調製した。この光触媒体分散液１００質量部中の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量は５質量部であった。この光触媒体分散液は、保管中に凝集粒子が生成し、固液分離が起こった。なお、この酸化チタン分散液〔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。
Comparative Example 1
Instead of the photocatalytic titanium oxide dispersion liquid obtained in Reference Example 1, a commercially available titanium oxide dispersion liquid (manufactured by Ishihara Sangyo Co., Ltd., “STS-01”, containing nitric acid, average dispersion particle size 50 nm) was used. In the same manner as in No. 3, a photocatalyst dispersion liquid was prepared. The total amount of photocatalytic titanium oxide particles and photocatalytic tungsten oxide particles in 100 parts by mass of this photocatalyst dispersion liquid was 5 parts by mass. In this photocatalyst dispersion, aggregated particles were generated during storage, and solid-liquid separation occurred. The zeta potential of the titanium oxide particles contained in this titanium oxide dispersion [STS-01] was +40.1 mV.
得られた光触媒体分散液を用いた以外は、実施例３と同様に操作して、光触媒体コーティング液を調製した。光触媒酸化チタン粒子と光触媒酸化タングステン粒子の合計量に対し、蓚酸ジルコニウム、非晶質Ｚｒ−Ｏ系粒子、及びケイ酸エチルの重量は、酸化物換算でそれぞれ、０．０３１質量倍、０．０９４質量倍、及び０．１３質量倍であった。 A photocatalyst coating liquid was prepared in the same manner as in Example 3 except that the obtained photocatalyst dispersion liquid was used. With respect to the total amount of the photocatalytic titanium oxide particles and the photocatalytic tungsten oxide particles, the weights of zirconium oxalate, amorphous Zr—O-based particles, and ethyl silicate are 0.031 times by mass and 0.094 times in terms of oxide, respectively. The mass was 0.13 times the mass.
上で得られた光触媒体コーティング液を用いて、実施例３と同様にしてスライド硝子の片面全体にバインダー含有光触媒体膜を形成し、その後塗膜の密着性を調べたところ、塗膜の状態はＥであった。 Using the photocatalyst coating liquid obtained above, a binder-containing photocatalyst film was formed on one entire surface of the slide glass in the same manner as in Example 3, and then the adhesion of the paint film was examined. Was E.
比較例２
参考例１で得た光触媒酸化チタン分散液に代えて、市販の酸化チタン分散液〔石原産業社製、「ＳＴＳ−０１」、硝酸含有、平均分散粒径５０ｎｍ〕を用いた以外は、実施例３と同様に操作して、光触媒体分散液を調製した。この光触媒体分散液１００質量部中の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量は５質量部であった。この光触媒体分散液は、保管中に凝集粒子が生成し、固液分離が起こった。
Comparative Example 2
Instead of the photocatalytic titanium oxide dispersion liquid obtained in Reference Example 1, a commercially available titanium oxide dispersion liquid (manufactured by Ishihara Sangyo Co., Ltd., “STS-01”, containing nitric acid, average dispersion particle size 50 nm) was used. In the same manner as in No. 3, a photocatalyst dispersion liquid was prepared. The total amount of photocatalytic titanium oxide particles and photocatalytic tungsten oxide particles in 100 parts by mass of this photocatalyst dispersion liquid was 5 parts by mass. In this photocatalyst dispersion, aggregated particles were generated during storage, and solid-liquid separation occurred.
得られた光触媒体分散液を用いた以外は、実施例４と同様に操作して、光触媒体コーティング液を調製した。光触媒酸化チタン粒子と光触媒酸化タングステン粒子の合計量に対し、蓚酸ジルコニウム、非晶質Ｚｒ−Ｏ系粒子、及びケイ酸エチルの重量は、酸化物換算でそれぞれ、０．０５３質量倍、０．１４質量倍、及び０．０６３質量倍であった。 A photocatalyst coating liquid was prepared in the same manner as in Example 4 except that the obtained photocatalyst dispersion liquid was used. With respect to the total amount of the photocatalytic titanium oxide particles and the photocatalytic tungsten oxide particles, the weights of zirconium oxalate, amorphous Zr-O-based particles, and ethyl silicate are 0.053 times by mass and 0.14 respectively in terms of oxide. They were mass times and 0.063 times mass.
