JP2011078930A - Photocatalyst dispersion and photocatalyst functional product using the same - Google Patents
Photocatalyst dispersion and photocatalyst functional product using the same Download PDFInfo
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- JP2011078930A JP2011078930A JP2009234427A JP2009234427A JP2011078930A JP 2011078930 A JP2011078930 A JP 2011078930A JP 2009234427 A JP2009234427 A JP 2009234427A JP 2009234427 A JP2009234427 A JP 2009234427A JP 2011078930 A JP2011078930 A JP 2011078930A
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- Prior art keywords
- photocatalyst
- dispersion
- dispersion liquid
- oxide particles
- mass
- Prior art date
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 188
- 239000006185 dispersion Substances 0.000 title claims abstract description 161
- 239000002245 particle Substances 0.000 claims abstract description 167
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 77
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 70
- 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 abstract description 69
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 64
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000002612 dispersion medium Substances 0.000 claims abstract description 19
- 150000002497 iodine compounds Chemical class 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims description 100
- 229910000510 noble metal Inorganic materials 0.000 claims description 37
- 239000002243 precursor Substances 0.000 claims description 30
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 229910052697 platinum Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 15
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 10
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 6
- 229910052741 iridium Inorganic materials 0.000 claims description 5
- 229910052703 rhodium Inorganic materials 0.000 claims description 5
- 230000001699 photocatalysis Effects 0.000 abstract description 51
- 229910052740 iodine Inorganic materials 0.000 abstract description 10
- 230000001747 exhibiting effect Effects 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 54
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 38
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 24
- 239000000126 substance Substances 0.000 description 19
- 239000002253 acid Substances 0.000 description 18
- 239000000463 material Substances 0.000 description 18
- 239000007787 solid Substances 0.000 description 18
- 239000007864 aqueous solution Substances 0.000 description 16
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 11
- 238000000926 separation method Methods 0.000 description 11
- 238000003860 storage Methods 0.000 description 11
- 241000588724 Escherichia coli Species 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 241000191967 Staphylococcus aureus Species 0.000 description 9
- 241000700605 Viruses Species 0.000 description 9
- 239000011630 iodine Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 241000712461 unidentified influenza virus Species 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000010931 gold Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 7
- 239000000654 additive Substances 0.000 description 7
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 244000052616 bacterial pathogen Species 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- QFWPJPIVLCBXFJ-UHFFFAOYSA-N glymidine Chemical compound N1=CC(OCCOC)=CN=C1NS(=O)(=O)C1=CC=CC=C1 QFWPJPIVLCBXFJ-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- -1 oxynitrides Chemical class 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 244000052769 pathogen Species 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 229910052721 tungsten Inorganic materials 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 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
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 description 4
- 239000010970 precious metal Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 101150003085 Pdcl gene Proteins 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 description 3
- 239000001230 potassium iodate Substances 0.000 description 3
- 235000006666 potassium iodate Nutrition 0.000 description 3
- 229940093930 potassium iodate Drugs 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 3
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 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
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 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 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 229910002094 inorganic tetrachloropalladate Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- NALMPLUMOWIVJC-UHFFFAOYSA-N n,n,4-trimethylbenzeneamine oxide Chemical compound CC1=CC=C([N+](C)(C)[O-])C=C1 NALMPLUMOWIVJC-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 229910052762 osmium Inorganic materials 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- INIOZDBICVTGEO-UHFFFAOYSA-L palladium(ii) bromide Chemical compound Br[Pd]Br INIOZDBICVTGEO-UHFFFAOYSA-L 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
- 230000001717 pathogenic effect Effects 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 229910052702 rhenium Inorganic materials 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011697 sodium iodate Substances 0.000 description 2
- 235000015281 sodium iodate Nutrition 0.000 description 2
- 229940032753 sodium iodate Drugs 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- 229910052713 technetium Inorganic materials 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 229910052716 thallium Inorganic materials 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 241000193738 Bacillus anthracis Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 206010008631 Cholera Diseases 0.000 description 1
- PTGJVXFGOMJCCW-UHFFFAOYSA-J Cl[Au](Cl)(Cl)(Cl)[K] Chemical compound Cl[Au](Cl)(Cl)(Cl)[K] PTGJVXFGOMJCCW-UHFFFAOYSA-J 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 241000589248 Legionella Species 0.000 description 1
- 208000007764 Legionnaires' Disease Diseases 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 241000872931 Myoporum sandwicense Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 241001263478 Norovirus Species 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- JYDBGJYYVQRPTE-UHFFFAOYSA-L P(=O)(O)([O-])[O-].[Pt+2] Chemical compound P(=O)(O)([O-])[O-].[Pt+2] JYDBGJYYVQRPTE-UHFFFAOYSA-L 0.000 description 1
- 206010035148 Plague Diseases 0.000 description 1
- 241000315672 SARS coronavirus Species 0.000 description 1
- 241000607768 Shigella Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 206010043376 Tetanus Diseases 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- KZNMRPQBBZBTSW-UHFFFAOYSA-N [Au]=O Chemical compound [Au]=O KZNMRPQBBZBTSW-UHFFFAOYSA-N 0.000 description 1
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 description 1
- GMTXBUZKCHNBCH-UHFFFAOYSA-L [K].[Pt](Cl)Cl Chemical compound [K].[Pt](Cl)Cl GMTXBUZKCHNBCH-UHFFFAOYSA-L 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- YKIOKAURTKXMSB-UHFFFAOYSA-N adams's catalyst Chemical compound O=[Pt]=O YKIOKAURTKXMSB-UHFFFAOYSA-N 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 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
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229940107816 ammonium iodide Drugs 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
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003125 aqueous solvent Substances 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
- 229940065181 bacillus anthracis Drugs 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 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
- 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
- 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
- 206010013023 diphtheria Diseases 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- ATGIETUGWDAYPU-UHFFFAOYSA-M gold monoiodide Chemical compound [Au]I ATGIETUGWDAYPU-UHFFFAOYSA-M 0.000 description 1
- 229910001922 gold oxide Inorganic materials 0.000 description 1
- KPQDSKZQRXHKHY-UHFFFAOYSA-N gold potassium Chemical compound [K].[Au] KPQDSKZQRXHKHY-UHFFFAOYSA-N 0.000 description 1
- PMCMJPXEJUKOAO-UHFFFAOYSA-M gold(1+);bromide Chemical compound [Au]Br PMCMJPXEJUKOAO-UHFFFAOYSA-M 0.000 description 1
- 229910021505 gold(III) hydroxide Inorganic materials 0.000 description 1
- WDZVNNYQBQRJRX-UHFFFAOYSA-K gold(iii) hydroxide Chemical compound O[Au](O)O WDZVNNYQBQRJRX-UHFFFAOYSA-K 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000005342 ion exchange Methods 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
- 229910052745 lead 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
- 230000007246 mechanism Effects 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- JVJQPDTXIALXOG-UHFFFAOYSA-N nitryl fluoride Chemical class [O-][N+](F)=O JVJQPDTXIALXOG-UHFFFAOYSA-N 0.000 description 1
- 235000019645 odor Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 1
- VVRQVWSVLMGPRN-UHFFFAOYSA-N oxotungsten Chemical class [W]=O VVRQVWSVLMGPRN-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
- 239000000123 paper Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 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
- NFOHLBHARAZXFQ-UHFFFAOYSA-L platinum(2+);dihydroxide Chemical compound O[Pt]O NFOHLBHARAZXFQ-UHFFFAOYSA-L 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 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
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 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
- 239000002994 raw material Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 150000003377 silicon compounds Chemical class 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
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 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
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- KGYLMXMMQNTWEM-UHFFFAOYSA-J tetrachloropalladium Chemical compound Cl[Pd](Cl)(Cl)Cl KGYLMXMMQNTWEM-UHFFFAOYSA-J 0.000 description 1
- 238000009283 thermal hydrolysis Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 201000008827 tuberculosis Diseases 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Abstract
Description
本発明は、高い光触媒活性を示す光触媒体分散液、およびこの光触媒体分散液を用いて得られる光触媒機能製品に関する。 The present invention relates to a photocatalyst dispersion liquid exhibiting high photocatalytic activity, and a photocatalytic functional product obtained using the photocatalyst dispersion liquid.
半導体にバンドギャップ以上のエネルギーを持つ光を照射すると、価電子帯の電子が伝導帯に励起され、価電子帯に正孔が、伝導帯に電子がそれぞれ生成する。かかる正孔および電子は、それぞれ強い酸化力と還元力を有することから、半導体に接触した分子種に酸化還元作用を及ぼす。この酸化還元作用は光触媒作用と呼ばれており、かかる光触媒作用を示し得る半導体は、光触媒体と呼ばれている。このような光触媒体としては、酸化チタン粒子や酸化タングステン粒子などの粒子状のものが知られている。 When a semiconductor is irradiated with light having energy higher than the band gap, electrons in the valence band are excited to the conduction band, and holes are generated in the valence band and electrons are generated in the conduction band. Since these holes and electrons have strong oxidizing power and reducing power, respectively, they exert a redox action on the molecular species in contact with the semiconductor. This redox action is called a photocatalytic action, and a semiconductor that can exhibit such a photocatalytic action is called a photocatalyst. As such a photocatalyst, particulates such as titanium oxide particles and tungsten oxide particles are known.
酸化チタン粒子や酸化タングステン粒子は、通常、分散媒中に分散させ、光触媒体分散液として光触媒体層の形成に利用されており、例えば、酸化チタン粒子および酸化タングステン粒子を分散媒中に分散させた光触媒体粒子分散液が特許文献１に開示されている。かかる光触媒体粒子分散液を基材の表面に塗布することにより、基材表面に、酸化チタン粒子および酸化タングステン粒子を含み、光触媒作用を示す光触媒体層を容易に形成することができる。 Titanium oxide particles and tungsten oxide particles are usually dispersed in a dispersion medium and used as a photocatalyst dispersion to form a photocatalyst layer. For example, titanium oxide particles and tungsten oxide particles are dispersed in a dispersion medium. A photocatalyst particle dispersion is disclosed in Patent Document 1. By applying such a photocatalyst particle dispersion to the surface of the substrate, a photocatalyst layer that includes titanium oxide particles and tungsten oxide particles and exhibits a photocatalytic action can be easily formed on the surface of the substrate.
しかしながら、酸化チタン粒子および酸化タングステン粒子を分散媒中に分散させた従来の光触媒体粒子分散液を用いて形成された光触媒体層では、例えばトルエン等の揮発性有機化合物の分解において、充分に満足しうるだけの光触媒活性は得られなかった。 However, the photocatalyst layer formed using a conventional photocatalyst particle dispersion liquid in which titanium oxide particles and tungsten oxide particles are dispersed in a dispersion medium is sufficiently satisfactory in decomposing volatile organic compounds such as toluene. As much photocatalytic activity as possible was not obtained.
そこで、本発明の課題は、高い光触媒活性を発現する光触媒体層を形成しうる光触媒体分散液と、これを用いた光触媒機能製品とを提供することにある。 Then, the subject of this invention is providing the photocatalyst dispersion liquid which can form the photocatalyst body layer which expresses high photocatalytic activity, and a photocatalyst functional product using the same.
本発明者は、上記課題を解決すべく鋭意研究を重ねた。その結果、光触媒体分散液に対して、ヨウ素化合物を含有させると、該分散液により形成された塗膜（光触媒体層）の光触媒活性が飛躍的に向上することを見出し、本発明を完成した。 The present inventor has intensively studied to solve the above problems. As a result, it was found that when an iodine compound is contained in the photocatalyst dispersion liquid, the photocatalytic activity of the coating film (photocatalyst body layer) formed by the dispersion liquid is dramatically improved, and the present invention has been completed. .
