WO2003061828A1 - Materiau composite photocatalytique et son procede de preparation - Google Patents
Materiau composite photocatalytique et son procede de preparation Download PDFInfo
- Publication number
- WO2003061828A1 WO2003061828A1 PCT/JP2002/007598 JP0207598W WO03061828A1 WO 2003061828 A1 WO2003061828 A1 WO 2003061828A1 JP 0207598 W JP0207598 W JP 0207598W WO 03061828 A1 WO03061828 A1 WO 03061828A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- film
- photocatalyst
- titanium oxide
- vapor
- fiber
- Prior art date
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 80
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 47
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 138
- 239000011941 photocatalyst Substances 0.000 claims abstract description 95
- 239000000835 fiber Substances 0.000 claims abstract description 86
- 239000000758 substrate Substances 0.000 claims abstract description 76
- 238000007740 vapor deposition Methods 0.000 claims abstract description 68
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 66
- 238000010438 heat treatment Methods 0.000 claims abstract description 53
- 239000002243 precursor Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000012784 inorganic fiber Substances 0.000 claims abstract description 14
- 230000001590 oxidative effect Effects 0.000 claims abstract description 9
- 238000004821 distillation Methods 0.000 claims abstract description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 125
- 239000000463 material Substances 0.000 claims description 41
- 239000003365 glass fiber Substances 0.000 claims description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 27
- 239000007789 gas Substances 0.000 claims description 17
- 238000000151 deposition Methods 0.000 claims description 16
- 230000008021 deposition Effects 0.000 claims description 15
- 238000004040 coloring Methods 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- 238000000746 purification Methods 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 8
- 230000007613 environmental effect Effects 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000001023 inorganic pigment Substances 0.000 claims description 6
- 239000000049 pigment Substances 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 4
- 238000005019 vapor deposition process Methods 0.000 claims description 4
- 210000002268 wool Anatomy 0.000 claims description 4
- 239000002759 woven fabric Substances 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 2
- 239000004745 nonwoven fabric Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 150000003623 transition metal compounds Chemical class 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 239000005749 Copper compound Substances 0.000 claims 1
- 150000001880 copper compounds Chemical class 0.000 claims 1
- 230000008020 evaporation Effects 0.000 claims 1
- 229910000314 transition metal oxide Inorganic materials 0.000 claims 1
- 239000004744 fabric Substances 0.000 abstract description 28
- 239000011521 glass Substances 0.000 abstract description 22
- 239000011248 coating agent Substances 0.000 abstract description 17
- 238000000576 coating method Methods 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 14
- 239000004408 titanium dioxide Substances 0.000 abstract description 6
- 239000010408 film Substances 0.000 description 131
- 238000012360 testing method Methods 0.000 description 43
- 239000010409 thin film Substances 0.000 description 43
- 239000002585 base Substances 0.000 description 21
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 16
- 239000000047 product Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 12
- 239000003973 paint Substances 0.000 description 11
- 239000000919 ceramic Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- -1 titanium alkoxide Chemical class 0.000 description 10
- 238000000354 decomposition reaction Methods 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- 230000007062 hydrolysis Effects 0.000 description 7
- 238000006460 hydrolysis reaction Methods 0.000 description 7
- 150000003609 titanium compounds Chemical class 0.000 description 7
- 230000007423 decrease Effects 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 238000005336 cracking Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000000844 anti-bacterial effect Effects 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000000843 anti-fungal effect Effects 0.000 description 3
- 229940121375 antifungal agent Drugs 0.000 description 3
- 239000004566 building material Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 238000004332 deodorization Methods 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000011491 glass wool Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000001004 secondary ion mass spectrometry Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000004904 UV filter Substances 0.000 description 1
- INNSZZHSFSFSGS-UHFFFAOYSA-N acetic acid;titanium Chemical compound [Ti].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O INNSZZHSFSFSGS-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910001502 inorganic halide Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 239000010454 slate Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0238—Impregnation, coating or precipitation via the gaseous phase-sublimation
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/12—General methods of coating; Devices therefor
- C03C25/22—Deposition from the vapour phase
- C03C25/223—Deposition from the vapour phase by chemical vapour deposition or pyrolysis
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/42—Coatings containing inorganic materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20707—Titanium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/80—Type of catalytic reaction
- B01D2255/802—Photocatalytic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/90—Odorous compounds not provided for in groups B01D2257/00 - B01D2257/708
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/71—Photocatalytic coatings
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
Definitions
- the present invention relates to a photocatalytic composite material having high activity, good durability and relatively low cost in the form of a fiber aggregate such as a woven fabric or any other form, and a method for producing the same.
- the present invention also relates to a product having an environmental purification function comprising the photocatalyst composite material.
- Vigorous attempts are being made to immobilize titanium oxide as a thin film on a base material of various shapes and materials mainly as a thin film, and apply its photocatalytic action to environmental purification such as deodorization, antibacterial, antifungal, decomposition of attached dirt, and decomposition of harmful substances. It has been done.
- Fiber aggregates made of glass fibers, such as glass wool and glass cloth, have a large reaction area and are not decomposed by the oxidizing power of photocatalysts.
- Japanese Patent Application Laid-Open No. 7-96202 discloses that a glass fiber is immersed in a solution in which a photocurable organic resin and a precursor of titanium oxide (such as titanium alkoxide, titanium tetrachloride, and titanium acetate) are dissolved.
- a photocurable organic resin and a precursor of titanium oxide such as titanium alkoxide, titanium tetrachloride, and titanium acetate
- a photocatalyst for treating harmful substances in liquid has been disclosed, in which a titanium oxide thin film is formed on the fiber surface by removing organic substances by drying and baking after application.
- a method of forming a titanium oxide thin film by applying a solution of a hydrolyzable organic titanium compound such as a titanium alkoxide to a substrate and then firing the solution is well known as a sol-gel method.
- JP-A-2000-72575 discloses a photocatalytic tile in which a titanium oxide thin film having a thickness of 0.8 ⁇ m or more is formed using titanium tetrachloride vapor. Is disclosed.
- the peeling or cracking of the titanium oxide thin film occurs because the stress inevitably generated in the titanium oxide thin film during film formation is relaxed. Since a thin film of titanium oxide does not have the flexibility of an organic resin, peeling and cracking are likely to occur due to stress relaxation. In particular, on glass fibers having a small diameter, stress is easily relieved in the circumferential direction, and cracks and peeling, and sometimes a lack of a film, are often observed in the formed oxide thin film.