上で得られた光触媒体コーティング液を用いて、実施例３と同様にしてスライド硝子の片面全体にバインダー含有光触媒体膜を形成し、その後塗膜の密着性を調べたところ、塗膜の状態はDであった。 Using the photocatalyst coating liquid obtained above, a binder-containing photocatalyst film was formed on one entire surface of the slide glass in the same manner as in Example 3, and then the adhesion of the paint film was examined. Was D.
比較例３
参考例１で得た光触媒酸化チタン分散液に代えて、市販の酸化チタン分散液〔石原産業社製、「ＳＴＳ−０１」、硝酸含有、平均分散粒径５０ｎｍ〕を用いた以外は、実施例３と同様に操作して、光触媒体分散液を調製した。この光触媒体分散液１００質量部中の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量は５質量部であった。この光触媒体分散液は、保管中に凝集粒子が生成し、固液分離が起こった。
Comparative Example 3
Instead of the photocatalytic titanium oxide dispersion liquid obtained in Reference Example 1, a commercially available titanium oxide dispersion liquid (manufactured by Ishihara Sangyo Co., Ltd., “STS-01”, containing nitric acid, average dispersion particle size 50 nm) was used. In the same manner as in No. 3, a photocatalyst dispersion liquid was prepared. The total amount of photocatalytic titanium oxide particles and photocatalytic tungsten oxide particles in 100 parts by mass of this photocatalyst dispersion liquid was 5 parts by mass. In this photocatalyst dispersion, aggregated particles were generated during storage, and solid-liquid separation occurred.
得られた光触媒体分散液を用いた以外は、実施例５と同様に操作して、光触媒体コーティング液を調製した。光触媒酸化チタン粒子と光触媒酸化タングステン粒子の合計量に対し、蓚酸ジルコニウム、非晶質Ｚｒ−Ｏ系粒子、及びケイ酸エチルの重量は、酸化物換算でそれぞれ、０．０９４質量倍、０．０３２質量倍、及び０．１３質量倍であった。 A photocatalyst coating liquid was prepared in the same manner as in Example 5 except that the obtained photocatalyst dispersion was used. With respect to the total amount of the photocatalytic titanium oxide particles and the photocatalytic tungsten oxide particles, the weights of zirconium oxalate, amorphous Zr—O-based particles, and ethyl silicate are 0.094 times by mass and 0.032 times in terms of oxide, respectively. The mass was 0.13 times the mass.
上で得られた光触媒体コーティング液を用いて、実施例３と同様にしてスライド硝子の片面全体にバインダー含有光触媒体膜を形成し、その後塗膜の密着性を調べたところ、塗膜の状態はＥであった。 Using the photocatalyst coating liquid obtained above, a binder-containing photocatalyst film was formed on one entire surface of the slide glass in the same manner as in Example 3, and then the adhesion of the paint film was examined. Was E.
比較例４
参考例１で得た光触媒酸化チタン分散液に代えて、市販の酸化チタン分散液〔石原産業社製、「ＳＴＳ−０１」、硝酸含有、平均分散粒径５０ｎｍ〕を用いた以外は、実施例３と同様に操作して、光触媒体分散液を調製した。この光触媒体分散液１００質量部中の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量は５質量部であった。この光触媒体分散液は、保管中に凝集粒子が生成し、固液分離が起こった。
Comparative Example 4
Instead of the photocatalytic titanium oxide dispersion liquid obtained in Reference Example 1, a commercially available titanium oxide dispersion liquid (manufactured by Ishihara Sangyo Co., Ltd., “STS-01”, containing nitric acid, average dispersion particle size 50 nm) was used. In the same manner as in No. 3, a photocatalyst dispersion liquid was prepared. The total amount of photocatalytic titanium oxide particles and photocatalytic tungsten oxide particles in 100 parts by mass of this photocatalyst dispersion liquid was 5 parts by mass. In this photocatalyst dispersion, aggregated particles were generated during storage, and solid-liquid separation occurred.
