JP2000014755A - Metal plate having photocatalytic function - Google Patents
Metal plate having photocatalytic functionInfo
- Publication number
- JP2000014755A JP2000014755A JP10182625A JP18262598A JP2000014755A JP 2000014755 A JP2000014755 A JP 2000014755A JP 10182625 A JP10182625 A JP 10182625A JP 18262598 A JP18262598 A JP 18262598A JP 2000014755 A JP2000014755 A JP 2000014755A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- photocatalyst
- photocatalytic
- metal plate
- photocatalyst layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 71
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 34
- 239000002184 metal Substances 0.000 title claims abstract description 34
- 239000011941 photocatalyst Substances 0.000 claims abstract description 125
- 239000002245 particle Substances 0.000 claims abstract description 52
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 30
- 239000010959 steel Substances 0.000 claims abstract description 30
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000314 lubricant Substances 0.000 claims abstract description 26
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 22
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 6
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 5
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 5
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 5
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 4
- 229910052788 barium Inorganic materials 0.000 claims abstract description 3
- 238000011282 treatment Methods 0.000 claims description 32
- 239000010953 base metal Substances 0.000 claims description 13
- 239000010935 stainless steel Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 18
- 229910052759 nickel Inorganic materials 0.000 abstract description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract 2
- 239000010408 film Substances 0.000 description 44
- 238000012360 testing method Methods 0.000 description 41
- 238000000576 coating method Methods 0.000 description 37
- 239000011248 coating agent Substances 0.000 description 35
- 239000003973 paint Substances 0.000 description 32
- 238000000034 method Methods 0.000 description 22
- 239000001993 wax Substances 0.000 description 20
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 16
- 238000001035 drying Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- -1 polyethylene Polymers 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 239000004698 Polyethylene Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 238000000465 moulding Methods 0.000 description 9
- 229920000573 polyethylene Polymers 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 230000037303 wrinkles Effects 0.000 description 9
- 238000000354 decomposition reaction Methods 0.000 description 8
- 229910019142 PO4 Inorganic materials 0.000 description 7
- 150000004703 alkoxides Chemical class 0.000 description 7
- 239000008199 coating composition Substances 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 235000021317 phosphate Nutrition 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 239000002518 antifoaming agent Substances 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 6
- ZARVOZCHNMQIBL-UHFFFAOYSA-N oxygen(2-) titanium(4+) zirconium(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4] ZARVOZCHNMQIBL-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 6
- 239000010452 phosphate Substances 0.000 description 6
- 238000007747 plating Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 241000208125 Nicotiana Species 0.000 description 5
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 235000019504 cigarettes Nutrition 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000002932 luster Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 230000003373 anti-fouling effect Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000004566 building material Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000010960 cold rolled steel Substances 0.000 description 3
- 239000008119 colloidal silica Substances 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 125000002496 methyl group Chemical class [H]C([H])([H])* 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229920002050 silicone resin Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- 229910018137 Al-Zn Inorganic materials 0.000 description 2
- 229910018573 Al—Zn Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000809 air pollutant Substances 0.000 description 2
- 231100001243 air pollutant Toxicity 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229920006125 amorphous polymer Polymers 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000004332 deodorization Methods 0.000 description 2
- 230000001877 deodorizing effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 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
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910018131 Al-Mn Inorganic materials 0.000 description 1
- 229910018461 Al—Mn Inorganic materials 0.000 description 1
- 101100316860 Autographa californica nuclear polyhedrosis virus DA18 gene Proteins 0.000 description 1
- 102100032566 Carbonic anhydrase-related protein 10 Human genes 0.000 description 1
- 102100033029 Carbonic anhydrase-related protein 11 Human genes 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 102100022626 Glutamate receptor ionotropic, NMDA 2D Human genes 0.000 description 1
- 101000867836 Homo sapiens Carbonic anhydrase-related protein 10 Proteins 0.000 description 1
- 101000867841 Homo sapiens Carbonic anhydrase-related protein 11 Proteins 0.000 description 1
- 101001075218 Homo sapiens Gastrokine-1 Proteins 0.000 description 1
- 101000972840 Homo sapiens Glutamate receptor ionotropic, NMDA 2D Proteins 0.000 description 1
- 101000650817 Homo sapiens Semaphorin-4D Proteins 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 101100219325 Phaseolus vulgaris BA13 gene Proteins 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 101001062854 Rattus norvegicus Fatty acid-binding protein 5 Proteins 0.000 description 1
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 1
- 102100027744 Semaphorin-4D Human genes 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
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- 238000009833 condensation Methods 0.000 description 1
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- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- LRCFXGAMWKDGLA-UHFFFAOYSA-N dioxosilane;hydrate Chemical compound O.O=[Si]=O LRCFXGAMWKDGLA-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 210000003746 feather Anatomy 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
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- 238000010304 firing Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
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- 239000010687 lubricating oil Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910000734 martensite Inorganic materials 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
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- 230000033116 oxidation-reduction process Effects 0.000 description 1
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- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
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- 230000005855 radiation Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- VIDTVPHHDGRGAF-UHFFFAOYSA-N selenium sulfide Chemical compound [Se]=S VIDTVPHHDGRGAF-UHFFFAOYSA-N 0.000 description 1
- 229960005265 selenium sulfide Drugs 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、大気汚染物質や排
水中などの有害物質を分解し、防臭、防汚（固体表面の
汚れ防止）、殺菌等に有効な光触媒層を設けた光触媒機
能を有する金属板に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocatalytic function having a photocatalytic layer provided for decomposing air pollutants and harmful substances in wastewater, and effective for deodorization, antifouling (prevention of contamination of solid surfaces), sterilization, and the like. And a metal plate having the same.
【０００２】[0002]
【従来の技術】酸化チタン、酸化亜鉛、酸化鉄等の金属
化合物半導体に、そのバンドギャップ以上のエネルギー
を持つ波長の光を照射すると、照射面に還元作用を有す
る電子と酸化作用を有する正孔を生じ、半導体表面に接
触した有機物はその酸化還元作用によって分解される。
近年、半導体のこのような光触媒作用を、ＮＯｘ（窒素
酸化物）等の大気汚染物質の分解や、防臭、防汚、殺
菌、水の浄化等の様々な環境浄化に応用する試みがなさ
れている。2. Description of the Related Art When a metal compound semiconductor such as titanium oxide, zinc oxide or iron oxide is irradiated with light having a wavelength having energy equal to or greater than its band gap, electrons having a reducing effect and holes having an oxidizing effect are irradiated on the irradiated surface. Is generated, and the organic matter in contact with the semiconductor surface is decomposed by the redox action.
In recent years, attempts have been made to apply such a photocatalytic action of a semiconductor to various environmental purifications such as decomposition of air pollutants such as NOx (nitrogen oxide), deodorization, antifouling, sterilization, and water purification. .
【０００３】光触媒作用を有する半導体は、従来、粉末
状のものを溶液中に懸濁させるか、ガラス、プラスチッ
クス、金属などの基体表面に薄膜状に固定して使用され
てきた。光触媒活性を高く維持する観点からは光触媒の
表面積を大きくできる懸濁状態で使用するのがよいが、
この方法では使用方法が限定される。基体の表面に光触
媒を薄膜状に固定して使用する方法は、取り扱いが容易
であるので実用性が高い。Conventionally, semiconductors having a photocatalytic action have been used by suspending a powdery one in a solution or fixing it in a thin film form on the surface of a substrate such as glass, plastics or metal. From the viewpoint of maintaining a high photocatalytic activity, it is preferable to use the photocatalyst in a suspended state where the surface area can be increased,
This method has limited use. The method of using the photocatalyst fixed on the surface of the substrate in the form of a thin film is easy to handle and has high practicality.
【０００４】従来、基体表面に光触媒層を形成するに
は、光触媒粒子を含む塗料組成物を浸漬やスプレー等の
方法で塗装し、焼付け乾燥して成膜する方法が採用され
ていた。光触媒層の酸化還元作用により基体や塗膜が化
学変化すると光触媒機能が低下するうえ、光触媒層の密
着性が必ずしも良好ではなかったので、これらに対する
改善方法が提案されている。Conventionally, in order to form a photocatalyst layer on the surface of a substrate, a method has been employed in which a coating composition containing photocatalyst particles is applied by a method such as dipping or spraying, and then baked and dried to form a film. When the substrate or the coating film chemically changes due to the oxidation-reduction action of the photocatalyst layer, the photocatalytic function is lowered, and the adhesion of the photocatalyst layer is not always good.
【０００５】特開平３−８４４８号公報には、金属等の
基体上にバインダと光触媒材を混合して塗料化したもの
を塗布したり、光触媒材を低温溶射したりして被覆する
方法などが開示されている。Japanese Patent Application Laid-Open No. Hei 3-8448 discloses a method in which a binder and a photocatalyst material are mixed and formed into a coating on a base material such as a metal, or the photocatalyst material is coated by spraying at a low temperature. It has been disclosed.
【０００６】特開平７−１７１４０８号公報には、フッ
素系ポリマー、シリコン系ポリマー等からなる難分解性
結着剤を介して光触媒粒子を基体上に接着させた光触媒
体およびその製造方法が開示されている。ここにはま
た、基体表面上に光触媒粒子を含有しない結着剤からな
る第１層を設け、その上に、光触媒粒子と難分解性結着
剤とを含有する第２層を備えた光触媒体も開示されてい
る。JP-A-7-171408 discloses a photocatalyst in which photocatalyst particles are adhered to a substrate via a hardly decomposable binder made of a fluorine-based polymer, a silicon-based polymer or the like, and a method for producing the same. ing. Here, a photocatalyst comprising a first layer made of a binder not containing photocatalyst particles provided on the surface of the substrate, and a second layer containing photocatalyst particles and a hardly decomposable binder provided thereon. Are also disclosed.
【０００７】特開平９−１７３８６５号公報には、基体
の表面にシリカ粒子からなる担持層を設け、この担持層
の表面にシリカよりも小さなチタニア粒子を設けた光触
媒体が開示されている。これは、基体に接する側の担持
層のシリカ粒子の大きさを小さくして基体と担持層の密
着力を高め、光触媒粒子と接する側の大きさを大きくし
て光触媒粒子を担持層に強固に接着させるものである。
その製造方法は、基体をＳｉＯ2 コーティング溶液に浸
漬して表面にゾル状のシリカ皮膜を形成し、さらにＴｉ
Ｏ2 水溶液に浸漬して形成される皮膜をゲル化し、焼成
して形成されるものである。これらの光触媒体では、基
体と光触媒粒子の間に結着剤や担持層を介在させること
により光触媒粒子の密着性を改善しようとするものであ
る。Japanese Patent Application Laid-Open No. 9-173865 discloses a photocatalyst in which a support layer made of silica particles is provided on the surface of a substrate, and titania particles smaller than silica are provided on the surface of the support layer. This is because the size of the silica particles in the carrier layer on the side in contact with the substrate is reduced to increase the adhesion between the substrate and the carrier layer, and the size on the side in contact with the photocatalyst particles is increased, so that the photocatalyst particles are firmly attached to the carrier layer. It is to be bonded.
The production method is such that a substrate is immersed in a SiO 2 coating solution to form a sol-like silica film on the surface,
The film formed by immersion in an O 2 aqueous solution is gelled and fired. These photocatalysts are intended to improve the adhesion of the photocatalyst particles by interposing a binder or a support layer between the substrate and the photocatalyst particles.
【０００８】成形が終了した製品の表面に塗料を塗装し
て光触媒層を設ける方法は、塗料ロスが大きく歩留が低
いためにコストが高いうえ、塗布対象物が成形品である
ため、塗料を塗布後乾燥する大型の乾燥オーブンやスペ
ースが必要である。このため、光触媒効果を持つ薄膜が
建材、家電製品、自動車用の成形物基体に適用されてい
る例はごく一部に過ぎない。The method of providing a photocatalyst layer by applying a paint on the surface of a molded product is expensive because of large paint loss and low yield, and the coating object is a molded product because the object to be coated is a molded product. A large drying oven and space for drying after application are required. For this reason, there are only a few examples in which a thin film having a photocatalytic effect is applied to a molded material base for building materials, home appliances, and automobiles.
【０００９】ステンレス鋼、チタン、アルミニウム、あ
るいは表面にアルミニウムや亜鉛等の各種の耐食性金属
をめっきしためっき鋼材は、その優れた耐食性と金属光
沢を有する外観を生かして、洗濯機、家電製品、厨房機
器、外装用建材など、成形加工され組み立てられて、金
属表面をそのまま最終製品の表面として使用される場合
が多い。これらの金属板の外観を損なうことなく防汚や
抗菌、消臭などの機能を兼ね備えさせるために、密着性
が良く透明な光触媒層を備えた金属板が望まれている。[0009] Plated steel materials obtained by plating stainless steel, titanium, aluminum, or various corrosion-resistant metals such as aluminum and zinc on the surface thereof are used for washing machines, home appliances, and kitchens, taking advantage of their excellent corrosion resistance and metallic luster. In many cases, equipment, exterior building materials, etc. are formed and assembled, and the metal surface is used as it is as the surface of the final product. In order to combine the functions of antifouling, antibacterial, deodorizing, and the like without impairing the appearance of these metal plates, a metal plate provided with a transparent photocatalyst layer having good adhesion is desired.
