JPH07222928A - Production of member having catalyst containing metal fine particles - Google Patents
Production of member having catalyst containing metal fine particlesInfo
- Publication number
- JPH07222928A JPH07222928A JP6337417A JP33741794A JPH07222928A JP H07222928 A JPH07222928 A JP H07222928A JP 6337417 A JP6337417 A JP 6337417A JP 33741794 A JP33741794 A JP 33741794A JP H07222928 A JPH07222928 A JP H07222928A
- Authority
- JP
- Japan
- Prior art keywords
- fine particles
- particles
- metal fine
- photocatalytic activity
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 86
- 239000002184 metal Substances 0.000 title claims abstract description 86
- 239000010419 fine particle Substances 0.000 title claims abstract description 67
- 239000003054 catalyst Substances 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 230000001699 photocatalysis Effects 0.000 claims abstract description 104
- 239000002245 particle Substances 0.000 claims abstract description 102
- 239000000463 material Substances 0.000 claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 39
- 150000003839 salts Chemical class 0.000 claims abstract description 33
- 239000000243 solution Substances 0.000 claims description 43
- 239000000758 substrate Substances 0.000 claims description 40
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 23
- 239000001301 oxygen Substances 0.000 claims description 23
- 229910052760 oxygen Inorganic materials 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 16
- 239000002923 metal particle Substances 0.000 claims description 11
- 229910001111 Fine metal Inorganic materials 0.000 claims description 10
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims 1
- 150000002978 peroxides Chemical class 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 7
- 238000013461 design Methods 0.000 abstract description 6
- 229920005989 resin Polymers 0.000 description 72
- 239000011347 resin Substances 0.000 description 72
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 61
- 239000002585 base Substances 0.000 description 42
- 239000011230 binding agent Substances 0.000 description 42
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 36
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 27
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 24
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 22
- 230000000844 anti-bacterial effect Effects 0.000 description 22
- 229910052709 silver Inorganic materials 0.000 description 21
- 239000004332 silver Substances 0.000 description 21
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 20
- 238000000576 coating method Methods 0.000 description 19
- 239000000203 mixture Substances 0.000 description 18
- 229920001187 thermosetting polymer Polymers 0.000 description 18
- 239000007864 aqueous solution Substances 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- 239000010949 copper Substances 0.000 description 16
- 229910052802 copper Inorganic materials 0.000 description 16
- 239000011941 photocatalyst Substances 0.000 description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 16
- 239000002781 deodorant agent Substances 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 14
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 238000001723 curing Methods 0.000 description 13
- 239000010409 thin film Substances 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 12
- 239000000725 suspension Substances 0.000 description 11
- 239000011344 liquid material Substances 0.000 description 10
- 229910052763 palladium Inorganic materials 0.000 description 10
- 238000005507 spraying Methods 0.000 description 10
- 239000007858 starting material Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 9
- 229910052737 gold Inorganic materials 0.000 description 9
- 239000010931 gold Substances 0.000 description 9
- 230000001678 irradiating effect Effects 0.000 description 9
- 229910052725 zinc Inorganic materials 0.000 description 9
- 239000011701 zinc Substances 0.000 description 9
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 229910017052 cobalt Inorganic materials 0.000 description 8
- 239000010941 cobalt Substances 0.000 description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 8
- 229910052697 platinum Inorganic materials 0.000 description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000003085 diluting agent Substances 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- -1 inorganic acid salt Chemical class 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 229910001961 silver nitrate Inorganic materials 0.000 description 7
- 150000004703 alkoxides Chemical class 0.000 description 6
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 6
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 6
- 229940112669 cuprous oxide Drugs 0.000 description 6
- 230000001877 deodorizing effect Effects 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 230000003373 anti-fouling effect Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000003618 dip coating Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 230000006698 induction Effects 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 238000007540 photo-reduction reaction Methods 0.000 description 4
- 238000013032 photocatalytic reaction Methods 0.000 description 4
- 239000005871 repellent Substances 0.000 description 4
- 230000008719 thickening Effects 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 235000014692 zinc oxide Nutrition 0.000 description 4
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 3
- 229910021612 Silver iodide Inorganic materials 0.000 description 3
- 230000001580 bacterial effect Effects 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 238000004042 decolorization Methods 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 230000003100 immobilizing effect Effects 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229940045105 silver iodide Drugs 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 150000001298 alcohols Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000004332 deodorization Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000005566 electron beam evaporation Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- UACOWKKZSFRPRK-UHFFFAOYSA-L Br[Au]Br Chemical compound Br[Au]Br UACOWKKZSFRPRK-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UCOBJOONLGFYMF-UHFFFAOYSA-L Cl[Au]Cl Chemical compound Cl[Au]Cl UCOBJOONLGFYMF-UHFFFAOYSA-L 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 241001302584 Escherichia coli str. K-12 substr. W3110 Species 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 239000004277 Ferrous carbonate Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910005540 GaP Inorganic materials 0.000 description 1
- 229910021575 Iron(II) bromide Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- ZSILVJLXKHGNPL-UHFFFAOYSA-L S(=S)(=O)([O-])[O-].[Ag+2] Chemical compound S(=S)(=O)([O-])[O-].[Ag+2] ZSILVJLXKHGNPL-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 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
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- AVWLPUQJODERGA-UHFFFAOYSA-L cobalt(2+);diiodide Chemical compound [Co+2].[I-].[I-] AVWLPUQJODERGA-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- BZRRQSJJPUGBAA-UHFFFAOYSA-L cobalt(ii) bromide Chemical compound Br[Co]Br BZRRQSJJPUGBAA-UHFFFAOYSA-L 0.000 description 1
- IQYVXTLKMOTJKI-UHFFFAOYSA-L cobalt(ii) chlorate Chemical compound [Co+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O IQYVXTLKMOTJKI-UHFFFAOYSA-L 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- RFKZUAOAYVHBOY-UHFFFAOYSA-M copper(1+);acetate Chemical compound [Cu+].CC([O-])=O RFKZUAOAYVHBOY-UHFFFAOYSA-M 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 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
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- WIVXEZIMDUGYRW-UHFFFAOYSA-L copper(i) sulfate Chemical compound [Cu+].[Cu+].[O-]S([O-])(=O)=O WIVXEZIMDUGYRW-UHFFFAOYSA-L 0.000 description 1
- IJCCOEGCVILSMZ-UHFFFAOYSA-L copper;dichlorate Chemical compound [Cu+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O IJCCOEGCVILSMZ-UHFFFAOYSA-L 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001017 electron-beam sputter deposition Methods 0.000 description 1
- 229940023064 escherichia coli Drugs 0.000 description 1
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 description 1
- 229940046149 ferrous bromide Drugs 0.000 description 1
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 description 1
- 235000019268 ferrous carbonate Nutrition 0.000 description 1
- 229960004652 ferrous carbonate Drugs 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 229940076136 ferrous iodide Drugs 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- HZXMRANICFIONG-UHFFFAOYSA-N gallium phosphide Chemical compound [Ga]#P HZXMRANICFIONG-UHFFFAOYSA-N 0.000 description 1
- GKYAEPNRZNDEMO-UHFFFAOYSA-L gold(1+);sulfate Chemical compound [Au+].[Au+].[O-]S([O-])(=O)=O GKYAEPNRZNDEMO-UHFFFAOYSA-L 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- JRSGPUNYCADJCW-UHFFFAOYSA-K iron(3+);trichlorate Chemical compound [Fe+3].[O-]Cl(=O)=O.[O-]Cl(=O)=O.[O-]Cl(=O)=O JRSGPUNYCADJCW-UHFFFAOYSA-K 0.000 description 1
- HEJPGFRXUXOTGM-UHFFFAOYSA-K iron(3+);triiodide Chemical compound [Fe+3].[I-].[I-].[I-] HEJPGFRXUXOTGM-UHFFFAOYSA-K 0.000 description 1
- 229910000015 iron(II) carbonate Inorganic materials 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 description 1
- BQZGVMWPHXIKEQ-UHFFFAOYSA-L iron(ii) iodide Chemical compound [Fe+2].[I-].[I-] BQZGVMWPHXIKEQ-UHFFFAOYSA-L 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- TVWWSIKTCILRBF-UHFFFAOYSA-N molybdenum trisulfide Chemical compound S=[Mo](=S)=S TVWWSIKTCILRBF-UHFFFAOYSA-N 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 description 1
- RZLUIDROFNIMHF-UHFFFAOYSA-L nickel(2+);dichlorate Chemical compound [Ni+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O RZLUIDROFNIMHF-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- BFSQJYRFLQUZKX-UHFFFAOYSA-L nickel(ii) iodide Chemical compound I[Ni]I BFSQJYRFLQUZKX-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 235000019645 odor Nutrition 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 239000002504 physiological saline solution Substances 0.000 description 1
- PQTLYDQECILMMB-UHFFFAOYSA-L platinum(2+);sulfate Chemical compound [Pt+2].[O-]S([O-])(=O)=O PQTLYDQECILMMB-UHFFFAOYSA-L 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 description 1
- LFAGQMCIGQNPJG-UHFFFAOYSA-N silver cyanide Chemical compound [Ag+].N#[C-] LFAGQMCIGQNPJG-UHFFFAOYSA-N 0.000 description 1
- 229940098221 silver cyanide Drugs 0.000 description 1
- 229940096017 silver fluoride Drugs 0.000 description 1
- REYHXKZHIMGNSE-UHFFFAOYSA-M silver monofluoride Chemical compound [F-].[Ag+] REYHXKZHIMGNSE-UHFFFAOYSA-M 0.000 description 1
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- GTLDTDOJJJZVBW-UHFFFAOYSA-N zinc cyanide Chemical compound [Zn+2].N#[C-].N#[C-] GTLDTDOJJJZVBW-UHFFFAOYSA-N 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、タイル、ガラス
（鏡）、衛生陶器あるいは樹脂板等の表面に、下地の
色、模様等のデザインを活かしつつ抗菌、脱臭、汚れ防
止等の効果を有する金属粒子と光触媒の混合物層を形成
する方法に関する。FIELD OF THE INVENTION The present invention has effects such as antibacterial, deodorant, and stain-proof on the surface of tiles, glass (mirrors), sanitary ware, resin plates, etc. while utilizing the design of the background color, pattern, etc. The present invention relates to a method for forming a mixture layer of metal particles and a photocatalyst.
【０００２】[0002]
【従来技術】近年、抗菌、防臭に関する意識が高まり、
種々の提案がなされている。その１つの方法に光触媒を
利用した方法がある。2. Description of the Related Art In recent years, awareness of antibacterial and deodorant has increased,
Various proposals have been made. One of the methods is a method using a photocatalyst.
【０００３】例えば、特公平５−５０２９４号におい
て、光半導体微粒子を基材表面に固定化してなる光滅菌
性充填材を有することを特徴とする滅菌性リアクターが
開示されており、それにより３時間で９９％以上の滅菌
に成功している。For example, Japanese Examined Patent Publication No. 5-50294 discloses a sterilizable reactor characterized by having a photosterilizable filler formed by fixing optical semiconductor fine particles on the surface of a base material, and thereby for 3 hours. Has successfully sterilized more than 99%.
【０００４】しかし、上記のものは高分子物質や塵芥の
混合物が、光触媒反応を起こす触媒である半導体表面に
付着し、これを覆ってしまうため、触媒まで紫外線が達
せず、触媒がエネルギーを受けにくくなり、光触媒反応
が低下し、反応劣化を引き起こすのである。そこで、特
公平６−７９０５号には、半導体からなる光触媒層と、
それに対向して設けられた紫外線灯および発熱体と、送
風機からなり、光触媒層全体が順次加熱されるように、
光触媒層あるいは発熱体、または光触媒層及び発熱体が
移動する光触媒による脱臭装置が開示されているが、光
触媒層の活性再生手段を要することから脱臭装置が複雑
化してしまう。However, in the above, a mixture of polymer substances and dust adheres to and covers the surface of the semiconductor, which is a catalyst that causes a photocatalytic reaction, so that ultraviolet rays do not reach the catalyst and the catalyst receives energy. It becomes difficult, the photocatalytic reaction is lowered, and the reaction is deteriorated. Therefore, in Japanese Patent Publication No. 6-7905, a photocatalyst layer made of a semiconductor,
It consists of an ultraviolet lamp and a heating element provided opposite to it, and a blower so that the entire photocatalyst layer is heated sequentially,
A deodorizing device using a photocatalyst layer or a heating element, or a photocatalyst in which the photocatalyst layer and the heating element move has been disclosed, but the deodorizing device becomes complicated because an active regeneration means of the photocatalyst layer is required.
【０００５】また、光触媒層を構成する物質が酸化チタ
ンである場合には、９００℃以上の高温で光触媒活性の
高いアナターゼ型から光触媒活性の低いルチル型へと相
転移してしまう。したがって、熱処理のみにより酸化チ
タン粒子間を固相焼結で形成したネック部で結合させよ
うとすると、かなり小さな微粒の酸化チタンを出発原料
にして、低温で撓結させないかぎり、ルチル型へと相転
移して光触媒活性が低下してしまう。Further, when the material constituting the photocatalytic layer is titanium oxide, the phase transitions from anatase type having high photocatalytic activity to rutile type having low photocatalytic activity at a high temperature of 900 ° C. or higher. Therefore, if it is attempted to bond the titanium oxide particles by the neck portion formed by solid-phase sintering only by heat treatment, it becomes a rutile type unless titanium oxide of a fairly small particle is used as a starting material and the titanium oxide is flexed at low temperature. The photocatalytic activity is reduced by the transfer.
【０００６】[0006]
【発明が解決すべき課題】上記２つの問題を同時に解決
する方法として、光触媒活性を有する微粒子の活性点を
銀、銅、白金、パラジウム、金、ニッケル、鉄、コバル
ト、亜鉛等の金属微粒子で覆う方法がある。しかし、か
かる金属は有色金属であるため、多量に塗布すると基材
の表面に固有の色が付いてしまい、基材の色、模様等の
デザインを損なってしまう。As a method for solving the above two problems at the same time, the active sites of photocatalytic fine particles are made of metal fine particles such as silver, copper, platinum, palladium, gold, nickel, iron, cobalt and zinc. There is a way to cover. However, since such a metal is a colored metal, if it is applied in a large amount, the surface of the base material is given a unique color, which impairs the design of the color, pattern, etc. of the base material.