得られた光触媒体分散液を用いた以外は、実施例６と同様に操作して、光触媒体コーティング液を調製した。光触媒酸化チタン粒子と光触媒酸化タングステン粒子の合計量に対し、蓚酸ジルコニウム、非晶質Ｚｒ−Ｏ系粒子、及びケイ酸エチルの重量は、酸化物換算でそれぞれ、０．１０６質量倍、０．０９４質量倍、及び０．０６３質量倍であった。 A photocatalyst coating liquid was prepared in the same manner as in Example 6 except that the obtained photocatalyst dispersion was used. With respect to the total amount of the photocatalytic titanium oxide particles and the photocatalytic tungsten oxide particles, the weights of zirconium oxalate, amorphous Zr-O-based particles, and ethyl silicate are 0.106 mass times and 0.094, respectively, in terms of oxide. They were mass times and 0.063 times mass.
上で得られた光触媒体コーティング液を用いて、実施例３と同様にしてスライド硝子の片面全体にバインダー含有光触媒体膜を形成し、その後塗膜の密着性を調べたところ、塗膜の状態はＥであった。 Using the photocatalyst coating liquid obtained above, a binder-containing photocatalyst film was formed on one entire surface of the slide glass in the same manner as in Example 3, and then the adhesion of the paint film was examined. Was E.
比較例５
水０．８１０ｇに非晶質Ｚｒ−Ｏ系粒子の分散液（商品名：ＺＳＬ−１０Ｔ，第一稀元素化学製，濃度１０．５重量％）０．２８６ｇを添加し、更に高純度正ケイ酸エチル（多摩化学製）０．１０４ｇを添加した。こうして得られたバインダーに、実施例３の光触媒体分散液（濃度５重量％）４．８ｇ加え、光触媒体コーティング液を得た。光触媒酸化チタン粒子と光触媒酸化タングステン粒子の合計量に対し、非晶質Ｚｒ−Ｏ系粒子とケイ酸エチルの重量は、酸化物換算でそれぞれ、０．１３質量倍、及び０．１３質量倍であった。
Comparative Example 5
0.286 g of a dispersion of amorphous Zr—O-based particles (trade name: ZSL-10T, manufactured by Daiichi Rare Elemental Chemical, concentration 10.5% by weight) is added to 0.810 g of water. 0.104 g of ethyl acid (manufactured by Tama Chemical) was added. To the binder thus obtained, 4.8 g of the photocatalyst dispersion liquid (concentration: 5% by weight) of Example 3 was added to obtain a photocatalyst coating liquid. With respect to the total amount of photocatalytic titanium oxide particles and photocatalytic tungsten oxide particles, the weights of amorphous Zr-O-based particles and ethyl silicate are 0.13 times and 0.13 times, respectively, in terms of oxide. there were.
上で得られた光触媒体コーティング液を用いて、実施例３と同様にしてスライド硝子の片面全体にバインダー含有光触媒体膜を形成し、その後塗膜の密着性を調べたところ、塗膜の状態はDであった。 Using the photocatalyst coating liquid obtained above, a binder-containing photocatalyst film was formed on one entire surface of the slide glass in the same manner as in Example 3, and then the adhesion of the paint film was examined. Was D.
比較例６
実施例２で得られた蓚酸ジルコニウム（ＺｒＯ２換算濃度：１１．２重量％）０．０３３ｇを水０．９０３ｇに分散し、非晶質Ｚｒ−Ｏ系粒子の分散液（商品名：ＺＳＬ−１０Ｔ，第一稀元素化学製，濃度１０．５重量％）０．１０７ｇを添加した。その後、更にそこに高純度正ケイ酸エチル（多摩化学製）０．１５６ｇを添加した。こうして得られたバインダーに、実施例３の光触媒体分散液（濃度５重量％）４．８ｇ加え、光触媒体コーティング液を得た。光触媒酸化チタン粒子と光触媒酸化タングステン粒子の合計量に対し、蓚酸ジルコニウム、非晶質Ｚｒ−Ｏ系粒子、及びケイ酸エチルの重量は、酸化物換算でそれぞれ、０．０１５質量倍、０．０４７質量倍、及び０．１９質量倍であった。
Comparative Example 6
0.033 g of zirconium oxalate (ZrO 2 equivalent concentration: 11.2 wt%) obtained in Example 2 was dispersed in 0.903 g of water, and a dispersion of amorphous Zr—O-based particles (trade name: ZSL— 10T, manufactured by Daiichi Rare Elemental Chemical Co., Ltd., concentration of 10.5% by weight) was added. Thereafter, 0.156 g of highly pure ethyl silicate (manufactured by Tama Chemical) was further added thereto. To the binder thus obtained, 4.8 g of the photocatalyst dispersion liquid (concentration: 5% by weight) of Example 3 was added to obtain a photocatalyst coating liquid. With respect to the total amount of the photocatalytic titanium oxide particles and the photocatalytic tungsten oxide particles, the weights of zirconium oxalate, amorphous Zr-O-based particles, and ethyl silicate are 0.015 times by mass and 0.047 times in terms of oxide, respectively. They were mass times and 0.19 mass times.