【００１０】しかしながら、金属板の表面に光触媒層を
設ける場合、１回の塗料塗布で形成できる塗膜の厚さが
０．２〜０．３μｍ以下の極く薄い塗膜しか形成できな
い。However, when a photocatalyst layer is provided on the surface of a metal plate, only a very thin coating film having a thickness of 0.2 to 0.3 μm or less can be formed by one coating application.
【００１１】上記の値を超えて厚く塗装すると、乾燥時
に塗膜の収縮現象などにより表面が平滑で仕上がりが良
好な塗膜が得られないのである。このため、１回の塗膜
形成作業のみでは十分な光触媒活性が得られず、実用性
がある光触媒層を得るためには、光触媒塗料を何回か重
ね塗りをするなどの方法が必要になるが、生産性が悪く
経済性が損なわれるのが問題であった。If the coating is applied thicker than the above-mentioned value, a coating film having a smooth surface and a good finish cannot be obtained due to shrinkage of the coating film during drying. For this reason, sufficient photocatalytic activity cannot be obtained by only one coating film forming operation, and a method such as repeatedly applying the photocatalytic paint several times is required to obtain a practical photocatalytic layer. However, there was a problem that productivity was poor and economic efficiency was impaired.
【００１２】さらに、光触媒層を備えた金属板に深絞り
成形等の厳しい加工を施すと、割れ、型かじり、寸法形
状不良や、光触媒層の剥離などが生じるため、光触媒層
を有する素材を成形加工して、光触媒層を有する製品を
安価に製作することが困難であった。Further, when a metal plate provided with a photocatalyst layer is subjected to severe processing such as deep drawing, cracks, galling, poor dimensional shape and peeling of the photocatalyst layer are caused. It was difficult to process and manufacture a product having a photocatalyst layer at low cost.
【００１３】[0013]
【発明が解決しようとする課題】本発明が解決しようと
する課題は、上記問題点を解決し、建材や家電製品への
成形加工に耐え、優れた光触媒機能を発揮できる光触媒
層を備えた金属板を提供することにある。An object of the present invention is to solve the above-mentioned problems and to provide a metal having a photocatalytic layer capable of exhibiting excellent photocatalytic functions while withstanding molding processing into building materials and home electric appliances. To provide a board.
【００１４】[0014]
【課題を解決するための手段】基体金属板と光触媒層の
間に、基体金属板の表面に化学的に吸着し、さらに光触
媒層を構成する物質を強固に吸着し、あるいは、光触媒
層と化学的結合を形成する性質を有し、光触媒作用に対
して安定な物質からなる下地処理層を設けることによ
り、通常の直接塗装方法では形成できない厚さの光触媒
層を１回の塗装、乾燥および焼き付け工程で形成させる
ことができる。下地処理層を形成する物質としては、そ
の形態が、光触媒層に対して効果を発揮するのに好適な
形態を有するものであればなお好ましい。Means for Solving the Problems Between the base metal plate and the photocatalyst layer, the surface of the base metal plate is chemically adsorbed, and the substance constituting the photocatalyst layer is strongly adsorbed. By providing an undercoating layer made of a material that is stable to photocatalysis and has the property of forming a thermal bond, a photocatalytic layer having a thickness that cannot be formed by a normal direct coating method is applied once, dried and baked. It can be formed in a process. It is more preferable that the material for forming the undercoating treatment layer has a form suitable for exhibiting an effect on the photocatalyst layer.
【００１５】光触媒層に有機潤滑剤を含有させることに
より、光触媒層が工具表面に押圧された際の摩擦係数を
小さくし、上述の成形不良を防止し耐剥離性を向上させ
ることができる。有機潤滑剤の種類を適切に選択するこ
とにより、成形加工後には、光触媒機能により光触媒層
の表面から有機潤滑剤を分解除去させて、良好な光触媒
活性を発揮させることができる。By including an organic lubricant in the photocatalyst layer, it is possible to reduce the coefficient of friction when the photocatalyst layer is pressed against the tool surface, to prevent the above-mentioned molding defects, and to improve the peeling resistance. By appropriately selecting the type of the organic lubricant, the organic lubricant can be decomposed and removed from the surface of the photocatalyst layer by the photocatalytic function after the molding process, so that good photocatalytic activity can be exhibited.
【００１６】光触媒層を構成する光触媒粒子としては、
ＺｎＯ、ＦｅＯ、Ｆｅ2 Ｏ3 、酸化チタン、ＣｄＳ、Ｃ
ｄＳｅなどが知られているが、金属板の金属光沢や外観
を生かすためには、無色透明な光触媒層を形成すること
が望ましい。特に酸化チタンは透明で且つ良好な光触媒
効果を有し、さらに、酸化チタンと結晶質のチタン酸ジ
ルコニウムとの結合体を含有するものを用いれば、光触
媒効果をさらに向上させることができる。The photocatalyst particles constituting the photocatalyst layer include:
ZnO, FeO, Fe 2 O 3 , titanium oxide, CdS, C
Although dSe and the like are known, it is desirable to form a colorless and transparent photocatalyst layer in order to utilize the metallic luster and appearance of the metal plate. In particular, titanium oxide is transparent and has a good photocatalytic effect, and the photocatalytic effect can be further improved by using a material containing a combination of titanium oxide and crystalline zirconium titanate.
【００１７】酸化チタン−チタン酸ジルコニウム結合体
は、酸化チタンと結晶質のチタン酸ジルコニウムとを単
に混合したものではなく、Ｔｉ−Ｏ−Ｚｒ結合を介して
両者を一体化させたものである。酸化チタンとチタン酸
ジルコニウムをこのような結合体として粒子中に含有さ
せることにより、酸化チタン単体の光触媒粒子を用いた
場合に較べ光触媒機能を大幅に向上させることができ
る。The titanium oxide-zirconium titanate combination is not simply a mixture of titanium oxide and crystalline zirconium titanate, but is a combination of the two via a Ti-O-Zr bond. By including titanium oxide and zirconium titanate in the particles as such a combination, the photocatalytic function can be greatly improved as compared with the case where the titanium oxide alone photocatalyst particles are used.
【００１８】基体金属板としては光触媒層に対して耐食
性を有する金属を用いる。これにより光触媒層から酸化
還元反応をもたらされても基体が化学変化することが少
ないので光触媒作用を長期にわたって安定して発揮させ
ることができる。As the base metal plate, a metal having corrosion resistance to the photocatalyst layer is used. Thereby, even if an oxidation-reduction reaction is caused from the photocatalyst layer, the substrate is less likely to undergo a chemical change, so that the photocatalysis can be stably exhibited for a long period of time.
【００１９】本発明はこれらの技術思想を基にして完成
されたものであり、その要旨は下記（１）ないし（３）
に記載の光触媒機能を有する金属板にある。The present invention has been completed based on these technical ideas, and the gist of the invention is as follows (1) to (3).
Wherein the metal plate has a photocatalytic function.
【００２０】（１）基体金属板と、その表面に設けた下
地処理層と、さらに該下地処理層の上に設けた光触媒層
とから成り、前記下地処理層が、Ｃａ、Ｍｇ、Ｓｒ、Ｂ
ａ、Ｚｎ、Ｃｏ、Ｃｒ、Ｓｉ、Ａｌ、Ｐ、Ｍｏ、Ｍｎ、
Ｎｉ、Ｗ、Ｖ、Ｎｂ、Ｚｒから成る群から選ばれる１種
または２種以上の元素の酸化物を合計で５０重量％以上
含み、その厚さが０．１〜５μｍであり、前記光触媒層
が１０〜９０重量％の光触媒粒子、および０〜１０重量
％の有機潤滑剤を含み、厚さが０．５μｍ以上であるこ
とを特徴とする光触媒機能を備えた金属板。(1) A base metal plate, a base treatment layer provided on the surface thereof, and a photocatalytic layer provided on the base treatment layer, wherein the base treatment layer is composed of Ca, Mg, Sr, B
a, Zn, Co, Cr, Si, Al, P, Mo, Mn,
The photocatalyst layer containing at least 50% by weight of a total of oxides of one or more elements selected from the group consisting of Ni, W, V, Nb, and Zr, having a thickness of 0.1 to 5 μm; A metal plate having a photocatalytic function, comprising 10 to 90% by weight of photocatalyst particles and 0 to 10% by weight of an organic lubricant, and having a thickness of 0.5 μm or more.
【００２１】（２）光触媒粒子が酸化チタンと結晶質の
チタン酸ジルコニウムとの結合体を含有するものである
ことを特徴とする上記（１）に記載の光触媒機能を備え
た金属板。(2) The metal plate having the photocatalytic function according to the above (1), wherein the photocatalyst particles contain a combination of titanium oxide and crystalline zirconium titanate.
【００２２】（３）基体金属板がステンレス鋼板、また
はＡｌ系めっき鋼板であることを特徴とする上記（１）
または（２）に記載の光触媒機能を備えた金属板。(3) The above (1), wherein the base metal plate is a stainless steel plate or an Al-based plated steel plate.
Or the metal plate provided with the photocatalyst function as described in (2).
【００２３】[0023]
【発明の実施の形態】以下に本発明の実施の形態につい
て詳細に説明する。基体金属板：基体金属板は、大気中
や腐食環境での裸使用に耐える耐食性と良好な金属光沢
を有する金属板が好ましい。この様な金属としては、ス
テンレス鋼、チタン、アルミニウム、または、各種のめ
っき金属板があるが、中でも安価で汎用性があり耐食性
に優れ良好な金属光沢を有する、フェライト系、オース
テナイト系、マルテンサイト系等公知の各種のステンレ
ス鋼板、および、ステンレス鋼板や公知の炭素鋼板の表
面に、Ａｌめっき、５５％Ａｌ−Ｚｎ合金めっき、５％
Ａｌ−Ｚｎ合金めっき、Ａｌ−Ｍｎ合金めっきなどのＡ
ｌ系めっき皮膜を配したＡｌ系めっき鋼板が好適であ
る。Embodiments of the present invention will be described below in detail. Base metal plate: The base metal plate is preferably a metal plate having corrosion resistance enough to withstand naked use in the air or a corrosive environment and having good metallic luster. Examples of such metals include stainless steel, titanium, aluminum, and various types of plated metal plates. Among them, ferrite, austenite, and martensite are inexpensive, versatile, have excellent corrosion resistance, and have excellent metallic luster. Plating, 55% Al-Zn alloy plating, 5%
A such as Al-Zn alloy plating and Al-Mn alloy plating
An Al-based plated steel sheet provided with an l-based plating film is preferable.
【００２４】下地処理層：下地処理層は、Ｃａ、Ｍｇ、
Ｓｒ、Ｂａ、Ｚｎ、Ｃｏ、Ｃｒ、Ｓｉ、Ａｌ、Ｐ、Ｍ
ｏ、Ｍｎ、Ｎｉ、Ｗ、Ｖ、Ｎｂ、Ｚｒから成る群から選
ばれる１種または２種以上の元素（以下、単に「下地構
成元素」とも記す）の酸化物を合計で、下地処理層の重
量に対して５０％以上含有する。酸化物としては、これ
らの中でも安価で入手が容易なＣｒ2 Ｏ3 、ＳｉＯ2 、
Ａｌ2 Ｏ3 、ＭｎＯ2 、Ｐ2 Ｏ5 等の内の１種あるいは
２種以上を組み合わせて用いるのがよい。Base treatment layer: The base treatment layer is made of Ca, Mg,
Sr, Ba, Zn, Co, Cr, Si, Al, P, M
o, Mn, Ni, W, V, Nb, and Zr, oxides of one or more elements selected from the group consisting of oxides (hereinafter, also simply referred to as “underlying constituent elements”) in total, 50% or more by weight. Among the oxides, Cr 2 O 3 , SiO 2 , which are inexpensive and easily available among these,
Al 2 O 3, MnO 2, it is preferable to use a combination of one or more kinds of such P 2 O 5.
【００２５】上記の酸化物の形態は、粒状のものでもア
モルファス状の高分子のものでもよい。粒状の場合は、
平均粒径が１μｍを超えると下地処理層の密着性が損な
われる場合があり、また、０．００５μｍに満たないも
のは通常の手段では得にくい。このため、平均粒径が直
径で０．００５〜１μｍのものが好ましい。この粒径
は、透過型電子顕微鏡や走査型電子顕微鏡で測定され
る。The form of the above-mentioned oxide may be granular or amorphous polymer. If granular,
If the average particle size exceeds 1 μm, the adhesion of the undercoat layer may be impaired, and if it is less than 0.005 μm, it is difficult to obtain by ordinary means. Therefore, those having an average particle diameter of 0.005 to 1 μm in diameter are preferable. This particle size is measured by a transmission electron microscope or a scanning electron microscope.