すなわち、本発明の光触媒体分散液は、以下の構成からなる。
（１）光触媒体粒子および分散媒を含む光触媒体分散液であって、さらにヨウ素化合物をヨウ素原子換算で、光触媒体粒子の合計量１００質量部に対して、０．０１〜３．０質量部含むことを特徴とする光触媒体分散液。
（２）貴金属または貴金属前駆体を含む前記（１）に記載の光触媒体分散液。
（３）前記光触媒体粒子が酸化タングステン粒子および酸化チタン粒子である前記（１）または（２）に記載の光触媒体分散液。
（４）前記酸化タングステン粒子および／または酸化チタン粒子が貴金属を担持した前記（３）に記載の光触媒分散液。
（５）前記貴金属または貴金属前駆体が、Ｃｕ、Ｐｔ、Ａｕ、Ｐｄ、Ａｇ、Ｒｕ、Ｉｒ、およびＲｈからなる群より選ばれる１種以上の金属原子またはその前駆体である前記（２）〜（４）のいずれかに記載の光触媒体分散液。
（６）リン酸またはその塩を含む前記（１）〜（５）のいずれかに記載の光触媒体分散液。
本発明の光触媒機能製品は、表面に光触媒体層を備えるものであって、前記光触媒体層が前記（１）〜（６）のいずれかに記載の光触媒体分散液を用いて形成されていることを特徴とする。
That is, the photocatalyst dispersion liquid of the present invention has the following configuration.
(1) A photocatalyst dispersion liquid containing photocatalyst particles and a dispersion medium, and further an iodine compound in terms of iodine atoms and 0.01 to 3.0 parts by mass with respect to 100 parts by mass of the total amount of photocatalyst particles A photocatalyst dispersion liquid comprising:
(2) The photocatalyst dispersion liquid according to (1), which contains a noble metal or a noble metal precursor.
(3) The photocatalyst dispersion liquid according to (1) or (2), wherein the photocatalyst particles are tungsten oxide particles and titanium oxide particles.
(4) The photocatalyst dispersion liquid according to (3), wherein the tungsten oxide particles and / or titanium oxide particles carry a noble metal.
(5) The above (2) to (2), wherein the noble metal or noble metal precursor is one or more metal atoms selected from the group consisting of Cu, Pt, Au, Pd, Ag, Ru, Ir, and Rh, or a precursor thereof. (4) The photocatalyst dispersion liquid according to any one of the above.
(6) The photocatalyst dispersion liquid according to any one of (1) to (5), comprising phosphoric acid or a salt thereof.
The photocatalytic functional product of the present invention comprises a photocatalyst layer on the surface, and the photocatalyst layer is formed using the photocatalyst dispersion liquid described in any one of (1) to (6). It is characterized by that.
本発明によれば、高い光触媒活性を発現する光触媒体層を容易に形成することが可能になる。かかる光触媒体層を表面に有する光触媒機能製品は、トルエン等の揮発性有機化合物の分解において、優れた光触媒活性を発揮する。 According to the present invention, it is possible to easily form a photocatalyst layer that exhibits high photocatalytic activity. A photocatalytic functional product having such a photocatalyst layer on the surface exhibits excellent photocatalytic activity in the decomposition of volatile organic compounds such as toluene.
（光触媒体分散液）
本発明の光触媒体分散液は、光触媒体が溶媒に分散された分散液である。光触媒体とは、例えば、紫外線や可視光線の照射により光触媒作用を発現する半導体であり、具体的には、特定の結晶構造を示す金属元素と酸素、窒素、硫黄、フッ素との化合物等が挙げられる。金属元素としては、例えば、Ｔｉ、Ｚｒ、Ｈｆ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、Ｗ、Ｍｎ、Ｔｃ、Ｒｅ、Ｆｅ、Ｃｏ、Ｎｉ、Ｒｕ、Ｒｈ、Ｐｄ、Ｏｓ、Ｉｒ、Ｐｔ、Ｃｕ、Ａｇ、Ａｕ、Ｚｎ、Ｃｄ、Ｇａ、Ｉｎ、Ｔｌ、Ｇｅ、Ｓｎ、Ｐｂ、Ｂｉ、Ｌａ、Ｃｅなどが挙げられる。その化合物としては、これら金属の１種類または２種類以上の酸化物、窒化物、硫化物、酸窒化物、酸硫化物、窒弗化物、酸弗化物、酸窒弗化物などが挙げられる。なかでも、Ｔｉ、Ｗ、Ｎｂの酸化物が好ましく、とりわけ酸化チタン、酸化タングステンが好ましい。なお、光触媒体は単独で用いてもよいし２種類以上を併用してもよく、特に本発明における光触媒体は酸化チタンと酸化タングステンの組合わせが好ましい。
(Photocatalyst dispersion)
The photocatalyst dispersion liquid of the present invention is a dispersion liquid in which a photocatalyst body is dispersed in a solvent. The photocatalyst is, for example, a semiconductor that exhibits photocatalytic action by irradiation with ultraviolet rays or visible light, and specifically includes a compound of a metal element having a specific crystal structure and oxygen, nitrogen, sulfur, fluorine, and the like. It is done. Examples of metal elements include Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, and Cu. , Ag, Au, Zn, Cd, Ga, In, Tl, Ge, Sn, Pb, Bi, La, Ce, and the like. Examples of the compound include one or more oxides, nitrides, sulfides, oxynitrides, oxysulfides, nitrofluorides, oxyfluorides, and oxynitrofluorides of these metals. Of these, oxides of Ti, W, and Nb are preferable, and titanium oxide and tungsten oxide are particularly preferable. The photocatalyst may be used alone or in combination of two or more. In particular, the photocatalyst in the present invention is preferably a combination of titanium oxide and tungsten oxide.
上記酸化チタン粒子は、光触媒作用を示す粒子状の酸化チタンであれば、特に制限はされないが、例えば、メタチタン酸粒子、結晶型がアナターゼ型、ブルッカイト型、ルチル型などである二酸化チタン〔ＴｉＯ2〕粒子等が挙げられる。なお、酸化チタン粒子は、単独で用いてもよいし、２種以上を併用してもよい。 The titanium oxide particles are not particularly limited as long as they are particulate titanium oxide exhibiting a photocatalytic action. For example, metatitanic acid particles, titanium dioxide having a crystal type of anatase type, brookite type, rutile type, etc. [TiO 2 ] And the like. In addition, a titanium oxide particle may be used independently and may use 2 or more types together.
メタチタン酸粒子は、例えば、硫酸チタニルの水溶液を加熱して加水分解させる方法により得ることができる。
二酸化チタン粒子は、例えば、（ｉ）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、この沈殿物を焼成する方法、（ｉｉ）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、この沈殿物を焼成する方法、（ｉｉｉ）メタチタン酸を焼成する方法などによって得ることができる。これらの方法で得られる二酸化チタン粒子は、焼成する際の焼成温度や焼成時間を調整することにより、アナターゼ型、ブルッカイト型またはルチル型などの所望の結晶型にすることができる。
Metatitanic acid particles can be obtained, for example, by a method in which an aqueous solution of titanyl sulfate is heated and hydrolyzed.
The titanium dioxide particles can be obtained, for example, by (i) a method of obtaining a precipitate by adding a base thereto without heating an aqueous solution of titanyl sulfate or titanium chloride, and firing the precipitate; In addition, an aqueous solution of an acid or an aqueous solution of a base is added to obtain a precipitate, and the precipitate is fired, or (iii) a metatitanic acid is fired. The titanium dioxide particles obtained by these methods can be made into a desired crystal type such as anatase type, brookite type or rutile type by adjusting the baking temperature and baking time when baking.
本発明の光触媒体分散液を構成する酸化チタン粒子としては、上記の他にも、特開２００１−７２４１９号公報、特開２００１−１９０９５３号公報、特開２００１−３１６１１６号公報、特開２００１−３２２８１６号公報、特開２００２−２９７４９号公報、特開２００２−９７０１９号公報、ＷＯ０１／１０５５２パンフレット、特開２００１−２１２４５７号公報、特開２００２−２３９３９５号公報、ＷＯ０３／０８０２４４パンフレット、ＷＯ０２／０５３５０１パンフレット、特開２００７−６９０９３号公報、Ｃｈｅｍｉｓｔｒｙ Ｌｅｔｔｅｒｓ, Ｖｏｌ.３２, ＮＯ．２, Ｐ.１９６−１９７(２００３)、Ｃｈｅｍｉｓｔｒｙ Ｌｅｔｔｅｒｓ, Ｖｏｌ.３２, ＮＯ．４, Ｐ.３６４−３６５(２００３)、Ｃｈｅｍｉｓｔｒｙ Ｌｅｔｔｅｒｓ, Ｖｏｌ.３２, ＮＯ．８, Ｐ.７７２−７７３(２００３)、Ｃｈｅｍ． Ｍａｔｅｒ., １７, Ｐ.１５４８−１５５２(２００５)等に記載の酸化チタン粒子を用いてもよい。また、特開２００１−２７８６２５号公報、特開２００１−２７８６２６号公報、特開２００１−２７８６２７号公報、特開２００１−３０２２４１号公報、特開２００１−３３５３２１号公報、特開２００１−３５４４２２号公報、特開２００２−２９７５０号公報、特開２００２−４７０１２号公報、特開２００２−６０２２１号公報、特開２００２−１９３６１８号公報、特開２００２−２４９３１９号公報などに記載の方法により得られる酸化チタン粒子を用いることもできる。 In addition to the above, the titanium oxide particles constituting the photocatalyst dispersion liquid of the present invention include JP-A-2001-72419, JP-A-2001-190953, JP-A-2001-316116, JP-A-2001-2001. 322816, JP2002-29749, JP200297019, WO01 / 10552 pamphlet, JP2001-212457, JP2002-239395, WO03 / 080244 pamphlet, WO02 / 053501 pamphlet JP 2007-69093 A, Chemistry Letters, Vol. 32, NO. 2, P.196-197 (2003), Chemistry Letters, Vol.32, NO. 4, P.364-365 (2003), Chemistry Letters, Vol.32, NO. 8, P. 772-773 (2003), Chem. Mater., 17, P. 1548-1552 (2005), etc. may be used. JP 2001-278625 A, JP 2001-278626 A, JP 2001-278627 A, JP 2001-302241 A, JP 2001-335321 A, JP 2001-354422 A, Titanium oxide particles obtained by the methods described in JP 2002-29750 A, JP 2002-47012 A, JP 2002-60221 A, JP 2002-193618 A, JP 2002-249319 A, etc. Can also be used.
前記酸化チタン粒子の粒子径は、特に制限されないが、光触媒作用の観点からは、平均分散粒子径で、通常２０〜１５０ｎｍ、好ましくは４０〜１００ｎｍである。
前記酸化チタン粒子のＢＥＴ比表面積は、特に制限されないが、光触媒作用の観点からは、通常１００〜５００ｍ2／ｇ、好ましくは３００〜４００ｍ2／ｇである。
The particle diameter of the titanium oxide particles is not particularly limited, but from the viewpoint of photocatalysis, the average dispersed particle diameter is usually 20 to 150 nm, preferably 40 to 100 nm.
BET specific surface area of the titanium oxide particles is not particularly limited, from the viewpoint of photocatalytic activity, usually 100 to 500 m 2 / g, preferably from 300~400m 2 / g.