【０００７】[0007]
【課題を解決するための手段】本発明では上記課題を解
決すべく、基材上に光触媒活性を有する粒子と有色の金
属微粒子を固定する工程、前記金属微粒子と溶液または
気体を反応させて少なくとも金属微粒子表面に無色化ま
たは白色化した塩を形成する工程からなることを特徴と
する金属微粒子を含む触媒を有する部材の作製すること
にし、高い光触媒活性を維持しつつ基材の色、模様等の
デザインを損なわない脱色方法を提案することを目的と
する。In the present invention, in order to solve the above problems, a step of fixing particles having photocatalytic activity and colored metal fine particles on a substrate, at least by reacting the metal fine particles with a solution or gas. We decided to produce a member having a catalyst containing metal fine particles, which is characterized by comprising a step of forming a colorless or whitened salt on the surface of the metal fine particles, and the color, pattern, etc. of the substrate while maintaining high photocatalytic activity. The purpose is to propose a bleaching method that does not impair the design.
【０００８】光触媒活性を有する粒子とは、抗菌機能、
脱臭機能等の光触媒機能を発揮するのに充分なバンド・
ギャップを有する半導体粒子のことである。光触媒粒子
が抗菌性を有する理由としては所定以上の電圧が印加さ
れることにより感電死するという説もあるが、一般には
脱臭機能と同様に、光照射時に生じる活性酸素のためと
考えられている。活性酸素を生成するためには、半導体
の伝導帯の位置がバンド・モデルで表すとき水素発生電
位より上方にあり、かつ価電子帯の上端が酸素発生電位
より下方にあることを要する。この条件を満たす半導体
には、酸化チタン、チタン酸ストロンチウム、酸化亜
鉛、炭化ケイ素、リン化ガリウム、硫化カドミウム、セ
レン化カドミウム、三硫化モリブデン等がある。また微
粒化すると伝導帯の位置は上方に移動するので、１〜１
０ｎｍ程度の微粒子ならば、酸化スズ、三酸化タングス
テン、酸化第二鉄、三酸化二ビスマス等も活性酸素を生
成しうる可能性がある。このうち化学的に安定で、安価
に活性の高い微粒子を得ることができることから、アナ
ターゼ型酸化チタンが特に好ましい。Particles having photocatalytic activity mean antibacterial function,
A band that is sufficient to exert photocatalytic functions such as deodorizing function.
It is a semiconductor particle having a gap. There is a theory that the photocatalyst particles have an antibacterial property that they are electrocuted when a voltage higher than a predetermined level is applied, but it is generally considered to be due to active oxygen generated during light irradiation, like the deodorizing function. . In order to generate active oxygen, it is necessary that the position of the conduction band of the semiconductor is above the hydrogen generation potential and the upper end of the valence band is below the oxygen generation potential in the band model. Semiconductors that satisfy this condition include titanium oxide, strontium titanate, zinc oxide, silicon carbide, gallium phosphide, cadmium sulfide, cadmium selenide, molybdenum trisulfide and the like. When atomized, the position of the conduction band moves upward.
If the particles are about 0 nm, tin oxide, tungsten trioxide, ferric oxide, dibismuth trioxide, etc. may be able to generate active oxygen. Of these, anatase-type titanium oxide is particularly preferable because it is chemically stable and inexpensive highly active fine particles can be obtained.
【０００９】有色の金属微粒子とは、銀、銅、白金、パ
ラジウム、金、ニッケル、鉄、コバルト、亜鉛等のイオ
ン化傾向が小さく、自身が還元されやすい金属微粒子を
いう。水溶液反応により無色化または白色化した塩を形
成する場合、または金属微粒子を含む触媒を液体中で用
いる場合は、形成される無色化または白色化した塩は難
溶性または不溶性のほうがよい。尚、無色化、白色化し
たとは、色差で下地に対し、２以下程度まで、脱色した
ことをいい、必ずしも、無色または純白色である必要は
ない。The colored fine metal particles are fine metal particles such as silver, copper, platinum, palladium, gold, nickel, iron, cobalt and zinc which have a small ionization tendency and are easily reduced. When a colorless or whitened salt is formed by an aqueous solution reaction, or when a catalyst containing fine metal particles is used in a liquid, the colorless or whitened salt formed is preferably insoluble or insoluble. It should be noted that the terms "colorless and whitened" means that the ground color is decolorized to about 2 or less by color difference, and it is not necessarily required to be colorless or pure white.
【００１０】ここで上記した２つの工程を行う順番は順
不同であり、どちらから行っても構わない。光触媒活性
を有する粒子を予め基材に固定しておいてから金属微粒
子を含む触媒を作製してもよいし、金属微粒子を含む触
媒を作製した後、基材に固定してもよい。The order of performing the above-mentioned two steps is not specified, and either order may be performed. The particles having photocatalytic activity may be fixed to the base material in advance and then the catalyst containing the metal fine particles may be prepared, or the catalyst containing the metal fine particles may be prepared and then fixed to the base material.
【００１１】ここで用いる基材の材質は、セラミック、
陶磁器材料、金属、ガラス、熱硬化性樹脂、熱可塑性樹
脂あるいはそれらの複合物等基本的に何でもよい。基材
の形状も基本的にどのようなものでもよく、例えば、タ
イル、壁材、床材等の板状物や棒状物、球状物、円柱状
物、円筒状物、角柱状物、中空の角柱状物などの単純形
状のものでも、衛生陶器、洗面台、浴槽、流し台等およ
びその付属品などの複雑形状のものでも構わない。The material of the substrate used here is ceramic,
Basically, any material such as ceramic material, metal, glass, thermosetting resin, thermoplastic resin, or a composite thereof may be used. The shape of the base material may be basically any, for example, plate-like materials such as tiles, wall materials, flooring materials, rod-like objects, spherical objects, columnar objects, cylindrical objects, prismatic objects, hollow objects. It may have a simple shape such as a prismatic shape, or may have a complicated shape such as sanitary ware, a wash basin, a bathtub, a sink and the like and its accessories.
【００１２】光触媒活性を有する粒子を予め基材に固定
しておいてから金属微粒子を含む触媒を作製する場合の
第一の態様は、基材に光触媒活性を有する粒子層を形成
する工程、その上に有色の金属微粒子を固定化する工
程、前記有色の金属微粒子を覆うように無色化または白
色化した塩を形成する工程を順次行うことによる。The first embodiment in the case of preparing the catalyst containing the metal fine particles after fixing the particles having photocatalytic activity to the base material in advance is the step of forming a particle layer having photocatalytic activity on the base material. By sequentially performing the step of immobilizing colored metal fine particles on the top and the step of forming a colorless or whitened salt so as to cover the colored metal fine particles.
【００１３】基材に光触媒活性を有する粒子層を形成す
る工程は、基本的に出発原料あるいはそれに適当な処理
を施したものを基材表面に塗布後、熱処理することによ
り行う。出発原料としては、光触媒活性を有する物質の
ゾルや、光触媒活性を有する物質を構成する金属元素を
含むアルコキシド、有機金属塩、無機酸塩、ハロゲン化
物塩等を用いる。例えば、出発原料としてアナターゼ型
酸化チタンゾルを用いる場合は、酸化チタンの等電点が
ＰＨ６．５とほぼ中性であることから、酸またはアルカ
リで分散した懸濁液を用いて基材表面に塗布すると均一
に塗布しやすい。The step of forming a particle layer having photocatalytic activity on a substrate is basically carried out by applying a starting material or a material obtained by subjecting the starting material to an appropriate treatment on the surface of the substrate and then heat-treating it. As a starting material, a sol of a substance having photocatalytic activity, an alkoxide containing a metal element forming the substance having photocatalytic activity, an organic metal salt, an inorganic acid salt, a halide salt, or the like is used. For example, when anatase type titanium oxide sol is used as a starting material, since the isoelectric point of titanium oxide is approximately pH 6.5, it is applied to the surface of the substrate using a suspension dispersed with an acid or alkali. Then it is easy to apply evenly.
【００１４】このような分散処理において、基材が金属
の場合は耐蝕性の観点からアルカリ分散が好ましい。陶
磁器、タイル、セラミック等の場合は酸、アルカリいず
れの分散液を用いてもよい。このとき用いる酸として
は、硝酸、硫酸、塩酸、酢酸、リン酸、有機酸等が挙げ
られる。アルカリの場合はアンモニア、アルカリ金属ま
たはアルカリ土類金属を含む水酸化物等が挙げられる
が、熱処理後に金属汚染物が生成しないことからアンモ
ニアが特に好ましい。これらの分散液に、さらに有機
系、リン酸系の分散剤、表面活性剤、表面処理剤等を添
加してもよい。In such dispersion treatment, alkali dispersion is preferable from the viewpoint of corrosion resistance when the substrate is a metal. In the case of ceramics, tiles, ceramics, etc., either an acid or alkali dispersion may be used. Examples of the acid used at this time include nitric acid, sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, organic acids and the like. Examples of the alkali include ammonia and hydroxides containing an alkali metal or an alkaline earth metal, but ammonia is particularly preferable because no metal contaminant is generated after the heat treatment. An organic or phosphoric acid-based dispersant, a surface-active agent, a surface-treating agent or the like may be further added to these dispersions.
【００１５】また出発原料としてゾルを用いる場合は、
光触媒活性を有する物質のゾルの平均粒径は０．０５μ
ｍ以下好ましくは０．０１μｍ以下がよい。粒径が小さ
いほど光触媒活性が高いからである。ここで平均粒径
は、ゾルを粉末Ｘ線回折したときの結晶の最大ピークの
積分幅からＳｃｈｅｒｒｅｒ式により求められる。When sol is used as the starting material,
The average particle size of the sol of the substance having photocatalytic activity is 0.05μ
m or less, preferably 0.01 μm or less. This is because the smaller the particle size, the higher the photocatalytic activity. Here, the average particle diameter is obtained by the Scherrer equation from the integrated width of the maximum peak of the crystal when the sol is subjected to powder X-ray diffraction.
【００１６】出発原料としてゾルを用いる場合、基材表
面への塗布方法としては、ゾルの懸濁液をスプレー・コ
ーティング、ロール・コーティング、ディップ・コーテ
ィング、スピン・コーティング、ＣＶＤ、電子ビーム蒸
着、スパッタなどして塗布する方法があり、そのいずれ
でもよいし、それ以外の方法でもよい。ただし、スプレ
ー・コーティング、ロール・コーティング、ディップ・
コーティングは、ＣＶＤ、電子ビーム蒸着、スパッタな
どと比較して特別の設備を要せず、安価に塗膜可能であ
る利点がある。When a sol is used as a starting material, the sol suspension may be applied by spray coating, roll coating, dip coating, spin coating, CVD, electron beam evaporation, sputtering. There is a method of applying the above, and any of them may be used, or any other method. However, spray coating, roll coating, dip coating
The coating is advantageous in that it does not require special equipment and can be applied at a low cost, as compared with CVD, electron beam evaporation, sputtering, and the like.
【００１７】出発原料としてアルコキシドを用いる場合
は、アルコキシドに適当な希釈剤と必要ならば塩酸等の
加水分解抑制剤を添加した混合液を塗布する。ここで適
当な希釈剤とは、エタノール、プロパノール、メタノー
ル等のアルコール類が好ましいがそれに限定されるもの
ではない。ただし水はできる限り含まないほうがよい。
水が含まれるとチタンアルコキシド等の多くのアルコキ
シドにおいて加水分解が爆発的に促進され、クラックの
一因をなすからである。アルコキシドの基材への塗布方
法は、例えば、乾燥空気をキャリヤーとしてフロー・コ
ーティング法により塗布する。When an alkoxide is used as a starting material, a mixed solution containing an appropriate diluent and, if necessary, a hydrolysis inhibitor such as hydrochloric acid is applied to the alkoxide. Here, the suitable diluent is preferably alcohols such as ethanol, propanol and methanol, but is not limited thereto. However, it is better not to include water as much as possible.
This is because when water is contained, hydrolysis is explosively promoted in many alkoxides such as titanium alkoxide, which contributes to cracking. The alkoxide is applied to the base material by, for example, a flow coating method using dry air as a carrier.
【００１８】出発原料としてアルコキシド、有機金属
塩、無機酸塩、ハロゲン化物塩等を用いた場合には、塗
布後の熱処理はこれら前駆体が酸化物に変化しかつ結晶
化すると同時に、このようにして得た光触媒活性を有す
る粒子が基材表面へ高い密着強度で固定化される温度で
行う。その温度は例えば、光触媒活性を有する粒子がア
ナターゼ型酸化チタンである場合には４００℃以上８０
０℃以下である。When an alkoxide, an organic metal salt, an inorganic acid salt, a halide salt or the like is used as a starting material, the heat treatment after coating changes the precursor into an oxide and crystallizes at the same time. It is carried out at a temperature at which the particles having photocatalytic activity thus obtained are immobilized on the surface of the substrate with high adhesion strength. The temperature is, for example, 400 ° C. or higher and 80 ° C. or higher when the particles having photocatalytic activity are anatase type titanium oxide.
It is 0 ° C or lower.
【００１９】それに対し、出発原料としてゾルを用いた
場合には、既に酸化物結晶であるので、単に光触媒活性
を有する粒子が基材表面へ高い密着強度で固定化される
温度で熱処理すればよい。しかしゾルは余程の微粒でな
いかぎり上記前駆体と比較して基材への密着強度が相対
的に弱いので、例えば光触媒活性を有する粒子が酸化チ
タンである場合、粒度配合等の特別の手段を用いない限
り８００℃以上の高温で熱処理する必要がある。On the other hand, when a sol is used as the starting material, since it is already an oxide crystal, it may be simply heat-treated at a temperature at which the particles having photocatalytic activity are fixed to the surface of the substrate with high adhesion strength. . However, unless the sol is fine particles, the adhesion strength to the base material is relatively weaker than that of the above precursor, so, for example, when the particles having photocatalytic activity are titanium oxide, special means such as particle size blending should be used. Unless used, it is necessary to perform heat treatment at a high temperature of 800 ° C or higher.