【００２６】アモルファス状の高分子の酸化物として
は、Ｃｒ2 Ｏ3 であれば、塗布型クロメート処理、反応
型クロメート処理、電解型クロメート処理等公知のクロ
メート処理方法で形成できるものがよい。また、例えば
Ｚｒ酸化物とＰ酸化物との複合酸化物（ＺｒＯ2 ・ Ｐ2
Ｏ5 ）やＭｏ酸化物とＰ酸化物の複合酸化物（ＭｏＯ3・
Ｐ2 Ｏ5 ）、あるいはＡｌ水酸化物の１種である羽毛
状形態のベーマイトゾルなどを使用してもよい。さら
に、Ｃａ、Ｍｇ、Ｓｒ、Ｂａ、Ｓｉ、Ａｌ、Ｎｂ、Ｖ、
Ｚｒ等の内のいずれかの元素を含む有機アルコキシドを
出発物質としたゾルゲル法により形成される酸化物また
は複合酸化物も、下地処理層の主成分として適用可能で
ある。さらにＡｌ、Ｍｇ、Ｃａ、ＺｎまたはＭｏなどの
リン酸塩も好適である。As the amorphous polymer oxide, if it is Cr 2 O 3 , it is preferable that the oxide can be formed by a known chromate treatment method such as a coating type chromate treatment, a reaction type chromate treatment, and an electrolytic type chromate treatment. Further, for example, a composite oxide of Zr oxide and P oxide (ZrO 2 .P 2
O 5 ) or a composite oxide of Mo oxide and P oxide (MoO 3.
P 2 O 5 ) or feather-like boehmite sol, which is one kind of Al hydroxide, may be used. Further, Ca, Mg, Sr, Ba, Si, Al, Nb, V,
An oxide or a composite oxide formed by a sol-gel method using an organic alkoxide containing any of the elements such as Zr as a starting material is also applicable as a main component of the base treatment layer. Further, phosphates such as Al, Mg, Ca, Zn or Mo are also suitable.
【００２７】これらの酸化物は金属板表面に化学的に吸
着するとともに、上層に施される光触媒層の構成物質を
強固に吸着し固着する作用を有する。これらの酸化物は
一般的に多孔質であるので、これを利用したアンカー効
果が期待できるうえ、部分的ではあるが下地処理層と光
触媒層との間に強固な化学結合をも形成する。従来のよ
うに基体表面に直接塗装する方法では１回の塗装作業で
０．５〜３μｍの厚さの光触媒層を設けるのは困難であ
るが、このような下地処理層の上であればこのような厚
さの光触媒層を１回の塗装作業で形成させることができ
る。These oxides have a function of chemically adsorbing to the surface of the metal plate and firmly adsorbing and fixing the constituent material of the photocatalytic layer provided on the upper layer. Since these oxides are generally porous, an anchor effect utilizing such oxides can be expected, and a strong chemical bond is formed between the undercoating layer and the photocatalyst layer, though partially. It is difficult to provide a photocatalyst layer having a thickness of 0.5 to 3 μm in a single coating operation by the conventional method of directly coating the substrate surface, but if it is on such an undercoating layer, A photocatalyst layer having such a thickness can be formed in one coating operation.
【００２８】酸化物の含有量は下地処理層の重量に対し
て、５０重量％以上とする。５０重量％に満たない場合
には、下地処理層の塗膜強度が不足して加工性が好まし
くなくなるうえ、光触媒作用によるチョーキングが生じ
て、下地処理層が剥離することがあるので好ましくな
い。より好ましくは７０重量％以上である。The content of the oxide is 50% by weight or more based on the weight of the undercoat layer. If the amount is less than 50% by weight, undesirably, the coating property of the undercoat layer is insufficient and the processability is not good, and the undercoat layer may be peeled off due to the occurrence of choking due to the photocatalytic action. It is more preferably at least 70% by weight.
【００２９】下地処理層の主成分は上述の酸化物のみで
もよいが、上述の酸化物に加えてポリアクリル酸、ポリ
メタクリル酸、ポリエステル、ポリスチレン、ポリウレ
タン、ポリエステル−メラミン架橋体、ポリエチレン、
ポリプロピレン、フッ素系の有機高分子などの内の１種
または２種以上の混合物を加えてもよい。また、下地構
成元素を含有するアルコキシド類やシリコン系樹脂、シ
ランカップリング剤、チタネート系カップリング剤など
の有機官能基を有する化合物、あるいは、それらが加水
分解して生成した有機官能基が残存したオリゴマーやコ
ロイドなどの無機物質（以下、これらを総称して「有機
無機複合物質」と記す）をあわせて含有させるのもよ
い。The main component of the undercoat layer may be only the above-mentioned oxide, but in addition to the above-mentioned oxide, polyacrylic acid, polymethacrylic acid, polyester, polystyrene, polyurethane, polyester-melamine crosslinked product, polyethylene,
One or a mixture of two or more of polypropylene, a fluorine-based organic polymer, and the like may be added. Further, compounds having organic functional groups such as alkoxides and silicon-based resins containing a base constituent element, silane coupling agents, titanate-based coupling agents, and the like, or organic functional groups generated by hydrolysis thereof remained. Inorganic substances such as oligomers and colloids (hereinafter collectively referred to as “organic-inorganic composite substances”) may be contained together.
【００３０】これらの有機物質または有機無機複合物質
を前述の酸化物に混合して用いれば、酸化物単独使用で
は得られない柔軟性に富む皮膜が得られ、難加工製品な
どへの適用が容易になる効果が得られる。さらに下地処
理層には、反応促進剤、架橋剤、消泡剤、レベリング剤
等の公知の塗料用添加剤が含有されてもよい。When these organic substances or organic-inorganic composite substances are used in a mixture with the above-mentioned oxide, a film having high flexibility, which cannot be obtained by using the oxide alone, is obtained, and application to difficult-to-process products is easy. Is obtained. Further, the undercoating layer may contain known paint additives such as a reaction accelerator, a crosslinking agent, an antifoaming agent, and a leveling agent.
【００３１】下地処理層の上に、光触媒層を形成するた
めの塗料組成物（以下、単に「光触媒層用塗料」と記
す。塗料組成物が下地処理層用のものである場合は「下
地処理層用塗料」と記す。）を塗布し乾燥する際に、光
触媒層用塗料の揮発分の脱離に伴い光触媒層が収縮す
る。その際下地処理層の厚さが０．１μｍに満たない場
合には、下地処理層が追随できないために皮膜に割れが
生じ、均一で厚い光触媒塗膜が得られない。これを防止
するために下地処理層の厚さは０．１μｍ以上とする。
好ましくは０．５μｍ以上である。下地処理層の厚さが
５μｍを超えると、光触媒層に対する密着性向上効果が
飽和するため、５μｍを超える厚さの塗膜を備えるのは
経済性に欠ける。より好ましくは３μｍ以下である。最
も好ましい厚さは１〜２μｍの範囲である。A coating composition for forming a photocatalyst layer on the undercoat layer (hereinafter simply referred to as “coating for photocatalyst layer”. If the coating composition is for the undercoat layer, it is referred to as “undercoat layer”. Layer coating ") is applied and dried, the photocatalyst layer shrinks due to the removal of volatile components of the photocatalyst layer coating. At that time, if the thickness of the undercoat layer is less than 0.1 μm, the undercoat layer cannot follow, and the film is cracked, so that a uniform and thick photocatalytic coating film cannot be obtained. In order to prevent this, the thickness of the base treatment layer is set to 0.1 μm or more.
Preferably it is 0.5 μm or more. If the thickness of the undercoating layer exceeds 5 μm, the effect of improving the adhesion to the photocatalyst layer is saturated, so providing a coating film with a thickness exceeding 5 μm is not economical. More preferably, it is 3 μm or less. The most preferred thickness is in the range of 1-2 μm.
【００３２】光触媒層：光触媒粒子としては公知の酸化
チタン、酸化亜鉛、硫化カドミウムや硫化セレンなどが
使用できるが、光触媒粒子そのものの安全性、入手のし
やすさ、基体金属板の光沢維持に好ましいこと等の理由
から、透明性に優れた酸化チタンが好適である。更に高
い光触媒活性を望む場合には、酸化チタンとチタン酸ジ
ルコニウムとの結合体（以下、これを単に「酸化チタン
−チタン酸ジルコニウム結合体」とも記す）を含有する
粒子がよい。Photocatalyst layer: As the photocatalyst particles, known titanium oxide, zinc oxide, cadmium sulfide, selenium sulfide and the like can be used, but they are preferable for safety of the photocatalyst particles themselves, easy availability, and maintenance of gloss of the base metal plate. For these reasons, titanium oxide excellent in transparency is preferable. When higher photocatalytic activity is desired, particles containing a conjugate of titanium oxide and zirconium titanate (hereinafter, also simply referred to as “titanium oxide-zirconium titanate conjugate”) are preferred.
【００３３】酸化チタン−チタン酸ジルコニウム結合体
は、酸化チタンと結晶質のチタン酸ジルコニウムとを単
に混合したものではなく、Ｔｉ−Ｏ−Ｚｒ結合を介して
両者を一体化させたものであり、チタン化合物とジルコ
ニウム化合物との反応生成物を大気雰囲気下で焼成する
などの方法で得ることができる。The titanium oxide-zirconium titanate conjugate is not simply a mixture of titanium oxide and crystalline zirconium titanate, but is formed by integrating both via a Ti—O—Zr bond. The reaction product of the titanium compound and the zirconium compound can be obtained by a method such as firing in an air atmosphere.
【００３４】光触媒粒子の大きさは、透過型電子顕微鏡
で観察される平均粒径で０．０５〜１μｍの範囲が好ま
しい。その理由は、光触媒粒子は平均粒径が小さいほど
触媒活性が良好であり、１μｍを超える場合には光触媒
活性が低下するからであり、また、平均粒径が０．０５
μｍに満たないものは分級が困難なため、入手しにくい
ためである。The size of the photocatalyst particles is preferably in the range of 0.05 to 1 μm as the average particle size observed with a transmission electron microscope. The reason is that the smaller the average particle size of the photocatalyst particles is, the better the catalytic activity is. If the average particle size exceeds 1 μm, the photocatalytic activity is reduced.
This is because those less than μm are difficult to classify and are difficult to obtain.
【００３５】光触媒粒子を構成する結晶子サイズは、５
〜５０ｎｍが好ましい。結晶子サイズは小さいほど光触
媒活性がよいのでいくら小さくても構わないが、５ｎｍ
に満たないものは通常の手段では入手しにくい。結晶子
サイズが５０ｎｍを超えると光触媒活性が低下するので
好ましくない。結晶子サイズは、Ｘ線回折で得られる酸
化チタン結晶の（１０１）面からの回折ピークから算出
することができる。The crystallite size constituting the photocatalyst particles is 5
~ 50 nm is preferred. The smaller the crystallite size, the better the photocatalytic activity.
Those less than are difficult to obtain by ordinary means. If the crystallite size exceeds 50 nm, the photocatalytic activity is undesirably reduced. The crystallite size can be calculated from the diffraction peak from the (101) plane of the titanium oxide crystal obtained by X-ray diffraction.
【００３６】光触媒層の厚さは０．５μｍ以上とする。
光触媒層の厚さが０．５μｍに満たない場合には光触媒
効果、特に有機質の汚染物質（たばこのヤニやコーヒー
などの色素によるシミなど）の分解作用が十分ではな
い。好ましくは０．７μｍ以上である。光触媒層の厚さ
が５μｍを超えると光触媒効果が飽和するうえ、皮膜の
厚さが厚くなるにつれて加工性が低下するため、その厚
さは５μｍ以下とするのが好ましい。加工が厳しい場合
には３μｍ以下とするのがなお好ましい。The thickness of the photocatalyst layer is 0.5 μm or more.
If the thickness of the photocatalyst layer is less than 0.5 μm, the photocatalytic effect, particularly the decomposition action of organic contaminants (stains by dyes such as cigarette tar and coffee) is not sufficient. Preferably it is 0.7 μm or more. When the thickness of the photocatalyst layer exceeds 5 μm, the photocatalytic effect is saturated, and as the thickness of the film increases, the workability decreases. Therefore, the thickness is preferably 5 μm or less. When processing is severe, it is more preferable that the thickness be 3 μm or less.