- JP-A-7-96202 when a titanium oxide thin film is formed using a coating solution containing an organic resin, the organic resin is removed by thermal decomposition during the film formation, so that the volume of the film is reduced. Shrinkage and the resulting stresses are even greater. Therefore, cracks and peeling tend to occur not only in the circumferential direction but also in the fiber length direction.
- burning for a long time is required for baking and removing the organic portion after application. Prolonged calcination not only costs a lot, but also the growth of titanium oxide particles progresses excessively during that time, and the photocatalytic activity may decrease.
- An object of the present invention is to provide a method capable of forming a photocatalytic film comprising a continuous film of titanium oxide having high activity and excellent peeling resistance on various substrates at a relatively low cost, and a photocatalyst composite obtained in this manner.
- Another object of the present invention is to provide a photocatalyst composite material having a fiber assembly as a base material and capable of maintaining a high photocatalytic function, and a method for producing the same at a relatively low cost. Disclosure of the invention
- the present inventors have found that when vapor deposition using titanium tetrachloride and subsequent heating are performed under specific temperature conditions, a continuous film of a photocatalyst composed of titanium oxide having a small average crystallite diameter and high activity can be formed. And the application of this method to a fiber assembly provides a highly active and durable photocatalyst in which the surface of each fiber is coated with a continuous film of titanium oxide that is substantially free of delamination, cracking and chipping It has been found that a composite material can be obtained.
- the present invention is a photocatalyst composite material comprising an aggregate of inorganic fibers, wherein the surface of each fiber is covered with a continuous film of a photocatalyst made of titanium oxide.
- Each fiber means a fiber of the minimum unit constituting the fiber aggregate, and in the case of a filament fiber, means a filament. In this case, each filament is covered with a continuous film of photocatalyst.
- the coating of a titanium oxide photocatalyst with a “continuous film” means that a thin film of titanium oxide is formed over the entire surface of each fiber with a substantially constant film thickness (ie, substantially free from chipping, peeling, and cracking). Means that. Whether the film is a continuous film or not can be determined by observing the appearance of the composite material with SEM (scanning electron microscope), AFM (atomic force microscope), STM (scanning tunnel microscope), or the like. Since the end of the fiber may cause disturbance of the membrane, whether or not it is a continuous film is determined at a site other than the end of the fiber.
- the present invention provides a photocatalyst continuous film comprising a substrate having an inorganic surface, wherein at least a part of the inorganic surface is formed of titanium oxide having an average crystallite diameter of 50 nm or less formed by vapor deposition.
- the substrate can take any shape.
- the photocatalyst composite material of the first aspect is characterized in that an aggregate of inorganic fibers heated to 100 to 300 ° C. is brought into contact with titanium tetrachloride vapor and water vapor, and the surface of each fiber is coated with titanium oxide.
- the photocatalyst composite material according to the second aspect is characterized in that titanium tetrachloride vapor and water vapor are brought into contact with at least a part of the surface of a substrate having an inorganic surface heated to 100 to 300 ° C.
- the present invention also provides a product having an environmental purification function and a fiber product comprising the above photocatalyst composite material. These products exhibit environmental purification functions such as deodorization, antibacterial, antifungal, adhering and decomposing, and decomposition of harmful substances by photocatalytic activity.
- products and textiles mean not only finished products but also semi-finished products and materials.
- FIG. 1 is an explanatory view showing an outline of an apparatus configuration that can be used in the method for producing a photocatalyst composite material of the present invention.
- FIGS. 2A and 2B are SEM diagrams at 500 ⁇ and 2000 ⁇ magnification, respectively, showing the appearance of the photocatalyst composite material according to the present invention manufactured by vapor deposition using glass fiber as a base material.
- FIGS. 3A and 3B are SEM diagrams at 500 ⁇ and 2000 ⁇ magnification, respectively, showing the appearance of a comparative photocatalyst composite manufactured by a wet method. .
- 4 and 5 are SEM diagrams at a magnification of 7500 times showing the appearance of a photocatalytic composite material based on glass fiber, in which the substrate temperature during vapor deposition is outside the range of the present invention.
- FIG. 6 is a SEM diagram showing a cross section of a photocatalytic film formed on a quartz plate by the method according to the present invention. '
- FIG. 7 is an SEM diagram showing a cross section of a photocatalytic film formed on a quartz plate in which the substrate temperature during vapor deposition is out of the range of the present invention. Description of embodiments of the invention
- the photocatalyst composite material according to the present invention has a base material surface coated with a continuous film of titanium oxide having photocatalytic activity (hereinafter, also referred to as a photocatalytic film).
- a photocatalytic film When the substrate is a fiber aggregate, the surface of the individual fibers (generally, filaments) constituting the fiber aggregate is coated with a photocatalytic film.
- the surface of the substrate on which the photocatalyst film is formed is made of an inorganic material so as not to be decomposed or deteriorated by the photocatalyst film.
- the substrate itself can be made of an organic substance (eg, heat-resistant resin) as long as it can withstand the heating in the heating step after vapor deposition.
- the surface on which the photocatalytic film is formed is made of an inorganic substance in advance.
- Examples of base materials other than fibers include, for example, ceramic products such as tiles, ceramics and ceramics, especially for building materials or outdoors, glass plates and glass products, stone materials, building materials such as lightweight concrete and slate, and metals. Plates, in particular, stainless steel plates, aluminum plates, titanium plates, etc. used without painting are exemplified.
- the base material may be a porous body (eg, zeolite particles or molded body, foamed metal, foamed ceramic, porous metal sintered body).
- the substrate is a fiber aggregate
- an aggregate of inorganic fibers is used.
- the inorganic fibers it is preferable to use inexpensive and various types of glass fibers, but ceramic fibers such as alumina and silicon carbide, and metal fibers such as stainless steel, copper, and steel can also be used.
- the base material is an aggregate of glass fibers.
- the present invention is similarly applied in principle. Can be implemented.
- the type of glass fiber used in the present invention is not particularly limited.
- the average fiber diameter of the glass fibers is not limited, but is preferably about 5 to 50 m.
- the fiber diameter is preferably small when the treatment substance to be decomposed by photocatalysis is a gas or liquid having high diffusivity. Conversely, in the case of adhered dirt, it is preferable to select a fiber with a large fiber diameter.