【００２０】基材に光触媒活性を有する粒子層を形成す
る工程は、基材と光触媒活性を有する粒子層との間にバ
インダー層を介して形成してもよい。このようにするこ
とにより、光触媒活性を有する粒子層と基材との結合を
より強固なものにすることができる。In the step of forming the particle layer having photocatalytic activity on the base material, a binder layer may be interposed between the base material and the particle layer having photocatalytic activity. By doing so, the bond between the particle layer having photocatalytic activity and the substrate can be made stronger.
【００２１】ここでバインダーには、釉薬、無機ガラス
質、熱可塑性樹脂、半田等の熱可塑性バインダーおよび
熱硬化性樹脂、光硬化性樹脂等の硬化性バインダーの双
方が利用できる。Here, as the binder, both a glaze, an inorganic glass material, a thermoplastic resin, a thermoplastic binder such as solder, and a curable binder such as a thermosetting resin and a photocurable resin can be used.
【００２２】熱可塑性バインダーを用いる場合は、例え
ば、基材表面にバインダー層を形成する工程、バインダ
ー層上に光触媒活性を有する層を形成する工程、光触媒
活性を有する層の最表面が露出されかつ下層の一部が前
記バインダー層に埋設されるような温度で熱処理する工
程を順次行うことにより、基材上に光触媒活性を有する
粒子層を形成する。When a thermoplastic binder is used, for example, the step of forming a binder layer on the surface of the substrate, the step of forming a layer having photocatalytic activity on the binder layer, the outermost surface of the layer having photocatalytic activity being exposed and A particle layer having photocatalytic activity is formed on the base material by sequentially performing a heat treatment process at a temperature at which a part of the lower layer is embedded in the binder layer.
【００２３】ここで基材表面にバインダー層を形成する
工程は、基材にその軟化温度が基材よりも低いバインダ
ー成分を塗布することにより行う。このときのバインダ
ー成分は必ずしも部材完成時のバインダー層の組成と一
致している必要はない。例えば、バインダーが無機ガラ
ス質の場合の塗布物は、粒状、フリット状、塊状、粉末
等の無機ガラス質組成物の懸濁液でもよいし、構成金属
成分を含む塩の混合液でもよい。塗布方法には、スプレ
ー・コーティング法、ロール・コーティング法、ディッ
プ・コーティング法等があるがそのいずれでもよい。The step of forming the binder layer on the surface of the base material is performed by applying a binder component having a softening temperature lower than that of the base material to the base material. The binder component at this time does not necessarily have to match the composition of the binder layer when the member is completed. For example, when the binder is an inorganic glass, the applied material may be a suspension of an inorganic glassy composition in the form of particles, frit, lump, powder or the like, or may be a mixed solution of salts containing constituent metal components. The coating method includes a spray coating method, a roll coating method, a dip coating method and the like, and any of them may be used.
【００２４】バインダー層の上に光触媒活性を有する粒
子層を形成する工程を行う前に、塗布したバインダー層
を乾燥し、水分等を蒸発させてもよい。この際の乾燥方
法は、室温放置による方法、基材とともに加熱する方法
等がある。バインダー層の上に光触媒活性を有する粒子
層を形成する工程を行う前に、塗布したバインダー層を
基材の軟化温度より低く、バインダー層が部材完成時の
バインダー層の組成に変化しなおかつ軟化する温度で熱
処理してもよい。この方法によればバインダー層の上に
光触媒活性を有する粒子層を形成する時に予めバインダ
ー層がより平滑になるので、塗布する光触媒活性を有す
る粒子が少量でも充分な効果を発揮できるようになる。Before the step of forming the particle layer having photocatalytic activity on the binder layer, the applied binder layer may be dried to evaporate water and the like. The drying method at this time includes a method of standing at room temperature, a method of heating with a base material, and the like. Before the step of forming a particle layer having photocatalytic activity on the binder layer, the applied binder layer is lower than the softening temperature of the base material, and the binder layer is changed to the composition of the binder layer when the member is completed and softens. You may heat-process at temperature. According to this method, the binder layer becomes smoother in advance when the particle layer having photocatalytic activity is formed on the binder layer, so that a sufficient effect can be exhibited even with a small amount of photocatalytically active particles to be applied.
【００２５】バインダー層の上に光触媒活性を有する粒
子層を形成する工程は、基材上に光触媒活性を有する粒
子層を直接形成する場合と基本的に同様である。光触媒
活性を有する層の最表面が露出されかつ下層の一部が前
記バインダー層に埋設されるような温度で熱処理する工
程は、基材の軟化点より低く、バインダー層が部材完成
時のバインダー層の組成に変化しなおかつ軟化する温度
で処理することにより行う。一般的にはバインダー層の
軟化温度より２０〜３２０℃高い温度で熱処理するとよ
い。そうすることにより、光触媒活性を有する粒子は適
度にバインダー層中に移動し、光触媒活性を有する層の
最表面が露出されかつ下層の一部が前記バインダー層に
埋設される状態になる。また熱硬化性バインダーを用い
る場合は、例えばバインダーを硬化剤と混合して基材に
塗布する工程、前記混合物を増粘する工程、光触媒活性
を有する粒子を塗布する工程、熱処理によりバインダー
を硬化させる工程を順次行うことにより、基材上に光触
媒活性を有する粒子層を形成する。The step of forming the photocatalytically active particle layer on the binder layer is basically the same as the case of directly forming the photocatalytically active particle layer on the substrate. The step of heat treatment at a temperature such that the outermost surface of the layer having photocatalytic activity is exposed and a part of the lower layer is embedded in the binder layer is lower than the softening point of the base material, and the binder layer is a binder layer when the member is completed. It is carried out by treating at a temperature at which the composition of the composition changes and is softened. Generally, the heat treatment may be performed at a temperature 20 to 320 ° C. higher than the softening temperature of the binder layer. By doing so, the particles having photocatalytic activity appropriately move into the binder layer, the outermost surface of the layer having photocatalytic activity is exposed, and part of the lower layer is embedded in the binder layer. When a thermosetting binder is used, for example, a step of mixing the binder with a curing agent and applying it to a substrate, a step of thickening the mixture, a step of applying particles having photocatalytic activity, and a heat treatment to cure the binder. By sequentially performing the steps, a particle layer having photocatalytic activity is formed on the base material.
【００２６】バインダーを硬化剤と混合して基材に塗布
する方法は、例えば熱硬化性樹脂に希釈剤を添加し、次
いで硬化剤を添加して得た混合液を基材表面に塗布する
ことにより行う。ここで希釈剤は、混合液の粘性を低下
させ、基材表面に該混合液を塗布しやすくするために塗
布する。したがって、ここで使用する希釈剤はこの目的
を達成しうる溶媒であれば基本的に何でもよい。例え
ば、水、エタノール、プロパノール等が使用できる。The method of mixing the binder with the curing agent and applying it to the substrate is, for example, to add a diluent to the thermosetting resin and then apply the mixture obtained by adding the curing agent to the surface of the substrate. By. Here, the diluent is applied in order to reduce the viscosity of the mixed solution and to facilitate the application of the mixed solution onto the surface of the base material. Therefore, the diluent used here may basically be any solvent that can achieve this purpose. For example, water, ethanol, propanol or the like can be used.
【００２７】混合液の基材への塗布方法も、スプレー・
コーティング法、ロール・コーティング法、ディップ・
コーティング法、スピン・コーティング法等があるが、
そのいずれを用いてもよいし、それ以外の方法でもよ
い。The method for applying the mixed liquid to the substrate is also spraying.
Coating method, roll coating method, dip coating
There are coating method, spin coating method, etc.
Either of them may be used, or any other method may be used.
【００２８】混合物を増粘する工程において、混合物の
増粘は熱処理または放置することにより行う。増粘粘性
は１０５ｐｏｓｉｓｅ以上１０７．５ｐｏｉｓｅ未満に
することが望ましい。１０５ｐｏｉｓｅ以上の高粘性値
にしてから光触媒活性を有する粒子を塗布することによ
り、光触媒活性を有する粒子がバインダー層中に完全に
埋没してしまわない状態での埋設が可能となり、また１
０７．５ｐｏｉｓｅ未満にすることにより、光触媒活性
を有する粒子層の少なくとも最下層部はその一部がバイ
ンダー上層に埋設されうるようになるからである。In the step of thickening the mixture, the thickening of the mixture is performed by heat treatment or leaving it to stand. The thickening viscosity is preferably 10 5 poise or more and less than 10 7.5 poise. By coating the particles having the photocatalytic activity with a high viscosity value of 10 5 poise or more, the particles having the photocatalytic activity can be embedded in the binder layer without being completely embedded therein.
This is because when it is less than 0 7.5 poise, at least the lowermost layer of the particle layer having photocatalytic activity can be partially embedded in the binder upper layer.
【００２９】光触媒活性を有する粒子層の上に有色の金
属微粒子を固定化する工程は、銀、銅、白金、パラジウ
ム、金、ニッケル、鉄、コバルト、亜鉛等の少なくとも
１種の有色の金属を含む溶液を塗布し、塗布面に紫外線
を含む光を照射することにより行う。In the step of immobilizing colored metal fine particles on the particle layer having photocatalytic activity, at least one kind of colored metal such as silver, copper, platinum, palladium, gold, nickel, iron, cobalt and zinc is used. It is carried out by applying a solution containing the composition and irradiating the application surface with light containing ultraviolet rays.
【００３０】ここで有色の金属を含む溶液には、上記金
属の可溶性塩の溶液が好ましく、例えば、硝酸銀、硫酸
銀、酢酸銀、フッ化銀、塩素酸銀、酢酸第一銅、酢酸第
二銅、塩素酸第二銅、塩化第二銅、硫酸第一銅、硫酸第
二銅、臭化第二銅、硝酸第二銅、塩化第一鉄、塩化第二
鉄、硫酸第一鉄、硫酸第二鉄、ヨウ化第一鉄、臭化第一
鉄、臭化第二鉄、シュウ酸第二鉄、酢酸第一鉄、酢酸第
二鉄、塩素酸第一鉄、塩素酸第二鉄、硝酸第一鉄、硝酸
第二鉄、塩化コバルト、硫酸コバルト、ヨウ化コバル
ト、臭化コバルト、酢酸コバルト、塩素酸コバルト、硝
酸コバルト、塩化ニッケル、硫酸ニッケル、ヨウ化ニッ
ケル、臭化ニッケル、酢酸ニッケル、塩素酸ニッケル、
硝酸ニッケル、硫酸パラジウム、塩化パラジウム、塩化
白金酸、硫酸白金、塩化第二金、硫酸第二金、臭化第二
金、塩化亜鉛、硫酸亜鉛、ヨウ化亜鉛、臭化亜鉛、酢酸
亜鉛、塩素酸亜鉛、硝酸亜鉛等の溶液およびその混合溶
液が使用できる。溶液の塗布方法は、基本的にどのよう
な方法でもよいが、スプレー・コーティング法が簡便で
ある。また、使用する溶液の量が少なくてすむこと、均
一に塗布できること、膜厚を制御しやすいこと、裏面に
付けたくないときにそれが可能であることなどの長所
も、スプレー・コーティング法は有しており好ましい。The solution containing a colored metal is preferably a solution of a soluble salt of the above metal, and examples thereof include silver nitrate, silver sulfate, silver acetate, silver fluoride, silver chlorate, cuprous acetate and second acetate. Copper, cupric chlorate, cupric chloride, cuprous sulfate, cupric sulfate, cupric bromide, cupric nitrate, ferrous chloride, ferric chloride, ferrous sulfate, sulfuric acid Ferric iron, ferrous iodide, ferrous bromide, ferric bromide, ferric oxalate, ferrous acetate, ferric acetate, ferrous chlorate, ferric chlorate, Ferrous nitrate, ferric nitrate, cobalt chloride, cobalt sulfate, cobalt iodide, cobalt bromide, cobalt acetate, cobalt chlorate, cobalt nitrate, nickel chloride, nickel sulfate, nickel iodide, nickel bromide, nickel acetate , Nickel chlorate,
Nickel nitrate, palladium sulfate, palladium chloride, chloroplatinic acid, platinum sulfate, gold (II) chloride, gold (II) sulfate, gold (II) bromide, zinc chloride, zinc sulfate, zinc iodide, zinc bromide, zinc acetate, chlorine A solution of zinc acid, zinc nitrate or the like and a mixed solution thereof can be used. The method of applying the solution may be basically any method, but the spray coating method is convenient. In addition, the spray coating method has the advantages that it requires a small amount of solution, can be applied uniformly, can easily control the film thickness, and can do it when it is not desired to attach it to the back surface. And is preferable.
【００３１】スプレー・コーティング法により溶液を塗
布する場合は、紫外線を含む光を照射する前に塗布物を
乾燥させたほうがよい。塗布量に対する金属の固定化率
が向上するので、コスト上有利だからである。スプレー
・コーティング法により溶液を塗布する場合の溶媒も基
本的に限定されるものでなく、水、エタノール、プロパ
ノール、メタノール等種々の溶媒を利用できる。このう
ち分散性が同一ならばエタノールを使用することが最も
好ましい。エタノールは水系よりも乾燥速度が速いので
乾燥工程にかかる時間を短縮でき、生産性が向上するか
らである。また表面張力が低いので光触媒活性を有する
粒子層への濡れもよい。さらにメタノール等の他の揮発
性溶媒と比較して毒性がなく、無害である。また分散性
等の理由により水を使用しなければならない場合は、ア
ルコール類、不飽和炭化水素等の犠牲酸化剤を少量添加
すると光還元反応がより迅速に進行するので好ましい。When the solution is applied by the spray coating method, it is preferable to dry the applied material before irradiating with light including ultraviolet rays. This is because the metal immobilization rate with respect to the coating amount is improved, which is advantageous in terms of cost. The solvent used for applying the solution by the spray coating method is not particularly limited, and various solvents such as water, ethanol, propanol and methanol can be used. Of these, ethanol is most preferably used if the dispersibility is the same. This is because ethanol has a faster drying rate than an aqueous system, so that the time required for the drying step can be shortened and the productivity is improved. Further, since the surface tension is low, it is good to wet the particle layer having photocatalytic activity. Furthermore, it is less toxic and harmless than other volatile solvents such as methanol. When water must be used for reasons such as dispersibility, it is preferable to add a small amount of a sacrificial oxidizer such as alcohols and unsaturated hydrocarbons because the photoreduction reaction will proceed more rapidly.