【００３７】光触媒粒子は、光触媒層の重量に対して１
０〜９０重量％含有させる。含有量が１０重量％に満た
ない場合には、光触媒層の厚さが０．５μｍ以上であっ
ても光触媒機能が不十分な場合がある。光触媒粒子の含
有量が増すにつれて光触媒効果が大きくなるが、９０重
量％を超えると光触媒層の表面に亀裂や割れが増すので
好ましくない。The photocatalyst particles are 1 to the weight of the photocatalyst layer.
0-90% by weight is contained. If the content is less than 10% by weight, the photocatalytic function may be insufficient even if the thickness of the photocatalytic layer is 0.5 μm or more. As the content of the photocatalyst particles increases, the photocatalytic effect increases. However, when the content exceeds 90% by weight, cracks and cracks increase on the surface of the photocatalyst layer, which is not preferable.
【００３８】光触媒層に有機潤滑剤を含有させておけ
ば、光触媒層を備えた金属板の成形加工性をさらに向上
させることができる。有機潤滑剤は、粒子状の固体潤滑
剤を用いるのがよい。液状の潤滑剤は光触媒粒子表面を
被覆して光触媒機能を阻害するうえ、成形加工後に潤滑
剤を除去する工程を追加する必要があるので生産性がよ
くない。また、光触媒作用により分解される性質を有す
る有機潤滑剤を用いれば、製品として使用中にこれらの
有機分が分解、除去されるので光触媒活性を良好に維持
できる。If an organic lubricant is contained in the photocatalyst layer, the formability of a metal plate provided with the photocatalyst layer can be further improved. As the organic lubricant, a particulate solid lubricant is preferably used. The liquid lubricant coats the surface of the photocatalyst particles and impairs the photocatalytic function, and furthermore, it is necessary to add a step of removing the lubricant after the molding process, so that the productivity is not good. In addition, if an organic lubricant having the property of being decomposed by photocatalysis is used, these organic components are decomposed and removed during use as a product, so that good photocatalytic activity can be maintained.
【００３９】このような要求を満たすものとしては例え
ば、天然ワックス、ポリオレフィン系ワックス、酸化ポ
リオレフィン系ワックス、変成ポリオレフィン系ワック
ス、マイクロクリスタリン系ワックスなどがあり、これ
らの内の一種または２種以上を組み合わせて用いるのが
よい。これらのワックス粒子は、分散性を向上させるた
めに有機シラン、有機チタン、および有機アルミニウム
系化合物のいずれかで表面処理されているものでもかま
わない。Examples of those satisfying such requirements include natural waxes, polyolefin-based waxes, oxidized polyolefin-based waxes, modified polyolefin-based waxes, microcrystalline waxes, and the like, and one or more of these may be used in combination. It is better to use it. These wax particles may be surface-treated with any of organic silanes, organic titanium, and organic aluminum compounds in order to improve dispersibility.
【００４０】有機潤滑剤の粒径は、レーザー回折法で測
定される平均粒径で、光触媒層の厚さ以上とするのがよ
い。平均粒径が光触媒層の厚さよりも小さくなると潤滑
効果が不十分である。平均粒径が過度に大きくなると、
成形加工時に光触媒層から有機潤滑剤が脱落し、それら
が絞り加工後の表面に付着して表面性状を損なう。この
ため、平均粒径は、光触媒層の厚さ＋５μｍ以下とする
のがよい。さらに好ましくは、光触媒層の厚さ＋３μｍ
以下がよい。The particle size of the organic lubricant is preferably an average particle size measured by a laser diffraction method and is equal to or larger than the thickness of the photocatalyst layer. If the average particle size is smaller than the thickness of the photocatalyst layer, the lubricating effect is insufficient. If the average particle size becomes too large,
During the forming process, the organic lubricant drops off from the photocatalyst layer, and they adhere to the surface after the drawing process to impair the surface properties. For this reason, the average particle size is preferably not more than the thickness of the photocatalyst layer + 5 μm. More preferably, the thickness of the photocatalyst layer + 3 μm
The following is good.
【００４１】成形加工性を向上させる目的で有機潤滑剤
を含有させる場合には、有機潤滑剤を光触媒層の重量に
対して０．１％以上含有させるのがよい。成形加工後の
光触媒層表面に残留している有機潤滑剤は、前述したよ
うに製品使用中に光触媒効果により酸化分解される。し
かし、有機潤滑剤の含有量が１０重量％を超えると、光
触媒粒子による分解効率が著しく低下する。このため、
有機潤滑剤の含有量の上限は光触媒層の重量に対して１
０重量％とする。より好ましくは５重量％以下である。When an organic lubricant is contained for the purpose of improving moldability, it is preferred that the organic lubricant be contained in an amount of 0.1% or more based on the weight of the photocatalyst layer. The organic lubricant remaining on the surface of the photocatalyst layer after the molding process is oxidatively decomposed by the photocatalytic effect during use of the product as described above. However, when the content of the organic lubricant exceeds 10% by weight, the decomposition efficiency by the photocatalyst particles is significantly reduced. For this reason,
The upper limit of the content of the organic lubricant is 1 to the weight of the photocatalyst layer.
0% by weight. It is more preferably at most 5% by weight.
【００４２】光触媒層には、さらに、皮膜の強度や密着
性を向上させるためにシリコン系樹脂、フッ素系樹脂、
コロイド状アルミナ、クロム酸、クロム酸塩、リン酸、
リン酸塩等などの造膜助剤または造膜機能を有する化合
物、あるいはコロイド状シリカ、コロイド状アルミナな
どの光触媒層の顔料となりうる化合物を、合計で光触媒
層の重量に対して９０％まで含有しても構わない。ま
た、光触媒層形成塗料に不可避的に含まれる解膠剤（硝
酸イオン、塩化物イオン等の陰イオン）が残留物として
含有されても構わない。The photocatalyst layer further includes a silicon-based resin, a fluorine-based resin, and the like in order to improve the strength and adhesion of the film.
Colloidal alumina, chromate, chromate, phosphoric acid,
Contains up to 90% of the total weight of the photocatalyst layer of a film-forming auxiliary such as phosphate or a compound having a film-forming function, or a compound that can be a pigment of the photocatalyst layer such as colloidal silica or colloidal alumina. It does not matter. Further, a deflocculant (an anion such as nitrate ion or chloride ion) which is inevitably contained in the photocatalytic layer forming paint may be contained as a residue.
【００４３】製造方法：本発明の光触媒機能を備えた金
属板は、基体金属板の表面に、下地処理層用塗料を塗布
し乾燥して下地処理層を形成し、その上に光触媒層用塗
料を塗布し、乾燥して光触媒層を形成して製造される。Manufacturing method: The metal plate having a photocatalytic function of the present invention is obtained by applying a coating for a base treatment layer on the surface of a base metal plate and drying to form a base treatment layer, and then forming a coating for the photocatalyst layer on the base treatment layer. Is applied and dried to form a photocatalyst layer.
【００４４】下地処理層用塗料は、下地構成元素の酸化
物、下地構成元素を含む有機アルコキシド類、これらの
アルコキシド類が加水分解し縮合反応して生成するオリ
ゴマーや有機錯体（イオン）またはコロイド等の内のい
ずれかが溶解または分散した塗料に、反応促進剤、架橋
剤、消泡剤、レベリング剤等の公知の塗料用添加剤を適
量、溶媒に分散させて下地処理層用塗料とする。The coating for the undercoat layer may be an oxide of the undercoat element, an organic alkoxide containing the undercoat element, an oligomer, an organic complex (ion) or a colloid formed by hydrolysis and condensation of these alkoxides. A known coating additive such as a reaction accelerator, a cross-linking agent, an antifoaming agent, or a leveling agent is dispersed in a solvent in an appropriate amount in a solvent in which any one of the above has been dissolved or dispersed to prepare a coating for a base treatment layer.
【００４５】反応促進剤としては、各種の酸、例えば硝
酸やリン酸、珪フッ化水素酸、硼フッ化水素酸などが使
用できる。架橋剤としては公知のシランカップリング
剤、メラミン・イソシアネート化合物などを用いること
ができる。消泡剤としてはプルロニック系界面活性剤、
ポリプロピレングリコール等公知のものが使用できる。
レベリング剤としてはジメチルポリシロキサン、ポリア
クリル酸塩等、公知のものを用いることができる。溶剤
としては、水、各種のアルコール類、トルエン、キシレ
ン等公知のものを用いることができる。As the reaction accelerator, various acids, for example, nitric acid, phosphoric acid, hydrosilicic acid, borofluoric acid and the like can be used. Known silane coupling agents, melamine / isocyanate compounds, and the like can be used as the crosslinking agent. Pluronic surfactants as antifoaming agents,
Known materials such as polypropylene glycol can be used.
Known leveling agents such as dimethylpolysiloxane and polyacrylate can be used. Known solvents such as water, various alcohols, toluene and xylene can be used as the solvent.
【００４６】光触媒層用塗料は、前述の半導体光触媒粒
子のゾル、無機バインダ、架橋剤、消泡剤、レベリング
剤等の公知の塗料用添加剤を用い、これらを適量、上述
の公知の溶媒に分散させて塗料組成物とする。加工性が
要求される場合には、さらに前述の有機潤滑剤を混合し
て塗料とする。The coating for the photocatalyst layer is prepared by using known coating additives such as the above-mentioned sol of semiconductor photocatalyst particles, an inorganic binder, a crosslinking agent, an antifoaming agent, and a leveling agent. Disperse to form a coating composition. When workability is required, the above-mentioned organic lubricant is further mixed to form a paint.
【００４７】塗料の塗布は、刷毛塗り、スプレー方式、
浸漬方式など公知の方法が適用できるが、塗装速度が大
きくでき、塗料や製品歩留が良好で製品の表面性状も優
れるロールコート方式が好適である。塗装時の膜厚は、
乾燥後の膜厚が、下地処理層では０．１〜５μｍ、光触
媒層では０．５〜５μｍとなるように塗布する。[0047] The paint is applied by brushing, spraying,
Although a known method such as an immersion method can be applied, a roll coating method which can increase the coating speed, has a good paint and product yield, and has excellent surface properties of the product is preferable. The film thickness at the time of painting
The coating is performed so that the film thickness after drying is 0.1 to 5 μm for the base treatment layer and 0.5 to 5 μm for the photocatalytic layer.
【００４８】下地処理層塗布後の乾燥温度は常温でもよ
いが、乾燥時間を短縮し光触媒層の密着性を向上させる
ために６０〜４００℃の範囲とするのがよい。光触媒層
塗布後の乾燥温度は１００〜５００℃がよい。１００℃
未満では乾燥が不十分であり良好な密着性が得られず、
５００℃を超える温度では基体金属板の表面が酸化し、
着色や皮膜の剥離が生じたりすることがあるからであ
る。より好ましくは４００℃以下である。光触媒層乾燥
後の冷却速度は５〜１００℃／秒とするのがよい。５℃
／秒未満であると冷却に時間を要するので経済性に欠け
る。また、１００℃／秒を超えると皮膜に亀裂や剥離が
生じることがあるからである。The drying temperature after application of the undercoat layer may be room temperature, but is preferably in the range of 60 to 400 ° C. in order to shorten the drying time and improve the adhesion of the photocatalyst layer. The drying temperature after application of the photocatalyst layer is preferably 100 to 500C. 100 ℃
If less than this, drying is insufficient and good adhesion cannot be obtained,
At a temperature exceeding 500 ° C., the surface of the base metal plate is oxidized,
This is because coloring or peeling of the film may occur. More preferably, it is 400 ° C. or lower. The cooling rate after drying the photocatalyst layer is preferably 5 to 100 ° C./sec. 5 ℃
If it is less than / sec, it takes a long time for cooling, so that it is not economical. On the other hand, if the temperature exceeds 100 ° C./sec, the coating may be cracked or peeled off.
【００４９】以上述べた以外の処理方法は公知の方法で
よい。塗料の塗布、乾燥等の一連の処理は、切り板を用
いてバッチ式に処理しても構わないが、２コート２ベー
ク型の連続コイル塗装設備を使用してコイル状の基体鋼
板を用いて処理するのが品質と経済性に優れるので好ま
しい。The processing methods other than those described above may be known methods. A series of treatments such as application and drying of paint may be performed in batches using cut plates, but using a coil-shaped base steel plate using a two-coat two-bake type continuous coil coating facility. Processing is preferred because of its excellent quality and economy.
【００５０】[0050]
【実施例】（本発明例１）テトラエトキシシラン１６
６．４ｇ、メチルトリエトキシシラン３５．６ｇと、エ
タノール１３８ｇ、イオン交換水１３０ｇからなる分散
液を５０℃で２時間撹拌した後、泡立ち防止剤、レベリ
ング剤を加え下地処理層用塗料とした（以下、この塗料
を「下地用塗料Ａ」と記す）。EXAMPLES (Example 1 of the present invention) Tetraethoxysilane 16
A dispersion composed of 6.4 g, 35.6 g of methyltriethoxysilane, 138 g of ethanol, and 130 g of ion-exchanged water was stirred at 50 ° C. for 2 hours, and then a foaming inhibitor and a leveling agent were added to obtain a paint for a base treatment layer ( Hereinafter, this paint is referred to as “base paint A”).
