CN103429555A - 卫生陶器 - Google Patents
卫生陶器 Download PDFInfo
- Publication number
- CN103429555A CN103429555A CN201280013232XA CN201280013232A CN103429555A CN 103429555 A CN103429555 A CN 103429555A CN 201280013232X A CN201280013232X A CN 201280013232XA CN 201280013232 A CN201280013232 A CN 201280013232A CN 103429555 A CN103429555 A CN 103429555A
- Authority
- CN
- China
- Prior art keywords
- sanitary ware
- zirconium
- titanium
- photocatalyst layer
- alkoxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011941 photocatalyst Substances 0.000 claims abstract description 51
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002243 precursor Substances 0.000 claims abstract description 24
- 210000003298 dental enamel Anatomy 0.000 claims description 20
- 229910052726 zirconium Inorganic materials 0.000 claims description 16
- -1 acyl pyruvic acid titanium Chemical compound 0.000 claims description 15
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000013522 chelant Substances 0.000 claims description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 7
- UNRQTHVKJQUDDF-UHFFFAOYSA-N acetylpyruvic acid Chemical compound CC(=O)CC(=O)C(O)=O UNRQTHVKJQUDDF-UHFFFAOYSA-N 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 238000000354 decomposition reaction Methods 0.000 claims description 5
- JTQPTNQXCUMDRK-UHFFFAOYSA-N propan-2-olate;titanium(2+) Chemical compound CC(C)O[Ti]OC(C)C JTQPTNQXCUMDRK-UHFFFAOYSA-N 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- YQEVIZPKEOELNL-UHFFFAOYSA-N CCCCO[Zr] Chemical compound CCCCO[Zr] YQEVIZPKEOELNL-UHFFFAOYSA-N 0.000 claims description 3
- 241000194370 Cyclocephala pan Species 0.000 claims description 3
- OBTVATRSWTWNGS-UHFFFAOYSA-N acetyl 2-oxopropanoate Chemical class CC(=O)OC(=O)C(C)=O OBTVATRSWTWNGS-UHFFFAOYSA-N 0.000 claims description 3
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 claims description 2
- FOSFJJXKILWJLU-UHFFFAOYSA-N C(C(=O)C)(=O)OC(C)=O.C(CCC)O[Zr] Chemical compound C(C(=O)C)(=O)OC(C)=O.C(CCC)O[Zr] FOSFJJXKILWJLU-UHFFFAOYSA-N 0.000 claims description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- NIOLTQNBOYMEQK-UHFFFAOYSA-N butan-1-olate;zirconium(2+) Chemical compound [Zr+2].CCCC[O-].CCCC[O-] NIOLTQNBOYMEQK-UHFFFAOYSA-N 0.000 claims description 2
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 claims description 2
- UARGAUQGVANXCB-UHFFFAOYSA-N ethanol;zirconium Chemical compound [Zr].CCO.CCO.CCO.CCO UARGAUQGVANXCB-UHFFFAOYSA-N 0.000 claims description 2
- ZEIWWVGGEOHESL-UHFFFAOYSA-N methanol;titanium Chemical compound [Ti].OC.OC.OC.OC ZEIWWVGGEOHESL-UHFFFAOYSA-N 0.000 claims description 2
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 claims description 2
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 2
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 claims description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- 238000005299 abrasion Methods 0.000 abstract description 2
- 238000010304 firing Methods 0.000 abstract description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 abstract 2
- 229910001928 zirconium oxide Inorganic materials 0.000 abstract 2
- 230000001699 photocatalysis Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 38
- 239000011248 coating agent Substances 0.000 description 18
- 238000000576 coating method Methods 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 239000000919 ceramic Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000009736 wetting Methods 0.000 description 5
- 238000012790 confirmation Methods 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 230000000007 visual effect Effects 0.000 description 4
- 229910003849 O-Si Inorganic materials 0.000 description 3
- 229910003872 O—Si Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 239000010433 feldspar Substances 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 229910003088 Ti−O−Ti Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical class CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000012850 discrimination method Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical group [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/87—Ceramics
-
- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47K—SANITARY EQUIPMENT NOT OTHERWISE PROVIDED FOR; TOILET ACCESSORIES
- A47K1/00—Wash-stands; Appurtenances therefor
- A47K1/04—Basins; Jugs; Holding devices therefor
-
- 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
- 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
- B01J21/066—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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/0081—Uses not provided for elsewhere in C04B2111/00 as catalysts or catalyst carriers
- C04B2111/00827—Photocatalysts
-
- E—FIXED CONSTRUCTIONS
- E03—WATER SUPPLY; SEWERAGE
- E03C—DOMESTIC PLUMBING INSTALLATIONS FOR FRESH WATER OR WASTE WATER; SINKS
- E03C1/00—Domestic plumbing installations for fresh water or waste water; Sinks
- E03C1/12—Plumbing installations for waste water; Basins or fountains connected thereto; Sinks
- E03C1/14—Wash-basins connected to the waste-pipe
-
- E—FIXED CONSTRUCTIONS
- E03—WATER SUPPLY; SEWERAGE
- E03D—WATER-CLOSETS OR URINALS WITH FLUSHING DEVICES; FLUSHING VALVES THEREFOR
- E03D11/00—Other component parts of water-closets, e.g. noise-reducing means in the flushing system, flushing pipes mounted in the bowl, seals for the bowl outlet, devices preventing overflow of the bowl contents; devices forming a water seal in the bowl after flushing, devices eliminating obstructions in the bowl outlet or preventing backflow of water and excrements from the waterpipe
- E03D11/02—Water-closet bowls ; Bowls with a double odour seal optionally with provisions for a good siphonic action; siphons as part of the bowl
-
- 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
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/131—Glass, ceramic, or sintered, fused, fired, or calcined metal oxide or metal carbide containing [e.g., porcelain, brick, cement, etc.]