【００３２】紫外線を含む光を照射する光源は、紫外線
を照射しうるものであればよく、例えば、紫外線ラン
プ、ＢＬＢランプ、キセノンランプ、水銀灯、蛍光灯な
どが挙げられる。紫外線を含む光を照射するときに、照
射面に垂直に光があたるように試料を配置するのが好ま
しい。照射効率が最も優れるからである。The light source for irradiating light including ultraviolet rays may be any one capable of irradiating ultraviolet rays, and examples thereof include an ultraviolet lamp, a BLB lamp, a xenon lamp, a mercury lamp and a fluorescent lamp. When irradiating with light including ultraviolet rays, it is preferable to arrange the sample so that the light is irradiated perpendicularly to the irradiation surface. This is because the irradiation efficiency is the best.
【００３３】有色の金属微粒子を覆うように無色化また
は白色化した塩を形成する工程は、例えば、上記有色の
金属微粒子と反応して金属微粒子の少なくとも表面に無
色化または白色化した塩を形成しうる溶液を金属微粒子
に接触させる方法、または上記有色の金属微粒子と反応
して金属微粒子の少なくとも表面に無色化または白色化
した塩を形成しうる反応ガスを金属微粒子に接触させる
方法で行う。In the step of forming a colorless or whitened salt so as to cover the colored metal fine particles, for example, a colorless or whitened salt is formed on at least the surface of the metal fine particles by reacting with the colored metal fine particles. A method of contacting the metal fine particles with a possible solution or a method of contacting the fine metal particles with a reaction gas capable of reacting with the colored metal fine particles to form a colorless or whitened salt on at least the surface of the metal fine particles.
【００３４】上記有色の金属微粒子の塩で白色化または
無色化したものは、難溶性または不溶性の塩であること
が好ましい。水溶液反応で金属微粒子の少なくとも表面
に塩を容易に形成でき、また水のある環境で安定に使用
できるからである。The whitened or colorless salt of the colored metal fine particles is preferably a sparingly soluble or insoluble salt. This is because a salt can be easily formed on at least the surface of the metal fine particles by an aqueous solution reaction and can be stably used in an environment with water.
【００３５】上記有色の金属微粒子の塩で白色化または
無色化するものとしては、例えば、塩化銀、臭化銀、ヨ
ウ化銀、シユウ酸銀、チオ硫酸銀、シアン化銀、ロダン
化銀、塩化第一銅、臭化第一銅、シアン化第一銅、ロダ
ン化第一銅、酸化第一銅、リン酸亜鉛、シュウ酸亜鉛、
シアン化亜鉛、シアン化パラジウム、硫化亜鉛、炭酸亜
鉛、炭酸第一鉄、酸化亜鉛等が挙げられる。上記塩を形
成しうる溶液は、例えば塩化銀の場合には、塩化カリウ
ム溶液、塩化ナトリウム溶液、塩化アンモニウム溶液、
塩化第二鉄溶液等、ヨウ化銀の場合には、ヨウ化カリウ
ム溶液、ヨウ化ナトリウム溶液、ヨウ化第二鉄溶液等が
挙げられるがそれに限定されるものではなく、各々の塩
の陰イオンを含む可溶性塩溶液であれば広く使用でき
る。その他、上記各種塩が酸化亜鉛、酸化第一銅等の酸
化物ならば、過酸化水素水、オゾン水等の酸化剤水溶液
を用いることもできる。The salts of the colored metal fine particles which are whitened or colorless are, for example, silver chloride, silver bromide, silver iodide, silver oxalate, silver thiosulfate, silver cyanide, silver rhodanide, Cuprous chloride, cuprous bromide, cuprous cyanide, cuprous rhodanide, cuprous oxide, zinc phosphate, zinc oxalate,
Examples thereof include zinc cyanide, palladium cyanide, zinc sulfide, zinc carbonate, ferrous carbonate, zinc oxide and the like. The solution capable of forming the salt is, for example, in the case of silver chloride, potassium chloride solution, sodium chloride solution, ammonium chloride solution,
In the case of silver iodide such as ferric chloride solution, potassium iodide solution, sodium iodide solution, ferric iodide solution and the like can be mentioned, but not limited thereto, and anions of each salt. It can be widely used as long as it is a soluble salt solution containing. In addition, if the above-mentioned various salts are oxides such as zinc oxide and cuprous oxide, an aqueous oxidant solution such as hydrogen peroxide solution and ozone water can be used.
【００３６】また上記塩を形成しうる反応ガスも各々の
塩の陰イオン元素を含む気体であれば広く使用できる。
例えば上記塩が酸化亜鉛、酸化第一銅等の酸化物なら
ば、大気中、酸素中、水蒸気中等で加熱することによ
り、また、オゾン等の酸化剤で反応させることにより金
属微粒子表面を酸化して表面に酸化物層を形成させるこ
とができる。The reaction gas capable of forming the above-mentioned salt can be widely used as long as it is a gas containing an anion element of each salt.
For example, if the salt is an oxide such as zinc oxide or cuprous oxide, the surface of the metal fine particles is oxidized by heating in air, oxygen, steam, etc., or by reacting with an oxidizing agent such as ozone. Can form an oxide layer on the surface.
【００３７】また基材に光触媒活性を有する粒子層は、
光触媒活性を有する粒子と樹脂との混合層で形成しても
よい。このような構造にしてもやはり光触媒活性を有す
る粒子層と基材との結合をより強固なものにすることが
できる。しかもこの場合、光触媒活性を有する粒子が外
気と接するように露出させる必要がなくなるので、基材
上に塗布する場合に光触媒活性を有する粒子を塗布する
工程とバインダーを塗布する工程を分けて行う必要がな
くなり、例えば光触媒活性を有する粒子とバインダーを
混練して１度で塗布することが可能となる。したがって
工程の簡略化が実現でき、製造コストの低減を図ること
ができる。The particle layer having photocatalytic activity on the substrate is
It may be formed of a mixed layer of particles having photocatalytic activity and a resin. Even with such a structure, the bond between the particle layer having photocatalytic activity and the substrate can be made stronger. Moreover, in this case, since it is not necessary to expose the photocatalytically active particles so as to contact with the outside air, it is necessary to separately perform the step of applying the photocatalytically active particles and the step of applying the binder when applying on the substrate. Therefore, it becomes possible to knead the particles having photocatalytic activity and the binder and apply them once. Therefore, the process can be simplified and the manufacturing cost can be reduced.
【００３８】ここで樹脂は、極度に紫外線を吸収する物
質でなく、かつ光に対しある程度の耐蝕性のある素材で
あれば、熱可塑性、熱硬化性、光硬化性のいずれの性質
を有する樹脂でもよい。この場合、多くの光触媒活性を
有する粒子が樹脂中に埋もれることになるので、光触媒
活性が生じないことが懸念されるが、実際には銀、銅、
白金、パラジウム、金、ニッケル、鉄、コバルト、亜鉛
等の金属微粒子が担持されることにより、光触媒活性は
失われない。この機構について以下に略述する。Here, the resin is a resin that is not a substance that extremely absorbs ultraviolet rays, and has any of the properties of thermoplasticity, thermosetting, and photocuring as long as it is a material that has a certain degree of corrosion resistance to light. But it's okay. In this case, since many particles having photocatalytic activity are buried in the resin, there is a concern that no photocatalytic activity will occur, but in reality, silver, copper,
The photocatalytic activity is not lost by supporting fine metal particles such as platinum, palladium, gold, nickel, iron, cobalt, and zinc. This mechanism will be briefly described below.
【００３９】光触媒活性を有する粒子上での光触媒反応
は以下のように進行すると解される。まず第一段階とし
て、光子が電子と正孔に分解する反応が生じる。すなわ
ち、 ｈυ→ｈ＋＋ｅ− （１） 次に生成した正孔が空気または層中の酸素または水分と
反応して活性酸素種を生成する。（２）、（３）式に水
分と反応した場合の化学反応式を示す。 Ｈ２Ｏ→Ｈ＋＋ＯＨ− （２） ＯＨ−＋ｈ＋→ＯＨ・ （３） ここで生じた活性酸素種ＯＨ・が悪臭成分や菌に作用し
て防臭性、抗菌性が発揮されるのである。ただし、
（３）式の反応は（４）式に示す正孔と電子が再結合し
て光子に戻る反応と競合する。 ｈ＋＋ｅ−→ｈυ （４）It is understood that the photocatalytic reaction on the particles having photocatalytic activity proceeds as follows. First, as a first step, a reaction occurs in which photons are decomposed into electrons and holes. That is, hυ → h + + e − (1) Next, the generated holes react with oxygen or moisture in the air or layer to generate active oxygen species. Equations (2) and (3) show chemical reaction equations in the case of reacting with water. H2O → H + + OH − (2) OH − + h + → OH · (3) The active oxygen species OH · generated here act on malodorous components and bacteria to exert deodorant and antibacterial properties. However,
The reaction of the formula (3) competes with the reaction shown in the formula (4) in which holes and electrons are recombined to return to photons. h + + e − → hυ (4)
【００４０】まず光触媒活性を有する粒子が露出してい
る場合について考察する。この場合には、空気中または
層中の酸素または水分は光触媒活性を有する粒子と直接
接触することができるので、光触媒活性を有する粒子上
には（１）式で示される光の分解反応が生じたときに正
孔、電子の他、酸素または水分が存在する。したがって
この場合（３）式と（４）式は競争反応となる。したが
ってある確率（アナターゼ型酸化チタンの場合は約２０
％程度）で（３）式により活性酸素が生成する。この活
性酸素の作用により、防臭、抗菌等の光触媒反応が起こ
ることになる。次に光触媒活性を有する粒子が上記金属
が周囲にない状態でバインダーに完全に覆われた場合に
ついて考察する。バインダーに覆われることにより酸素
または水分は光触媒に直接接触することができなくな
る。したがって酸素または水分と正孔とが（３）式によ
り反応するためには、酸素または水分が光触媒活性を有
する粒子上へ拡散するか、または正孔が酸素または水分
の存在する最表面に拡散するか、若しくはその双方の拡
散が生じる必要がある。その分誘導期間が生じることに
なる。一方、電子は光子の分解反応が生じたときにすで
に光触媒活性を有する粒子上に存在する。そのため上記
拡散が生じる前に、すなわち誘導期間中に（４）式によ
る反応が生じることになり、そのため（３）式による活
性酸素生成反応はほとんど生じなくなる。First, the case where particles having photocatalytic activity are exposed will be considered. In this case, since oxygen or water in the air or the layer can directly contact the photocatalytically active particles, the photolytic reaction represented by the formula (1) occurs on the photocatalytically active particles. In addition to holes and electrons, oxygen or water is present. Therefore, in this case, equations (3) and (4) are competitive reactions. Therefore, there is a certain probability (about 20 for anatase type titanium oxide).
%), Active oxygen is generated by the equation (3). Due to the action of this active oxygen, photocatalytic reactions such as deodorization and antibacterial will occur. Next, the case where the particles having photocatalytic activity are completely covered with the binder in the absence of the above metal will be considered. When covered with the binder, oxygen or moisture cannot directly contact the photocatalyst. Therefore, in order for oxygen or moisture to react with holes according to the formula (3), oxygen or moisture diffuses onto particles having photocatalytic activity, or holes diffuse onto the outermost surface where oxygen or moisture exists. Either or both must be diffused. An induction period will occur accordingly. On the other hand, the electrons are already present on the particles having photocatalytic activity when the photon decomposition reaction occurs. Therefore, the reaction according to the formula (4) occurs before the diffusion occurs, that is, during the induction period, so that the active oxygen generation reaction according to the formula (3) hardly occurs.
【００４１】以上のことから光触媒活性を有する粒子が
上記金属が周囲にない状態でバインダーに大部分覆われ
ている場合には、光触媒活性を有する粒子が露出してい
る部分のみある確率で活性酸素が生じることになる。そ
のため生成する活性酸素の量が少ないので充分な防臭、
抗菌等の光触媒機能が発揮されないのである。From the above, when most of the particles having photocatalytic activity are covered with the binder in the state where the above metal is not present in the surroundings, there is a probability that only a portion where the particles having photocatalytic activity are exposed has active oxygen. Will occur. Therefore, the amount of active oxygen generated is small, so sufficient deodorization,
The photocatalytic function such as antibacterial is not exerted.
【００４２】一方、光触媒活性を有する粒子の近傍（必
ずしも、光触媒活性を有する粒子と接触していなくても
よい状態）に上記金属微粒子がある場合は、光触媒活性
を有する粒子がバインダーに完全に覆われていても、
（１）式で生成した電子はこれら金属微粒子に捕捉され
るので、（４）式の再結合反応が生じにくくなり、正孔
が長時間消滅せずに残留しうるようになる。したがっ
て、光触媒活性を有する粒子がバインダーに覆われて
（３）式の活性酸素生成反応が上記理由により誘導期間
を有するようになっても、正孔が（４）式により消滅し
にくくなるので、誘導期間に（３）式の活性酸素生成反
応が生じるようになる。On the other hand, when the metal fine particles are present in the vicinity of the particles having photocatalytic activity (necessarily not in contact with the particles having photocatalytic activity), the particles having photocatalytic activity are completely covered with the binder. Even if
Since the electrons generated by the formula (1) are captured by these metal fine particles, the recombination reaction of the formula (4) is less likely to occur, and holes can remain without disappearing for a long time. Therefore, even if the particles having photocatalytic activity are covered with the binder and the active oxygen generation reaction of the formula (3) has an induction period for the above reason, the holes are less likely to disappear by the formula (4). During the induction period, the active oxygen generation reaction of formula (3) comes to occur.
【００４３】以上の機構により、銀、銅、白金、パラジ
ウム、金、ニッケル、鉄、コバルト、亜鉛等の金属微粒
子の少なくとも１種が含まれていれば、光触媒活性を有
する粒子の大部分が樹脂に覆われるにもかかわらず、防
臭、抗菌等の光触媒機能が発揮されるのである。By the above mechanism, if at least one kind of metal fine particles such as silver, copper, platinum, palladium, gold, nickel, iron, cobalt and zinc is contained, most of the particles having photocatalytic activity are resin. Even though it is covered with odors, it exerts photocatalytic functions such as deodorant and antibacterial.