【００５１】平均粒径が約１００ｎｍで結晶子サイズが
１０ｎｍの酸化チタン粒子を、乾燥固形分の重量に対す
る割合（以下、単に「乾燥固形分重量比」と記す）が１
５％となるように含有する酸化チタンゾルの水分散液１
００ｇに、皮膜の表面性状を向上させる目的で乾燥固形
分重量比が２０％のコロイダルシリカを６０ｇ加え、さ
らに消泡剤を加えて光触媒層用塗料とした（以下、この
塗料を「酸化チタン塗料」と記す）。Titanium oxide particles having an average particle diameter of about 100 nm and a crystallite size of 10 nm were mixed with a dry solid content by weight (hereinafter simply referred to as “dry solid content weight ratio”) of 1
Aqueous dispersion 1 of titanium oxide sol containing 5%
In order to improve the surface properties of the film, 60 g of colloidal silica having a dry solid content of 20% by weight was added to 00 g, and a defoaming agent was further added to prepare a photocatalyst layer paint (hereinafter, this paint was referred to as “titanium oxide paint”). ").
【００５２】ＪＩＳ−Ｇ−４３０５で規定される厚さが
０．５ｍｍのＳＵＳ３０４冷間圧延鋼板を基体とし、そ
の両面に下地用塗料Ａを乾燥膜厚が１．０μｍとなるよ
うにロールコートし、２８０℃で６０秒間乾燥してＳｉ
Ｏ2 を含有する下地処理層を形成した。その上に酸化チ
タン塗料を乾燥膜厚が０．８μｍとなるようにロールコ
ートし、２００℃で５０秒間連続炉で乾燥して光触媒層
を形成した。A SUS304 cold-rolled steel sheet having a thickness of 0.5 mm as specified in JIS-G-4305 was used as a substrate, and both sides of the substrate were roll-coated with a base coating material A so as to have a dry film thickness of 1.0 μm. , Dried at 280 ° C for 60 seconds
An underlayer treatment layer containing O 2 was formed. A titanium oxide paint was roll-coated thereon to a dry film thickness of 0.8 μm and dried in a continuous furnace at 200 ° C. for 50 seconds to form a photocatalyst layer.
【００５３】（本発明例２）結晶質のチタン酸ジルコニ
ウム１０重量部と酸化チタン９０重量部を混合し、大気
中で５００℃で２時間焼成した後粉砕し、水に分散させ
て光触媒粒子を１０重量％含有するスラリを作製した。
このスラリを水酸化ナトリウムを用いてｐＨ１０に調整
し、オートクレーブで１５０℃で３時間水熱処理を施し
た。その後、濃度６０％の硝酸を加えてｐＨ７に調整
し、ろ過して酸化チタン−チタン酸ジルコニウム結合体
を含有する光触媒粒子を得た。その平均粒径は１００ｎ
ｍ、平均結晶子サイズは８ｎｍであった。この酸化チタ
ン−チタン酸ジルコニウム結合体粒子を１５重量％含有
させた水分散液１００ｇに、皮膜の表面性状を向上させ
る目的で乾燥固形分重量比が２０重量％であるコロイダ
ルシリカを６０ｇ加え、さらに消泡剤を加えて塗料組成
物を得た（以下、「チタン酸ジルコニウム含有塗料」と
記す）。本発明例１で使用したのと同じステンレス鋼板
に、下地用塗料Ａを本発明例１と同じ条件で塗布、乾燥
して厚さ１．０μｍの下地処理層を形成し、その上にチ
タン酸ジルコニウム含有塗料を乾燥膜厚が０．８μｍと
なるようにロールコートし、２００℃で５０秒間連続炉
で乾燥して光触媒層を形成した。(Invention Example 2) 10 parts by weight of crystalline zirconium titanate and 90 parts by weight of titanium oxide were mixed, fired at 500 ° C. for 2 hours in the air, pulverized, and dispersed in water to obtain photocatalyst particles. A slurry containing 10% by weight was prepared.
This slurry was adjusted to pH 10 using sodium hydroxide, and subjected to a hydrothermal treatment at 150 ° C. for 3 hours in an autoclave. Then, the pH was adjusted to 7 by adding nitric acid having a concentration of 60%, followed by filtration to obtain photocatalyst particles containing a titanium oxide-zirconium titanate conjugate. The average particle size is 100n
m, the average crystallite size was 8 nm. To 100 g of an aqueous dispersion containing 15 wt% of the titanium oxide-zirconium titanate conjugate particles, 60 g of colloidal silica having a dry solid content weight ratio of 20 wt% was added for the purpose of improving the surface properties of the film. A coating composition was obtained by adding an antifoaming agent (hereinafter referred to as "zirconium titanate-containing coating"). Undercoating A was applied to the same stainless steel plate as used in Inventive Example 1 under the same conditions as in Inventive Example 1, and dried to form a 1.0 μm-thick undercoating layer. The zirconium-containing paint was roll-coated so as to have a dry film thickness of 0.8 μm, and dried in a continuous furnace at 200 ° C. for 50 seconds to form a photocatalyst layer.
【００５４】（本発明例３）下地処理層用塗料として、
４０重量％の燐酸Ａｌ、燐酸Ｍｇおよび燐酸Ｃａのいず
れかを含有する水溶液を、ＪＩＳ−Ｇ−４３０５に規定
されるＳＵＳ４０９冷間圧延鋼板の表面に乾燥膜厚が
０．３μｍとなるように塗布し、３３０℃で８０秒間焼
付けて下地処理層を形成させた。その上に、本発明例２
で使用したのと同じ酸化チタン−チタン酸ジルコニウム
結合体粒子を１５重量％含有する水分散液と市販のポリ
エチレンワックス分散液（平均粒径３μ）とを混合して
ペイントシェーカーで振とうし、有機潤滑剤を含有する
光触媒層用の塗料を作製した。その際の光触媒層に対す
る光触媒粒子の乾燥固形分重量比は５５％、ポリエチレ
ンワックスの光触媒層に対する乾燥固形分重量比が５％
になるように混合量を調整した。このようにして得られ
た塗料を、上述の３種類のリン酸塩皮膜からなる下地処
理層のうえに乾燥膜厚が０．８μとなるように塗布後、
２３０℃で５０秒乾燥した。(Example 3 of the present invention)
An aqueous solution containing 40% by weight of any of Al phosphate, Mg phosphate and Ca phosphate is applied to the surface of a SUS409 cold-rolled steel sheet specified in JIS-G-4305 so as to have a dry film thickness of 0.3 µm. Then, the substrate was baked at 330 ° C. for 80 seconds to form a base treatment layer. In addition, the present invention example 2
An aqueous dispersion containing 15% by weight of the same titanium oxide-zirconium titanate conjugate particles as used in Example 1 was mixed with a commercially available polyethylene wax dispersion (average particle size: 3 μm), and the mixture was shaken with a paint shaker to give an organic compound. A coating material for a photocatalyst layer containing a lubricant was prepared. At that time, the dry solid content weight ratio of the photocatalyst particles to the photocatalyst layer was 55%, and the dry solid content weight ratio of the polyethylene wax to the photocatalyst layer was 5%.
The mixing amount was adjusted so that After applying the paint thus obtained on the undercoating layer composed of the above three types of phosphate films so that the dry film thickness becomes 0.8 μm,
It was dried at 230 ° C. for 50 seconds.
【００５５】（比較例１）本発明例１で使用したのと同
じＳＵＳ３０４鋼板に、下地処理層を設けないで直接本
発明例２に記載したのと同一のチタン酸ジルコニウム含
有塗料を乾燥膜厚が０．８μｍとなるようにロールコー
トし、２００℃で５０秒間乾燥した。(Comparative Example 1) The same zirconium titanate-containing paint as described in Inventive Example 2 was directly applied to the same SUS304 steel plate as used in Inventive Example 1 without providing an undercoating layer. Was 0.8 μm, and dried at 200 ° C. for 50 seconds.
【００５６】（比較例２）チタン酸ジルコニウム含有塗
料の乾燥膜厚が０．２μｍとなるようにした以外は比較
例１と同様に処理して比較用の試験片を作製した。得ら
れた試験片の性能を以下の方法で評価した。(Comparative Example 2) A test piece for comparison was prepared in the same manner as in Comparative Example 1 except that the dry film thickness of the zirconium titanate-containing paint was set to 0.2 μm. The performance of the obtained test piece was evaluated by the following method.
【００５７】一次密着性試験：試験片の２０ｍｍ×２０
ｍｍの領域の皮膜をカッターナイフで２ｍｍ間隔でクロ
スカットし、１０マス×１０マスの碁盤目状に切り分
け、粘着テープによる剥離試験をおこない、剥離しない
で鋼板上に残存したマス数を測定し、９５マス以上残存
した場合を良好と判断して評価した。Primary adhesion test: 20 mm × 20 test pieces
The film in the area of 2 mm was cross-cut with a cutter knife at intervals of 2 mm, cut into a grid of 10 squares × 10 squares, subjected to a peeling test with an adhesive tape, and the number of squares remaining on the steel plate without peeling was measured. A case where 95 or more squares remained was judged to be good and evaluated.
【００５８】二次密着性試験：一次密着性を評価したの
と同様に皮膜表面を碁盤目状に切り分けた後、イオン交
換水に浸漬して１時間煮沸し、上記と同様に粘着テープ
による剥離試験をおこない、剥離しないで鋼板上に残存
したマス数が９５マス以上の場合を良好と判断して評価
した。Secondary adhesion test: The film surface was cut in a grid pattern in the same manner as in the evaluation of the primary adhesion, then immersed in ion-exchanged water, boiled for 1 hour, and peeled off with an adhesive tape as described above. A test was conducted, and a case where the number of squares remaining on the steel sheet without peeling was 95 or more was judged to be good and evaluated.
【００５９】光触媒活性：以下に示すアセトアルデヒド
の消臭分解試験方法（以下、単に「アセトアルデヒド分
解試験」と記す）により光触媒活性を評価した。前述の
二次密着試験で粘着テープによる剥離試験をおこなった
試験片を、容積５リットルの透明ガラス製容器に入れ、
内部に濃度１００ｐｐｍとなるようにアセトアルデヒド
を加え、光量０．０８ｍＷ／ｃｍ2 の紫外線を照射しな
がらガラス容器の中のアセトアルデヒド量の推移をガス
クロマトグラフィーにて測定した。Photocatalytic activity: The photocatalytic activity was evaluated by the following test method for deodorizing and decomposing acetaldehyde (hereinafter simply referred to as “acetaldehyde decomposition test”). The test piece subjected to the peel test with the adhesive tape in the above-described secondary adhesion test was placed in a transparent glass container having a volume of 5 liters,
Acetaldehyde was added to the inside so as to have a concentration of 100 ppm, and the transition of the amount of acetaldehyde in the glass container was measured by gas chromatography while irradiating ultraviolet rays having a light amount of 0.08 mW / cm 2 .
【００６０】密着性評価結果を表１に示した。なお表１
の性能評価欄の数値は、（残存したマス数／試験したマ
ス数）を表す。Table 1 shows the results of the evaluation of adhesion. Table 1
The numerical value in the performance evaluation column indicates (the number of remaining cells / the number of cells tested).
【００６１】[0061]
【表１】 [Table 1]
【００６２】表１に示すように、本発明の規定する範囲
内の下地処理層を備えた本発明例１、２および３の試験
片は皮膜の剥離が生じないか、剥離しても極めて僅かで
あった。これに対し、下地処理層を設けなかった比較例
１および比較例２の試験片は密着性がよくなかった。通
常、皮膜の厚さが薄いほど密着性が良好になるが、比較
例２は光触媒層の膜厚が本発明例に比べて薄いにもかか
わらず、十分な密着性、特に二次密着性が得られなかっ
た。これは、光触媒層が薄すぎるため、一次密着性は有
る程度確保されるものの、煮沸時に光触媒層と基体との
界面に水分が浸入し密着性が低下したものと考えられ
る。As shown in Table 1, the test pieces of Examples 1, 2 and 3 having the undercoating layer within the range specified by the present invention did not peel off the film, or even when peeled off, Met. On the other hand, the test pieces of Comparative Example 1 and Comparative Example 2 in which the undercoating layer was not provided had poor adhesion. In general, the smaller the thickness of the film, the better the adhesion. In Comparative Example 2, though the thickness of the photocatalyst layer is smaller than that of the present invention, sufficient adhesion, particularly secondary adhesion, is obtained. Could not be obtained. This is presumably because the photocatalyst layer is too thin and the primary adhesion is secured to a certain degree, but the moisture has penetrated into the interface between the photocatalyst layer and the substrate during boiling, and the adhesion has decreased.