- Aggregates of inorganic fibers are usually mechanical aggregates of inorganic fibers, with no junctions at the intersections of the fibers. However, it is also possible to bond the intersections of the fibers by fusion or the like. In this case, the surface of each fiber except for the connection is covered with a photocatalytic film.
- the form of the glass fiber aggregate includes a bundle of filaments (mouth-to-mouth), chopped strands, yarn spun filaments (whether or not twisted), a woven cloth called glass cloth, a nonwoven fabric, or a filament. It is possible to use wool-like glass wool in which the components are entangled randomly.
- a glass fiber cloth that is, a glass cloth, is easy to handle.
- the weave of the glass cloth can be any weave, such as plain weave, twill weave, or satin weave.
- the driving density, thickness, tensile strength, etc. of the glass cloth are not limited, but the driving density is 10 to 100 pieces / inch in both the vertical and horizontal directions, the cloth thickness is 0.01 to 2.0 mm, and the tensile strength is 5 kgf. / Inch (19 N / cm) or more is preferred.
- each glass fiber (ie, filament) constituting the fiber aggregate of the base material is coated with a continuous film of a photocatalyst made of titanium oxide. Uncoated discontinuities in the coating, such as delaminations, cracks, and drops, reduce the photocatalytic activity over time.
- the titanium oxide forming the continuous film may be either amorphous or crystalline, and may be a mixture of these. However, from the viewpoint of photocatalytic activity, it is preferable to use crystalline, particularly anatase-type titanium oxide. When the titanium oxide is crystalline, the photocatalytic activity decreases when the crystal becomes coarse. Therefore, the photocatalytic film preferably has an average crystallite diameter of titanium oxide of 50 nm or less. This average crystallite size is more preferably 30 nm or less. If the average crystallite diameter of the titanium oxide is too large, not only the photocatalytic activity but also the adhesion of the photocatalytic film to the base material is reduced, and thus the durability of the photocatalytic composite material is adversely affected. The average crystallite diameter of titanium oxide can be controlled by the temperature of the substrate during the deposition and the heating conditions after the deposition.
- the titanium oxide of the photocatalyst may contain one or more of oxides of silicon, zinc, zirconium and aluminum for activation.
- the structure of the photocatalyst may be such that each oxide and titanium oxide may be mixed, or at least partially a composite oxide formed by the reaction of each oxide and titanium oxide. May be contained.
- the structure of the titanium oxide serving as the base may be amorphous or crystalline.
- the structure of the contained metal oxide or the composite oxide generated in some cases may be amorphous or crystalline.
- the content of each oxide of silicon, zinc, zirconium and aluminum in titanium oxide is such that the ratio of the total amount of these metals (M) to titanium (M / Ti) is in the range of 0.1 to 50 at%. It is preferable to do so. Outside this range, high photocatalytic activity may not be obtained.
- the more preferable range of ⁇ / ⁇ is 1 to 30 at%.
- titanium oxide exhibits photocatalytic activity by absorbing visible light by partially doping a transition metal into an oxygen-deficient structure.
- the titanium oxide used as a photocatalyst in the present invention may be titanium oxide having such a visible light response.
- Preferred doping transition metals can be selected from the group consisting of V, Zn, Ru, Rh, Pt, Ag, Pd and Cu.
- the function of the metal itself for example, antibacterial properties can be imparted to Zn, Ag, and Cu.
- the thickness of the photocatalytic film covering the glass fiber is preferably in the range of 10 nm to 2.0 m. If the film thickness is less than 10 nm, sufficient photocatalytic activity cannot be obtained. Conversely, if the film thickness exceeds 2.0 m, the thickness becomes so uneven that a discontinuous surface is easily formed, and the film is easily cracked and peeled. Also, when the substance to be decomposed is dirt, the dirt tends to adhere more depending on the increase in the thickness of titanium oxide. For this reason, in environments such as indoors where only weak light can be expected, it takes a long time to disassemble and dirt is conspicuous. A more preferred thickness range is from 20 nm to 0.8 wm. In this range, a high photocatalytic activity is exhibited, and a good photocatalyst composite material with little film cracking and peeling is obtained.
- the photocatalyst composite material of the present invention using a glass fiber as a base material can be colored for the purpose of imparting a design property or the like.
- Coloring can be performed by various methods, such as using a fiber made of colored glass, forming a colored film on the fiber using a coloring paint containing a pigment, or including a coloring pigment in a photocatalytic film.
- a colored film may be formed on the fiber first, and then a photocatalytic film may be formed on the fiber, or conversely, a photocatalytic film may be formed first, and then a colored film may be formed thereon. You can also.
- Organic pigments can be used as pigments in coloring paints, but organic materials are photocatalysts. It is preferable to use an inorganic pigment, since it may be decomposed by the oxidizing power of the inorganic pigment. For the same reason, it is preferable to use a hardly decomposable substance or its precursor such as alumina, silicone resin, silica and titanium oxide as the binder in the coloring paint.
- the thickness of the colored coating varies depending on the type of pigment used and its hiding power, but is preferably about 0.1 to 100.
- the glass fiber itself is glossy, but its gloss may be impaired by coating with titanium oxide or coloring. In this case, if desired, a glossy film may be formed on the colored film.
- the surface of the substrate or the photocatalytic film can be colored using the pigment as described above.
- the photocatalyst composite of the present invention is manufactured by a vapor deposition method.
- This method comprises: a vapor deposition step of forming a titanium oxide precursor film on the surface of a substrate by bringing titanium tetrachloride vapor and water vapor into contact with the surface of the substrate heated to 100 to 300 ° C; Heating in a oxidizing atmosphere to form a continuous film of a photocatalyst made of titanium oxide on the surface of the substrate.
- the base material is an aggregate of inorganic fibers
- vapor deposition is performed on the already processed or integrated fiber aggregate to obtain a photocatalyst composite material in which individual fibers are coated with a continuous film of a photocatalyst.
- the photocatalytic film may be damaged and peeled off during processing, so the fiber surface is coated with a continuous photocatalytic film. It is difficult to stably produce a manufactured fiber product.
- the fibers When vapor deposition is applied to a fiber aggregate such as a glass cloth, the fibers are in close contact with each other at a portion where the fibers are in contact with each other, for example, at a yarn or at an intersection of fibers or a fiber contact portion inside the yarn. There is concern that a titanium oxide thin film may not be formed.