上記酸化タングステン粒子は、光触媒作用を示す粒子状の酸化タングステンであれば、特に制限はされないが、例えば、三酸化タングステン〔ＷＯ3〕粒子等が挙げられる。なお、酸化タングステン粒子は、単独で用いてもよいし、２種以上を併用してもよい。 The tungsten oxide particles are not particularly limited as long as they are particulate tungsten oxide exhibiting a photocatalytic action, and examples thereof include tungsten trioxide [WO 3 ] particles. The tungsten oxide particles may be used alone or in combination of two or more.
三酸化タングステン粒子は、例えば、（イ）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、このタングステン酸を焼成する方法、（ロ）メタタングステン酸アンモニウム、パラタングステン酸アンモニウムを加熱することにより熱分解する方法などによって得ることができる。 Tungsten trioxide particles are obtained by, for example, (a) adding tungstic acid in an aqueous solution to obtain tungstic acid as a precipitate, and firing this tungstic acid, (b) ammonium metatungstate, paratungstic acid It can be obtained by a method in which ammonium is thermally decomposed by heating.
前記酸化タングステン粒子の粒子径は、特に制限されないが、光触媒作用の観点からは、平均分散粒子径で、通常５０〜２００ｎｍ、好ましくは８０〜１３０ｎｍであるのがよい。
前記酸化タングステン粒子のＢＥＴ比表面積は、特に制限されないが、光触媒作用の観点からは、通常５〜１００ｍ2／ｇ、好ましくは２０〜５０ｍ2／ｇであるのがよい。
The particle diameter of the tungsten oxide particles is not particularly limited, but from the viewpoint of photocatalysis, the average dispersed particle diameter is usually 50 to 200 nm, preferably 80 to 130 nm.
BET specific surface area of the tungsten oxide particles is not particularly limited, from the viewpoint of photocatalytic activity, typically 5 to 100 m 2 / g, it's good preferably 20 to 50 m 2 / g.
本発明の光触媒体分散液において、酸化チタン粒子と酸化タングステン粒子を光触媒体として用いる場合、これらの混合比率（酸化チタン粒子：酸化タングステン粒子）は、質量比で、通常１：４〜４：１、好ましくは２：３〜３：２である。酸化チタンの比率が上記比率を下回る場合は、光触媒体の分散性が低下して、分散液が固液分離するおそれがあり、酸化チタンが上記比率を超える場合は、光触媒体への可視光照射下において光触媒活性が十分に得られなくなるおそれがある。 In the photocatalyst dispersion liquid of the present invention, when titanium oxide particles and tungsten oxide particles are used as a photocatalyst, the mixing ratio thereof (titanium oxide particles: tungsten oxide particles) is usually 1: 4 to 4: 1 in terms of mass ratio. The ratio is preferably 2: 3 to 3: 2. When the ratio of titanium oxide is lower than the above ratio, the dispersibility of the photocatalyst may be reduced, and the dispersion may be separated into solid and liquid. When the titanium oxide exceeds the above ratio, visible light irradiation to the photocatalyst is possible. There is a possibility that sufficient photocatalytic activity may not be obtained below.
本発明の光触媒体分散液は、貴金属またはその前駆体をも含有することが好ましい。貴金属とは、光触媒体の表面に担持されて電子吸引性を発揮しうる元素であり、貴金属の前駆体とは、光触媒体の表面で貴金属に遷移しうる化合物（例えば、光照射により貴金属に還元されうる化合物）である。貴金属が光触媒体の表面に担持されて存在すると、光の照射により伝導帯に励起された電子と価電子帯に生成した正孔との再結合が抑制され、光触媒作用をより高めることができる。 The photocatalyst dispersion liquid of the present invention preferably contains a noble metal or a precursor thereof. A noble metal is an element that is supported on the surface of a photocatalyst and can exhibit electron withdrawing properties, and a precursor of a noble metal is a compound that can transition to a noble metal on the surface of a photocatalyst (for example, reduced to a noble metal by light irradiation). Compound). When the noble metal is supported on the surface of the photocatalyst, recombination between electrons excited in the conduction band by irradiation of light and holes generated in the valence band is suppressed, and the photocatalytic action can be further enhanced.
前記貴金属またはその前駆体は、Ｃｕ、Ｐｔ、Ａｕ、Ｐｄ、Ａｇ、Ｒｕ、Ｉｒ、およびＲｈからなる群より選ばれる１種以上の金属原子を含有してなるものであることが好ましい。より好ましくは、Ｃｕ、Ｐｔ、ＡｕおよびＰｄのうちの１種以上の金属原子を含有してなるものである。例えば、前記貴金属としては、前記金属原子からなる金属、もしくは、これらの金属の酸化物や水酸化物等が挙げられ、貴金属の前駆体としては、前記金属原子からなる金属の硝酸塩、硫酸塩、ハロゲン化物、有機酸塩、炭酸塩、リン酸塩等が挙げられる。 The noble metal or precursor thereof preferably contains one or more metal atoms selected from the group consisting of Cu, Pt, Au, Pd, Ag, Ru, Ir, and Rh. More preferably, it contains one or more metal atoms of Cu, Pt, Au and Pd. For example, the noble metal includes a metal composed of the metal atom, or an oxide or hydroxide of these metals, and the noble metal precursor includes a metal nitrate composed of the metal atom, a sulfate, Halides, organic acid salts, carbonates, phosphates and the like can be mentioned.
貴金属の好ましい具体例としては、Ｃｕ、Ｐｔ、Ａｕ、Ｐｄ等の金属が挙げられる。また、貴金属の前駆体の好ましい具体例としては、Ｃｕを含む前駆体として、硝酸銅〔Ｃｕ(ＮＯ3)2〕、硫酸銅〔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)〕、ジニトロアジアミン白金〔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〕、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〕等が；それぞれ挙げられる。なお、貴金属またはその前駆体は、それぞれ単独で用いてもよいし、２種以上を併用してもよい。また、１種以上の貴金属と１種以上の前駆体とを併用してもよいことは勿論である。 Preferable specific examples of the noble metal include metals such as Cu, Pt, Au, and Pd. Moreover, as a preferable specific example of the precursor of a noble metal, as a precursor containing 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 chloride [Cu (NH 4 ) 2 Cl 4 ], copper oxychloride [Cu 2 Cl (OH) 3 ] , Copper acetate [CH 3 COOCu, (CH 3 COO) 2 Cu], copper formate [(HCOO) 2 Cu], copper carbonate [CuCO 3 ], copper oxalate [CuC 2 O 4 ], copper citrate [Cu 2 C 6 H 4 O 7 ], copper phosphate [CuPO 4 ], etc .; as precursors containing Pt, platinum chloride [PtCl 2 , PtCl 4 ], platinum bromide [PtBr 2 , PtBr 4 ], platinum iodide [PtI] 2, PtI 4], potassium platinum chloride [K 2 (PtCl 4)], hexachloro Aurate [H 2 PtCl 6], platinum sulfite [H 3 Pt (SO 3) 2 OH ], platinum oxide [PtO 2], tetraammine platinum chloride [Pt (NH 3) 4 Cl 2], bicarbonate tetraammineplatinum [C 2 H 14 N 4 O 6 Pt], tetraammine platinum hydrogen phosphate [Pt (NH 3 ) 4 HPO 4 ], tetraammine platinum hydroxide [Pt (NH 3 ) 4 (OH) 2 ], tetraammine platinum nitrate [Pt (NO 3 ) 2 (NH 3 ) 4 ], tetraammine platinum tetrachloro platinum [(Pt (NH 3 ) 4 ) (PtCl 4 )], dinitroadiamine platinum [Pt (NO 2 ) 2 (NH 3 ) 2 ] and the like; As precursors containing Au, gold chloride [AuCl], gold bromide [AuBr], gold iodide [AuI], gold hydroxide [Au (OH) 2 ], tetrachloroauric acid [HAuCl 4 ], tetrachlorogold potassium acid [KAuCl 4], tetrabromophthalic gold potassium Arm [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 ], tetrachloropalladium acid Potassium [K 2 (PdCl 4 )], potassium tetrabromopalladate [K 2 (PdBr 4 )], tetraammine palladium nitrate [Pd (NH 3 ) 4 (NO 3 ) 2 ], tetraammine palladium tetrachloropalladate [(Pd (NH 3) 4) (PdCl 4) ], ammonium tetrachloropalladate [(NH 4) 2 PdCl 4], tetraamminepalladium chloride [Pd (NH 3) 4 Cl 2], tetraammine palladium bromide [Pd (NH 3) 4 Br 2] and the like are; like, respectively. In addition, a noble metal or its precursor may be used independently, respectively and may use 2 or more types together. Of course, one or more kinds of precious metals and one or more kinds of precursors may be used in combination.
前記貴金属またはその前駆体をも含有させる場合、その含有量は、金属原子換算で、光触媒体粒子の合計量１００質量部に対して、通常０．００５〜０．６質量部、好ましくは０．０１〜０．４質量部である。貴金属またはその前駆体が金属原子換算で、光触媒体粒子の合計量１００質量部に対して、０．００５質量部未満であると、貴金属による光触媒活性の向上効果が充分に得られないおそれがあり、一方、０．６質量部を超えると、却って光触媒作用が低下するおそれがある。光触媒体粒子として酸化タングステン粒子と酸化チタン粒子を併用する場合、どちらか一方または両方に前記貴金属を担持させればよく、特に酸化タングステンに前記貴金属を担持させるのが好ましい。 When the precious metal or a precursor thereof is also contained, the content thereof is usually 0.005 to 0.6 parts by mass, preferably 0. 0 to 100 parts by mass in terms of the total amount of photocatalyst particles in terms of metal atoms. 01 to 0.4 parts by mass. If the noble metal or its precursor is less than 0.005 parts by mass in terms of metal atoms, with respect to 100 parts by mass of the total amount of photocatalyst particles, the effect of improving the photocatalytic activity by the noble metal may not be sufficiently obtained. On the other hand, if it exceeds 0.6 parts by mass, the photocatalytic action may be lowered. When tungsten oxide particles and titanium oxide particles are used in combination as the photocatalyst particles, the noble metal may be supported on one or both, and it is particularly preferable that the noble metal is supported on tungsten oxide.
本発明の光触媒体分散液を構成する分散媒としては、特に制限はなく、通常は、水を主成分とする水性溶媒が用いられる。具体的には、分散媒は、水単独であってもよいし、水と水溶性有機溶媒との混合溶媒であってもよい。水と水溶性有機溶媒との混合溶媒を用いる場合には、混合溶媒総量に対して水の含有量が５０質量％以上であることが好ましい。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等が挙げられる。なお、分散媒は、単独で用いてもよいし、２種以上を併用してもよい。 There is no restriction | limiting in particular as a dispersion medium which comprises the photocatalyst body dispersion liquid of this invention, Usually, the aqueous solvent which has water as a main component is used. Specifically, the dispersion medium may be water alone or a mixed solvent of water and a water-soluble organic solvent. When a mixed solvent of water and a water-soluble organic solvent is used, the content of water is preferably 50% by mass or more based on the total amount of the mixed solvent. Examples of the water-soluble organic solvent include water-soluble alcohol solvents such as methanol, ethanol, propanol, and butanol, acetone, and methyl ethyl ketone. In addition, a dispersion medium may be used independently and may use 2 or more types together.