上で得られた光触媒体コーティング液を用いて、実施例３と同様にしてスライド硝子の片面全体にバインダー含有光触媒体膜を形成し、その後塗膜の密着性を調べたところ、塗膜の状態はBCであった。 Using the photocatalyst coating liquid obtained above, a binder-containing photocatalyst film was formed on one entire surface of the slide glass in the same manner as in Example 3, and then the adhesion of the paint film was examined. Was BC.
比較例７
実施例２で得られた蓚酸ジルコニウム（ＺｒＯ２換算濃度：１１．２重量％）０．１０１ｇを水０．９０８ｇに分散し、非晶質Ｚｒ−Ｏ系粒子の分散液（商品名：ＺＳＬ−１０Ｔ，第一稀元素化学製，濃度１０．５重量％）０．０３５７ｇを添加した。その後、更にそこに高純度正ケイ酸エチル（多摩化学製）０．１５６ｇを添加した。こうして得られたバインダーに、実施例３の光触媒体分散液（濃度５重量％）４．８ｇ加え、光触媒体コーティング液を得た。光触媒酸化チタン粒子と光触媒酸化タングステン粒子の合計量に対し、蓚酸ジルコニウム、非晶質Ｚｒ−Ｏ系粒子、及びケイ酸エチルの重量は、酸化物換算でそれぞれ、０．０４７質量倍、０．０１６質量倍、及び０．１９質量倍であった。
Comparative Example 7
0.101 g of zirconium oxalate (ZrO 2 equivalent concentration: 11.2 wt%) obtained in Example 2 was dispersed in 0.908 g of water, and a dispersion of amorphous Zr—O-based particles (trade name: ZSL— 10T, manufactured by Daiichi Rare Elemental Chemical Co., Ltd., concentration 10.5% by weight) was added. Thereafter, 0.156 g of highly pure ethyl silicate (manufactured by Tama Chemical) was further added thereto. To the binder thus obtained, 4.8 g of the photocatalyst dispersion liquid (concentration: 5% by weight) of Example 3 was added to obtain a photocatalyst coating liquid. With respect to the total amount of the photocatalytic titanium oxide particles and the photocatalytic tungsten oxide particles, the weights of zirconium oxalate, amorphous Zr-O-based particles, and ethyl silicate are 0.047 mass times and 0.016, respectively, in terms of oxide. They were mass times and 0.19 mass times.
上で得られた光触媒体コーティング液を用いて、実施例３と同様にしてスライド硝子の片面全体にバインダー含有光触媒体膜を形成し、その後塗膜の密着性を調べたところ、塗膜の状態はCであった。 Using the photocatalyst coating liquid obtained above, a binder-containing photocatalyst film was formed on one entire surface of the slide glass in the same manner as in Example 3, and then the adhesion of the paint film was examined. Was C.
比較例８
実施例２で得られた蓚酸ジルコニウム（ＺｒＯ２換算濃度：１１．２重量％）０．２６８ｇを水０．８２８ｇに分散し、更に高純度正ケイ酸エチル（多摩化学製）０．１０４ｇを添加した。こうして得られたバインダーに、実施例３の光触媒体分散液（濃度５重量％）４．８ｇ加え、光触媒体コーティング液を得た。光触媒酸化チタン粒子と光触媒酸化タングステン粒子の合計量に対し、蓚酸ジルコニウムとケイ酸エチルの重量は、酸化物換算でどちらも０．１３質量倍であった。
Comparative Example 8
Disperse 0.268 g of zirconium oxalate (ZrO 2 equivalent concentration: 11.2 wt%) obtained in Example 2 in 0.828 g of water, and further add 0.104 g of high purity ethyl silicate (manufactured by Tama Chemical). did. To the binder thus obtained, 4.8 g of the photocatalyst dispersion liquid (concentration: 5% by weight) of Example 3 was added to obtain a photocatalyst coating liquid. With respect to the total amount of the photocatalytic titanium oxide particles and the photocatalytic tungsten oxide particles, the weights of zirconium oxalate and ethyl silicate were both 0.13 mass times in terms of oxide.