【００４４】この場合の光触媒活性を有する粒子層の形
成方法の一態様は、例えば、光触媒活性を有する物質の
ゾルを分散した懸濁液に熱硬化性樹脂を添加する工程、
前記ゾルと樹脂の混合物の懸濁液を溶媒で希釈する工
程、前記希釈液にさらに硬化剤を添加する工程、硬化剤
を添加した液状物を基材に塗布する工程、液状物を塗布
した基材を熱処理する工程を順次行うことによる。そし
てこの場合には光触媒活性を有する粒子に有色の金属微
粒子を固定化する工程、前記金属微粒子と溶液または気
体を反応させて少なくとも金属微粒子表面に無色化また
は白色化した塩を形成する工程は上述した方法と同様に
行う。One aspect of the method for forming the photocatalytically active particle layer in this case is, for example, a step of adding a thermosetting resin to a suspension in which a sol of a photocatalytically active substance is dispersed,
A step of diluting a suspension of the mixture of the sol and the resin with a solvent, a step of further adding a curing agent to the diluent, a step of applying a liquid material to which a curing agent has been added to a base material, a substrate on which the liquid material is applied. By sequentially performing the steps of heat treating the material. And in this case, the step of fixing colored metal fine particles to the particles having photocatalytic activity, the step of reacting the metal fine particles with a solution or gas to form a colorless or whitened salt at least on the surface of the metal fine particles is as described above. The procedure is the same as that described above.
【００４５】ここで、有色の金属微粒子を溶液または気
体と反応させて、金属微粒子表面に無色化または白色化
した塩を形成する工程は、樹脂と混合する前に光触媒活
性を有する粒子表面に担持させた後に行ってもよいし、
金属微粒子の表面に無色化または白色化した塩を形成し
た後、この金属微粒子と光触媒活性を有する粒子とを樹
脂と共に混合し、上記と同様にして、基材上に金属微粒
子を含む触媒を有する部材を作成してもよい。Here, the step of reacting the colored metal fine particles with a solution or gas to form a colorless or whitened salt on the surface of the metal fine particles is carried on the surface of the particles having photocatalytic activity before mixing with the resin. You may go after doing it,
After forming a colorless or whitened salt on the surface of the metal fine particles, the metal fine particles and the particles having photocatalytic activity are mixed with a resin, and the catalyst containing the metal fine particles is provided on the substrate in the same manner as above. You may create a member.
【００４６】ここでゾルと樹脂の混合物の懸濁液を溶媒
で希釈する工程で用いる希釈剤、粘度を低下させ、基材
への塗布をしやすくする目的で加えるものであり、この
目的が達せられるものであれば、基本的に何でもよい。
例えば、エタノール、プロパノール、水等が挙げられ
る。 硬化剤を添加した液状物を基材に塗布する工程
と、液状物を塗布した基材を熱処理する工程との間に乾
燥工程を挿入してもよい。硬化剤を添加した液状物の基
材への塗布方法は基本的にどのような方法を用いてもよ
いが、スプレー・コーティング法またはロール・コーテ
ィング法が比較的簡便である。Here, the diluent used in the step of diluting the suspension of the mixture of the sol and the resin with the solvent is added for the purpose of lowering the viscosity and facilitating the coating on the substrate, and this purpose is not achieved. Basically, anything that can be used.
Examples thereof include ethanol, propanol, water and the like. You may insert a drying process between the process of apply | coating the liquid material which added the hardening | curing agent to a base material, and the process of heat-treating the base material which applied the liquid material. Although any method may be basically used to apply the liquid material to which the curing agent is added to the substrate, the spray coating method or the roll coating method is relatively simple.
【００４７】熱処理は１００℃未満の低温で長時間かけ
て行ってもよいし、１００℃以上かつ基材及び熱硬化性
樹脂の耐熱温度未満で短時間で行ってもよい。一般に光
触媒活性を有する粒子の方が熱硬化性樹脂よりも比重が
大きいので、１００℃以上かつ基材及び熱硬化性樹脂の
耐熱温度未満で短時間で熱処理したほうが光触媒活性を
有する粒子が基材表面下層部に埋没するおそれがなく望
ましい。基材に光触媒活性を有する粒子層を光触媒活性
を有する粒子と樹脂との混合層で形成する場合の、光触
媒活性を有する粒子層の形成方法の他の実施態様は、例
えば、光触媒活性を有する物質のゾルを分散した懸濁液
に、銀、銅、白金、パラジウム、金、ニッケル、鉄、コ
バルト、亜鉛等のうちの少なくとも１種の金属を含む溶
液を混合する工程、前記混合液に紫外線を含む光を照射
することにより金属を光触媒活性を有する物質のゾルに
固定する工程、前記金属微粒子と溶液または気体を反応
させて少なくとも金属微粒子表面に無色化または白色化
した塩を形成する工程、前記混合液に熱硬化性樹脂を添
加する工程、前記ゾルと樹脂の混合物の懸濁液を溶媒で
希釈する工程、前記希釈液にさらに硬化剤を添加する工
程、添加した液状物を基材に塗布する工程、液状物を塗
布した基材を熱処理する工程を順次行うことにより行
う。この場合は金属微粒子を含む触媒粒子を予め形成し
てから基材に固定することになる。The heat treatment may be carried out at a low temperature of less than 100 ° C. for a long time, or at a temperature of 100 ° C. or higher and below the heat resistant temperature of the base material and the thermosetting resin in a short time. In general, particles having photocatalytic activity have a larger specific gravity than thermosetting resins, so particles having photocatalytic activity should be treated in a short time at a temperature of 100 ° C. or higher and below the heat resistant temperature of the substrate and thermosetting resin. It is desirable because it will not be buried in the lower layer of the surface. Another embodiment of the method for forming a particle layer having photocatalytic activity when a particle layer having photocatalytic activity is formed on a substrate as a mixed layer of particles having photocatalytic activity and a resin is, for example, a substance having photocatalytic activity. A step of mixing a solution containing at least one metal selected from the group consisting of silver, copper, platinum, palladium, gold, nickel, iron, cobalt, zinc, etc. with the suspension in which the sol is dispersed; Fixing a metal to a sol of a substance having photocatalytic activity by irradiating light containing light, reacting the solution or gas with the metal fine particles to form a colorless or whitened salt on at least the surface of the metal fine particles, A step of adding a thermosetting resin to the mixed solution, a step of diluting a suspension of the mixture of the sol and the resin with a solvent, a step of further adding a curing agent to the diluted solution, and the added liquid material as a base material. Carried out by sequentially performing the step of heat-treating the coating to process, the substrate coated with the liquid material. In this case, the catalyst particles containing the metal fine particles are formed in advance and then fixed on the base material.
【００４８】ここで光触媒活性を有する物質のゾルを分
散した懸濁液に、銀、銅、白金、パラジウム、金、ニッ
ケル、鉄、コバルト、亜鉛等のうちの少なくとも１種の
金属を含む溶液を混合する工程は、光触媒活性を有する
物質のゾルを分散した懸濁液に、前記懸濁液とほぼ同じ
ＰＨに調整した金属塩溶液を添加するようにするとよ
い。液中の光触媒活性を有する物質のゾルのゼータ電位
をなるべく変化させないようにすることで、光触媒活性
を有する物質のゾルの分散性を維持できるからである。Here, a solution containing at least one metal selected from silver, copper, platinum, palladium, gold, nickel, iron, cobalt, zinc and the like is added to a suspension in which a sol of a substance having photocatalytic activity is dispersed. In the mixing step, a metal salt solution adjusted to have substantially the same pH as that of the suspension may be added to a suspension in which a sol of a substance having photocatalytic activity is dispersed. This is because dispersibility of the sol of the substance having the photocatalytic activity can be maintained by preventing the zeta potential of the sol of the substance having the photocatalytic activity in the liquid from changing as much as possible.
【００４９】混合液に紫外線を含む光を照射することに
より金属を光触媒活性を有する物質のゾルに固定する工
程は、攪拌しながら行うほうがよい。そのほうが光触媒
活性を有する物質のゾルに金属を万便なく付着させやす
いからである。このときの攪拌装置としては、例えば超
音波振動器、スターラー、ホモジナイザー等が使用でき
る。The step of fixing the metal to the sol of the substance having photocatalytic activity by irradiating the mixed solution with light including ultraviolet rays is preferably performed with stirring. This is because it is easier for the metal to adhere to the sol of the substance having photocatalytic activity. As the stirring device at this time, for example, an ultrasonic vibrator, a stirrer, a homogenizer or the like can be used.
【００５０】紫外線を含む光の照射方法も基本的には問
わないが、容器上方から照射するほうがよい。容器によ
る紫外線の吸収がないからである。基材に光触媒活性を
有する粒子層を光触媒活性を有する粒子と樹脂との混合
層で形成する場合の、上記２つの光触媒活性を有する粒
子層の形成方法において、基材に予め熱硬化性樹脂を塗
布していてもよい。このように基材と光触媒活性を有す
る粒子と樹脂との混合層との間に熱硬化性樹脂層を介す
ることにより、以下に示す効果がある。The method of irradiating the light containing ultraviolet rays is not particularly limited, but it is better to irradiate from above the container. This is because the container does not absorb ultraviolet rays. In the method for forming a particle layer having a photocatalytic activity and a resin mixed layer of a particle having a photocatalytic activity on a base material, in the method for forming the two particle layer having a photocatalytic activity, a thermosetting resin is previously applied to the base material. It may be applied. By thus interposing the thermosetting resin layer between the base material, the mixed layer of the particles having photocatalytic activity and the resin, the following effects can be obtained.
【００５１】第一に基材と光触媒活性を有する粒子と樹
脂との混合層とをより強固に結合することができ、耐剥
離性を向上させることができる。熱硬化性樹脂のみの膜
のほうが、熱硬化性樹脂と無機結晶質の光触媒活性を有
する粒子との混合物よりなる膜より膜強度が高く、接着
性にも優れるからである。First, the base material and the mixed layer of the photocatalytically active particles and the resin can be more firmly bonded, and the peeling resistance can be improved. This is because the film containing only the thermosetting resin has higher film strength and excellent adhesiveness than the film containing the mixture of the thermosetting resin and the inorganic crystalline particles having photocatalytic activity.
【００５２】第二にこのように熱硬化性樹脂層を介する
ことにより膜強度を向上できるので、基材表面の光触媒
活性を有する粒子と樹脂との混合層中の熱硬化性樹脂量
を低減することができる。このことにより光触媒活性を
有する粒子の分布をより最表面付近に集中させることが
可能となるので、光触媒活性をより発揮しやすくなり、
抗菌性、防臭性等の光触媒機能が向上する。Secondly, since the film strength can be improved by interposing the thermosetting resin layer in this way, the amount of the thermosetting resin in the mixed layer of the particles having the photocatalytic activity on the surface of the base material and the resin is reduced. be able to. This makes it possible to concentrate the distribution of particles having photocatalytic activity closer to the outermost surface, making it easier to exhibit photocatalytic activity,
The photocatalytic function such as antibacterial property and deodorant property is improved.
【００５３】第三にここで挿入する樹脂は、必ずしも光
触媒活性を有する粒子と樹脂との混合層中の樹脂と同種
である必要がない。例えば、光触媒活性を有する粒子と
樹脂との混合層中の樹脂はある程度の光耐蝕性があるほ
うが望ましいが、ここで挿入する樹脂にはその必要はな
いので、より安価な樹脂や着色樹脂で形成してもよい。
また基材と光触媒活性を有する粒子との熱膨張差が著し
く大きい場合には、挿入する樹脂を弾力性のある樹脂や
中間的な熱膨張係数を有する樹脂で形成すると、熱処理
時にクラック等が生じるおそれを解消することができ
る。Thirdly, the resin to be inserted here does not necessarily have to be the same kind as the resin in the mixed layer of the particles having photocatalytic activity and the resin. For example, it is desirable that the resin in the mixed layer of the particles having photocatalytic activity and the resin has some degree of photocorrosion resistance, but since the resin to be inserted here is not required, it is formed of a cheaper resin or a colored resin. You may.
Further, when the difference in thermal expansion between the base material and the particles having photocatalytic activity is extremely large, when the resin to be inserted is made of an elastic resin or a resin having an intermediate thermal expansion coefficient, cracks or the like occur during heat treatment. The fear can be eliminated.
【００５４】この場合の光触媒活性を有する粒子と樹脂
との混合層中の樹脂量は５重量％以上５０重量％以下で
あることが好ましい。５重量％未満では基材表面の耐摩
耗性が充分でなく、５０重量％をこえると光触媒活性を
有する粒子の絶対量が不足して、充分な防臭、抗菌効果
が得られないからである。In this case, the amount of resin in the mixed layer of the particles having photocatalytic activity and the resin is preferably 5% by weight or more and 50% by weight or less. If it is less than 5% by weight, the abrasion resistance of the surface of the substrate is not sufficient, and if it exceeds 50% by weight, the absolute amount of particles having photocatalytic activity is insufficient, and sufficient deodorizing and antibacterial effects cannot be obtained.
【００５５】基材に予め熱硬化性樹脂を塗布する方法
は、溶媒中に熱硬化性樹脂を分散する工程、前記分散液
に硬化剤を添加する工程、硬化剤を添加した液状物を基
材に塗布する工程、基材に塗布した液状物を乾燥する工
程を順次行うことによる。The method of applying the thermosetting resin to the substrate in advance includes the steps of dispersing the thermosetting resin in a solvent, adding the curing agent to the dispersion, and adding the curing agent-added liquid to the substrate. By sequentially performing the step of applying the liquid and the step of drying the liquid material applied to the substrate.