本発明の光触媒体分散液において、前記分散媒の含有量は、光触媒体粒子の合計量に対して、通常５〜２００質量倍、好ましくは１０〜１００質量倍である。分散媒が５質量倍未満であると、光触媒体粒子が沈降し易くなり、一方、２００質量倍を超えると、容積効率の点で不利となるので、いずれも好ましくない。 In the photocatalyst dispersion liquid of the present invention, the content of the dispersion medium is usually 5 to 200 times by mass, preferably 10 to 100 times by mass, with respect to the total amount of the photocatalyst particles. If the dispersion medium is less than 5 times by mass, the photocatalyst particles are liable to settle, while if it exceeds 200 times by mass, it is disadvantageous in terms of volumetric efficiency.
本発明の光触媒体分散液は、ヨウ素化合物を含有する。このヨウ素化合物を含有する光触媒体分散液を用いて形成される塗膜（光触媒体層）は光触媒活性が格段に向上する。光触媒体分散液にヨウ素化合物を含有させると、なぜ光触媒活性が高くなるのか理由は定かではないが、例えば酸化タングステンと酸化チタンを含む光触媒体では、ヨウ素化合物が酸化タングステンと酸化チタンとの電子の受け渡しを、円滑に仲介するために十分な紫外線照射下でなくとも酸化チタンの高い光触媒活性を発現させているのではないかと推測される。
ヨウ素化合物としては、例えばヨウ素（Ｉ2）、ヨウ化水素（ＨＩ）、ヨウ化ナトリウム（ＮａＩ）、ヨウ化カリウム（ＫＩ）、ヨウ化アンモニウム（ＮＨ4Ｉ）、ヨウ素酸（ＨＩＯ3）、ヨウ素酸ナトリウム（ＮａＩＯ3）、ヨウ素酸カリウム（ＫＩＯ3）などが挙げられ、これらのなかでもヨウ化カリウム、ヨウ素酸、ヨウ素酸ナトリウム、ヨウ素酸カリウムを用いるのが好ましい。尚、ヨウ素化合物は、それぞれ、単独で用いてもよいし、２種以上を併用してもよい。
The photocatalyst dispersion liquid of the present invention contains an iodine compound. The coating film (photocatalyst layer) formed using the photocatalyst dispersion containing the iodine compound has a significantly improved photocatalytic activity. The reason why the photocatalytic activity is increased when an iodine compound is contained in the photocatalyst dispersion liquid is not clear, but in a photocatalyst containing, for example, tungsten oxide and titanium oxide, the iodine compound contains electrons of tungsten oxide and titanium oxide. It is presumed that the high photocatalytic activity of titanium oxide is expressed even without sufficient ultraviolet irradiation to mediate delivery smoothly.
Examples of the iodine compound include iodine (I 2 ), hydrogen iodide (HI), sodium iodide (NaI), potassium iodide (KI), ammonium iodide (NH 4 I), iodic acid (HIO 3 ), iodine Examples thereof include sodium acid (NaIO 3 ) and potassium iodate (KIO 3 ). Among these, potassium iodide, iodic acid, sodium iodate, and potassium iodate are preferably used. In addition, an iodine compound may each be used independently and may use 2 or more types together.
本発明の光触媒体分散液において、前記ヨウ素化合物の含有量は、ヨウ素原子換算で、光触媒体粒子の合計量１００質量部に対して、０．０１〜３．０質量部であることが好ましく、より好ましくは０．０２〜０．５０質量部である。前記ヨウ素化合物の含有量がヨウ素原子換算で、光触媒体粒子の合計量１００質量部に対して、０．０１質量部未満であると、光触媒活性の向上効果が充分に得られなくなるおそれがあり、一方、３．０質量部を超えると、光触媒体粒子の分散性が低下して、分散液が固液分離するおそれがある。なお、本発明の光触媒体分散液が２種以上のヨウ素化合物を含有する場合には、それらの合計含有量が前記範囲であればよい。 In the photocatalyst dispersion liquid of the present invention, the content of the iodine compound is preferably 0.01 to 3.0 parts by mass in terms of iodine atoms with respect to 100 parts by mass of the total amount of photocatalyst particles, More preferably, it is 0.02-0.50 mass part. If the iodine compound content is less than 0.01 parts by mass with respect to 100 parts by mass of the total amount of the photocatalyst particles in terms of iodine atoms, the effect of improving the photocatalytic activity may not be sufficiently obtained, On the other hand, when the amount exceeds 3.0 parts by mass, the dispersibility of the photocatalyst particles may be reduced, and the dispersion may be solid-liquid separated. In addition, when the photocatalyst dispersion liquid of this invention contains 2 or more types of iodine compounds, those total content should just be the said range.
本発明の光触媒体分散液は、さらに、リン酸およびその塩（以下、リン酸（塩）という）をも含有することが好ましい。これにより、例えば、光触媒体が酸化チタン粒子と酸化タングステン粒子の場合、分散液中でのこれら粒子の凝集を抑制することができ、その結果、分散液が固液分離しにくくなる、という効果が得られる。つまり、分散液中にリン酸（塩）を含有させた場合、酸化チタン粒子近傍に存在するリン酸（塩）は、酸化チタン粒子の表面に吸着した状態になり、この状態の酸化チタン粒子が酸化タングステン粒子と凝集しにくい性質を有することから、酸化チタン粒子と酸化タングステン粒子との凝集を抑制できるのである。 The photocatalyst dispersion liquid of the present invention preferably further contains phosphoric acid and a salt thereof (hereinafter referred to as phosphoric acid (salt)). Thereby, for example, when the photocatalyst is a titanium oxide particle and a tungsten oxide particle, the aggregation of these particles in the dispersion can be suppressed, and as a result, the dispersion becomes difficult to separate into solid and liquid. can get. That is, when phosphoric acid (salt) is contained in the dispersion, phosphoric acid (salt) present in the vicinity of the titanium oxide particles is adsorbed on the surface of the titanium oxide particles. Since it has the property of not easily aggregated with the tungsten oxide particles, aggregation of the titanium oxide particles and the tungsten oxide particles can be suppressed.
前記リン酸（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。 Examples of the 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. Is preferred. In addition, phosphoric acid (salt) may be used independently and may use 2 or more types together.
本発明の光触媒体分散液において、前記リン酸（塩）の含有量は、光触媒体粒子に対して０．００１〜０．２モル倍であることが好ましく、より好ましくは、下限は０．０１モル倍以上、上限は０．１モル倍以下である。リン酸（塩）の含有量が光触媒体粒子に対して０．００１モル倍未満であると、分散液中の粒子の凝集抑制効果が充分に発揮されないおそれがあり、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 dispersion liquid of the present invention, the phosphoric acid (salt) content is preferably 0.001 to 0.2 mol times the photocatalyst particles, and more preferably the lower limit is 0.01. More than mol times and an upper limit is 0.1 mol times or less. If the phosphoric acid (salt) content is less than 0.001 mol times the photocatalyst particles, the aggregation suppressing effect of the particles in the dispersion may not be sufficiently exhibited. Even if it is used in excess of the amount, a further effect corresponding to the amount cannot be obtained, which is economically disadvantageous.
本発明の光触媒体分散液は、その水素イオン濃度が、通常ｐＨ２．０〜ｐＨ７．０、好ましくはｐＨ２．５〜ｐＨ６．０である。水素イオン濃度がｐＨ２．０未満であると、酸性が強すぎて取扱いが面倒であり、一方、ｐＨ７．０を超えると、光触媒体が例えば酸化タングステン粒子の場合、酸化タングステン粒子が溶解するおそれがあるので、いずれも好ましくない。光触媒体分散液の水素イオン濃度は、通常、酸を加えることにより調整すればよい。水素イオン濃度の調整に用いることのできる酸としては、例えば、硝酸、塩酸、硫酸、リン酸、ギ酸、酢酸、蓚酸等が挙げられる。 The hydrogen ion concentration of the photocatalyst dispersion liquid of the present invention is usually pH 2.0 to pH 7.0, preferably pH 2.5 to pH 6.0. When the hydrogen ion concentration is less than pH 2.0, the acidity is too strong and handling is troublesome. On the other hand, when the pH exceeds 7.0, the tungsten oxide particles may be dissolved when the photocatalyst is, for example, tungsten oxide particles. None of them are preferred. The hydrogen ion concentration of the photocatalyst dispersion liquid may be usually adjusted by adding an acid. Examples of the acid that can be used for adjusting the hydrogen ion concentration include nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, oxalic acid, and the like.
本発明の光触媒体分散液は、本発明の効果を損なわない範囲で、従来公知の各種添加剤を含んでいてもよい。なお、添加剤は、それぞれ単独で用いてもよいし、２種以上を併用してもよい。 The photocatalyst dispersion liquid of the present invention may contain conventionally known various additives as long as the effects of the present invention are not impaired. In addition, an additive may each be used independently and may use 2 or more types together.
前記添加剤としては、例えば非晶質シリカ、シリカゾル、水ガラス、オルガノポリシロキサンなどのケイ素化合物、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、カオリナイトなどのアルミノケイ酸塩、酸化マグネシウム、酸化カルシウム、酸化ストロンチウム、酸化バリウムなどのアルカリ土類金属酸化物、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水酸化物、Ｔｉ、Ｚｒ、Ｈｆ、Ｖ、Ｔａ、Ｃｒ、Ｍｏ、Ｗ、Ｍｎ、Ｔｃ、Ｒｅ、Ｆｅ、Ｃｏ、Ｎｉ、Ｒｕ、Ｒｈ、Ｏｓ、Ｉｒ、Ａｇ、Ｚｎ、Ｃｄ、Ｇａ、Ｉｎ、Ｔｌ、Ｇｅ、Ｐｂ、Ｂｉ、Ｌａ、Ｃｅなどの金属元素の水酸化物や酸化物、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。これらの添加剤を添加して用いる場合、それぞれ単独で、又は２種類以上を組み合わせて用いることができる。 Examples of the additive include silicon compounds such as amorphous silica, silica sol, water glass, organopolysiloxane, aluminum compounds such as amorphous alumina, alumina sol, and aluminum hydroxide, aluminosilicates such as zeolite and kaolinite, Alkaline earth metal oxides such as magnesium oxide, calcium oxide, strontium oxide, barium oxide, alkaline earth metal hydroxides such as magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, Ti, Zr, Hf V, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Co, Ni, Ru, Rh, Os, Ir, Ag, Zn, Cd, Ga, In, Tl, Ge, Pb, Bi, La , Hydroxides and oxides of metal elements such as Ce, calcium phosphate, molecular sieves Activated carbon, a polycondensation product of an organopolysiloxane compound, phosphate, a fluorine-based polymer, silicone-based polymers, acrylic resins, polyester resins, melamine resins, urethane resins, alkyd resins. When these additives are added and used, they can be used alone or in combination of two or more.
前記添加剤は、本発明における光触媒体を用いて基材の表面に光触媒体層を形成する際に、光触媒体粒子をより強固に基材の表面に保持させるためのバインダー等に用いることもできる（例えば、特開平８−６７８３５号公報、特開平９−２５４３７号公報、特開平１０―１８３０６１号公報、特開平１０―１８３０６２号公報、特開平１０―１６８３４９号公報、特開平１０―２２５６５８号公報、特開平１１―１６２０号公報、特開平１１―１６６１号公報、特開２００４―０５９６８６号公報、特開２００４―１０７３８１号公報、特開２００４―２５６５９０号公報、特開２００４―３５９９０２号公報、特開２００５―１１３０２８号公報、特開２００５―２３０６６１号公報、特開２００７―１６１８２４号公報など参照）。 The additive can also be used as a binder for holding the photocatalyst particles more firmly on the surface of the substrate when the photocatalyst layer is formed on the surface of the substrate using the photocatalyst in the present invention. (For example, JP-A-8-67835, JP-A-9-25437, JP-A-10-183061, JP-A-10-183062, JP-A-10-168349, JP-A-10-225658 JP-A-11-1620, JP-A-11-1661, JP-A-2004-059686, JP-A-2004-107381, JP-A-2004-256590, JP-A-2004-359902, (See JP 2005-113028, JP 2005-230661, JP 2007-161824, etc.).