【００６３】図１にアセトアルデヒド分解試験の結果を
示す。図１に示されているように、本発明例１と２の試
験片では光照射時間に応じてアセトアルデヒド量が減少
した。本発明例１に比較して、酸化チタン−チタン酸ジ
ルコニウム結合体粒子を含有する光触媒層を備えた本発
明例２の方がアセトアルデヒドの分解速度が速かった。
比較例１および２の光触媒活性は極めて僅かであった。
これは光触媒層がほとんど剥離してしまっているためと
考えられる。FIG. 1 shows the results of the acetaldehyde decomposition test. As shown in FIG. 1, the amount of acetaldehyde in the test pieces of Examples 1 and 2 of the present invention decreased in accordance with the light irradiation time. Compared with Inventive Example 1, Inventive Example 2 provided with a photocatalyst layer containing titanium oxide-zirconium titanate conjugate particles had a higher acetaldehyde decomposition rate.
The photocatalytic activities of Comparative Examples 1 and 2 were extremely low.
This is probably because the photocatalyst layer was almost completely peeled off.
【００６４】（本発明例４）本発明例３に記載したのと
同一の燐酸Ａｌ水溶液を使用して本発明例３に記載した
のと同様の方法で、ＳＵＳ４０９鋼板の表面に乾燥膜厚
が０．３μｍの下地処理層を設け、その上に、有機潤滑
剤の含有量が光触媒層の重量に対して１０％以下の範囲
の種々の値になるように変更した以外は、本発明例３に
記載したのと同様の条件でポリエチレンワックスを有機
潤滑剤として含有する厚さが０．８μｍの光触媒層を設
けた。(Example 4 of the Invention) Using the same aqueous solution of Al phosphate as described in Example 3 of the present invention, in the same manner as described in Example 3 of the present invention, the surface of the SUS409 steel sheet was dried to a thickness of not less than 10 mm. Inventive Example 3 except that a 0.3 μm undercoating layer was provided, and that the content of the organic lubricant was changed to various values in the range of 10% or less with respect to the weight of the photocatalytic layer thereon. A photocatalytic layer having a thickness of 0.8 μm and containing polyethylene wax as an organic lubricant was provided under the same conditions as described in (1).
【００６５】（比較例３）ポリエチレンワックスの乾燥
固形分重量比を１２％とした以外は本発明例４と同様に
して比較用の試験片を作製した。また、ポリエチレンワ
ックスの乾燥固形分重量比を１〜１２％の範囲で変更
し、光触媒層の厚さを０．２μｍとした以外は本発明例
４に記載したのと同様の条件で比較用の試験片を作製し
た。Comparative Example 3 A test piece for comparison was prepared in the same manner as in Example 4 of the present invention except that the dry solid content ratio of polyethylene wax was changed to 12%. The dry solid content ratio of the polyethylene wax was changed in the range of 1 to 12%, and the thickness of the photocatalyst layer was set to 0.2 μm, except that the thickness was 0.2 μm. Test pieces were prepared.
【００６６】本発明例４と比較例３の試験片について、
以下の成形加工条件で試験片の円筒深絞り試験をおこな
い、深絞り加工後の円筒側壁部の皮膜残存状況を目視観
察し、皮膜外観が正常であった場合を〇、皮膜層の粉化
が生じていた場合を×として評価した。With respect to the test pieces of Inventive Example 4 and Comparative Example 3,
A cylindrical deep drawing test of the test piece was performed under the following molding conditions, and the state of the film remaining on the cylindrical side wall after the deep drawing was visually observed. When it occurred, it was evaluated as x.
【００６７】成形加工条件：ブランク径１０２ｍｍ、ダ
イの内径５２．４ｍｍ、ダイ肩半径５ｍｍ、ポンチ直径
５０ｍｍ、ポンチ肩半径５ｍｍ、しわ押さえ圧力０．５
トン。Forming conditions: blank diameter 102 mm, die inner diameter 52.4 mm, die shoulder radius 5 mm, punch diameter 50 mm, punch shoulder radius 5 mm, wrinkle holding pressure 0.5
T.
【００６８】その後、上記深絞り成形後の側壁部からサ
ンプルを切り出し、前述のアセトアルデヒド分解試験を
おこない、ガラス容器中のアセトアルデヒド量が１００
ｐｐｍから１ｐｐｍ以下になるまでに要したブラックラ
イトの照射時間を計測して、光触媒活性を下記の基準で
評価した。Thereafter, a sample was cut out from the side wall portion after the above deep drawing, and the acetaldehyde decomposition test was performed.
The irradiation time of the black light required from 1 ppm to 1 ppm or less was measured, and the photocatalytic activity was evaluated based on the following criteria.
【００６９】 ◎：９０分以下、 ○：９０分超、１２０分以下、 △：１２０分超、１５０分以下、 ×：１５０分超。 得られた結果を表２に示した。◎: 90 minutes or less, ：: more than 90 minutes, 120 minutes or less, Δ: more than 120 minutes, 150 minutes or less, ×: more than 150 minutes. Table 2 shows the obtained results.
【００７０】[0070]
【表２】 [Table 2]
【００７１】表２に示されているように、光触媒層中に
１０重量％以下のワックスを有する試験番号９〜１３で
は円筒深絞り後の側壁には光触媒層が良好かつ十分に残
存していた。試験番号１４および１８に示すようにワッ
クスの含有量が１０重量％を超えると、皮膜強度が低下
して皮膜表面にポリエチレンワックス粉の粉化が生じ、
成型品の外観が著しく損なわれた。As shown in Table 2, in Test Nos. 9 to 13 in which the photocatalyst layer contained 10% by weight or less of wax in the photocatalyst layer, the photocatalyst layer remained well and sufficiently on the side wall after the cylindrical deep drawing. . When the content of the wax exceeds 10% by weight as shown in Test Nos. 14 and 18, the film strength is reduced and the polyethylene wax powder is formed on the film surface,
The appearance of the molded article was significantly impaired.
【００７２】光触媒活性は、ワックス量が１〜５重量％
の範囲で最も優れていた。ワックス含有量が光触媒層の
重量に対して１０％を超えると光触媒活性が劣化した。
光触媒層の厚さが本発明の規定する下限よりも薄い試験
番号１５〜１７では、ワックス含有量が１０重量％以下
の範囲であっても光触媒活性が劣り、１０重量％を超え
た試験番号１８は光触媒効果がほとんどなかった。The photocatalytic activity was such that the wax amount was 1 to 5% by weight.
The range was the best. When the wax content exceeded 10% based on the weight of the photocatalyst layer, the photocatalytic activity deteriorated.
In Test Nos. 15 to 17 in which the thickness of the photocatalyst layer was smaller than the lower limit specified in the present invention, even when the wax content was in the range of 10% by weight or less, the photocatalytic activity was inferior, and Test No. 18 in which the wax content exceeded 10% by weight. Had almost no photocatalytic effect.
【００７３】本発明例４および比較例３で得た試験片の
動摩擦係数を、鋼球の押し付け荷重を１ｋｇｆ、摺動速
度を１０ｍｍ／秒とするバウデン式摩擦試験により測定
した。また、前述したのと同様の条件で円筒深絞り試験
をおこない、ブランクが破断しないで成形できる最大の
しわ押さえ力（限界しわ押さえ力）を調査した。限界し
わ押さえ力が大きいほど深絞り性が良いことを意味す
る。The coefficient of kinetic friction of the test pieces obtained in Inventive Example 4 and Comparative Example 3 was measured by a Bowden friction test in which the pressing load of a steel ball was 1 kgf and the sliding speed was 10 mm / sec. Further, a cylindrical deep drawing test was performed under the same conditions as described above, and the maximum wrinkle pressing force (limit wrinkle pressing force) that could be formed without breaking the blank was investigated. The greater the limit wrinkle holding force, the better the deep drawability.
【００７４】図２に、これらの試験で得られた動摩擦係
数と限界しわ押さえ力との関係を示した。図中の％表示
は、光触媒層中に含有されている有機潤滑剤の含有量
（重量％）を表す。図２からわかるように、光触媒層中
に有機潤滑剤を含有しない場合には動摩擦係数が０．４
前後と高く、限界しわ押さえ力が０．５トン前後であり、
容易に破断した。しかし光触媒層中に有機潤滑剤を含有
する場合には、その含有量が増すにつれて動摩擦係数が
０．１以下の極めて良好な潤滑性を示し、大きいしわ押
さえ力でも成形加工が可能であった。ワックス含有量が
１０重量％を超えても、限界しわ押さえ力は上昇せず成
形性は飽和し、それ以上の改善効果は認められなかっ
た。FIG. 2 shows the relationship between the dynamic friction coefficient obtained in these tests and the limit wrinkle pressing force. The percentages shown in the figures represent the content (% by weight) of the organic lubricant contained in the photocatalyst layer. As can be seen from FIG. 2, when the organic catalyst was not contained in the photocatalyst layer, the dynamic friction coefficient was 0.4.
The front and back are high, and the limit wrinkle holding force is around 0.5 tons,
Easily broken. However, when an organic lubricant was contained in the photocatalyst layer, as the content increased, extremely good lubricity with a kinetic friction coefficient of 0.1 or less was exhibited, and molding was possible even with a large wrinkle suppressing force. Even when the wax content exceeds 10% by weight, the limit wrinkle suppressing force does not increase, the moldability is saturated, and no further improvement effect is recognized.
【００７５】（本発明例５）ＪＩＳ−Ｇ−４３０５に規
定されるＳＵＳ４３０ＬＸの厚さが０．５ｍｍの冷間圧
延鋼板の片面に、市販の羽毛状態で平均粒子径が１００
ｎｍのコロイダルアルミナを乾燥膜厚が０．３μｍとな
るように塗布し２５０℃で４０秒間乾燥して下地処理層
を設けた。本発明例１に記載したのと同一の酸化チタン
含有塗料、および、本発明例２に記載したのと同一のチ
タン酸ジルコニウム含有塗料にそれぞれポリエチレンワ
ックスを乾燥固形分重量比で５％となるように混合して
２種類の塗料組成物を準備した。これらの塗料を上述の
下地処理を施した鋼板に膜厚が０．３μｍとなるように
塗布し、２００℃で５０秒間乾燥して２種類の光触媒層
を有するステンレス鋼板を得た。(Example 5 of the Present Invention) A cold rolled steel sheet having a thickness of 0.5 mm and having a thickness of 0.5 mm, which is SUS430LX specified in JIS-G-4305, is coated with a commercially available feather having an average particle diameter of 100%.
nm of colloidal alumina was applied so as to have a dry film thickness of 0.3 μm, and dried at 250 ° C. for 40 seconds to provide a base treatment layer. The same titanium oxide-containing paint as described in Inventive Example 1 and the same zirconium titanate-containing paint as described in Inventive Example 2 were each provided with a polyethylene wax in a dry solid content weight ratio of 5%. To prepare two types of coating compositions. These paints were applied to a steel sheet which had been subjected to the above-mentioned base treatment so that the film thickness became 0.3 μm, and dried at 200 ° C. for 50 seconds to obtain a stainless steel sheet having two types of photocatalytic layers.
【００７６】（比較例４）本発明例５で使用した同一の
酸化チタンとポリエチレンワックスを含有する塗料組成
物を、本発明例５で使用したのと同一のＳＵＳ４３０Ｌ
Ｘ鋼板の表面に下地処理層を設けないで直接、乾燥膜厚
が０．３μとなるように塗布し２００℃で５０秒間乾燥
した。Comparative Example 4 The same coating composition containing titanium oxide and polyethylene wax used in Example 5 of the present invention was used in the same SUS430L as used in Example 5 of the present invention.
The X steel sheet was directly coated on the surface of the X steel sheet without providing a base treatment layer so as to have a dry film thickness of 0.3 μm, and dried at 200 ° C. for 50 seconds.
【００７７】（比較例５）本発明例５で使用したのと同
一のＳＵＳ４３０ＬＸ鋼板表面に本発明例５と同一の条
件で下地処理のみを施した鋼板を比較材として準備し
た。(Comparative Example 5) A comparative steel sheet was prepared by subjecting the same SUS430LX steel sheet surface used in Inventive Example 5 to only the base treatment under the same conditions as in Inventive Example 5.