【００５６】[0056]
【作用】光触媒活性を有する粒子の活性点を銀、銅、白
金、パラジウム、金、鉄、ニッケル、コバルト、亜鉛等
の有色金属で覆うことにより、高分子や塵芥の付着によ
る光触媒活性の低下を防止することができる。また基材
上に光触媒活性を有する粒子を強固に固定するために高
温処理等を行い、そのために低下した光触媒活性を上記
有色金属で覆うことにより、回復させることができる。
さらに前記金属微粒子の少なくとも表面を溶液または気
体と反応させて白色化または無色化した塩を形成する方
法によれば、基材の色、模様等のデザインを損なわずに
脱色できる。[Function] By covering the active sites of the particles having photocatalytic activity with a colored metal such as silver, copper, platinum, palladium, gold, iron, nickel, cobalt, zinc, etc., the photocatalytic activity is reduced due to the adhesion of polymers and dust. Can be prevented. Further, high temperature treatment or the like may be performed in order to firmly fix the particles having photocatalytic activity on the base material, and the photocatalytic activity lowered due to the treatment may be recovered by coating with the colored metal.
Further, according to the method of forming a whitened or colorless salt by reacting at least the surface of the metal fine particles with a solution or a gas, decolorization can be performed without impairing the design such as the color and pattern of the base material.
【００５７】[0057]
（実施例１）１５ｃｍ角のタイル基材表面に、平均粒径
０．０１μｍの酸化チタンゾルを塗布後、９００℃で熱
処理し、ルチル型酸化チタン薄膜を形成した。この段階
で止めた試料を比較試料１とする。その後、硝酸銀水溶
液をスプレー・コーティング法にて塗布し、２０ＷのＢ
ＬＢランプを光源として１０分光照射し、銀をルチル型
酸化チタン薄膜上に固定した。このときの銀の担持量は
１．２μｇ／ｃｍ２であり、茶色に呈色した。この段階
で止めた試料を比較試料２とする。その後、０．１ｍｏ
ｌ／リットルのヨウ化カリウム水溶液を比較試料２上に
０．１ｃｃ／ｃｍ２の割合で塗布し反応させた。その結
果、試料表面は黄白色へと変化し、白色化された。ヨウ
化銀層が形成されたためと考えられる。この試料を実施
試料１とする。Example 1 Titanium oxide sol having an average particle size of 0.01 μm was applied to a 15 cm square tile base material surface, followed by heat treatment at 900 ° C. to form a rutile type titanium oxide thin film. The sample stopped at this stage is referred to as Comparative sample 1. After that, an aqueous solution of silver nitrate is applied by the spray coating method to obtain 20 W of B.
The LB lamp was used as a light source to irradiate 10 spectra to fix silver on the rutile type titanium oxide thin film. The amount of silver supported at this time was 1.2 μg / cm 2, and the color was brown. The sample stopped at this stage is referred to as Comparative sample 2. After that, 0.1mo
A 1 / liter aqueous solution of potassium iodide was applied on Comparative Sample 2 at a rate of 0.1 cc / cm 2 and reacted. As a result, the surface of the sample changed to yellowish white and turned white. It is considered that the silver iodide layer was formed. This sample is referred to as a working sample 1.
【００５８】これら試料について、色差、光活性、防臭
特性および抗菌性を評価した。色差の測定は分光式色差
計（東京電色（株）製）で測定した。その際、標準試料
は比較試料１とした。結果を図１に示す。その結果、比
較試料２では色差３．５であったのに対し、ヨウ化カリ
ウム水溶液で処理したことにより、実施試料１では色差
１に減少し、呈色の度合いが減少した。These samples were evaluated for color difference, photoactivity, deodorant property and antibacterial property. The color difference was measured with a spectroscopic color difference meter (manufactured by Tokyo Denshoku Co., Ltd.). At that time, the standard sample was Comparative sample 1. The results are shown in Fig. 1. As a result, the color difference of the comparative sample 2 was 3.5, whereas the color difference of the practical sample 1 was decreased to 1 by the treatment with the potassium iodide aqueous solution, and the degree of coloration was decreased.
【００５９】光活性については△ＰＨ試験で評価した。
△ＰＨ試験とは、試料表面にヨウ化カリウム水溶液を滴
下し、次いで滴下したヨウ化カリウム水溶液に３０分間
紫外線を照射し、照射前のヨウ化カリウム水溶液のＰＨ
と照射後のヨウ化カリウム水溶液のＰＨとの差により光
活性を評価する方法である。すなわちこの方法によれば
試料表面の光活性が高ければ下記に示すような酸化還元
反応がより進行するので照射後のＰＨは照射前のＰＨよ
り高くなっていく。 酸化反応：２Ｉ−＋２ｈ＋＝Ｉ２ 還元反応：Ｏ２＋２Ｈ２Ｏ＋４ｅ−＝４ＯＨ− The photoactivity was evaluated by the ΔPH test.
The ΔPH test is to drop the potassium iodide aqueous solution on the surface of the sample, and then irradiate the dropped potassium iodide aqueous solution with ultraviolet rays for 30 minutes to measure the pH of the potassium iodide aqueous solution before irradiation.
And the pH of the potassium iodide aqueous solution after irradiation is a method of evaluating photoactivity. That is, according to this method, if the photoactivity of the surface of the sample is high, the redox reaction as shown below will proceed more, so that the PH after irradiation becomes higher than the PH before irradiation. Oxidation reaction: 2I − + 2h + = I2 Reduction reaction: O2 + 2H2O + 4e − = 4OH −
【００６０】また防臭特性はＲ３０（Ｌ）で評価した。
Ｒ３０（Ｌ）とは光照射後の悪臭除去率のことで、具体
的には１１Ｌのガラス容器内に試料を入れ、試料の薄膜
を形成した面を光源（ＢＬＢ蛍光灯４Ｗ）から８ｃｍの
距離に配置し、メチルメルカプタンガスを初期濃度３ｐ
ｐｍとなるように容器内に注入し、３０分間光照射した
ときの濃度変化を測定することで得られる。The deodorant property was evaluated by R30 (L).
R30 (L) is the rate of removal of malodor after light irradiation. Specifically, the sample is placed in a glass container of 11 L, and the surface on which the thin film of the sample is formed is 8 cm away from the light source (BLB fluorescent lamp 4W). And place methyl mercaptan gas at an initial concentration of 3 p
It can be obtained by injecting into a container so as to be pm and measuring the change in concentration when irradiated with light for 30 minutes.
【００６１】光活性および防臭特性の結果を図２に示
す。比較試料１と２との比較により、銀を担持したこと
によって、比較試料２では光活性が回復し、△ＰＨもＲ
３０（Ｌ）も良好な結果を示した。また実施試料１と比
較試料２を比較すると、△ＰＨもＲ３０（Ｌ）もともに
ほぼ同程度の値となり、脱色処理によっても光活性には
変化を生じず、良好な特性が維持できることが判明し
た。The results of photoactivity and deodorant properties are shown in FIG. Comparison between Comparative Samples 1 and 2 shows that by supporting silver, the photoactivity is recovered in Comparative Sample 2, and ΔPH is also R.
30 (L) also showed good results. Further, when comparing the practical sample 1 and the comparative sample 2, both ΔPH and R30 (L) have almost the same value, and it has been found that the photoactivity does not change even by the decolorization treatment and good characteristics can be maintained. .
【００６２】また抗菌性については、大腸菌（Ｅｓｃｈ
ｅｒｉｃｈｉａ ｃｏｌｉ Ｗ３１１０株）を用いて試
験した。予め７０％エタノールで殺菌した試料の最表面
に菌液０．１５ｍｌ（２×１０４ＣＦＵ）を滴下し、ガ
ラス板（１００×１００）に載せて基材最表面に密着さ
せ、試料とした。白色灯（３５００ルクス）を所定時間
照射した試料（Ｌ）と、遮光条件下に維持した試料
（Ｄ）の菌液を滅菌ガーゼで拭いて生理食塩水１０ｍｌ
に回収し、生菌数を調べ評価した。Regarding antibacterial activity, Escherichia coli ( Esch
erichia coli W3110 strain). 0.15 ml (2 × 10 4 CFU) of the bacterial solution was dropped on the outermost surface of the sample that had been sterilized with 70% ethanol in advance, and the sample was placed on a glass plate (100 × 100) and brought into close contact with the outermost surface of the substrate. Bacteria solution of sample (L) irradiated with white light (3500 lux) for a predetermined time and sample (D) maintained under light-shielding conditions were wiped with sterile gauze to prepare 10 ml of physiological saline.
Then, the viable cell count was examined and evaluated.
【００６３】抗菌性に関する結果を図３に示す。比較試
料１では銀を担持していないので、暗時（Ｄ）の抗菌効
果は認められない。それに対し、実施試料１では脱色処
理で銀の表面が化合物に変化しているにもかかわらず暗
時（Ｄ）の抗菌効果が認められた。また光照射時（Ｌ）
にはより強い抗菌効果が観察され、銀の抗菌効果のみな
らず、ルチル型酸化チタン薄膜の光触媒活性回復効果も
観察された。The results regarding antibacterial properties are shown in FIG. Since comparative sample 1 does not carry silver, no antibacterial effect in the dark (D) is observed. On the other hand, in the practical sample 1, the antibacterial effect in the dark (D) was recognized even though the silver surface was changed to the compound by the decolorization treatment. Also during light irradiation (L)
A stronger antibacterial effect was observed, and not only the antibacterial effect of silver but also the photocatalytic activity recovery effect of the rutile type titanium oxide thin film was observed.
【００６４】（実施例２）フッ素樹脂をバインダーとし
てアナターゼ型酸化チタンに混合し、この混合物をアク
リル樹脂板に１００μｍ程度塗布した後、乾燥し密着さ
せたものに、０．００１重量％〜０．１重量％の硝酸銀
水溶液を塗布した後、紫外線を照射して酸化チタン薄膜
上に銀を析出せしめ、この表面に０．１ｍｏｌ／リット
ルのヨウ化カリウム水溶液を０．１ｃｃ／ｃｍ２の割合
で塗布し、紫外線を照射すると脱色され、色差が４→
１．２に減少した。また防臭特性Ｒ３０（Ｌ）も９０％
程度と良好であった。(Example 2) Fluorine resin as a binder was mixed with anatase type titanium oxide, and the mixture was applied to an acrylic resin plate to a thickness of about 100 μm, and then dried and adhered. After applying a 1 wt% silver nitrate aqueous solution, ultraviolet rays were irradiated to deposit silver on the titanium oxide thin film, and a 0.1 mol / liter potassium iodide aqueous solution was applied to this surface at a rate of 0.1 cc / cm 2. , When it is irradiated with ultraviolet rays, it is decolorized and the color difference is 4 →
It decreased to 1.2. Also, deodorant property R30 (L) is 90%
The degree was good.
【００６５】（実施例３）プラスチック製品を射出成形
するにあたり、前もって金型面にアナターゼ型酸化チタ
ン粉末と、銀粉末を混合したしたものを塗布しておく。
そして射出成形により、プラスチック表面に酸化チタン
と銀からなる層を設けた後、０．１ｍｏｌ／リットルの
ヨウ化カリウム水溶液中に浸漬し、紫外線を照射すると
脱色され、色差が３→０．８に減少した。また防臭特性
Ｒ３０（Ｌ）も８０％程度と良好であった。(Example 3) Before injection-molding a plastic product, a mixture of anatase type titanium oxide powder and silver powder was applied to the surface of the mold in advance.
After a layer of titanium oxide and silver was formed on the plastic surface by injection molding, it was immersed in a 0.1 mol / liter potassium iodide aqueous solution and irradiated with ultraviolet light to be decolorized, and the color difference was changed from 3 to 0.8. Diminished. The deodorizing property R30 (L) was also good at about 80%.
【００６６】（実施例４）１５ｃｍ角の衛生陶器成形素
地に釉薬を塗布後、１１００〜１２００℃で焼成後、平
均粒径０．０１μｍのアナターゼ型酸化チタンゾルを塗
布し、９００〜１０００℃で焼成し、衛生陶器素地基材
上にルチル型酸化チタン薄膜を固定した。この後、その
上に硝酸銀水溶液を塗布し、紫外線を照射して酸化チタ
ン薄膜上に銀を析出せしめた。さらにその上に塩化第二
鉄水溶液を塗布し、紫外線を照射すると脱色され、色差
が３→０．３に減少した。また抗菌性は、光照射時、暗
時ともに試料に３０分接触させることで、もとの菌数の
１０％未満しか生菌してないことが確認され、良好な結
果を示した。(Example 4) After applying a glaze to a 15 cm square sanitary ware molding base, baking it at 1100 to 1200 ° C, applying anatase type titanium oxide sol having an average particle diameter of 0.01 µm, and baking at 900 to 1000 ° C. Then, the rutile type titanium oxide thin film was fixed on the sanitary ware base material. After this, an aqueous silver nitrate solution was applied onto it and irradiated with ultraviolet rays to deposit silver on the titanium oxide thin film. Further, an aqueous solution of ferric chloride was applied onto it, and when it was irradiated with ultraviolet rays, it was decolorized and the color difference was reduced from 3 to 0.3. As for the antibacterial property, it was confirmed that less than 10% of the original number of bacteria was viable when the sample was contacted with the sample for 30 minutes both in the light irradiation and in the dark, showing a good result.
【００６７】（実施例５）平均粒径０．０１μｍのアナ
ターゼ型酸化チタンゾルの硝酸分散液と撥水性のあるシ
ロキサン・クリア・コート樹脂を所定の重量比で混合
し、プロパノールで希釈した後、硬化剤を添加した溶液
を塗布した。塗布後１５０℃で焼成して固化させ冷却し
た。さらにこの基材に酢酸銅水溶液をアルミナ基板に塗
布し、この後光還元（光源は２０ワットＢＬＢランプ、
光源から試料までの距離１０ｃｍ、照射時間１５分）し
て試料を得た。このようにして得られた混合層の膜厚は
約０．８μｍであり、結晶型はアナターゼであった。ま
た上記光還元処理を大気中で行うと、銅はすでに脱色さ
れた状態で固定される。このことは、ＥＳＣＡ（化学分
析のための電子分光法）により固定された銅が０価およ
び１価で存在することから、一度還元固定された銅の少
なくとも表面がアナターゼ型酸化チタンの光触媒作用に
より生成した活性酸素種と反応し、酸化第一銅へと変化
しているためと考えられ、この工程中に銅は脱色される
のである。得られた試料について防臭性、耐摩耗性、耐
水あか性について評価した。Example 5 A nitric acid dispersion of anatase type titanium oxide sol having an average particle diameter of 0.01 μm and a water-repellent siloxane clear coat resin were mixed at a predetermined weight ratio, diluted with propanol and then cured. The solution containing the agent was applied. After coating, it was baked at 150 ° C. to be solidified and cooled. Further, an aqueous solution of copper acetate was applied to this base material on an alumina substrate, and then photoreduction (a light source was a 20 watt BLB lamp,
A sample was obtained after the distance from the light source to the sample was 10 cm and the irradiation time was 15 minutes. The thickness of the mixed layer thus obtained was about 0.8 μm, and the crystal type was anatase. When the photoreduction treatment is performed in the atmosphere, copper is fixed in a decolorized state. This means that copper fixed by ESCA (electron spectroscopy for chemical analysis) exists in 0 valence and 1 valence, and therefore at least the surface of copper once reduced and fixed is due to the photocatalytic action of anatase type titanium oxide. It is considered that this is because it reacts with the generated active oxygen species and changes into cuprous oxide, and copper is decolorized during this step. The obtained sample was evaluated for deodorant property, abrasion resistance, and water stain resistance.