本発明の光触媒体分散液の製造方法は、特に制限されるものではなく、前述した各成分を分散媒中に適宜、添加、混合することにより光触媒体分散液が得られる。以下、各成分の混合順序や混合方法などについて、その一実施態様を述べる。 The method for producing the photocatalyst dispersion liquid of the present invention is not particularly limited, and a photocatalyst dispersion liquid can be obtained by appropriately adding and mixing the above-described components into the dispersion medium. Hereinafter, one embodiment of the mixing order and mixing method of each component will be described.
光触媒体として、例えば、酸化チタン粒子と酸化タングステン粒子を用いる場合、酸化チタン粒子と酸化タングステン粒子の混合は、酸化チタン粒子を分散媒中に添加して分散させた酸化チタン粒子分散液を調製し、これに、酸化タングステン粒子、もしくは酸化タングステン粒子を分散媒中に分散させた酸化タングステン粒子分散液を添加し、混合する態様が好ましい。より好ましくは、酸化チタン粒子分散液と酸化タングステン粒子分散液とを混合する態様である。酸化チタン粒子分散液または酸化タングステン粒子分散液を調製する際には、各粒子と分散媒とを混合した後、例えば媒体撹拌式分散機を用いるなど、従来公知の分散処理を施すことが好ましい。その際、分散液の一方または両方に貴金属またはその前駆体を含有させればよい。 For example, when titanium oxide particles and tungsten oxide particles are used as the photocatalyst, a mixture of titanium oxide particles and tungsten oxide particles is prepared by adding a titanium oxide particle in a dispersion medium and dispersing it. In addition, it is preferable to add and mix tungsten oxide particles or a tungsten oxide particle dispersion in which tungsten oxide particles are dispersed in a dispersion medium. More preferably, the titanium oxide particle dispersion and the tungsten oxide particle dispersion are mixed. When preparing the titanium oxide particle dispersion or the tungsten oxide particle dispersion, it is preferable to perform a conventionally known dispersion treatment such as using a medium agitating disperser after mixing each particle and the dispersion medium. At that time, one or both of the dispersions may contain a noble metal or a precursor thereof.
本発明の光触媒体分散液における必須成分であるヨウ素化合物は、任意の添加時機で混合すればよく、例えば、光触媒体として酸化チタン粒子と酸化タングステン粒子を用いる場合、酸化チタン粒子分散液に添加してもよいし、酸化タングステン粒子分散液に添加してもよいし、両者（酸化チタン粒子分散液および酸化タングステン粒子分散液）を混合した後に添加してもよい。また、前記ヨウ素化合物は、そのままの状態で混合してもよいし、分散媒に溶解または分散させた状態で混合してもよい。 The iodine compound that is an essential component in the photocatalyst dispersion liquid of the present invention may be mixed at any time of addition. For example, when titanium oxide particles and tungsten oxide particles are used as the photocatalyst, it is added to the titanium oxide particle dispersion liquid. Alternatively, it may be added to the tungsten oxide particle dispersion, or may be added after mixing both (titanium oxide particle dispersion and tungsten oxide particle dispersion). The iodine compound may be mixed as it is, or may be mixed in a state of being dissolved or dispersed in a dispersion medium.
貴金属またはその前駆体を含有させる場合、それらは、そのままの状態で混合してもよいし、貴金属またはその前駆体を分散媒に溶解または分散させた状態で光触媒体分散液と混合してもよい。 When the precious metal or its precursor is contained, they may be mixed as they are, or may be mixed with the photocatalyst dispersion liquid in a state where the precious metal or its precursor is dissolved or dispersed in a dispersion medium. .
前記貴金属の前駆体を光触媒体分散液に添加した場合には、その添加後に光照射を光触媒体分散液に行うことが好ましい。照射する光としては、光触媒体粒子のバンドギャップ以上のエネルギーを有する光であれば特に制限はなく、可視光線でもよいし、紫外線でもよい。光触媒体分散液に光照射を行うことにより、光励起によって生成した電子によって前駆体が還元されて貴金属となり、光触媒体粒子の表面に担持される。なお、前記前駆体を光触媒体分散液に添加した場合に、たとえ光触媒体分散液に光照射を行なわなくても、得られた光触媒体分散液により形成された光触媒体層に光が照射された時点で貴金属前駆体が貴金属へ変換されることになるので、その光触媒能が損なわれることはない。前記光照射は、前記前駆体を光触媒体分散液に添加後であれば、どの段階で行なってもよい。
また、前記貴金属の前駆体を光触媒体分散液に添加した場合には、より効率よく貴金属に還元する目的で、前記光照射の前に、本発明の効果を損なわない範囲で、適宜、メタノールやエタノールや蓚酸等を光触媒体分散液に加えることもできる。
When the noble metal precursor is added to the photocatalyst dispersion liquid, it is preferable to perform light irradiation on the photocatalyst dispersion liquid after the addition. The light to be irradiated is not particularly limited as long as the light has energy higher than the band gap of the photocatalyst particles, and may be visible light or ultraviolet light. When the photocatalyst dispersion liquid is irradiated with light, the precursor is reduced by electrons generated by photoexcitation to become a noble metal, and is supported on the surface of the photocatalyst particles. In addition, when the precursor was added to the photocatalyst dispersion liquid, the photocatalyst layer formed from the obtained photocatalyst dispersion liquid was irradiated with light even if the photocatalyst dispersion liquid was not irradiated with light. Since the noble metal precursor is converted to the noble metal at that time, the photocatalytic ability is not impaired. The light irradiation may be performed at any stage as long as the precursor is added to the photocatalyst dispersion.
Further, when the noble metal precursor is added to the photocatalyst dispersion liquid, for the purpose of more efficiently reducing to the noble metal, before the light irradiation, as long as the effect of the present invention is not impaired, methanol or Ethanol, oxalic acid, and the like can also be added to the photocatalyst dispersion.
前述した各種添加剤を含有させる場合は、それら添加剤の添加はどの段階で行なってもよい。 When the various additives described above are included, the additives may be added at any stage.
(光触媒機能製品)
本発明の光触媒機能製品は、本発明の光触媒体分散液を用いて形成された光触媒体層を表面に備えるものである。ここで、光触媒体層は、光触媒作用を示す光触媒体を主成分とし、さらに、光触媒活性を向上させる前述したヨウ素化合物由来の金属を含む場合もあり、光触媒体分散液を基材（製品）の表面に塗布した後に、分散媒を揮発させるなど、従来公知の成膜方法によって形成することができる。そして、本発明の光触媒体分散液が貴金属またはその前駆体を含む場合には、該貴金属は、光触媒粒子の表面に担持される。なお、貴金属前駆体は、例えば光が照射された光触媒体に接触することで、光触媒作用により貴金属に還元され、光触媒粒子の表面に担持される。また、光触媒体層の膜厚は、特に制限されるものではなく、通常、その用途等に応じて、数百ｎｍ〜数ｍｍまで適宜設定すればよい。光触媒体層は、基材（製品）の内表面または外表面であれば、どの部分に形成されていてもよいが、例えば、光（可視光線）が照射される面であって、かつ悪臭物質が発生する箇所や病原菌が存在する箇所と連続または断続して空間的につながる面に形成されていることが好ましい。なお、基材（製品）の材質は、形成される光触媒体層を実用に耐えうる強度で保持できる限り、特に制限されるものではなく、例えば、プラスチック、金属、セラミックス、木材、コンクリート、紙など、あらゆる材料からなる製品を対象にすることができる。
(Photocatalytic product)
The photocatalyst functional product of the present invention is provided with a photocatalyst layer formed on the surface using the photocatalyst dispersion liquid of the present invention. Here, the photocatalyst layer is mainly composed of a photocatalyst exhibiting a photocatalytic action, and may further contain the above-mentioned iodine compound-derived metal that improves the photocatalytic activity. After coating on the surface, it can be formed by a conventionally known film forming method such as volatilizing the dispersion medium. When the photocatalyst dispersion liquid of the present invention contains a noble metal or a precursor thereof, the noble metal is supported on the surface of the photocatalyst particles. Note that the noble metal precursor is reduced to the noble metal by photocatalysis by contacting the photocatalyst irradiated with light, for example, and is supported on the surface of the photocatalyst particles. Moreover, the film thickness of a photocatalyst body layer is not specifically limited, Usually, what is necessary is just to set suitably from several hundred nm-several mm according to the use. The photocatalyst layer may be formed on any part as long as it is an inner surface or an outer surface of the base material (product). For example, the photocatalyst layer is a surface irradiated with light (visible light), and a malodorous substance. It is preferably formed on a surface that is continuously or intermittently connected spatially with a site where the occurrence of a pathogen or a pathogen is present. The material of the base material (product) is not particularly limited as long as the formed photocatalyst layer can be held at a strength that can be practically used. For example, plastic, metal, ceramics, wood, concrete, paper, etc. , Products made of any material can be targeted.
本発明の光触媒機能製品の具体例としては、例えば、天井材、タイル、ガラス、壁紙、壁材、床等の建築資材、自動車内装材（自動車用インストルメントパネル、自動車用シート、自動車用天井材）、冷蔵庫やエアコン等の家電製品、衣類やカーテン等の繊維製品などが挙げられる。 Specific examples of the photocatalytic functional product of the present invention include, for example, building materials such as ceiling materials, tiles, glass, wallpaper, wall materials, floors, automobile interior materials (automobile instrument panels, automotive seats, automotive ceiling materials, etc. ), Home appliances such as refrigerators and air conditioners, and textile products such as clothes and curtains.
本発明の光触媒機能製品は、屋外においては勿論のこと、蛍光灯やナトリウムランプのような可視光源からの光しか受けない屋内環境においても、光照射によって高い光触媒作用を示す。したがって、本発明の光触媒体分散液を、例えば、天井材、タイル、ガラス、壁紙、壁材、床等の建築資材、自動車内装材（自動車インストルメントパネル、自動車用シート、自動車用天井材）、冷蔵庫やエアコン等の家電製品、衣類やカーテン等の繊維製品などに塗布して乾燥させると、屋内照明による光照射によって、ホルムアルデヒドやアセトアルデヒドなどの揮発性有機物、アルデヒド類、メルカプタン類、アンモニアなどの悪臭物質、窒素酸化物の濃度を低減させ、さらには黄色ブドウ球菌、大腸菌、炭疽菌、結核菌、コレラ菌、ジフテリア菌、破傷風菌、ペスト菌、赤痢菌、ボツリヌス菌、およびレジオネラ菌等の病原菌等や、インフルエンザウィルス、ＳＡＲＳウィルス、およびノロウィルス等のウィルス等を死滅、分解、除去することができる。 The photocatalytic functional product of the present invention exhibits a high photocatalytic action by light irradiation not only outdoors but also in an indoor environment receiving only light from a visible light source such as a fluorescent lamp and a sodium lamp. Therefore, the photocatalyst dispersion liquid of the present invention is, for example, a building material such as a ceiling material, tile, glass, wallpaper, wall material, floor, automobile interior material (automobile instrument panel, automobile seat, automobile ceiling material), When applied to household appliances such as refrigerators and air conditioners, textiles such as clothing and curtains, and dried, odors such as volatile organic substances such as formaldehyde and acetaldehyde, aldehydes, mercaptans, and ammonia are emitted by light from indoor lighting. Reduce the concentration of substances and nitrogen oxides, and even pathogenic bacteria such as Staphylococcus aureus, Escherichia coli, Bacillus anthracis, tuberculosis, cholera, diphtheria, tetanus, plague, shigella, botulinum, legionella, etc. And kill, decompose, and eliminate viruses such as influenza virus, SARS virus, and norovirus It can be.