- the vapor of titanium tetrachloride penetrates into even very small gaps, so that a titanium oxide thin film is formed at the place where the fibers are in contact with each other, Each fiber processed into a cloth is completed with a photocatalytic film. It becomes completely covered. Therefore, in the vapor deposition method, individual fibers can be covered with a photocatalytic film even if a titanium oxide thin film is formed after processing into a fiber aggregate such as a woven fabric.
- the base material is a porous body
- the titanium tetrachloride vapor reaches the inside of the pores, so that the inside of the pores can be covered with the photocatalytic film.
- titanium alkoxide and its partial hydrolyzate can be used in principle as a raw material for vapor deposition.
- titanium tetrachloride whose boiling point is as low as 136.4 ° C, is easy to form and has a small shrinkage during film formation, as described later, so that a good continuous titanium oxide thin film coating is formed on the fiber surface. Yes, it is also advantageous in terms of performance. Titanium tetrachloride also has advantages in availability and price.
- titanium tetrachloride is at least partially hydrolyzed to form a highly viscous titanium oxide precursor such as titanium oxide, which is heated to a predetermined temperature in advance.
- a highly viscous titanium oxide precursor such as titanium oxide
- the precursor deposited on the fiber becomes less viscous due to the heat of the glass fiber and flows, forming a continuous film of the titanium oxide precursor having a substantially uniform thickness.
- hydrolysis proceeds further to remove hydrochloric acid, and the hydrolyzate undergoes dehydration condensation to form a continuous film of titanium oxide on the fiber surface.
- the film of titanium tetrachloride-derived titanium oxide precursor formed in the vapor deposition step does not contain organic matter. Therefore, the volume shrinkage of the film in the next heating step is small, and the finally formed titanium oxide thin film is a continuous film substantially free from cracks and peeling.
- the organic matter thermally decomposes and disperses during heating, and the volume shrinkage of the titanium oxide thin film is large, causing cracks and peeling.
- a titanium oxide thin film containing is generated and does not become a continuous film.
- Both titanium tetrachloride vapor and water vapor are preferably diluted with dry air or an inert gas (eg, argon or nitrogen) to a concentration of 0.1 to 10% (vol l) and used for vapor deposition. . If the concentration is less than 0.1%, a high deposition rate cannot be obtained. On the other hand, if the concentration is greater than 10%, the proportion of titanium tetrachloride and water vapor that react with each other in the space when they are mixed before reaching the base material is increased, and The utilization rate of titanium oxide decreases.
- an inert gas eg, argon or nitrogen
- the dilute vapor of titanium tetrachloride can be prepared by passing dry air or an inert gas of diluent gas (carrier gas) through a container containing titanium tetrachloride and publishing according to a conventional method.
- the dilution steam can be prepared by adding water to the dilution gas and humidifying it.
- the H 2 0 / TiC and molar ratio is in the range of 0.05 to 4. If this molar ratio exceeds 4, hydrolysis and condensation of titanium tetrachloride in the gas phase prior to vapor deposition will proceed unnecessarily, and many titanium oxide fine particles will be generated, resulting in uneven contact with glass fibers. There is. A more preferred molar ratio is in the range of 0.05-1.
- the deposition of titanium tetrachloride is performed at a substrate temperature of 100 to 300 ° C. That is, the substrate is heated to 100 to 300 ° C during the deposition. In this case, the thickness of the titanium oxide precursor attached to the substrate by vapor deposition becomes uniform, and a continuous titanium oxide film can be formed stably.
- the substrate temperature at the time of vapor deposition is preferably in the range of 150 to 250 ° C. If the substrate temperature during the deposition is lower than 100, the adhesion of the formed titanium oxide thin film to the substrate is reduced, and the titanium oxide thin film is easily cracked, so that a continuous film cannot be formed stably. If the substrate temperature is higher than 300 ° C, the film formation by vapor deposition proceeds unevenly, making it difficult to obtain a smooth and excellently adherent titanium oxide thin film. Its durability decreases.
- This substrate temperature can be achieved by preheating the substrate before vapor deposition. Preheating can be performed inside the vapor deposition equipment, but in the case of continuous operation, it is performed externally before introduction into the vapor deposition equipment. Appropriate heating means may be provided to prevent the temperature of the base material from decreasing during vapor deposition. In the case of continuous operation, since the inside of the vapor deposition device is heated by heat radiation from the substrate, a heating means for maintaining the substrate temperature is not necessarily required.
- the temperature inside the deposition equipment may be somewhat If higher, it can be carried out at normal pressure.
- the vapor deposition can be performed only by spraying and contacting the titanium tetrachloride vapor and water vapor on the base material in the closed chamber, and no decompression is required, so that the equipment and operation costs are not much different from the application.
- a substrate having a continuous film of a titanium oxide precursor obtained in the vapor deposition step is heated to convert the precursor into titanium oxide, and a continuous photocatalyst comprising titanium oxide is formed on the surface of the substrate.
- the heating is performed in an oxidizing atmosphere, for example, in the air.
- the heating atmosphere preferably contains water vapor like the air. If necessary, steam may be supplied to the heating atmosphere.
- the heating temperature can be in the range of 100 to 1000 ° C, but is preferably in the range of 250 to 800 ° C, and more preferably in the range of 300 to 600 ° C, in order to enhance the photocatalytic activity.
- the heating time varies depending on the temperature and the composition of the thin film, but is preferably 120 minutes or less industrially.
- the heating temperature is in the range of 300 to 600 ° C.
- an average crystallite diameter of 50 nm or less is fine, and a continuous film of an anatase type crystalline titanium oxide photocatalyst can be formed.
- This photocatalyst film has very high activity and good adhesion to the substrate, so that a photocatalytic composite material having high activity and good durability can be obtained.
- the heating time is preferably set to 30 to 60 minutes. If it is less than 30 minutes, crystallization is insufficient, and if it exceeds 60 minutes, the crystallite diameter tends to be coarse.
- the average crystallite diameter is as small as 50 nm or less, high activity, and excellent exfoliation resistance is achieved by controlling the substrate temperature during the deposition and the subsequent heating conditions (temperature and heating time). This makes it possible to form the titanium oxide photocatalytic film at a relatively low cost.