- Y10T428/1317—Multilayer [continuous layer]
-
- 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
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
- Y10T428/264—Up to 3 mils
- Y10T428/265—1 mil or less
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Structural Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Public Health (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Sanitary Device For Flush Toilet (AREA)
- Bidet-Like Cleaning Device And Other Flush Toilet Accessories (AREA)
Abstract
本发明公开一种设置有光触媒层的卫生陶器，该光触媒层在维持良好的光触媒活性的同时具有高耐水性及耐磨损性。该卫生陶器为由具有瓷釉层与在其上设置的光触媒层而形成的卫生陶器，其特征为，所述光触媒层为同时烧成氧化钛的前体与氧化锆的前体而得到的氧化物被膜，且含有氧化钛65～90质量%及氧化锆10～35质量%。
Description
相关申请
本申请主张于2011年3月30日申请的日本国专利申请2011-74621号的优先权，通过引用该日本申请的说明书从而成为本申请公开的一部分。
技术领域
本发明涉及一种大便器、小便器、洗脸盆、洗手盆等的卫生陶器，进一步详细的说涉及一种在其表面具有优异的耐水性、耐磨损性的光触媒层的卫生陶器。
背景技术
已知有如下便器等的卫生陶器，在卫生陶器表面，例如在便器的盆面形成光触媒表面层，利用对其光触媒层照射紫外线而表现的亲水性来抑制污物附着，从而提高水洗性能。这样的卫生陶器有以下优点，通过亲水性抑制污物附着，同时也可以通过由光触媒进行的分解作用来抑制菌的繁殖，从而减轻其清扫负担。
作为这样的卫生陶器，例如，在日本国特开平9-78665号公报（专利文献1）中，公开有在其表面形成含有氧化钛与二氧化硅而形成的层，该层为通过紫外线照射产生的亲水性来防止脏污附着的便器。另外，在日本国特开平11-228865号公报（专利文献2）中，提出有为了提高光触媒层的膜硬度而使用烷氧基钛与烷氧基硅。再者，在日本国特开平10-114546号公报（专利文献3）中，公开有通过在氧化钛的层上被覆烷氧基锆并烧成从而维持长期的光触媒活性。
关于具有这样的光触媒层的卫生陶器，明确了由于卫生陶器设置在比较湿润的环境中，因此产生由水而引起的光触媒层的劣化。尤其还明白了由于自来水中溶存离子的影响会促进其劣化。因此，卫生陶器表面的光触媒层必须对水具有耐久性（以下，在本说明书中有时称为耐水性）。再者，虽然通过设置光触媒层来减少卫生陶器的清扫频率，但是清扫是用刷子等摩擦其表面，所以容易损伤光触媒层，因此，卫生陶器表面的光触媒层必须具有高耐磨损性。
专利文献1：日本国特开平9-78665号公报
专利文献2：日本国特开平11-228865号公报
专利文献3：日本国特开平10-114546号公报
发明内容
这次，本发明者们得到了以下见解，通过同时烧成氧化钛的前体与氧化锆的前体而形成构成光触媒层的氧化物被膜，可在卫生陶器的瓷釉表面上得到在维持良好的光触媒活性的同时具有高耐水性及耐磨损性的光触媒层。本发明是基于相关见解而进行的发明。