以下、本発明を実施例および比較例によって詳細に説明するが、本発明はこれらに限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention in detail, this invention is not limited to these.
なお、実施例および比較例における各物性の測定および光触媒活性の評価については、以下の方法で行った。 In addition, about the measurement of each physical property and evaluation of photocatalytic activity in an Example and a comparative example, it performed with the following method.
＜結晶型＞
Ｘ線回折装置（リガク社製「ＲＩＮＴ２０００／ＰＣ」）を用いてＸ線回折スペクトルを測定し、そのスペクトルから結晶型を決定した。
<Crystal type>
An X-ray diffraction spectrum was measured using an X-ray diffractometer (“RINT2000 / PC” manufactured by Rigaku Corporation), and a crystal type was determined from the spectrum.
＜ＢＥＴ比表面積＞
比表面積測定装置（湯浅アイオニクス社製「モノソーブ」）を用いて窒素吸着法により測定した。
<BET specific surface area>
It measured by the nitrogen adsorption method using the specific surface area measuring apparatus ("Monosorb" by Yuasa Ionics Co., Ltd.).
＜平均分散粒子径＞
サブミクロン粒度分布測定装置（コールター社製「Ｎ４Ｐｌｕｓ」）を用いて粒度分布を測定し、この装置に付属のソフトにより自動的に単分散モード解析して得られた結果を、平均分散粒子径（ｎｍ）とした。
<Average dispersed particle size>
The particle size distribution was measured using a sub-micron particle size distribution measuring device (“N4Plus” manufactured by Coulter, Inc.), and the result obtained by performing the monodisperse mode analysis automatically with the software attached to this device was used as the average dispersed particle size ( nm).
＜トルエン分解能の測定＞
光触媒活性は、蛍光灯の光の照射下でのトルエン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。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、酸化チタン粒子および酸化タングステン粒子の白金含有分散液を底面の単位面積あたりの固形分換算の滴下量が１ｇ／ｍ2となるように滴下し、シャーレの底面全体に均一に形成した。次いで、このシャーレを１１０℃の乾燥機内で大気中で１時間保持することにより乾燥させて、ガラス製シャーレの底面に光触媒体層を形成した。この光触媒体層に紫外線強度が２ｍＷ／ｃｍ2（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）となるようにブラックライトからの紫外線を１６時間照射して、これを光触媒活性測定用試料とした。
<Measurement of toluene resolution>
The photocatalytic activity was evaluated by measuring the first-order rate constant in the decomposition reaction of toluene under the irradiation of light from a fluorescent lamp. That is, in a glass petri dish (outer diameter 70 mm, inner diameter 66 mm, height 14 mm, capacity about 48 mL), a platinum-containing dispersion of titanium oxide particles and tungsten oxide particles was added in an amount of 1 g in terms of solid content per unit area of the bottom surface. / M 2 was added dropwise to form uniformly on the entire bottom of the petri dish. Next, the petri dish was dried by holding it in the air at 110 ° C. for 1 hour in the air to form a photocatalyst layer on the bottom of the glass petri dish. The photocatalyst layer has an ultraviolet intensity of 2 mW / cm 2 (measured by attaching a UV receiver “UD-36” to Topcon's UV intensity meter “UVR-2”). This was used as a sample for photocatalytic activity measurement after time irradiation.
次に、この光触媒活性測定用試料をシャーレごとガスバッグ（内容積１Ｌ）の中に入れて密閉し、次いで、このガスバッグ内を真空にした後、酸素と窒素との体積比が１：４である混合ガス０．６Ｌを封入し、さらにその中にトルエンを含む窒素ガスを、ガスバッグ中のトルエンの濃度が２０ｐｐｍとなるように封入して、暗所で室温下１時間保持した。その後、市販の白色蛍光灯を光源とし、測定用試料近傍での照度が６０００ｌｘ[ミノルタ社製照度計「Ｔ−１０」で測定]となるようにガスバッグの外から蛍光灯の光を照射し、トルエンの分解反応を行った。このとき、測定試料近傍の紫外線の強度は、４０μＷ／ｃｍ2[トプコン社製紫外線強度計「ＵＶＲ−２」に同社製受光部「ＵＤ−３６」を取り付けて測定]であった。蛍光灯の光照射を開始してから１．５時間毎にガスバッグ内のガスをサンプリングし、トルエンの濃度をガスクロマトグラフ[島津製作所社製「ＧＣ−１４Ａ」]にて測定した。そして照射時間に対するトルエンの濃度から一次反応速度定数を算出し、これをトルエン分解能として評価した。この一次反応速度定数が大きいほど、トルエンの分解能、すなわち光触媒活性が高いと言える。 Next, the sample for photocatalytic activity measurement is placed in a gas bag (internal volume 1 L) together with the petri dish, and then the inside of the gas bag is evacuated, and then the volume ratio of oxygen to nitrogen is 1: 4. Then, 0.6 L of the mixed gas was sealed, and nitrogen gas containing toluene was sealed therein so that the concentration of toluene in the gas bag was 20 ppm, and kept in the dark at room temperature for 1 hour. Then, using a commercially available white fluorescent lamp as the light source, irradiate the light from the fluorescent lamp from the outside of the gas bag so that the illuminance near the measurement sample is 6000 lx [measured with the illuminometer “T-10” manufactured by Minolta Co., Ltd.] The decomposition reaction of toluene was performed. At this time, the intensity of ultraviolet rays in the vicinity of the measurement sample was 40 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 was sampled every 1.5 hours after the light irradiation of the fluorescent lamp was started, and the concentration of toluene was measured with a gas chromatograph [“GC-14A” manufactured by Shimadzu Corporation]. The first-order reaction rate constant was calculated from the concentration of toluene with respect to the irradiation time, and this was evaluated as toluene resolution. It can be said that the higher the first-order reaction rate constant, the higher the resolution of toluene, that is, the photocatalytic activity.
（製造例１−酸化チタン粒子分散液の調製）
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。
粉砕メディア：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
流量 ：０．２５Ｌ／分
処理時間 ：約７６分
処理温度 ：２０℃
(Production Example 1-Preparation of titanium oxide particle dispersion)
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.
Grinding media: 1.85 kg of zirconia beads with a diameter of 0.05 mm
Stirring speed: peripheral speed 8.1m / sec
Flow rate: 0.25 L / min
Processing time: Approximately 76 minutes
Processing temperature: 20 ° C
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。 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.
（製造例２−酸化タングステン粒子分散液の調製）
分散媒としてイオン交換水４ｋｇに、酸化タングステン粒子（日本無機化学製）１ｋｇを加えて混合して混合物を得た。この混合物を湿式媒体撹拌ミル[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。
粉砕メディア：直径０．０５ｍｍのジルコニア製ビーズ１．８５ｋｇ
撹拌速度 ：周速１２．６ｍ／秒
流量 ：０．２５Ｌ／分
処理時間 ：約５０分
(Production Example 2-Preparation of tungsten oxide particle dispersion)
1 kg of tungsten oxide particles (manufactured by Nippon Inorganic Chemical Co., Ltd.) was added to 4 kg of ion exchange water as a dispersion medium and mixed to obtain a mixture. This mixture was subjected to a dispersion treatment under the following conditions using a wet medium stirring mill [“Ultra Apex Mill UAM-1” manufactured by Kotobuki Giken Co., Ltd.] to obtain a tungsten oxide particle dispersion.
Grinding media: 1.85 kg of zirconia beads with a diameter of 0.05 mm
Stirring speed: peripheral speed 12.6m / sec
Flow rate: 0.25 L / min
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、同じピーク形状であり、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２４時間保持したところ、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. In addition, when the mixture before the dispersion treatment was similarly vacuum-dried to obtain a solid content, and the solid content of the mixture before the dispersion treatment and the solid content after the dispersion treatment were measured and compared, The peak shape was the same, and no change in crystal form due to dispersion treatment was observed. At this time, when the obtained dispersion was kept at 20 ° C. for 24 hours, no solid-liquid separation was observed during storage.
この酸化タングステン粒子分散液にヘキサクロロ白金酸（Ｈ2ＰｔＣｌ6）の水溶液をヘキサクロロ白金酸が白金原子換算で酸化タングステン粒子の使用量１００質量部に対して０．１２質量部になるように加え、原料分散液としてヘキサクロロ白金酸含有酸化タングステン粒子分散液を得た。この分散液１００質量部中に含まれる固形分（酸化タングステン粒子の量）は、１７．６質量部（固形分濃度１７．６質量％）であった。この分散液のｐＨは２．０であった。 To this tungsten oxide particle dispersion, an aqueous solution of hexachloroplatinic acid (H 2 PtCl 6 ) was added so that hexachloroplatinic acid was 0.12 parts by mass with respect to 100 parts by mass of tungsten oxide particles in terms of platinum atoms, A hexachloroplatinic acid-containing tungsten oxide particle dispersion was obtained as a raw material dispersion. The solid content (amount of tungsten oxide particles) contained in 100 parts by mass of this dispersion was 17.6 parts by mass (solid content concentration 17.6% by mass). The pH of this dispersion was 2.0.
次いで、ｐＨ電極と、このｐＨ電極に接続され０．１質量％のアンモニア水を供給してｐＨを一定に調整する制御機構を有するｐＨコントローラ（ｐＨ＝３に設定）とを備え、水中殺菌灯[三共電気製「ＧＬＤ１５ＭＱ」]を設置したガラス管（内径３７ｍｍ、高さ３６０ｍｍ）からなる光照射装置で前記ヘキサクロロ白金酸含有酸化タングステン粒子分散液５００ｇを毎分１Ｌの速度で循環させ、光照射（紫外線）を行いながら、ｐＨコントローラーによりアンモニア水を加えてヘキサクロロ白金酸含有酸化タングステン粒子分散液のｐＨを３．０にした。光照射を行った時間は１．５時間であった。その後、引き続き循環させながら、更に５０質量％のメタノール水溶液を１５ｇ加えて、光（紫外線）を１．５時間照射し、白金担持酸化タングステン粒子分散液を得た。光照射中、ｐＨコントローラーによりアンモニア水が加えられ、分散液のｐＨは３．０に維持された。光照射前および光照射中に消費したアンモニア水の合計量は７１．６ｇであった。 Next, a pH electrode and a pH controller (set to pH = 3) connected to the pH electrode and having a control mechanism for adjusting the pH to a constant level by supplying 0.1% by mass of ammonia water, 500 g of the hexachloroplatinic acid-containing tungsten oxide particle dispersion was circulated at a rate of 1 L / min with a light irradiation device comprising a glass tube (inner diameter: 37 mm, height: 360 mm) provided with “Sankyo Denki“ GLD15MQ ””. While performing (ultraviolet rays), aqueous ammonia was added by a pH controller to adjust the pH of the hexachloroplatinic acid-containing tungsten oxide particle dispersion to 3.0. The time of light irradiation was 1.5 hours. Thereafter, while continuously circulating, 15 g of a 50% by mass aqueous methanol solution was further added and irradiated with light (ultraviolet rays) for 1.5 hours to obtain a platinum-supported tungsten oxide particle dispersion. During the light irradiation, aqueous ammonia was added by a pH controller, and the pH of the dispersion was maintained at 3.0. The total amount of ammonia water consumed before and during light irradiation was 71.6 g.