【００７８】図３は、光触媒層を備えた鋼板の光触媒活
性を調査するために使用した建築物の側壁パネルを模し
たフラットパネルの外観を示す斜視図である。本発明例
５、比較例５および比較例６で作成した試料片と、無処
理のＳＵＳ４３０ＬＸ鋼板を図３に示すフラットパネル
にプレス加工した。その際、光触媒層を設けた試験面を
凸面側にし、パネルの深さ３０ｍｍ、幅３００ｍｍ、長
さ７００ｍｍとした。これらのパネルを５階建てビルの
北面に設置し４月から１０月まで６ヶ月間屋外に暴露
し、６ケ月後の表面の汚染具合を目視観察して試験面の
汚れ状況を判定し、以下の基準で評価した。FIG. 3 is a perspective view showing the appearance of a flat panel simulating a side wall panel of a building used for investigating the photocatalytic activity of a steel sheet provided with a photocatalytic layer. The sample pieces prepared in Inventive Example 5, Comparative Examples 5 and 6, and an untreated SUS430LX steel plate were pressed into a flat panel shown in FIG. At that time, the test surface on which the photocatalyst layer was provided was on the convex surface side, and the panel had a depth of 30 mm, a width of 300 mm, and a length of 700 mm. These panels were installed on the north side of a five-story building and exposed outdoors for six months from April to October. After six months, the surface was visually inspected for contamination, and the stain on the test surface was determined. The evaluation was based on the following criteria.
【００７９】 ○：雨筋無く清浄な表面、 △：軽度の雨筋有り、光触媒層一部剥離有り、 ×：雨筋有り。 表３に上記の評価結果を示した。：: clean surface without rain streaks, Δ: slight rain streaks, partial peeling of the photocatalyst layer, ×: rain streaks. Table 3 shows the above evaluation results.
【００８０】[0080]
【表３】 [Table 3]
【００８１】表３に示されているように本発明に規定す
る範囲であるコロイダルアルミナの下地処理層の上に有
機潤滑剤を含有する光触媒層を備えた鋼板は、耐雨筋汚
染性が優れていた。しかしながら、下地処理層を設けな
いで光触媒層を直接塗布した試験番号２１では、成形加
工時に光触媒層が一部脱落したうえ金属板と光触媒層間
の経時密着性が弱く、光触媒層の一部に剥離を生じてお
り、剥離部分には雨筋が観察されて外観がよくなかっ
た。コロイダルアルミナの下地処理層のみを有し光触媒
層のない試験番号２２では雨筋による汚れが観察され、
外観がさらによくなかった。As shown in Table 3, a steel sheet provided with a photocatalyst layer containing an organic lubricant on a colloidal alumina base treatment layer within the range specified in the present invention has excellent rain streak stain resistance. Was. However, in Test No. 21, in which the photocatalyst layer was directly applied without providing the undercoating layer, the photocatalyst layer was partially dropped during molding and the temporal adhesion between the metal plate and the photocatalyst layer was weak. And a streak was observed in the peeled part, and the appearance was not good. In Test No. 22 having only a base treatment layer of colloidal alumina and no photocatalyst layer, dirt due to rain streaks was observed,
The appearance was not even better.
【００８２】（本発明例６）厚さが０．４ｍｍのＳＵＳ
３０４鋼板の片面に、有機分２５重量％のメチル基変成
の市販のシリコン樹脂を２５重量％含有するトルエン溶
液を、乾燥膜厚が０．２μとなるように塗布し２８０℃
で２分間乾燥してメチル基を有するＳｉＯ2を含む下地
処理層を形成した。その上に本発明例２で使用したのと
同一のチタン酸ジルコニウム含有塗料を、乾燥膜厚が
０．５μとなるように塗布し２００℃で４５秒間乾燥し
た。(Invention Example 6) SUS having a thickness of 0.4 mm
To one side of a 304 steel sheet, a toluene solution containing 25% by weight of a commercially available silicone resin having a methyl group modified with an organic content of 25% by weight is applied so as to have a dry film thickness of 0.2 μm.
For 2 minutes to form a base treatment layer containing SiO 2 having a methyl group. The same zirconium titanate-containing paint as used in Inventive Example 2 was applied thereon so as to have a dry film thickness of 0.5 μm, and dried at 200 ° C. for 45 seconds.
【００８３】（本発明例７）本発明例６に記載したのと
同一のシリコン樹脂と、市販のＰＭＭＡ（ポリメチルメ
タクリレート）を重量比で２：１または１：１の割合で
混合し、トルエンで希釈して上記有機分を２５重量％含
有する下地処理用塗料を作成した。この下地処理用塗料
の有機分を熱重量分析により測定したところそれぞれ３
５重量％および４２重量％であった。この下地処理用塗
料を厚さ０．５ｍｍのＳＵＳ３０４鋼板の片面に乾燥膜
厚が０．２μとなるように塗布し２８０℃で２分間乾燥
し、メチル基を有するＳｉＯ2 と有機高分子を含む下地
処理層を形成した。その上に本発明例２で使用したのと
同一のチタン酸ジルコニウム含有塗料を、乾燥膜厚が
０．５μとなるように塗布し２００℃で４５秒間乾燥し
た。(Inventive Example 7) The same silicone resin as described in Inventive Example 6 and commercially available PMMA (polymethyl methacrylate) were mixed at a weight ratio of 2: 1 or 1: 1 and toluene was mixed. To prepare a base coating material containing 25% by weight of the above organic component. The organic content of the undercoating paint was measured by thermogravimetric analysis and found to be 3
5% and 42% by weight. This undercoating paint is applied to one side of a SUS304 steel plate having a thickness of 0.5 mm so as to have a dry film thickness of 0.2 μm, dried at 280 ° C. for 2 minutes, and contains SiO 2 having a methyl group and an organic polymer. An underlayer was formed. The same zirconium titanate-containing paint as used in Inventive Example 2 was applied thereon so as to have a dry film thickness of 0.5 μm, and dried at 200 ° C. for 45 seconds.
【００８４】（比較例６）本発明例６に記載したのと同
一のシリコン樹脂と、市販のＰＭＭＡを重量比で１：２
の割合で混合し、トルエンで希釈して上記有機分を２５
重量％含有する下地処理用塗料を作製した。この下地処
理用塗料の有機分を熱重量分析により測定したところ５
６重量％であった。これらの下地用塗料を本発明例６に
記載したのと同一のＳＵＳ３０４鋼板の表面に乾燥膜厚
０．２μｍになるように塗布乾燥し、本発明例６に記載
したのと同様の光触媒層をその上に形成させた。Comparative Example 6 The same silicone resin as described in Example 6 of the present invention and commercially available PMMA were used in a weight ratio of 1: 2.
, And diluted with toluene to reduce the organic content to 25%.
An undercoating paint containing 1% by weight was prepared. The organic content of the undercoating paint was measured by thermogravimetric analysis.
It was 6% by weight. These primer paints were applied to the same SUS304 steel plate surface as described in Example 6 of the present invention so as to have a dry film thickness of 0.2 μm and dried to form a photocatalytic layer similar to that described in Example 6 of the present invention. It was formed on it.
【００８５】本発明例６、７および比較例６で作成した
試料片をＪＩＳ−Ｚ−８７１９に規定されるサンシャイ
ンウェザオメータを用いて、５００時間の耐候性試験
（以下、単に「ＷＭ試験」と記す）をおこなった。試験
後の鋼板表面を目視観察し、光触媒層の残存状態を目視
観察した。表４に上記の評価結果を示した。The test pieces prepared in Examples 6 and 7 of the present invention and Comparative Example 6 were subjected to a 500-hour weather resistance test (hereinafter simply referred to as “WM test”) using a sunshine weatherometer specified in JIS-Z-8719. Written). The steel sheet surface after the test was visually observed, and the remaining state of the photocatalyst layer was visually observed. Table 4 shows the above evaluation results.
【００８６】[0086]
【表４】 [Table 4]
【００８７】表４に示されているように、下地処理層中
の有機分の含有量が５０重量％を超えると光触媒の効果
により下地処理層が劣化し光触媒層が剥離した。ＷＭ試
験後の本発明例６および７の試料片について、本発明例
５等を評価したのと同様の６ヶ月間屋外暴露試験を行っ
たところ、雨筋も見られず清浄な表面を呈しており防汚
性は良好であった。As shown in Table 4, when the organic content in the undercoat layer exceeded 50% by weight, the undercoat layer deteriorated due to the effect of the photocatalyst and the photocatalyst layer was peeled off. The sample pieces of Examples 6 and 7 of the present invention after the WM test were subjected to a 6-month outdoor exposure test in the same manner as in the evaluation of Example 5 of the present invention. The antifouling property was good.
【００８８】（本発明例８）Ｂａ、Ｎｂ、Ｗ、Ｖ、Ｍｏ
およびＺｒの粉末をそれぞれ蓋付きフラスコに適量採取
し、非酸化性雰囲気中でエタノールと混合し、１００℃
で２４時間還流、精製をおこない、化学組成がそれぞ
れ、Ｂａ( ＯＣ2 Ｈ5)2 、Ｎｂ( ＯＣ2 Ｈ5)5、Ｗ (Ｏ
Ｃ2 Ｈ5)6 、Ｖ (ＯＣ2 Ｈ5)5 、Ｍｏ (ＯＣ2 Ｈ5)6 お
よびＺｒ (ＯＣ2 Ｈ5)4 であるそれぞれの元素を含有す
るアルコキシドを得た。各アルコキシド１ｍｏｌとＳｉ
(ＯＣ2 Ｈ5)4 、０．５ｍｏｌとを混合し、塩酸４×１
０-4ｍｏｌ、エタノール１３ｍｏｌおよびイオ交換水８
ｍｏｌを加え、５０℃で２４時間熟成して各金属アルコ
キシドを加水分解・縮重合させて、各金属酸化物を主成
分とするゾルを得た。ＳＵＳ４３０鋼板の片面に上記の
各ゾルを乾燥膜厚が０．１μｍとなるように塗布し、１
００℃で１０秒乾燥した後、さらに３００℃で３分間乾
燥して、ＺｒＯ2 、ＢａＯ、Ｎｂ2 Ｏ5 、ＷＯ3 、Ｖ2
Ｏ5 およびＭｏＯ３の内のいずれかとＳｉＯ２ とを含
有する６種類の下地処理層を形成した。その上に、本発
明例２で使用したのと同一のチタン酸ジルコニウム含有
塗料を乾燥膜厚が０．５μｍとなるように塗布し、２５
０℃で５０秒間乾燥した。(Example 8 of the present invention) Ba, Nb, W, V, Mo
And Zr powder were collected in appropriate amounts in flasks with lids, mixed with ethanol in a non-oxidizing atmosphere,
For 24 hours, and the chemical composition is Ba (OC 2 H 5 ) 2 , Nb (OC 2 H 5 ) 5 , W (O
Alkoxides containing respective elements of C 2 H 5 ) 6 , V (OC 2 H 5 ) 5 , Mo (OC 2 H 5 ) 6 and Zr (OC 2 H 5 ) 4 were obtained. 1 mol of each alkoxide and Si
(OC 2 H 5 ) 4 , and 0.5 mol of hydrochloric acid.
0 -4 mol, ethanol 13 mol and ion exchange water 8
Then, the mixture was aged at 50 ° C. for 24 hours to hydrolyze and polycondensate each metal alkoxide to obtain a sol containing each metal oxide as a main component. Each of the above sols is applied to one side of a SUS430 steel sheet so that the dry film thickness is 0.1 μm.
After drying at 00 ° C. for 10 seconds, further drying at 300 ° C. for 3 minutes, ZrO 2 , BaO, Nb 2 O 5 , WO 3 , V 2
Six types of underlayers containing SiO 2 and any one of O 5 and MoO 3 were formed. The same zirconium titanate-containing paint as used in Inventive Example 2 was applied thereon so that the dry film thickness was 0.5 μm, and 25
Dry at 0 ° C. for 50 seconds.
【００８９】上述の処理により得た各種の鋼板と比較用
の無処理のＳＵＳ４３０鋼板を、図３に示したフラット
パネルにプレス成形し、これらを密閉容器に封入し、内
部を真空状態にした後タバコの煙を内部に導入し、フラ
ットパネルの試験面にたばこのヤニを付着させた。たば
このヤニ付着量は本発明例８のサンプルで１．８ｍｇ／
ｍ2 、無処理のＳＵＳ４３０鋼板で０．８ｍｇ／ｍ2 で
あった。これらのフラットパネルを３階建てビルの外壁
に試験面に日射が差すように並べて設置し、１１月〜１
２月の間で３０日間暴露し、たばこのヤニ付着前とたば
このヤニ付着後３０日間暴露した後とのＪＩＳ−Ｚ−８
７２２記載の物体色の測定方法で色変化を調査した。The various steel sheets obtained by the above-described processing and the untreated SUS430 steel sheet for comparison were press-formed into the flat panel shown in FIG. 3, these were sealed in a closed container, and the inside was evacuated. Tobacco smoke was introduced into the interior, and the cigarette was attached to the test surface of the flat panel. The amount of the tobacco stain attached was 1.8 mg / sample for the sample of Example 8 of the present invention.
m 2 , 0.8 mg / m 2 for an untreated SUS430 steel plate. These flat panels were set up on the outer wall of a three-story building so that the test surface could receive solar radiation.
Exposure for 30 days between February and JIS-Z-8 before and after exposure to cigarettes after 30 days
The change in color was investigated by the method for measuring object color described in 722.