上で得られた光触媒体コーティング液を用いて、実施例３と同様にしてスライド硝子の片面全体にバインダー含有光触媒体膜を形成し、その後塗膜の密着性を調べたところ、塗膜の状態はDであった。 Using the photocatalyst coating liquid obtained above, a binder-containing photocatalyst film was formed on one entire surface of the slide glass in the same manner as in Example 3, and then the adhesion of the paint film was examined. Was D.
比較例９
実施例２で得られた蓚酸ジルコニウム（ＺｒＯ２換算濃度：１１．２重量％）０．２６８ｇを水０．６４６ｇに分散し、非晶質Ｚｒ−Ｏ系粒子の分散液（商品名：ＺＳＬ−１０Ｔ，第一稀元素化学製，濃度１０．５重量％）０．２８６ｇを添加した。こうして得られたバインダーに、実施例１の光触媒体分散液（濃度５重量％）４．８ｇ加え、光触媒体コーティング液を得た。光触媒酸化チタン粒子と光触媒酸化タングステン粒子の合計量に対し、蓚酸ジルコニウムと非晶質Ｚｒ−Ｏ系粒子の重量は、酸化物換算どちらも０．１３質量倍であった。
Comparative Example 9
0.268 g of zirconium oxalate (ZrO 2 equivalent concentration: 11.2 wt%) obtained in Example 2 was dispersed in 0.646 g of water, and a dispersion of amorphous Zr—O-based particles (trade name: ZSL- 10T, manufactured by Daiichi Rare Elemental Chemical Co., Ltd., concentration 10.5% by weight) 0.286 g was added. To the binder thus obtained, 4.8 g of the photocatalyst dispersion liquid (concentration 5% by weight) of Example 1 was added to obtain a photocatalyst coating liquid. With respect to the total amount of the photocatalytic titanium oxide particles and the photocatalytic tungsten oxide particles, the weight of the zirconium oxalate and the amorphous Zr—O-based particles was 0.13 times by mass in terms of oxide.
上で得られた光触媒体コーティング液を用いて、実施例３と同様にしてスライド硝子の片面全体にバインダー含有光触媒体膜を形成し、その後塗膜の密着性を調べたところ、塗膜の状態はＥであった。 Using the photocatalyst coating liquid obtained above, a binder-containing photocatalyst film was formed on one entire surface of the slide glass in the same manner as in Example 3, and then the adhesion of the paint film was examined. Was E.
比較例１０
参考例１で得た光触媒酸化チタン分散液に代えて、市販の酸化チタン分散液〔石原産業社製、「ＳＴＳ−０１」、硝酸含有、平均分散粒径５０ｎｍ〕を用いた以外は、実施例７と同様に操作して、光触媒体分散液を調製した。この光触媒体分散液１００質量部中の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量は５質量部であった。この光触媒体分散液は、保管中に凝集粒子が生成し、固液分離が起こった。
Comparative Example 10
Instead of the photocatalytic titanium oxide dispersion liquid obtained in Reference Example 1, a commercially available titanium oxide dispersion liquid (manufactured by Ishihara Sangyo Co., Ltd., “STS-01”, containing nitric acid, average dispersion particle size 50 nm) was used. In the same manner as in No. 7, a photocatalyst dispersion liquid was prepared. The total amount of photocatalytic titanium oxide particles and photocatalytic tungsten oxide particles in 100 parts by mass of this photocatalyst dispersion liquid was 5 parts by mass. In this photocatalyst dispersion, aggregated particles were generated during storage, and solid-liquid separation occurred.