- the thickness of the titanium oxide continuous film formed in the vapor deposition process is determined by the degree of dilution of titanium tetrachloride vapor (this depends on the temperature of the titanium tetrachloride container and the amount of diluent gas published), titanium tetrachloride vapor and It can be adjusted by the contact time of the substrate with the water vapor.
- the film formation amount per one time in the vapor deposition step be 500 nm or less in film thickness after the heating step.
- the film formation amount is larger than this, the volume shrinkage in the heating step becomes large, and a continuous film without cracks or peeling may not be obtained.
- Thicker than 500 nm When it is desired to form the photocatalyst film, it is preferable to repeat the heating process in the vapor deposition process to obtain a predetermined film thickness.
- titanium tetrachloride used in the vapor deposition step is purified by distillation.
- the purity of titanium tetrachloride by distillation purification is preferably 99.9% or more.
- an acid gas such as hydrochloric acid and chlorine is generated along with the hydrolysis of titanium tetrachloride, and titanium oxide, titanium hydroxide, titanium oxide and the like are produced. And titanium compounds containing unreacted titanium tetrachloride.
- the method of the present invention can further include a step of removing and treating an acidic gas and / or a titanium compound generated from at least one of the deposition step and the heating step.
- the acid gas may cause corrosion of the device, and if released into the atmosphere, adversely affects the environment. Therefore, it is preferable to remove the acid gas. Unreacted titanium tetrachloride and titanium oxide, if left unnecessarily in the equipment, adhere to the titanium oxide thin film and cause peeling and powdering, and also contaminate the equipment and produce products. May cause problems.
- the treatment means for removing the acid gas is not limited, but a treatment by contacting an alkali solution with the gas is reliable and preferable.
- the removal of the titanium compound can be performed by a method of supplying water vapor to cause hydrolysis and separating it as fine particles, or a method of removing by adsorption through a treatment tower filled with an adsorbent.
- a vapor of a compound of at least one element selected from silicon, zinc, zirconium, and aluminum may be mixed with titanium tetrachloride vapor.
- a photocatalyst composite material can be manufactured in which the formed titanium oxide thin film contains at least one of silicon oxide, zinc oxide, zirconium oxide, and aluminum oxide.
- the compound include a halide, an oxyhalide, and an alkoxide. As described for titanium tetrachloride, inorganic halides and oxyhalides are preferable.
- a small amount of a vapor of a transition metal compound preferably a halide or an oxyhalide, is applied. Mix in titanium chloride vapor.
- the photocatalyst composite of the present invention can be colored in a desired color.
- the coloring method is as described above. When coloring with a coloring paint using an inorganic pigment, it may be applied directly to the substrate or over the photocatalytic film. However, when a paint is applied on the photocatalyst film, some of the active sites of the photocatalyst may be lost and the activity may be reduced. For this reason, if activity is important, it is preferable to form a continuous titanium oxide film after coloring in advance.
- the coloring paint may be applied by a suitable method such as a dipping method or a spraying method, but it is preferable to apply the coloring paint by a dry method such as spraying since the colored coating film can be smoothed.
- the photocatalyst composite material of the present invention is preferable to use, for example, a continuous production apparatus as shown in FIG. 1 because it can cope with a roll-shaped fiber aggregate and can be mass-produced.
- a substrate eg, a glass fiber aggregate placed on a belt is preheated through a preheating furnace (1), and then sent to a vapor deposition apparatus (2).
- an inert gas or dry air is bubbled into a container containing a liquid of titanium tetrachloride, and the generated diluted titanium tetrachloride vapor is supplied to the evaporator (2) by, for example, spraying from a nozzle. Supply.
- the vaporizer (2) is also supplied with humidified air containing a certain amount of moisture, that is, diluted steam, from a gas supply device (6) by a steam generator.
- the diluted titanium tetrachloride vapor and the diluted water vapor are mixed in the vapor deposition device (2), and the titanium tetrachloride is partially hydrolyzed and comes into contact with the substrate surface, and the titanium oxide precursor is deposited on the surface .
- the substrate carried out of the steaming device is fed into a heating furnace (3) composed of a plurality of heating zones capable of setting different temperatures and heated.
- This manufacturing apparatus is equipped with a device (4) that sucks in the acid gas and titanium dioxide generated in the above manufacturing process and removes and treats them outside the device.
- the photocatalyst composite material of the present invention when exposed to light with an energy higher than the band gap of titanium oxide, exhibits an environmental purification function by photocatalysis, and decomposes, removes, detoxifies various harmful substances and attached substances, etc. Demonstrate excellent effects.
- This photocatalyst composite material can be widely used as a fiber product that exhibits the effects of purifying air or water, deodorizing, antibacterial, antifungal, decomposing adhering dirt, and decomposing harmful substances.
- Textile products having an environmental purification function produced from the photocatalyst composite material of the present invention include, for example, clothing, bedding, curtains, tablecloths and mats, cars, wall coverings, building sheets, tents, and car interiors. It can be used for materials, kitchen supplies (eg, kitchen counters, cloths, etc.) and bathroom supplies (eg, bathtub lining, unit bath panels).
- Non-fiber forms of photocatalytic composites include a wide variety of materials including, for example, building materials, window glass, roofing materials, masonry, tunnel interior materials, road barriers, signs, metal or ceramic porous materials, metal or ceramic particles. Useful for applications.
- Photocatalyst composites of test Nos. 1 to 10 using a glass fiber aggregate as a base material were produced as follows.
- humidified air containing water vapor so that the molar ratio was 3 was supplied to this apparatus with H 2 O / TiC, and mixed with titanium tetrachloride vapor in the vapor deposition apparatus.
- the test material was introduced into this vapor deposition device at 25 ° C., and was brought into contact with the mixed vapor for about 300 seconds to perform vapor deposition. After that, the test material was preheated to 200 ° C for 3 minutes in the preheating zone in the heating furnace, and then heated at 500 ° C for 60 minutes in the heating zone to produce a photocatalytic composite material. .
- the coating thickness is about 300 nm.
- a twill weave cloth made of high-purity silica fiber (fiber diameter of about 8.0 urn. Cloth thickness of 0.6 hidden, size of about 100 square) is used as a test material.
- Base material A silica cloth coated with a titanium oxide thin film was prepared in the same manner as in Test No. 1 except that the temperature was set to 200 ° C. SEM observation of this composite material confirmed that the fiber surface was covered with a continuous film of titanium oxide with a thickness of about 400 nm without cracks, peeling, or chipping.