得られた白金担持酸化タングステン粒子分散液を２０℃で２４時間保管したところ、保管後に固液分離は見られなかった。 When the obtained platinum-supported tungsten oxide particle dispersion was stored at 20 ° C. for 24 hours, no solid-liquid separation was observed after storage.
（製造例３−光触媒体原料分散液の調製）
製造例１で得た酸化チタン粒子分散液と、製造例２で得た白金担持酸化タングステン粒子分散液を、酸化チタン粒子と酸化タングステン粒子との比率が１：１（質量比）となるように混合して（これにより、分散液中の白金の含有量は、白金原子換算で、酸化チタン粒子と酸化タングステン粒子との合計使用量１００質量部に対して０．０６質量部となった）、酸化チタン粒子および酸化タングステン粒子の白金含有分散液を得た。この分散液１００質量部中に含まれる固形分（酸化チタン粒子と酸化タングステン粒子との合計量）は５質量部（固形分濃度５質量％）であり、ｐＨは４．３であった。
(Production Example 3-Preparation of Photocatalyst Material Dispersion)
In the titanium oxide particle dispersion obtained in Production Example 1 and the platinum-supported tungsten oxide particle dispersion obtained in Production Example 2, the ratio of titanium oxide particles to tungsten oxide particles is 1: 1 (mass ratio). Mixing (by this, the platinum content in the dispersion was 0.06 parts by mass in terms of platinum atoms with respect to 100 parts by mass of the total amount of titanium oxide particles and tungsten oxide particles) A platinum-containing dispersion of titanium oxide particles and tungsten oxide particles was obtained. The solid content (total amount of titanium oxide particles and tungsten oxide particles) contained in 100 parts by mass of this dispersion was 5 parts by mass (solid content concentration 5% by mass), and the pH was 4.3.
（実施例１）
製造例３で得られた酸化チタン粒子および酸化タングステン粒子の白金含有分散液に、ヨウ素原子換算の濃度が１質量％のヨウ素酸水溶液を、ヨウ素の量がヨウ素原子換算で酸化チタン粒子および酸化タングステン粒子の合計量１００質量部に対して０．０３質量部となるように添加して、本発明の光触媒体分散液を得た。この光触媒体分散液を２０℃で２４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。
Example 1
To the platinum-containing dispersion of titanium oxide particles and tungsten oxide particles obtained in Production Example 3, an iodic acid aqueous solution having a concentration of 1% by mass in terms of iodine atoms, and titanium oxide particles and tungsten oxides in terms of iodine atoms in terms of iodine atoms It added so that it might become 0.03 mass part with respect to 100 mass parts of total amounts of particle | grains, and the photocatalyst body dispersion liquid of this invention was obtained. When this photocatalyst dispersion was stored at 20 ° C. for 24 hours, no solid-liquid separation was observed during storage.
得られた光触媒体分散液を用いて形成した光触媒体層の光触媒活性を評価したところ、一次反応速度定数は０．４８７ｈ-1であった。 When the photocatalytic activity of the photocatalyst layer formed using the obtained photocatalyst dispersion liquid was evaluated, the first-order rate constant was 0.487 h −1 .
（実施例２）
実施例１で、ヨウ素の量がヨウ素原子換算で酸化チタン粒子および酸化タングステン粒子の合計量１００質量部に対して０．１質量部となるようにヨウ素酸水溶液を添加した以外は、実施例１と同様にして光触媒体分散液を調整した。得られた光触媒体分散液を２０℃で２４時間保管したところ、保管後に固液分離は見られなかった。
(Example 2)
Example 1 except that the iodic acid aqueous solution was added so that the amount of iodine in Example 1 was 0.1 parts by mass with respect to 100 parts by mass of the total amount of titanium oxide particles and tungsten oxide particles in terms of iodine atoms. The photocatalyst dispersion liquid was prepared in the same manner as described above. When the obtained photocatalyst dispersion liquid was stored at 20 ° C. for 24 hours, no solid-liquid separation was observed after storage.
得られた光触媒体分散液を用いて形成した光触媒体層の光触媒活性を評価したところ、一次反応速度定数は０．５０７ｈ-1であった。 When the photocatalytic activity of the photocatalyst layer formed using the resulting photocatalyst dispersion liquid was evaluated, the first-order rate constant was 0.507 h −1 .
（実施例３）
実施例１で、ヨウ素の量がヨウ素原子換算で酸化チタン粒子および酸化タングステン粒子の合計量１００質量部に対して０．３質量部となるようにヨウ素酸水溶液を添加した以外は、実施例１と同様にして光触媒体分散液を調整した。得られた光触媒体分散液を２０℃で２４時間保管したところ、保管後に固液分離は見られなかった。
(Example 3)
Example 1 except that the iodic acid aqueous solution was added so that the amount of iodine was 0.3 parts by mass with respect to 100 parts by mass of the total amount of titanium oxide particles and tungsten oxide particles in terms of iodine atoms in Example 1. The photocatalyst dispersion liquid was prepared in the same manner as described above. When the obtained photocatalyst dispersion liquid was stored at 20 ° C. for 24 hours, no solid-liquid separation was observed after storage.
得られた光触媒体分散液を用いて形成した光触媒体層の光触媒活性を評価したところ、一次反応速度定数は０．４９２ｈ-1であった。 When the photocatalytic activity of the photocatalyst layer formed using the obtained photocatalyst dispersion liquid was evaluated, the first-order reaction rate constant was 0.492 h −1 .
（実施例４）
実施例１で、ヨウ素の量がヨウ素原子換算で酸化チタン粒子および酸化タングステン粒子の合計量１００質量部に対して１．０質量部となるようにヨウ素酸水溶液を添加した以外は、実施例１と同様にして光触媒体分散液を調整した。得られた光触媒体分散液を２０℃で２４時間保管したところ、保管後に固液分離は見られなかった。
Example 4
Example 1 except that the iodic acid aqueous solution was added so that the amount of iodine in Example 1 was 1.0 part by mass with respect to 100 parts by mass of the total amount of titanium oxide particles and tungsten oxide particles in terms of iodine atoms. The photocatalyst dispersion liquid was prepared in the same manner as described above. When the obtained photocatalyst dispersion liquid was stored at 20 ° C. for 24 hours, no solid-liquid separation was observed after storage.
得られた光触媒体分散液を用いて形成した光触媒体層の光触媒活性を評価したところ、一次反応速度定数は０．３９３ｈ-1であった。 When the photocatalytic activity of the photocatalyst layer formed using the obtained photocatalyst dispersion liquid was evaluated, the first-order rate constant was 0.393 h −1 .
（実施例５）
製造例３で得られた酸化チタン粒子および酸化タングステン粒子の白金含有分散液に、ヨウ素原子換算の濃度が１質量％のヨウ化カリウム酸水溶液を、ヨウ素の量がヨウ素原子換算で酸化チタン粒子および酸化タングステン粒子の合計量１００質量部に対して０．１質量部となるように添加して、本発明の光触媒体分散液を得た。この光触媒体分散液を２０℃で２４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。
(Example 5)
To the platinum-containing dispersion of titanium oxide particles and tungsten oxide particles obtained in Production Example 3, a potassium iodide aqueous solution having a concentration of 1% by mass in terms of iodine atoms, titanium oxide particles in terms of iodine atoms in terms of iodine amount, and It added so that it might become 0.1 mass part with respect to 100 mass parts of total amounts of a tungsten oxide particle, and the photocatalyst body dispersion liquid of this invention was obtained. When this photocatalyst dispersion was stored at 20 ° C. for 24 hours, no solid-liquid separation was observed during storage.
得られた光触媒体分散液を用いて形成した光触媒体層の光触媒活性を評価したところ、一次反応速度定数は０．４４６ｈ-1であった。 When the photocatalytic activity of the photocatalyst layer formed using the obtained photocatalyst dispersion liquid was evaluated, the first-order rate constant was 0.446 h −1 .
（実施例６）
実施例５で、ヨウ素の量がヨウ素原子換算で酸化チタン粒子および酸化タングステン粒子の合計量１００質量部に対して０．３質量部となるようにヨウ化カリウム水溶液を添加した以外は、実施例５と同様にして光触媒体分散液を調整した。得られた光触媒体分散液を２０℃で２４時間保管したところ、保管後に固液分離は見られなかった。
(Example 6)
In Example 5, except that the potassium iodide aqueous solution was added so that the amount of iodine was 0.3 parts by mass with respect to 100 parts by mass of the total amount of titanium oxide particles and tungsten oxide particles in terms of iodine atoms. In the same manner as in 5, a photocatalyst dispersion liquid was prepared. When the obtained photocatalyst dispersion liquid was stored at 20 ° C. for 24 hours, no solid-liquid separation was observed after storage.
得られた光触媒体分散液を用いて形成した光触媒体層の光触媒活性を評価したところ、一次反応速度定数は０．４２４ｈ-1であった。 When the photocatalytic activity of the photocatalyst layer formed using the obtained photocatalyst dispersion liquid was evaluated, the first-order rate constant was 0.424 h −1 .
（実施例７）
実施例５で、ヨウ素の量がヨウ素原子換算で酸化チタン粒子および酸化タングステン粒子の合計量１００質量部に対して１．０質量部となるようにヨウ化カリウム水溶液を添加した以外は、実施例５と同様にして光触媒体分散液を調整した。得られた光触媒体分散液を２０℃で２４時間保管したところ、保管後に固液分離は見られなかった。
(Example 7)
In Example 5, except that the potassium iodide aqueous solution was added so that the amount of iodine was 1.0 part by mass with respect to 100 parts by mass of the total amount of titanium oxide particles and tungsten oxide particles in terms of iodine atoms. In the same manner as in 5, a photocatalyst dispersion liquid was prepared. When the obtained photocatalyst dispersion liquid was stored at 20 ° C. for 24 hours, no solid-liquid separation was observed after storage.
得られた光触媒体分散液を用いて形成した光触媒体層の光触媒活性を評価したところ、一次反応速度定数は０．４２５ｈ-1であった。 When the photocatalytic activity of the photocatalyst layer formed using the obtained photocatalyst dispersion liquid was evaluated, the first-order rate constant was 0.425 h −1 .
（実施例８）
製造例３で得られた酸化チタン粒子および酸化タングステン粒子の白金含有分散液に、ヨウ素原子換算の濃度が１質量％のヨウ素酸ナトリウム水溶液を、ヨウ素の量がヨウ素原子換算で酸化チタン粒子および酸化タングステン粒子の合計量１００質量部に対して０．３質量部となるように添加して、本発明の光触媒体分散液を得た。この光触媒体分散液を２０℃で２４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。
(Example 8)
To the platinum-containing dispersion of titanium oxide particles and tungsten oxide particles obtained in Production Example 3, an aqueous solution of sodium iodate having a concentration of 1% by mass in terms of iodine atoms, and titanium oxide particles and oxidation in terms of iodine atoms in terms of iodine atoms It added so that it might become 0.3 mass part with respect to 100 mass parts of total amounts of tungsten particle | grains, and the photocatalyst body dispersion liquid of this invention was obtained. When this photocatalyst dispersion was stored at 20 ° C. for 24 hours, no solid-liquid separation was observed during storage.