得られた光触媒体分散液を用いた以外は、実施例７と同様に操作して、光触媒体コーティング液を調製した。光触媒酸化チタン粒子と光触媒酸化タングステン粒子の合計量に対し、蓚酸ジルコニウム、非晶質Ｚｒ−Ｏ系粒子、及びケイ酸エチルの重量は、酸化物換算でそれぞれ、０．０８６質量倍、０．２５７質量倍、及び０．０８６質量倍であった。 A photocatalyst coating liquid was prepared in the same manner as in Example 7 except that the obtained photocatalyst dispersion liquid was used. With respect to the total amount of the photocatalytic titanium oxide particles and the photocatalytic tungsten oxide particles, the weights of zirconium oxalate, amorphous Zr-O-based particles, and ethyl silicate are 0.086 mass times and 0.257, respectively, in terms of oxide. The mass was 0.086 mass times.
上で得られた光触媒体コーティング液を用いて、実施例７と同様にしてスライド硝子の片面全体にバインダー含有光触媒体膜を形成し、その後塗膜の密着性を調べたところ、塗膜の状態はDであった。 Using the photocatalyst coating liquid obtained above, a binder-containing photocatalyst film was formed on one entire surface of the slide glass in the same manner as in Example 7, and then the adhesion of the coating film was examined. Was D.
実施例８
塗膜の密着性がＢＣ〜Ｃであった実施例３〜７、及び比較例６、７の光触媒体コーティング液を用いて光触媒活性の評価を行ったところ、表１の結果となった。
Example 8
When the photocatalytic activity was evaluated using the photocatalyst coating liquids of Examples 3 to 7 and Comparative Examples 6 and 7 in which the adhesion of the coating film was BC to C, the results shown in Table 1 were obtained.
表１
実施例９
実施例３〜７の光触媒体コーティング液を天井材に塗布・乾燥すると、屋内照明による光照射により、トルエン、ホルムアルデヒドやアセトアルデヒド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、更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。
Example 9
When the photocatalyst coating liquid of Examples 3 to 7 is applied to the ceiling material and dried, the concentration of volatile organic substances such as toluene, formaldehyde, and acetaldehyde and the concentration of malodorous substances can be reduced by light irradiation by indoor lighting. Pathogens such as S. aureus and E. coli can be killed.
実施例１０
実施例３〜７の光触媒体コーティング液をタイルに塗布・乾燥すると、屋内照明による光照射により、トルエン、ホルムアルデヒドやアセトアルデヒド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、更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。
Example 10
When the photocatalyst coating liquid of Examples 3 to 7 is applied to the tile and dried, the concentration of volatile organic substances such as toluene, formaldehyde and acetaldehyde and the concentration of malodorous substances can be reduced by light irradiation by indoor lighting, and further yellow Pathogens such as staphylococci and E. coli can be killed.
実施例１１
実施例３〜７の光触媒体コーティング液をガラスに塗布・乾燥すると、屋内照明による光照射により、トルエン、ホルムアルデヒドやアセトアルデヒド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、更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。
Example 11
When the photocatalyst coating liquid of Examples 3 to 7 is applied to glass and dried, the concentration of volatile organic substances such as toluene, formaldehyde and acetaldehyde and the concentration of malodorous substances can be reduced by irradiation with light from indoor lighting, and further yellow Pathogens such as staphylococci and E. coli can be killed.
実施例１２
実施例３〜７の光触媒体コーティング液を壁紙に塗布・乾燥すると、屋内照明による光照射により、トルエン、ホルムアルデヒドやアセトアルデヒド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、更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。
Example 12
When the photocatalyst coating liquid of Examples 3 to 7 is applied to wallpaper and dried, the concentration of volatile organic substances such as toluene, formaldehyde, and acetaldehyde and the concentration of malodorous substances can be reduced by light irradiation by indoor lighting, and further yellow Pathogens such as staphylococci and E. coli can be killed.
実施例１３
実施例３〜７の光触媒体コーティング液を壁材に塗布・乾燥すると、屋内照明による光照射により、トルエン、ホルムアルデヒドやアセトアルデヒド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、更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。
Example 13
When the photocatalyst coating liquid of Examples 3 to 7 is applied to the wall material and dried, the concentration of volatile organic substances such as toluene, formaldehyde, and acetaldehyde and the concentration of malodorous substances can be reduced by light irradiation with indoor lighting. Pathogens such as S. aureus and E. coli can be killed.