- a silicon cloth coated with a titanium oxide thin film was prepared in the same manner as in Test No. 2 except that the contact time with the mixed steam was 500 seconds. SEM observation of this composite material confirmed that the fiber surface was covered with a continuous film of titanium oxide with a thickness of about 500 nm without any cracks, peeling, or chipping on the surface.
- a silicic acid cloth coated with a titanium oxide thin film containing silicon oxide was prepared.
- the content of silicon oxide determined by SIMS (secondary ion mass spectrometry) was about 25% in terms of metal atomic ratio (S i / Ti).
- the titanium oxide-based thin film formed on the fiber surface was a continuous film with a thickness of about 400 nm without cracks, peeling, or dropping.
- the test material was a plain weave cloth made of T glass fiber (cloth thickness 0.6, marble size about 100), and the heating temperature was 450 ° C. A glass cloth coated with a thin film was prepared. According to SEM observation, the film was a continuous film, and its thickness was 350 nm.
- a photocatalyst composite material was obtained by the method described in Test No. 6, using a thread-like yarn made of E glass fiber (fiber diameter about 8 im, twisted, length 20 m) as a test material. SEM observation No cracks, peeling or chippings were observed on the surface of the fiber constituting the yarn, and it was confirmed that the yarn was covered with a continuous film of titanium oxide having a thickness of about 350 nm.
- a T-glass cloth coated with a titanium oxide thin film was prepared in the same manner as in Test No. 6, except that undistilled titanium tetrachloride, which was colored a little yellow and had a purity of 99% or less, was used.
- a titanium oxide film with a thickness of about 400 nm was observed on the fiber surface of the obtained composite material, and it was a continuous film by SEM observation.
- the test material was dried at 60 ° C. for 1 hour, and then heated at 450 ° C. for 5 hours to coat a silica wool fiber surface with titanium oxide.
- a test sample of each composite material cut out into a square of about 50 mm square was placed in a quartz reaction cell and connected to a closed circulation line (total internal volume is about 3.0.
- the material (yarn) was placed in a glass dish with an inner area of 50 x 50 mm and subjected to the test.Acetaldehyde (concentration: about 240 ppm) diluted with air was introduced into the system and circulated for 250 minutes.
- W UV filter one from a high pressure mercury lamp (manufactured by Toshiba UV-31) with ultraviolet radiation lines ivy throughout. UV intensity at 366 nm of the test sample surface was 0. 8 mW / cm 2. while ultraviolet irradiation,
- the concentration of acetate aldehyde was quantified using a gas chromatograph, and the photocatalytic performance was evaluated based on the removal rate of acetate aldehyde after 1 hour. Are shown in Table 1.
- FIGS. 2A and 2B SEM photographs of the photocatalyst composite material obtained in Test No. 2 are shown in FIGS. 2A and 2B (A is 500 times, B is 2000 times). Similarly, SEM photographs of the photocatalyst composite material obtained by the wet method of Test No. 11 are shown in FIGS. 3A and 3B. In addition, SEM photographs (500 times) of the photocatalyst composites of Test No. 5 (25 ° C) and Test No. 10 (400 ° C), in which the substrate temperature during the deposition is outside the range of the present invention, are shown in the figures. 4 and FIG.
- the photocatalytic film is a continuous film made of crystalline titanium oxide, the photocatalytic activity is extremely low.
- Photocatalyst composite materials of the present invention were produced under the following conditions. No. 12:
- a commercially available ceramic paint (light blue) containing an inorganic pigment, and then a ceramic gloss paint were spray applied to the same glass cloth made of T-glass fiber used in Test No. 6 of Example 1. . Thereafter, the coating was heated at 400 ° C. for 30 minutes to harden the colored film. Thereafter, a coating of a continuous film of titanium oxide was formed in the same manner as in Test No. 2 of Example 1 except that the heating temperature was changed to 450 ° C., and the glossy blue-colored photocatalyst composite of the present invention was formed. Materials were created.
- a photocatalytic composite material with a titanium oxide thin film on the quartz substrate was prepared by vapor deposition with high-purity titanium tetrachloride in the same manner as in Test No. 2 of Example 1. .
- the temperature of the base material (substrate) at the time of vapor deposition was changed in the range of 25 to 500.
- the contact time for vapor deposition was 300 seconds, and heating after vapor deposition was performed at 500 ° C for 60 minutes.
- Figures 6 and 7 show cross-sectional SEM photographs of the photocatalyst film with the substrate (substrate) temperature at the time of vapor deposition of 200 t and 500 ° C, respectively. From these figures, it can be seen that the crystal is fine when the substrate temperature is 200 ° C, but becomes very coarse when the substrate temperature is as high as 500 ° C.