【００６８】防臭性評価については以下に示す方法によ
り、悪臭ガスとしてメチルメルカプタンを用い、Ｒ３
０′を測定することにより評価した。Ｒ３０′とは、暗
時に濃度３ｐｐｍのメチルメルカプタンガスを１１Ｌの
ガラス容器内に注入し、１日放置してガスを試料に充分
に吸着させた後に、１日光照射（光源（ＢＬＢ蛍光灯４
Ｗ）は試料から８ｃｍの距離に配置）し吸着ガスを光分
解した後に、新たにメチルメルカプタンガスを初期濃度
３ｐｐｍとなるように容器内に注入し、暗時の３０分後
の濃度変化を測定することで得られる。For the evaluation of deodorant property, methyl mercaptan was used as a malodorous gas and R3
It was evaluated by measuring 0 '. R30 'means that methyl mercaptan gas having a concentration of 3 ppm in the dark is injected into an 11 L glass container and left for 1 day to allow the gas to be sufficiently adsorbed to the sample, and then 1 sun irradiation (light source (BLB fluorescent lamp 4
(W) is placed at a distance of 8 cm from the sample), and the adsorbed gas is photolyzed, and then methyl mercaptan gas is newly injected into the container so that the initial concentration is 3 ppm, and the concentration change after 30 minutes in the dark is measured. It is obtained by doing.
【００６９】耐摩耗性については、プラスチック消しゴ
ムを用いた摺動摩耗を行い、外観の変化を比較し、評価
した。評価基準を下記に示す。 ◎：４０回往復に対して変化なし ○：１０回以上４０回未満の摺動で傷が入り、光触媒層
が剥離 △：５回以上１０回未満の摺動で傷が入り、光触媒層が
剥離 ×：５回未満の摺動で傷が入り、光触媒層が剥離 耐水あか性については、以下に示す装置により評価し
た。すなわち試料の光触媒等からなる層を形成した面を
上方に向けて配置し、光を試料上方の面に照射しながら
公衆浴場で採取した風呂水を循環させながら連続的に滴
下した。そして１４日後の試料面を観察し、生じたぬめ
りの程度および無機系の汚れについて評価した。ぬめり
についての評価基準を下記に示す。 ◎：ぬめりは認められない ○：ややぬめりを感じる △：ぬめりが生じる ×：ぬめりがひどく生じる 無機系の汚れについての評価基準を下記に示す。 ◎：無機系の汚れが生じない ○：無機系の汚れが生じるが、簡単に拭き取れ、かすか
に跡が残る程度である △：無機系の汚れが生じるが、簡単に拭き取れ、わずか
に跡が残る程度である ×：無機系の汚れが生じ、強くこする程度では拭き取れ
ない 結果を図４〜７の黒点に示す。基材表面にアナターゼ粒
子からなる光触媒と銅（および酸化第一銅）とシロキサ
ン樹脂との混合層を形成することにより、基材表面の耐
摩耗性は向上し、混合層中のシロキサン樹脂を２０重量
％以上にすることにより◎または○となった（図４）。
また防臭特性はアナターゼ粒子を増加させると向上し、
シロキサン樹脂が２０重量％以下ではＲ３０′で５０％
以上となった（図５）。また無機汚れについてもシロキ
サン樹脂が２０重量％添加で○となった。さらにぬめり
についてもシロキサン樹脂が２０〜３０重量％添加で○
となり、防汚効果があることが見出だされた。さらに接
触角測定器によりぬれ角を測定したところ、シロキサン
樹脂が２０重量％で５０゜と下記の比較例に対して若干
の撥水作用が観察された。The abrasion resistance was evaluated by performing sliding abrasion using a plastic eraser and comparing changes in appearance. The evaluation criteria are shown below. ⊚: No change after 40 reciprocations ◯: Scratch occurred by sliding 10 times or more but less than 40 times and photocatalyst layer peeled off Δ: Scratch occurred by sliding 5 times or more but less than 10 times and photocatalyst layer peeled off Poor: Photocatalyst layer was peeled off by sliding less than 5 times. Water resistance was evaluated by the following device. That is, the surface of the sample on which the layer made of a photocatalyst or the like was formed was arranged to face upward, and while irradiating the surface above the sample with the water, the bath water collected in the public bath was circulated and continuously dropped. Then, after 14 days, the surface of the sample was observed and evaluated for the degree of sliminess and the inorganic stain. The evaluation criteria for slime are shown below. ◎: No sliminess is recognized ○: Some sliminess is felt △: Slimming occurs ×: Severe slimming occurs Evaluation criteria for inorganic stains are shown below. ⊚: No inorganic stains ○: Inorganic stains occur, but are easily wiped off, leaving a slight mark Δ: Inorganic stains are generated, easily wiped off, slightly leave marks Degree: Poor: Inorganic stains are formed and cannot be wiped off with strong rubbing. The results are shown by black dots in FIGS. By forming a mixed layer of a photocatalyst composed of anatase particles, copper (and cuprous oxide), and a siloxane resin on the surface of the base material, the abrasion resistance of the surface of the base material is improved, and the siloxane resin in the mixed layer is reduced to 20%. It became ◎ or ○ by making it more than weight% (Fig. 4).
In addition, the deodorant property improves with increasing anatase particles,
If the siloxane resin content is less than 20% by weight, R30 'is 50%
That is all (Fig. 5). With respect to inorganic stains, addition of 20% by weight of siloxane resin resulted in ◯. Regarding slime, addition of 20 to 30% by weight of siloxane resin
Then, it was found that it has an antifouling effect. Further, when the wetting angle was measured by a contact angle measuring device, the siloxane resin was 50% at 20% by weight, and a slight water repellency was observed with respect to the following comparative examples.
【００７０】それに対し、試料にアナターゼ粒子からな
る光触媒と銅（および酸化第一銅）のみを担持させた場
合（図中シロキサン樹脂０重量％；平均粒径０．０１μ
ｍの酸化チタンゾルの硝酸分散液を基材に塗布後、３０
０℃で焼成し、その後酢酸銅水溶液を塗布し、大気中で
光還元（光源は２０ワットＢＬＢランプ、光源から試料
までの距離１０ｃｍ、照射時間１５分））には汚れがア
ナターゼ粒子間に入りこむため防汚性が悪く、また基材
に対するアナターゼ粒子の密着性が悪いため耐摩耗性が
悪い。さらに接触角測定器によりぬれ角を測定したとこ
ろ、１２°であり、ほとんど撥水性は認められなかっ
た。On the other hand, when only the photocatalyst consisting of anatase particles and copper (and cuprous oxide) are supported on the sample (0% by weight of siloxane resin in the figure; average particle diameter 0.01 μ)
After applying the nitric acid dispersion liquid of titanium oxide sol of m to the substrate,
Baking at 0 ° C., then applying an aqueous solution of copper acetate, and in photoreduction in the air (light source is 20 watt BLB lamp, distance from light source to sample is 10 cm, irradiation time is 15 minutes), dirt enters between anatase particles. Therefore, the antifouling property is poor, and the wear resistance is poor because the adhesion of the anatase particles to the substrate is poor. Further, when the wetting angle was measured by a contact angle measuring device, it was 12 °, and almost no water repellency was recognized.
【００７１】また試料にシロキサン樹脂と銅のみを担持
させた場合（図中シロキサン樹脂１００重量％；予めプ
ロパノールで希釈した撥水性のあるシロキサン・クリア
コート樹脂に硬化剤を添加した液状物を１０ｃｍ角のア
ルミニウム基板に約１０μｍ塗布後１５０℃にて乾燥
し、次にこの基材に酢酸銅水溶液を塗布し、この後光照
射（光源は２０ワットＢＬＢランプ、光源から試料まで
の距離１０ｃｍ、照射時間１５分））にも光活性がな
く、一度吸着した気体を分解できないため防臭特性Ｒ３
０′は１０％と悪く、また防汚性も悪い。When only the siloxane resin and copper were carried on the sample (100% by weight of the siloxane resin in the figure; a liquid substance obtained by adding a curing agent to a water-repellent siloxane clear coat resin previously diluted with propanol, was 10 cm square. Of aluminum substrate of about 10 μm and then dried at 150 ° C., and then this substrate is coated with an aqueous solution of copper acetate, followed by light irradiation (light source is 20 watt BLB lamp, distance from light source to sample is 10 cm, irradiation time 15 minutes)) has no photoactivity and cannot decompose the gas once adsorbed, so it has deodorant property R3
0'is as bad as 10%, and the antifouling property is also bad.
【００７２】（実施例６）まず予めプロパノールで希釈
した撥水性のあるシロキサン・クリアコート樹脂に硬化
剤を添加した液状物を１０ｃｍ角のアルミニウム基板に
約１０μｍ塗布後１５０℃にて乾燥した。次に平均粒径
０．０１μｍの酸化チタンゾルの硝酸分散液と撥水性の
あるシロキサン・クリアコート樹脂を所定の重量比で混
合し、プロパノールで希釈した後、硬化剤を添加した液
状物を塗布した。塗布後１５０℃で焼成して固化させ冷
却した。さらにこの基材に酢酸銅水溶液を塗布し、この
後大気中で光還元（光源は２０ワットＢＬＢランプ、光
源から試料までの距離１０ｃｍ、照射時間１５分）して
脱色された試料を得た。このようにして得られた混合層
の膜厚は０．３μｍであり、中間のシロキサン樹脂層の
膜厚は０．５μｍであった。また酸化チタンの結晶型は
アナターゼであった。Example 6 First, a liquid material prepared by adding a curing agent to a water-repellent siloxane clear coat resin previously diluted with propanol was applied on an aluminum substrate of 10 cm square by about 10 μm and then dried at 150 ° C. Next, a nitric acid dispersion liquid of titanium oxide sol having an average particle diameter of 0.01 μm and a water-repellent siloxane-clear coat resin were mixed at a predetermined weight ratio, diluted with propanol, and then a liquid material containing a curing agent was applied. . After coating, it was baked at 150 ° C. to be solidified and cooled. Further, an aqueous solution of copper acetate was applied to this base material, and then photoreduced in the air (light source was 20 watt BLB lamp, distance from light source to sample was 10 cm, irradiation time was 15 minutes) to obtain a decolorized sample. The thickness of the mixed layer thus obtained was 0.3 μm, and the thickness of the intermediate siloxane resin layer was 0.5 μm. The crystal form of titanium oxide was anatase.
【００７３】結果を図４〜７の白抜き点で示す。中間に
シロキサン樹脂層を介したことにより、耐摩耗性は、混
合層中のシロキサン樹脂量が５重量％でも○となった。
また防臭特性もシロキサン樹脂量５０重量％でもＲ３
０′で９０％以上となり良好な結果を示した。したがっ
て中間にシロキサン樹脂層を介すると、混合層中のシロ
キサン樹脂量に対して逆の傾向を示す上記２特性の調和
を容易にとれるようになる。また防汚特性に関しても特
に有機成分を主とするぬめりについては中間にシロキサ
ン樹脂層を介する構造をとることにより改善され、シロ
キサン樹脂量５〜５０重量％で◎と良好な結果を示し
た。The results are shown by white dots in FIGS. By having the siloxane resin layer in the middle, the wear resistance was good even when the amount of the siloxane resin in the mixed layer was 5% by weight.
Also, the deodorant property is R3 even when the amount of siloxane resin is 50% by weight.
At 0 ', 90% or more, which is a good result. Therefore, by interposing the siloxane resin layer in the middle, it becomes easy to harmonize the above two characteristics showing the opposite tendency to the amount of the siloxane resin in the mixed layer. Also, the antifouling property was improved by taking a structure having a siloxane resin layer in the middle, particularly with respect to slime containing mainly organic components, and a good result was shown as ⊚ when the amount of siloxane resin was 5 to 50% by weight.
【００７４】（実施例７）１５ｃｍ角の衛生陶器成形素
地に釉薬を塗布後、１１００〜１２００℃で焼成した。
さらにその上に平均粒径０．０１μｍのアナターゼ型酸
化チタンゾルを塗布し、９００〜１０００℃で焼成し、
衛生陶器素地基材上にルチル型酸化チタン薄膜を固定し
た。この後、その上に硝酸銀水溶液を塗布し、紫外線を
照射して酸化チタン薄膜に銀を析出せしめた。さらに試
料をオゾナイザー付きのデシケーター中（オゾン濃度数
１０ｐｐｍ）に約２時間放置すると脱色された。また抗
菌性は、光照射時、暗時ともに試料に３時間接触させる
ことで、もとの菌数の１０％未満しか生菌していないこ
とが確認され、良好な結果を示した。Example 7 A glaze was applied to a 15 cm square sanitary ware molding base and then baked at 1100 to 1200 ° C.
Further, anatase-type titanium oxide sol having an average particle size of 0.01 μm is applied thereon and baked at 900 to 1000 ° C.,
A rutile type titanium oxide thin film was fixed on a sanitary ware base material. After that, an aqueous silver nitrate solution was applied onto it, and ultraviolet rays were irradiated to deposit silver on the titanium oxide thin film. Furthermore, the sample was decolorized by leaving it in a desiccator equipped with an ozonizer (ozone concentration: several 10 ppm) for about 2 hours. Regarding the antibacterial property, it was confirmed that less than 10% of the original bacterial number was viable by contacting the sample with the sample for 3 hours both in the light irradiation and in the dark, showing a good result.