得られた光触媒体分散液を用いて形成した光触媒体層の光触媒活性を評価したところ、一次反応速度定数は０．３９４ｈ-1であった。 When the photocatalytic activity of the photocatalyst layer formed using the obtained photocatalyst dispersion liquid was evaluated, the first-order rate constant was 0.394 h −1 .
（実施例９）
製造例３で得られた酸化チタン粒子および酸化タングステン粒子の白金含有分散液に、ヨウ素原子換算の濃度が１質量％のヨウ素酸カリウム水溶液を、ヨウ素の量がヨウ素原子換算で酸化チタン粒子および酸化タングステン粒子の合計量１００質量部に対して０．３質量部となるように添加して、本発明の光触媒体分散液を得た。この光触媒体分散液を２０℃で２４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。
Example 9
To the platinum-containing dispersion of titanium oxide particles and tungsten oxide particles obtained in Production Example 3, an aqueous solution of potassium iodate having a concentration of 1% by mass in terms of iodine atoms, and the amount of iodine in terms of iodine atoms and titanium oxide particles and oxidation It added so that it might become 0.3 mass part with respect to 100 mass parts of total amounts of tungsten particle | grains, and the photocatalyst body dispersion liquid of this invention was obtained. When this photocatalyst dispersion was stored at 20 ° C. for 24 hours, no solid-liquid separation was observed during storage.
得られた光触媒体分散液を用いて形成した光触媒体層の光触媒活性を評価したところ、一次反応速度定数は０．４４２ｈ-1であった。 When the photocatalytic activity of the photocatalyst layer formed using the obtained photocatalyst dispersion liquid was evaluated, the first-order rate constant was 0.442 h −1 .
（比較例）
製造例３で得られた酸化チタン粒子および酸化タングステン粒子の白金含有分散液を用いて形成した光触媒体層の光触媒活性を評価したところ、一次反応速度定数は０．２９２ｈ-1であった。
(Comparative example)
When the photocatalytic activity of the photocatalyst layer formed using the platinum-containing dispersion of titanium oxide particles and tungsten oxide particles obtained in Production Example 3 was evaluated, the first-order reaction rate constant was 0.292 h −1 .
上記の実施例および比較例の結果を表１に示す。 The results of the above examples and comparative examples are shown in Table 1.
実施例１〜９は、表１に示すように、酸化チタン粒子および酸化タングステン粒子の白金含有分散液にヨウ素化合物を添加することで、反応速度定数が比較例よりも、３０％以上高くなった。 In Examples 1 to 9, as shown in Table 1, by adding an iodine compound to the platinum-containing dispersion liquid of titanium oxide particles and tungsten oxide particles, the reaction rate constant was 30% or more higher than that of the comparative example. .
（参考例１）
実施例１〜９で得た光触媒体分散液を、天井を構成する天井材の表面に塗布し乾燥させることにより、天井材の表面に光触媒体層を形成することができ、これによって、屋内照明による光照射により屋内空間における揮発性有機物（例えば、ホルムアルデヒド、アセトアルデヒド、アセトン、トルエン等）や悪臭物質の濃度を低減することができ、さらには、黄色ブドウ球菌や大腸菌等の病原菌や、インフルエンザウィルス等のウィルスを死滅させることもできる。
(Reference Example 1)
By applying the photocatalyst dispersion liquid obtained in Examples 1 to 9 to the surface of the ceiling material constituting the ceiling and drying it, a photocatalyst layer can be formed on the surface of the ceiling material. Can reduce the concentration of volatile organic substances (for example, formaldehyde, acetaldehyde, acetone, toluene, etc.) and malodorous substances in indoor spaces, and pathogens such as Staphylococcus aureus and Escherichia coli, influenza viruses, etc. Can kill the virus.
（参考例２）
実施例１〜９で得た光触媒体分散液を、屋内の壁面に施工されたタイルに塗布し乾燥させることにより、タイル表面に光触媒体層を形成することができ、これによって、屋内照明による光照射により屋内空間における揮発性有機物（例えば、ホルムアルデヒド、アセトアルデヒド、アセトン、トルエン等）や悪臭物質の濃度を低減することができ、さらには、黄色ブドウ球菌や大腸菌等の病原菌や、インフルエンザウィルス等のウィルスを死滅させることもできる。
(Reference Example 2)
By applying and drying the photocatalyst dispersion liquid obtained in Examples 1 to 9 on a tile constructed on an indoor wall surface, a photocatalyst layer can be formed on the tile surface. Irradiation can reduce the concentration of volatile organic substances (for example, formaldehyde, acetaldehyde, acetone, toluene, etc.) and malodorous substances in indoor spaces, and pathogens such as Staphylococcus aureus and Escherichia coli, and viruses such as influenza virus Can also be killed.
（参考例３）
実施例１〜９で得た光触媒体分散液を、窓ガラスの屋内側表面に塗布し乾燥させることにより、ガラス表面に光触媒体層を形成することができ、これによって、屋内照明による光照射により屋内空間における揮発性有機物（例えば、ホルムアルデヒド、アセトアルデヒド、アセトン、トルエン等）や悪臭物質の濃度を低減することができ、さらには、黄色ブドウ球菌や大腸菌等の病原菌や、インフルエンザウィルス等のウィルスを死滅させることもできる。
(Reference Example 3)
By applying and drying the photocatalyst dispersion liquid obtained in Examples 1 to 9 on the indoor side surface of the window glass, a photocatalyst layer can be formed on the glass surface. It can reduce the concentration of volatile organic substances (for example, formaldehyde, acetaldehyde, acetone, toluene, etc.) and malodorous substances in indoor spaces, and kill pathogenic bacteria such as Staphylococcus aureus and Escherichia coli, and viruses such as influenza virus. It can also be made.
（参考例４）
実施例１〜９で得た光触媒体分散液を、壁紙に塗布し乾燥させることにより、壁紙の表面に光触媒体層を形成することができ、さらにこの壁紙を屋内の壁面に施工することによって、屋内照明による光照射により屋内空間における揮発性有機物（例えば、ホルムアルデヒド、アセトアルデヒド、アセトン、トルエン等）や悪臭物質の濃度を低減することができ、さらには、黄色ブドウ球菌や大腸菌等の病原菌や、インフルエンザウィルス等のウィルスを死滅させることもできる。
(Reference Example 4)
By applying the photocatalyst dispersion liquid obtained in Examples 1 to 9 to the wallpaper and drying it, a photocatalyst layer can be formed on the surface of the wallpaper, and by further applying this wallpaper to the indoor wall surface, Light irradiation by indoor lighting can reduce the concentration of volatile organic substances (for example, formaldehyde, acetaldehyde, acetone, toluene, etc.) and malodorous substances in indoor spaces, and pathogens such as Staphylococcus aureus and Escherichia coli, and influenza Viruses such as viruses can also be killed.
（参考例５）
実施例１〜９で得た光触媒体分散液を、屋内の床面に塗布し乾燥させることにより、床面に光触媒体層を形成することができ、これによって、屋内照明による光照射により屋内空間における揮発性有機物（例えば、ホルムアルデヒド、アセトアルデヒド、アセトン、トルエン等）や悪臭物質の濃度を低減することができ、さらには、黄色ブドウ球菌や大腸菌等の病原菌や、インフルエンザウィルス等のウィルスを死滅させることもできる。
(Reference Example 5)
By applying the photocatalyst dispersion liquid obtained in Examples 1 to 9 to the indoor floor surface and drying it, a photocatalyst layer can be formed on the floor surface. Can reduce the concentration of volatile organic substances (such as formaldehyde, acetaldehyde, acetone, toluene, etc.) and malodorous substances, and also kill pathogenic bacteria such as Staphylococcus aureus and Escherichia coli, and viruses such as influenza virus You can also.
（参考例６）
実施例１〜９で得た光触媒体分散液を、自動車用インストルメントパネル、自動車用シート、自動車の天井材などの自動車内装材の表面に塗布し乾燥させることにより、これら自動車内装材の表面に光触媒体層を形成することができ、これによって、車内照明による光照射により車内空間における揮発性有機物（例えば、ホルムアルデヒド、アセトアルデヒド、アセトン、トルエン等）や悪臭物質の濃度を低減することができ、さらには、黄色ブドウ球菌や大腸菌等の病原菌や、インフルエンザウィルス等のウィルスを死滅させることもできる。
(Reference Example 6)
By applying the photocatalyst dispersion liquid obtained in Examples 1 to 9 to the surface of an automobile interior material such as an automotive instrument panel, an automobile seat, or an automobile ceiling material, and drying it, the surface of these automobile interior materials is obtained. A photocatalyst layer can be formed, whereby the concentration of volatile organic substances (for example, formaldehyde, acetaldehyde, acetone, toluene, etc.) and malodorous substances in the interior space can be reduced by light irradiation by interior illumination. Can kill pathogenic bacteria such as Staphylococcus aureus and Escherichia coli, and viruses such as influenza virus.
（参考例７）
実施例１〜９で得た光触媒体分散液を、エアコンの表面に塗布し乾燥させることにより、エアコンの表面に光触媒体層を形成することができ、これによって、屋内照明による光照射により屋内空間における揮発性有機物（例えば、ホルムアルデヒド、アセトアルデヒド、アセトン、トルエン等）や悪臭物質の濃度を低減することができ、さらには、黄色ブドウ球菌や大腸菌等の病原菌や、インフルエンザウィルス等のウィルスを死滅させることもできる。
(Reference Example 7)
By applying the photocatalyst dispersion liquid obtained in Examples 1 to 9 to the surface of the air conditioner and drying it, a photocatalyst layer can be formed on the surface of the air conditioner. Can reduce the concentration of volatile organic substances (such as formaldehyde, acetaldehyde, acetone, toluene, etc.) and malodorous substances, and also kill pathogenic bacteria such as Staphylococcus aureus and Escherichia coli, and viruses such as influenza virus You can also.
（参考例８）
実施例１〜９で得た光触媒体分散液を、冷蔵庫の庫内に塗布し乾燥させることにより、冷蔵庫内に光触媒体層を形成することができ、これによって、屋内照明や冷蔵庫内の光源による光照射により冷蔵庫内における揮発性有機物（例えば、エチレン等）や悪臭物質の濃度を低減することができ、さらには、黄色ブドウ球菌や大腸菌等の病原菌や、インフルエンザウィルス等のウィルスを死滅させることもできる。
(Reference Example 8)
By applying the photocatalyst dispersion liquid obtained in Examples 1 to 9 in the refrigerator and drying it, a photocatalyst layer can be formed in the refrigerator. Light irradiation can reduce the concentration of volatile organic substances (such as ethylene) and malodorous substances in the refrigerator, and it can also kill pathogenic bacteria such as Staphylococcus aureus and Escherichia coli, and viruses such as influenza virus. it can.
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| JP2016538110A (en) * | 2013-09-26 | 2016-12-08 | エルジー・ハウシス・リミテッドＬｇ Ｈａｕｓｙｓ，Ｌｔｄ． | LED photocatalyst module using photocatalyst material |
| JP2016137463A (en) * | 2015-01-28 | 2016-08-04 | シャープ株式会社 | Photocatalytic material |
| JP2019069450A (en) * | 2019-02-18 | 2019-05-09 | シャープ株式会社 | Photocatalytic material |
| CN111495434A (en) * | 2020-04-21 | 2020-08-07 | 杭州职业技术学院 | Thermosensitive photocatalytic spray gel and preparation method thereof |
| CN111495434B (en) * | 2020-04-21 | 2023-01-31 | 杭州职业技术学院 | Thermosensitive photocatalytic spray gel and preparation method thereof |
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