- the substrate temperature is lower than 100 ° C, the average crystal grain size is small, so the photocatalytic activity is good, but the adhesion to the substrate is reduced, so the photocatalytic film is easily peeled off and the durability is predicted to be low. Is done.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/502,112 US20050214533A1 (en) | 2002-01-21 | 2002-07-26 | Photocatalytic composite material and method for preparation thereof |
EP02755663A EP1468737A4 (en) | 2002-01-21 | 2002-07-26 | PHOTOCATALYTIC COMPOSITE MATERIAL AND PROCESS FOR PREPARING THE SAME |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2002011734A JP3945255B2 (ja) | 2001-01-29 | 2002-01-21 | 光触媒複合材とその製造方法 |
JP2002-011734 | 2002-01-21 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2003061828A1 true WO2003061828A1 (fr) | 2003-07-31 |
Family
ID=27606019
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2002/007598 WO2003061828A1 (fr) | 2002-01-21 | 2002-07-26 | Materiau composite photocatalytique et son procede de preparation |
Country Status (4)
Country | Link |
---|---|
US (1) | US20050214533A1 (ja) |
EP (1) | EP1468737A4 (ja) |
CN (1) | CN1622858A (ja) |
WO (1) | WO2003061828A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7597930B2 (en) * | 1995-09-15 | 2009-10-06 | Saint-Gobain Glass France | Substrate with a photocatalytic coating |
CN108816228A (zh) * | 2018-06-28 | 2018-11-16 | 江苏朗逸环保科技有限公司 | 一种改性纳米级光催化材料及其制备方法 |
Families Citing this family (36)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7311942B2 (en) * | 2002-08-29 | 2007-12-25 | Micron Technology, Inc. | Method for binding halide-based contaminants during formation of a titanium-based film |
DE102004001644A1 (de) * | 2004-01-12 | 2005-08-04 | Mtu Aero Engines Gmbh | Halbzeug aus Verbundwerkstoff und Verfahren zur Herstellung eines Halbzeugs aus Verbundwerkstoff |
CN1319634C (zh) * | 2005-07-30 | 2007-06-06 | 大连理工大学 | 二氧化钛纳米管复合分离膜及其制备方法和应用 |
EP1962591B1 (en) * | 2005-12-22 | 2016-07-27 | Fmc Corporation | Formulations of bifenthrin and enriched cypermethrin |
CN100428984C (zh) * | 2006-11-17 | 2008-10-29 | 大连理工大学 | 掺硅二氧化钛纳米管复合分离膜及其制备方法和应用 |
WO2009021524A1 (en) * | 2007-08-14 | 2009-02-19 | Scf Technologies A/S | Method and compositions for producing optically clear photocatalytic coatings |
DE102008052098B4 (de) * | 2008-10-14 | 2013-04-04 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Verfahren zur Herstellung photokatalytisch aktiver Titandioxidschichten |
JP2011140210A (ja) * | 2009-06-24 | 2011-07-21 | Sumitomo Chemical Co Ltd | 成形体およびその製造方法、並びに触媒およびその製造方法 |
ES2930370T3 (es) | 2009-10-08 | 2022-12-09 | Delos Living Llc | Sistema de iluminación LED |
JP5472182B2 (ja) * | 2011-03-30 | 2014-04-16 | Toto株式会社 | 衛生陶器 |
US8609121B2 (en) | 2011-05-04 | 2013-12-17 | Stewart B. Averett | Titanium dioxide photocatalytic compositions and uses thereof |
WO2012155907A1 (en) * | 2011-05-16 | 2012-11-22 | Kjærulf Pedersen A/S | Cooled storing system for photo catalytic decomposition of ethylene |
US8828519B2 (en) * | 2011-10-05 | 2014-09-09 | Cristal Usa Inc. | Infrared-reflective coatings |
CN102650046B (zh) * | 2012-05-23 | 2013-08-21 | 徐明生 | 一种规模化连续制备二维纳米薄膜的装置 |
CN105779961A (zh) * | 2012-04-02 | 2016-07-20 | 徐明生 | 一种连续制备二维纳米薄膜的设备 |
WO2013149572A1 (zh) * | 2012-04-02 | 2013-10-10 | Xu Mingsheng | 规模化连续制备二维纳米薄膜的装备 |
CN102634769A (zh) * | 2012-04-02 | 2012-08-15 | 徐明生 | 一种连续制备二维纳米薄膜的设备 |
EP3702685A1 (en) | 2012-08-28 | 2020-09-02 | Delos Living LLC | Environmental control system and method of operation such system |
JP6028495B2 (ja) | 2012-09-27 | 2016-11-16 | Toto株式会社 | 光触媒部材 |
CN103566977B (zh) * | 2013-10-30 | 2015-09-30 | 西安工程大学 | 一种染料敏化纳米三氧化二铁包覆空心玻璃微珠方法 |
CN103599735B (zh) * | 2013-11-25 | 2016-05-25 | 江南大学 | 一种可提高织物亲水-疏水润湿转化速率的离子掺杂TiO2溶胶制备方法 |
WO2015112811A1 (en) * | 2014-01-23 | 2015-07-30 | Nano Precision Medical, Inc. | Implant device for drug delivery |
AU2015223112B2 (en) | 2014-02-28 | 2020-07-09 | Delos Living Llc | Systems, methods and articles for enhancing wellness associated with habitable environments |
AU2015280348B2 (en) | 2014-06-23 | 2019-05-16 | WELL Shield LLC | Reduction of infections in healthcare settings using photocatalytic compositions |
CN104324720A (zh) * | 2014-10-15 | 2015-02-04 | 华南理工大学 | 水净化薄膜及其制备方法 |
CN107251031A (zh) | 2015-01-13 | 2017-10-13 | 戴尔斯生活有限责任公司 | 用于监测和增强人体健康的系统、方法和制品 |
CN104722336B (zh) * | 2015-02-10 | 2017-03-01 | 西北师范大学 | 羽毛角蛋白修饰的硫化镉光催化剂的制备方法 |
JP6352204B2 (ja) * | 2015-02-18 | 2018-07-04 | 富士フイルム株式会社 | 透明導電部材用積層体、転写材料、透明導電部材、タッチパネル及びその製造方法、並びに、タッチパネル表示装置 |
CN105483650B (zh) * | 2015-12-14 | 2017-12-22 | 青岛水务集团有限公司科技中心 | 一种用于净水设备的光触媒二氧化钛镀膜玻璃丝及其制备方法 |
US11338107B2 (en) | 2016-08-24 | 2022-05-24 | Delos Living Llc | Systems, methods and articles for enhancing wellness associated with habitable environments |
WO2019046580A1 (en) | 2017-08-30 | 2019-03-07 | Delos Living Llc | SYSTEMS, METHODS AND ARTICLES FOR EVALUATING AND / OR IMPROVING HEALTH AND WELL-BEING |
WO2020055872A1 (en) | 2018-09-14 | 2020-03-19 | Delos Living Llc | Systems and methods for air remediation |