【００９０】図４に、下地処理層にＺｒＯ2 とＳｉＯ2
とを含有する下地処理層を用いたパネルに付着したたば
このヤニによる着色状況の変化を測定した結果を示す。
図４からわかるように、本発明例８の光触媒機能を有す
る鋼板を用いて作製したパネル面は１ヶ月間の屋外暴露
でたばこのヤニが著しく除去され、着色が無くなり、上
記の物体色測定方法で測定した黄色味を表すｂ値が０に
近づき、たばこのヤニ付着前の良好な金属光沢が回復し
た。光触媒機能を有しないＳＵＳ４３０鋼板では、たば
このヤニによる色調不良（黄色み）が回復されなかっ
た。上述の、ＺｒＯ2 以外の酸化物を含有する下地処理
層を用いた場合についても上記と同様の良好な結果が得
られた。FIG. 4 shows that ZrO 2 and SiO 2
7 shows the results of measuring the change in the coloration state due to the tobacco tar attached to the panel using the base treatment layer containing and.
As can be seen from FIG. 4, the panel surface produced by using the steel sheet having the photocatalytic function of Example 8 of the present invention was significantly exposed to outdoor exposure for one month, and the cigarette tar was significantly removed and the coloring was eliminated. The b-value representing the yellowish color measured in step (c) approached 0, and the good metallic luster before the tobacco was attached was restored. With the SUS430 steel plate having no photocatalytic function, poor color tone (yellowish color) due to tobacco tar was not recovered. The same good results as described above were obtained also when the above-described underlayer containing an oxide other than ZrO 2 was used.
【００９１】[0091]
【発明の効果】本発明の金属板は、優れた光触媒機能を
有するとともに光触媒層の密着性が良好である。光触媒
層には有機潤滑剤を共存させることができるので良好な
加工性も有する。本発明の金属板は種々の製品に加工で
きるので、優れた光触媒機能を有する構造物を製造する
のに好適である。The metal plate of the present invention has an excellent photocatalytic function and good adhesion of the photocatalyst layer. The photocatalyst layer also has good workability since an organic lubricant can coexist. Since the metal plate of the present invention can be processed into various products, it is suitable for producing a structure having an excellent photocatalytic function.
【図１】光触媒反応によるアセトアルデヒドの分解状況
を示す図である。FIG. 1 is a diagram showing the state of decomposition of acetaldehyde by a photocatalytic reaction.
【図２】成形加工時の動摩擦係数としわ押さえ力の関係
を示す図である。FIG. 2 is a diagram illustrating a relationship between a dynamic friction coefficient and a wrinkle holding force during molding.
【図３】光触媒層を備えた鋼板の光触媒活性を調査する
ための建築物の側壁パネルを模したフラットパネルの外
観を示す斜視図である。FIG. 3 is a perspective view showing the appearance of a flat panel simulating a side wall panel of a building for investigating the photocatalytic activity of a steel sheet provided with a photocatalytic layer.
【図４】パネルに付着したたばこのヤニによる着色状況
の変化を測定した結果の１例を示すグラフである。FIG. 4 is a graph showing an example of a result of measuring a change in a coloring state due to a cigarette sticking to a panel.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ２３Ｃ 22/24 Ｃ２３Ｃ 28/04 ４Ｋ０４４ 28/04 Ｂ０１Ｄ 53/36 Ｊ (72)発明者 正木 康浩 大阪市中央区北浜４丁目５番33号 住友金 属工業株式会社内 Ｆターム(参考） 4C080 AA07 BB02 BB05 BB06 CC01 HH05 JJ03 KK08 LL10 MM02 MM03 NN01 4D048 AA21 AA22 AB03 BA01X BA02X BA03X BA06X BA07X BA07Y BA08X BA08Y BA15X BA16X BA16Y BA23X BA24X BA25Y BA26X BA27X BA28Y BA36Y BA37Y BA38Y BA39X BA39Y BA41X BA41Y BA42X BA42Y BA44X BA46Y BB18 BB20 CC36 DA11 EA01 4F100 AA17B AA18B AA19B AA20B AA21C AA22B AA24B AA25B AA27B AA34C AB01A AB03A AB04A AB10A AH00C AH00H AK52 BA03 BA07 CA30C DE01C EH71A GB07 GB48 JA11C JC00 JK06 JL00 JL01 JL06 JL08C YY00B YY00C 4G069 AA03 AA08 BA01B BA03B BA17 BA18 BA48A BA48C BB04A BB04B BB04C BB06A BB06B BB06C BB07A BB07B BB07C BB09A BB14B BC09B BC10B BC12A BC13B BC16B BC35A BC36A BC50A BC50B BC50C BC51A BC51B BC51C BC54B BC55B BC58A BC59B BC60B BC62A BC66A BC67A BC68A BD09A CA01 CA10 EA08 EB18X EB18Y EE01 EE06 FA03 FB23 FB57 FC08 4K026 AA02 AA04 AA09 BA02 BA03 BA08 BA12 BB04 BB10 CA02 CA16 CA23 CA37 CA41 DA16 EB02 EB11 4K044 AA02 AA03 AB02 BA10 BA12 BA13 BA14 BA17 BB03 BB04 BC00 CA11 CA16 CA53 CA62──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C23C 22/24 C23C 28/04 4K0428 28/04 B01D 53/36 J (72) Inventor Yasuhiro Masaki Central in Osaka City 4-5-33 Kitahama-ku, Sumitomo Metal Industries, Ltd. F-term (reference) 4C080 AA07 BB02 BB05 BB06 CC01 HH05 JJ03 KK08 LL10 MM02 MM03 NN01 4D048 AA21 AA22 AB03 BA01X BA02X BA03X BA06X BA07X BA07Y BAX BAX BAX8 BA25Y BA26X BA27X BA28Y BA36Y BA37Y BA38Y BA39X BA39Y BA41X BA41Y BA42X BA42Y BA44X BA46Y BB18 BB20 CC36 DA11 EA01 4F100 AA17B AA18B AA19B AA20B AA21C AA22B AA24B AA25B AA27B AA34C AB01A AB03A AB04A AB10A AH00C AH00H AK52 BA03 BA07 CA30C DE01C EH71A GB07 GB48 JA11C JC00 JK06 JL00 JL01 JL06 JL08C YY00B YY00C 4G069 AA03 AA08 BA01B BA03B BA17 BA18 BA48A BA48C BB04A BB04B BB04C BB06A BB06B BB06C BB07A BB07B BB07C BB09A BB14B BC09B BC10B BC12A BC13B BC16B BC35A BC36A BC50A BC50B BC50C BC51A BC51B BC51C BC54B BC55B BC58A BC59B BC60B BC62A BC66A BC67A BC68A BD09A CA01 CA10 EA08 EB18X EB18Y EE01 EE06 FA03 FB23 FB57 FC08 4K026 AA02 AA04 AA09 BA02 BA03 BA08 BA12 BB04 BB10 CA02 CA16 CA23 CA37 CA41 DA16 EB02 EB11 4K044 AA02 AA03 AB02 BA10 BA12 BA13 BA14 BA17 BB03 BB04 BC00 CA11 CA16 CA53 CA62
Claims (3)
理層と、さらに該下地処理層の上に設けた光触媒層とか
ら成り、前記下地処理層が、Ｃａ、Ｍｇ、Ｓｒ、Ｂａ、
Ｚｎ、Ｃｏ、Ｃｒ、Ｓｉ、Ａｌ、Ｐ、Ｍｏ、Ｍｎ、Ｎ
ｉ、Ｗ、Ｖ、Ｎｂ、Ｚｒから成る群から選ばれる１種ま
たは２種以上の元素の酸化物を合計で５０重量％以上含
み、その厚さが０．１〜５μｍであり、前記光触媒層が
１０〜９０重量％の光触媒粒子、および０〜１０重量％
の有機潤滑剤を含み、厚さが０．５μｍ以上であること
を特徴とする光触媒機能を備えた金属板。1. A base metal plate, a base treatment layer provided on the surface of the base metal plate, and a photocatalytic layer provided on the base treatment layer, wherein the base treatment layer is composed of Ca, Mg, Sr, Ba,
Zn, Co, Cr, Si, Al, P, Mo, Mn, N
the photocatalyst layer containing at least 50% by weight of a total of oxides of one or more elements selected from the group consisting of i, W, V, Nb, and Zr, having a thickness of 0.1 to 5 μm; 10 to 90% by weight of photocatalyst particles, and 0 to 10% by weight
A metal plate having a photocatalytic function, wherein the metal plate comprises the organic lubricant of (1) and has a thickness of 0.5 μm or more.
ン酸ジルコニウムとの結合体を含有するものであること
を特徴とする請求項１に記載の光触媒機能を備えた金属
板。2. The metal plate having a photocatalytic function according to claim 1, wherein the photocatalytic particles contain a combination of titanium oxide and crystalline zirconium titanate.
ｌ系めっき鋼板であることを特徴とする請求項１または
２に記載の光触媒機能を備えた金属板。3. The base metal plate is made of a stainless steel plate or A
The metal plate having a photocatalytic function according to claim 1 or 2, which is an l-plated steel plate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10182625A JP2000014755A (en) | 1998-06-29 | 1998-06-29 | Metal plate having photocatalytic function |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10182625A JP2000014755A (en) | 1998-06-29 | 1998-06-29 | Metal plate having photocatalytic function |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000014755A true JP2000014755A (en) | 2000-01-18 |
Family
ID=16121568
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10182625A Withdrawn JP2000014755A (en) | 1998-06-29 | 1998-06-29 | Metal plate having photocatalytic function |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000014755A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001316849A (en) * | 2000-05-10 | 2001-11-16 | Nisshin Steel Co Ltd | Coated metal sheet excellent in visible light photocatalysis and machinability, and method for production thereof |
| US6833089B1 (en) | 1999-08-05 | 2004-12-21 | Nippon Sheet Glass Co., Ltd. | Article having photocatalytic activity |
| JP2010234622A (en) * | 2009-03-31 | 2010-10-21 | Kimoto & Co Ltd | Photocatalyst laminate |
| JP2012531527A (en) * | 2009-07-03 | 2012-12-10 | アトテツク・ドイチユラント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング | Anticorrosion treatment for zinc and zinc alloy surfaces |
| CN103007936A (en) * | 2012-12-28 | 2013-04-03 | 青岛信锐德科技有限公司 | Air purifier material, preparation method and use of air purifier material |
| WO2013125657A1 (en) | 2012-02-24 | 2013-08-29 | Ｊｆｅスチール株式会社 | Metal material surface treatment method, and metal material |
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| RU2675547C1 (en) * | 2017-07-17 | 2018-12-19 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Саратовский государственный технический университет имени Гагарина Ю.А." (СГТУ имени Гагарина Ю.А.) | Method for producing a material, photoactive in a visible region of a spectrum |
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-
1998
- 1998-06-29 JP JP10182625A patent/JP2000014755A/en not_active Withdrawn
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6833089B1 (en) | 1999-08-05 | 2004-12-21 | Nippon Sheet Glass Co., Ltd. | Article having photocatalytic activity |
| JP2001316849A (en) * | 2000-05-10 | 2001-11-16 | Nisshin Steel Co Ltd | Coated metal sheet excellent in visible light photocatalysis and machinability, and method for production thereof |
| JP4588164B2 (en) * | 2000-05-10 | 2010-11-24 | 日新製鋼株式会社 | Pre-coated metal plate and manufacturing method thereof |
| JP2010234622A (en) * | 2009-03-31 | 2010-10-21 | Kimoto & Co Ltd | Photocatalyst laminate |
| JP2012531527A (en) * | 2009-07-03 | 2012-12-10 | アトテツク・ドイチユラント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング | Anticorrosion treatment for zinc and zinc alloy surfaces |
| WO2013125657A1 (en) | 2012-02-24 | 2013-08-29 | Ｊｆｅスチール株式会社 | Metal material surface treatment method, and metal material |
| KR20140117579A (en) | 2012-02-24 | 2014-10-07 | 제이에프이 스틸 가부시키가이샤 | Metal material surface treatment method, and metal material |
| CN103007936A (en) * | 2012-12-28 | 2013-04-03 | 青岛信锐德科技有限公司 | Air purifier material, preparation method and use of air purifier material |
| JP2017064707A (en) * | 2015-09-30 | 2017-04-06 | Toto株式会社 | Photocatalyst coated body |
| RU2675547C1 (en) * | 2017-07-17 | 2018-12-19 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Саратовский государственный технический университет имени Гагарина Ю.А." (СГТУ имени Гагарина Ю.А.) | Method for producing a material, photoactive in a visible region of a spectrum |
| CN113332854A (en) * | 2021-06-28 | 2021-09-03 | 特灵空调***(中国)有限公司 | Photocatalyst environment purification material, preparation method thereof and air purifier |
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