【００７５】（実施例８）１５ｃｍ角の衛生陶器成形素
地に釉薬を塗布後、１０００〜１２００℃で焼成した。
さらにその上に、硝酸水溶液中に分散した平均粒径０．
０１μｍのアナターゼ型酸化チタンゾルと硝酸銀水溶液
との金剛液を塗布した後焼成し衛生陶器素地基材上に酸
化チタン薄膜を固定した。このとき７００℃未満の焼成
では茶色に呈色するが、７００℃以上で焼成すると脱色
された。銀表面が大気中成分と反応したためと解され
る。また８５０℃で焼成して衛生陶器素地基材上にアナ
ターゼ型酸化チタン薄膜を固定した試料について抗菌性
を測定すると、光照射時、暗時ともに試料に３時間接触
させることで、もとの菌数の１０％未満しか生菌してい
ないことが確認され、良好な結果を示した。Example 8 A glaze was applied to a 15 cm square sanitary ware molding base and then baked at 1000 to 1200 ° C.
Furthermore, an average particle size of 0.
The titanium oxide thin film was fixed on the sanitary ware base material after applying a gold-and-gold solution of anatase-type titanium oxide sol having a thickness of 01 μm and an aqueous silver nitrate solution and then firing. At this time, if it was baked below 700 ° C., it was colored brown, but if it was baked at 700 ° C. or higher, it was decolorized. It is considered that the surface of silver reacted with components in the atmosphere. In addition, the antibacterial property was measured for the sample in which the anatase type titanium oxide thin film was fixed on the sanitary ware substrate by firing at 850 ° C. It was confirmed that less than 10% of the number of viable cells were viable, and good results were shown.
【００７６】（実施例９）１５ｃｍ角の衛生陶器成形素
地に釉薬を塗布後、１１００〜１２００℃で焼成した。
さらにその上に平均粒径０．０１μｍのアナターゼ型酸
化チタンゾルを塗布し、９００〜１０００℃で焼成し、
衛生陶器素地基材上にルチル型酸化チタン薄膜を固定し
た。この後、その上に硝酸銀水溶液を塗布し、紫外線を
照射して酸化チタン薄膜に銀を析出せしめた。さらにそ
の上に過酸化水素水を塗布すると脱色された。また抗菌
性は、光照射時、暗時ともに試料に３時間接触させるこ
とで、もとの菌数の１０％未満しか生菌していないこと
が確認され、良好な結果を示した。Example 9 A glaze was applied to a 15 cm square sanitary ware molding base, and then baked at 1100 to 1200 ° C.
Further, anatase-type titanium oxide sol having an average particle size of 0.01 μm is applied thereon and baked at 900 to 1000 ° C.,
A rutile type titanium oxide thin film was fixed on a sanitary ware base material. After that, an aqueous silver nitrate solution was applied onto it, and ultraviolet rays were irradiated to deposit silver on the titanium oxide thin film. Furthermore, it was decolorized by applying hydrogen peroxide solution on it. Regarding the antibacterial property, it was confirmed that less than 10% of the original bacterial number was viable by contacting the sample with the sample for 3 hours both in the light irradiation and in the dark, showing a good result.
【００７７】[0077]
【発明の効果】光触媒活性を有する粒子に有色の金属微
粒子を固定化することにより、光触媒活性を高く維持、
向上できるとともに、前記有色の金属微粒子を溶液また
は気体と反応させて少なくとも金属微粒子表面に無色化
または白色化した塩を形成することにより膜を脱色する
ことができ、下地に形成したデザインを活かすことが可
能となる。EFFECT OF THE INVENTION By immobilizing colored metal fine particles on the particles having photocatalytic activity, the photocatalytic activity is maintained high,
In addition to being able to improve, it is possible to decolorize the film by reacting the colored metal fine particles with a solution or gas to form a colorless or whitened salt on at least the surface of the metal fine particles, and utilize the design formed on the base. Is possible.
【図１】本発明の実施例と比較例との色差△Ｅを示すグ
ラフFIG. 1 is a graph showing a color difference ΔE between an example of the present invention and a comparative example.
【図２】本発明の実施例と比較例との光活性△ｐＨを示
すグラフFIG. 2 is a graph showing the photoactivity ΔpH of the example of the present invention and the comparative example.
【図３】本発明の実施例と比較例との抗菌性を示すグラ
フFIG. 3 is a graph showing antibacterial properties of Examples of the present invention and Comparative Examples.
【図４】本発明の実施例を示す図で、シロキサン樹脂の
添加量と耐摩耗性との関係を示すグラフFIG. 4 is a graph showing an example of the present invention, which is a graph showing the relationship between the amount of siloxane resin added and wear resistance.
【図５】本発明の実施例を示す図で、シロキサン樹脂の
添加量と防臭性との関係を示すグラフFIG. 5 is a graph showing an example of the present invention and is a graph showing the relationship between the amount of siloxane resin added and the deodorant property.
【図６】本発明の実施例を示す図で、シロキサン樹脂の
添加量と無機汚れの関係を示すグラフFIG. 6 is a diagram showing an example of the present invention, and is a graph showing the relationship between the amount of siloxane resin added and inorganic stains.
【図７】本発明の実施例を示す図で、シロキサン樹脂の
添加量とぬめりとの関係を示すグラフFIG. 7 is a diagram showing an example of the present invention, and is a graph showing the relationship between the amount of siloxane resin added and sliminess.
フロントページの続き (72)発明者 千国 真 福岡県北九州市小倉北区中島２丁目１番１ 号 東陶機器株式会社内 (72)発明者 早川 信 福岡県北九州市小倉北区中島２丁目１番１ 号 東陶機器株式会社内 (72)発明者 渡部 俊也 福岡県北九州市小倉北区中島２丁目１番１ 号 東陶機器株式会社内Front page continuation (72) Inventor Makoto Senkoku 2-1-1 Nakajima, Kokurakita-ku, Kitakyushu, Fukuoka Prefecture Totoki Equipment Co., Ltd. (72) Shin Hayakawa 2-chome, Nakajima, Kitakyushu, Kitakyushu 2-1-1 No. 1 Totoki Equipment Co., Ltd. (72) Inventor Toshiya Watanabe 2-1-1 Nakajima, Kokurakita-ku, Kitakyushu City, Fukuoka Prefecture Totoki Equipment Co., Ltd.
Claims (7)
の金属微粒子を固定する工程、前記金属微粒子と溶液ま
たは気体を反応させて少なくとも金属微粒子表面に無色
化または白色化した塩を形成する工程からなることを特
徴とする金属微粒子を含む触媒を有する部材の作製方
法。1. A step of fixing particles having photocatalytic activity and colored metal fine particles on a substrate, and reacting the metal fine particles with a solution or gas to form a colorless or whitened salt on at least the surface of the metal fine particles. A method for producing a member having a catalyst containing fine metal particles, the method comprising the steps of:
の金属微粒子を固定する工程、前記金属微粒子と溶液ま
たは気体を反応させて少なくとも金属微粒子表面に無色
化または白色化した塩を形成する工程をこの順に行うこ
とを特徴とする金属微粒子を含む触媒を有する部材の作
製方法。2. A step of fixing particles having photocatalytic activity and colored metal fine particles on a substrate, and reacting the metal fine particles with a solution or gas to form a colorless or whitened salt on at least the surface of the metal fine particles. A method for producing a member having a catalyst containing metal fine particles, which comprises performing the steps in this order.
金属微粒子表面に無色化または白色化した塩を形成する
工程、基材上に光触媒活性を有する粒子と無色化又は白
色化した塩を表面に形成した金属微粒子を固定する工程
をこの順に行うことを特徴とする金属微粒子を含む触媒
を有する部材の作製方法。3. A step of reacting a solution or a gas to form a colorless or whitened salt on at least the surface of the fine metal particles, and forming particles having photocatalytic activity and a colorless or whitened salt on the surface of the base material. The method for producing a member having a catalyst containing metal fine particles, characterized in that the steps of fixing the metal fine particles are performed in this order.
含む触媒を有する部材の作製方法において、前記金属微
粒子と反応させる溶液は、有色の金属微粒子の少なくと
も表面に無色化又は白色化した不溶性または難溶性の塩
を形成する物質を含む溶液であることを特徴とする金属
微粒子を含む触媒を有する部材の作製方法。4. The method for producing a member having a catalyst containing metal fine particles according to claim 1, wherein the solution reacted with the metal fine particles is colorless or whitened on at least the surface of the colored metal fine particles. A method for producing a member having a catalyst containing fine metal particles, which is a solution containing a substance that forms an insoluble or sparingly soluble salt.
含む触媒を有する部材の作製方法において、前記金属微
粒子と反応させる溶液は、塩化第二鉄水溶液等のハロゲ
ン化塩溶液または過酸化水素水、オゾン水等の酸化剤を
含む溶液のうちから選ばれる物質の少なくとも１種から
なることを特徴とする金属微粒子を含む触媒を有する部
材の作製方法。5. The method for producing a member having a catalyst containing metal fine particles according to claim 1, wherein the solution reacted with the metal fine particles is a halide salt solution such as an aqueous ferric chloride solution or a peroxide. A method for producing a member having a catalyst containing fine metal particles, which comprises at least one substance selected from a solution containing an oxidizing agent such as hydrogen water and ozone water.
含む触媒を有する部材の作製方法において、前記金属微
粒子と反応させる気体は、酸素、水蒸気、オゾン等の酸
化剤からなることを特徴とする金属微粒子を含む触媒を
有する部材の作製方法。6. The method for producing a member having a catalyst containing metal fine particles according to claim 1, wherein the gas that reacts with the metal fine particles is an oxidizing agent such as oxygen, water vapor, or ozone. A method for producing a member having a catalyst containing fine metal particles.
を有する部材の作成方法において、気体と反応させて生
成する少なくとも金属微粒子表面に無色化または白色化
した塩は、不溶性又は難溶性であることを特徴とする金
属微粒子を含む触媒を有する部材の作製方法。7. The method for producing a member having a catalyst containing metal fine particles according to claim 6, wherein at least the surface of the metal fine particles, which is formed by reacting with gas, is colorless or whitened and is insoluble or sparingly soluble. A method for producing a member having a catalyst containing metal fine particles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33741794A JP3261909B2 (en) | 1993-12-14 | 1994-12-14 | Member having catalyst containing fine metal particles and method for producing the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5-313062 | 1993-12-14 | ||
| JP31306293 | 1993-12-14 | ||
| JP33741794A JP3261909B2 (en) | 1993-12-14 | 1994-12-14 | Member having catalyst containing fine metal particles and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07222928A true JPH07222928A (en) | 1995-08-22 |
| JP3261909B2 JP3261909B2 (en) | 2002-03-04 |
Family
ID=26567435
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33741794A Expired - Lifetime JP3261909B2 (en) | 1993-12-14 | 1994-12-14 | Member having catalyst containing fine metal particles and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3261909B2 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1081840A (en) * | 1996-07-19 | 1998-03-31 | Toto Ltd | Photocatalitic hydrophilic coating composition |
| JPH10237353A (en) * | 1997-02-24 | 1998-09-08 | Tao:Kk | Hydrophilic coating agent and surface hydrophilic substrate |
| JPH10237352A (en) * | 1997-02-24 | 1998-09-08 | Tao:Kk | Polyfunctional coating agent |
| JPH11512336A (en) * | 1995-09-15 | 1999-10-26 | ロディア シミ | Substrate with photocatalytic coating based on titanium dioxide and organic dispersion based on titanium dioxide |
| JPH11512337A (en) * | 1995-09-15 | 1999-10-26 | サン−ゴバン ビトラージュ | Substrate with photocatalytic coating |
| JP2007193917A (en) * | 2006-01-20 | 2007-08-02 | Toda Kogyo Corp | Compound nonmagnetic particle powder for nonmagnetic under layer of magnetic recording medium, nonmagnetic coating, and magnetic recording medium |
| JP2008024578A (en) * | 2006-06-20 | 2008-02-07 | Nagaoka Univ Of Technology | Method for producing thin film having photocatalytic activity in visible light range |
| WO2012132716A1 (en) * | 2011-03-30 | 2012-10-04 | パナソニック株式会社 | Water-repellent photocatalytic composition and water-repellent photocatalytic coating film |
| JP2012210556A (en) * | 2011-03-30 | 2012-11-01 | Panasonic Corp | Water purifier |
-
1994
- 1994-12-14 JP JP33741794A patent/JP3261909B2/en not_active Expired - Lifetime
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11512336A (en) * | 1995-09-15 | 1999-10-26 | ロディア シミ | Substrate with photocatalytic coating based on titanium dioxide and organic dispersion based on titanium dioxide |
| JPH11512337A (en) * | 1995-09-15 | 1999-10-26 | サン−ゴバン ビトラージュ | Substrate with photocatalytic coating |
| JPH1081840A (en) * | 1996-07-19 | 1998-03-31 | Toto Ltd | Photocatalitic hydrophilic coating composition |
| JPH10237353A (en) * | 1997-02-24 | 1998-09-08 | Tao:Kk | Hydrophilic coating agent and surface hydrophilic substrate |
| JPH10237352A (en) * | 1997-02-24 | 1998-09-08 | Tao:Kk | Polyfunctional coating agent |
| JP2007193917A (en) * | 2006-01-20 | 2007-08-02 | Toda Kogyo Corp | Compound nonmagnetic particle powder for nonmagnetic under layer of magnetic recording medium, nonmagnetic coating, and magnetic recording medium |
| JP2008024578A (en) * | 2006-06-20 | 2008-02-07 | Nagaoka Univ Of Technology | Method for producing thin film having photocatalytic activity in visible light range |
| WO2012132716A1 (en) * | 2011-03-30 | 2012-10-04 | パナソニック株式会社 | Water-repellent photocatalytic composition and water-repellent photocatalytic coating film |
| JP2012210557A (en) * | 2011-03-30 | 2012-11-01 | Panasonic Corp | Water-repellent photocatalytic composition and water-repellent photocatalytic coating film |
| JP2012210556A (en) * | 2011-03-30 | 2012-11-01 | Panasonic Corp | Water purifier |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3261909B2 (en) | 2002-03-04 |
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