WO2020176503A1 (en) | 2019-02-26 | 2020-09-03 | Delos Living Llc | Method and apparatus for lighting in an office environment |
US11898898B2 (en) | 2019-03-25 | 2024-02-13 | Delos Living Llc | Systems and methods for acoustic monitoring |
CN111744549A (zh) * | 2020-07-25 | 2020-10-09 | 合肥学院 | 一种玻璃纤维布负载W/BiVO4光催化剂的制备方法及应用 |
CN115262280B (zh) * | 2021-04-30 | 2023-10-27 | 中国科学院过程工程研究所 | 一种纤维纸及其制备方法和应用 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06320010A (ja) * | 1993-05-15 | 1994-11-22 | Nippon Muki Co Ltd | 有害物質処理用光触媒及び有害物質処理装置 |
JPH09947A (ja) * | 1995-06-21 | 1997-01-07 | Mitsubishi Rayon Co Ltd | 光触媒繊維及びその製造法 |
WO1998058736A1 (fr) * | 1997-06-20 | 1998-12-30 | Sumitomo Metal Industries, Ltd. | Photocatalyseur a base d'oxyde de titane, son procede de preparation et d'utilisation |
JPH11512337A (ja) * | 1995-09-15 | 1999-10-26 | サン−ゴバン ビトラージュ | 光触媒コーティングを備えた基材 |
JP2000072575A (ja) * | 1998-04-13 | 2000-03-07 | Inax Corp | 光触媒タイル及びその製造方法 |
JP2001335343A (ja) * | 2000-05-23 | 2001-12-04 | Central Glass Co Ltd | 光触媒膜付きガラスおよびその製造方法 |
JP2001333966A (ja) * | 2000-05-26 | 2001-12-04 | Matsushita Electric Works Ltd | 空気清浄器 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5919422A (en) * | 1995-07-28 | 1999-07-06 | Toyoda Gosei Co., Ltd. | Titanium dioxide photo-catalyzer |
US6074981A (en) * | 1996-08-05 | 2000-06-13 | Nippon Sheet Glass Co., Ltd. | Photocatalyst and process for the preparation thereof |
US20020081246A1 (en) * | 1997-08-25 | 2002-06-27 | Hoya Corporation | Photocatalytic filter |
JPH11179213A (ja) * | 1997-12-22 | 1999-07-06 | Mitsubishi Paper Mills Ltd | 環境浄化素材およびそれを用いた環境浄化材料 |
-
2002
- 2002-07-26 WO PCT/JP2002/007598 patent/WO2003061828A1/ja active Application Filing
- 2002-07-26 EP EP02755663A patent/EP1468737A4/en not_active Withdrawn
- 2002-07-26 CN CNA028286081A patent/CN1622858A/zh active Pending
- 2002-07-26 US US10/502,112 patent/US20050214533A1/en not_active Abandoned
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06320010A (ja) * | 1993-05-15 | 1994-11-22 | Nippon Muki Co Ltd | 有害物質処理用光触媒及び有害物質処理装置 |
JPH09947A (ja) * | 1995-06-21 | 1997-01-07 | Mitsubishi Rayon Co Ltd | 光触媒繊維及びその製造法 |
JPH11512337A (ja) * | 1995-09-15 | 1999-10-26 | サン−ゴバン ビトラージュ | 光触媒コーティングを備えた基材 |
US6103363A (en) | 1995-09-15 | 2000-08-15 | Saint-Gobain Recherche | Substrate with a photocatalytic coating |
WO1998058736A1 (fr) * | 1997-06-20 | 1998-12-30 | Sumitomo Metal Industries, Ltd. | Photocatalyseur a base d'oxyde de titane, son procede de preparation et d'utilisation |
JP2000072575A (ja) * | 1998-04-13 | 2000-03-07 | Inax Corp | 光触媒タイル及びその製造方法 |
JP2001335343A (ja) * | 2000-05-23 | 2001-12-04 | Central Glass Co Ltd | 光触媒膜付きガラスおよびその製造方法 |
JP2001333966A (ja) * | 2000-05-26 | 2001-12-04 | Matsushita Electric Works Ltd | 空気清浄器 |
Non-Patent Citations (1)
Title |
---|
See also references of EP1468737A4 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7597930B2 (en) * | 1995-09-15 | 2009-10-06 | Saint-Gobain Glass France | Substrate with a photocatalytic coating |
CN108816228A (zh) * | 2018-06-28 | 2018-11-16 | 江苏朗逸环保科技有限公司 | 一种改性纳米级光催化材料及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
US20050214533A1 (en) | 2005-09-29 |
EP1468737A4 (en) | 2005-09-21 |
CN1622858A (zh) | 2005-06-01 |
EP1468737A1 (en) | 2004-10-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2003061828A1 (fr) | Materiau composite photocatalytique et son procede de preparation | |
CA2624092C (en) | Titanium oxide photocatalyst, method for producing same and use thereof | |
US6235401B1 (en) | Method for coating amorphous titanium peroxide | |
JP3690864B2 (ja) | 光触媒体の製造法 | |
KR100696201B1 (ko) | 산화티탄졸, 박막 및 그들의 제조법 | |
JP3524342B2 (ja) | 薄膜形成用二酸化チタンゾル及び薄膜 | |
JP4957244B2 (ja) | 酸化チタン系光触媒とその製造方法、およびその利用 | |
CN102112416A (zh) | 具有TiO2或ZnO涂层的石聚结物板或石板 | |
EP1507751A1 (de) | Keramischer formkörper mit photokatalytischer beschichtung und verfahren zur herstellung desselben | |
JP2002505349A (ja) | 光触媒被覆を有する基体 | |
KR100993457B1 (ko) | 가시광 응답형 산화티탄 광촉매와 그 제조 방법 및 용도 | |
CA2681913C (en) | Process for making photocatalytic materials | |
JP2004057912A (ja) | 光触媒複合材とその製造方法 | |
JP2006336184A (ja) | 光触媒複合材 | |
US5919726A (en) | Method for producing photocatalyst material | |
JP3945255B2 (ja) | 光触媒複合材とその製造方法 | |
JP3748978B2 (ja) | 吸着機能体 | |
US10029236B2 (en) | Catalytic substrate surface | |
JP2007117999A (ja) | 酸化チタン系光触媒とその用途 | |
JP4207413B2 (ja) | 光触媒製品用の金属材とその金属材および製品の製造方法 | |
KR100572438B1 (ko) | 광촉매 산화물이 코팅된 자동차 사이드 미러의 코팅방법 | |
KR100631104B1 (ko) | 금속산화물이 코팅된 친수성 유리 및 그 제조방법 | |
JP2001031483A (ja) | 光触媒機能を備えるセラミックス建材の製造方法 | |
JP4187632B2 (ja) | 二酸化チタン薄膜の形成方法およびその二酸化チタン薄膜を有する触媒等 | |
JPH10113563A (ja) | 光触媒およびその製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ OM PH PL PT RO RU SD SE SG SI SK SL TJ TM TN TR TT TZ UA UG US UZ VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR IE IT LU MC NL PT SE SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2002755663 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 20028286081 Country of ref document: CN |
|
WWP | Wipo information: published in national office |
Ref document number: 2002755663 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 10502112 Country of ref document: US |