実施例１４
実施例３〜７の光触媒体コーティング液を床に塗布・乾燥すると、屋内照明による光照射により、トルエン、ホルムアルデヒドやアセトアルデヒド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、更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。
Example 14
When the photocatalyst coating liquid of Examples 3 to 7 is applied to the floor and dried, the concentration of volatile organic substances such as toluene, formaldehyde and acetaldehyde and the concentration of malodorous substances can be reduced by light irradiation with indoor lighting, and further yellow Pathogens such as staphylococci and E. coli can be killed.
実施例１５
実施例３〜７の光触媒体コーティング液を自動車内装材（自動車用インストルメントパネル、自動車用シート、自動車の天井材）に塗布・乾燥すると、屋内照明による光照射により、トルエン、ホルムアルデヒドやアセトアルデヒド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、更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。
Example 15
When the photocatalyst coating liquid of Examples 3 to 7 is applied to an automobile interior material (automobile instrument panel, automobile seat, automobile ceiling material) and dried, light such as toluene, formaldehyde, or acetaldehyde is irradiated by indoor illumination. The concentration of volatile organic substances and malodorous substances can be reduced, and pathogenic bacteria such as Staphylococcus aureus and Escherichia coli can be killed.
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| JP2010120805A (en) * | 2008-11-19 | 2010-06-03 | Sumitomo Chemical Co Ltd | Photocatalytic body dispersion |
| CN103635543B (en) | 2011-06-29 | 2016-09-21 | 信越化学工业株式会社 | Inorganic hydrophilic coating fluid and, thus obtained by hydrophilic film and use its parts |
| EP2857098B1 (en) * | 2012-06-01 | 2021-02-24 | Kabushiki Kaisha Toshiba | Aqueous dispersion, and coating using same, photocatalytic film, and product |
| JP6362010B2 (en) * | 2015-09-28 | 2018-07-25 | 森屋 市郎 | Improved carbon dioxide reduction method |
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| JP2742449B2 (en) * | 1989-07-21 | 1998-04-22 | 株式会社日本触媒 | High performance zirconia sol and method for producing the same |
| JP3284413B2 (en) * | 1991-07-25 | 2002-05-20 | 東ソー株式会社 | Method for producing hydrated zirconia sol and zirconia powder |
| JP3852131B2 (en) * | 1996-06-07 | 2006-11-29 | 旭硝子株式会社 | Film having photocatalytic activity and composition for forming the same |
| KR100318109B1 (en) * | 1996-10-08 | 2002-06-24 | 쓰끼하시 다미까따 | Photocatalyst Coating Composition and Photocatalyst Support Structure |
| JP4619601B2 (en) * | 1999-09-30 | 2011-01-26 | 昭和電工株式会社 | PHOTOCATALYTIC COATING COMPOSITION AND PRODUCT HAVING PHOTOCATALYTIC THIN FILM |
| JP2003096434A (en) * | 2001-07-19 | 2003-04-03 | Sumitomo Chem Co Ltd | Ceramics dispersion, method and apparatus for producing the same, and hydrophilicity-imparting agent by using the same |
| JP4738736B2 (en) * | 2001-10-12 | 2011-08-03 | 日本曹達株式会社 | Photocatalyst composite, coating solution for forming photocatalyst layer, and photocatalyst carrying structure |
| JP4199490B2 (en) * | 2002-07-26 | 2008-12-17 | パナソニック電工株式会社 | Coating material composition |
| JP4817596B2 (en) * | 2003-05-20 | 2011-11-16 | 旭化成ケミカルズ株式会社 | Photocatalyst composition and photocatalyst formed therefrom |
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| JP4963820B2 (en) * | 2005-09-02 | 2012-06-27 | 第一稀元素化学工業株式会社 | Method for producing sol using Zr-O-based particles as dispersoid |
| JP2008093630A (en) * | 2006-10-16 | 2008-04-24 | Sumitomo Chemical Co Ltd | Method of manufacturing photocatalyst dispersion |
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| JP5512934B2 (en) * | 2008-05-09 | 2014-06-04 | 住友化学株式会社 | Sol comprising amorphous Zr-O-based particles as a dispersoid, method for producing the same, photocatalyst coating liquid using the sol as a binder, and method for producing a photocatalytic functional product coated with the photocatalyst coating liquid |
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