因此，本发明的目的在于提供一种设置有在维持良好的光触媒活性的同时具有高耐水性及耐磨损性的光触媒层的卫生陶器及其制造方法。
其次，根据本发明的卫生陶器为由具有瓷釉层与在其上设置的光触媒层而形成的卫生陶器，其特征为，所述光触媒层为同时烧成氧化钛的前体与氧化锆的前体而得到的氧化物被膜，且含有氧化钛65～90质量%及氧化锆10～35质量%。
另外，根据本发明的上述卫生陶器的制造方法，其特征为，至少含有以下工序，将至少含有氧化钛的前体与氧化锆的前体的溶液应用于卫生陶器表面，然后进行烧成来作为光触媒层。
具体实施方式
定义
在本发明中，“卫生陶器”意指在卫生间及洗脸台周围使用的陶器制品，具体为大便器、小便器、便器的滤网、便器水箱、洗脸台的洗脸盆、洗手盆等。另外，“陶器”意指在陶瓷器中，坯料烧结为稍微具有吸水性的程度且在表面上施加瓷釉的陶器。
光触媒层
根据本发明的卫生陶器，其表面具有光触媒层，该光触媒层由同时烧成氧化钛的前体与氧化锆的前体而得到的氧化物被膜形成。
在本发明中，作为氧化钛的前体可适合地利用烷氧基钛及钛螯合物。烷氧基钛基本上以通式：Ti（OR）4进行表示，只要是通过水解产生光触媒性氧化钛的烷氧基钛就没有限定。式中的（OR）的一部分也可以被乙酰丙酮酸盐（C5H7O2）、乙酰乙酸乙酯（C6H9O3）取代。根据本发明的优选形态，烷氧基钛的烷氧化物（RO-）的有机基团R部分为低级（优选C1-6）烷基。作为其优选的具体例子，可列举四乙氧基钛、四异丙氧基钛、四n-丙氧基钛、四丁氧基钛、四甲氧基钛、二异丙氧基钛双（乙酰丙酮酸盐）、二异丙氧基钛双（乙酰乙酸乙酯）及它们的混合物。而且，作为钛螯合物可列举例如四乙酰丙酮酸钛。
而且，作为氧化锆的前体可适合地利用烷氧基锆及锆螯合物。烷氧基锆基本上以通式：Zr（OR）4进行表示，只要是通过水解产生氧化锆的烷氧基锆就没有限定。式中的（OR）的一部分也可以被乙酰丙酮酸盐（C5H7O2）、乙酰乙酸乙酯（C6H9O3）取代。根据本发明的优选形态，烷氧基锆的烷氧化物（RO-）的有机基团R部分为低级（优选C2-6）烷基。作为其优选的具体例子，可列举四乙氧基锆、四异丙氧基锆、四丁氧基锆、三丁氧基锆单乙酰丙酮酸盐、二丁氧基锆双（乙酰乙酸乙酯）、单丁氧基锆乙酰丙酮酸盐双（乙酰乙酸乙酯）及它们的混合物。而且，作为锆螯合物可列举例如四乙酰丙酮酸锆。
在本发明中，同时烧成氧化钛的前体与氧化锆的前体而得到氧化物被膜。烧成只要是在使氧化钛的前体成为光触媒性氧化钛，且使氧化锆的前体成为氧化锆所必需的温度与时间下进行即可。温度及时间只要能得到具有良好的光触媒活性的氧化钛与耐水性及耐磨损性的氧化物被膜就可以适当确定，例如可以在700～800℃的温度下进行0.5～3小时，优选在725～775℃的温度下进行1～2小时左右。
在本发明中，由同时烧成氧化钛的前体与氧化锆的前体而得到的氧化物被膜所形成的光触媒层具有高耐水性及耐磨损性。其理由虽然没有定论，但是可以进行以下那样考虑。另外，以下说明始终只是假设，本发明并不局限于此。即，可考虑以下的理由，即由于氧化锆在光触媒性即结晶性氧化钛的表面析出，形成化学性且物理性比Ti-O-Ti牢固的Zr-O-Ti键，而且通过在与瓷釉层的界面析出，形成化学性且物理性比Ti-O-Si牢固的Zr-O-Si键。可以认为该键与以烷氧基钛单独作为起始物料而得到的氧化钛或以化学稳定性比Ti-O-Ti键低的Ti-O-Si键存在的钛及烷氧基硅作为起始物料的氧化钛相比，具有优异的耐水性及耐磨损性。虽然可以认为它们的键的不同反应在氧化物被膜、即光触媒层的物理结构上，但是其微观上的不同极小，目前依据各种测定或鉴别方法尚无法明确确定，但就结果而言，明确了所得到的氧化物被膜存在高耐水性及耐磨损性。
在本发明中，光触媒层含有65～90质量%的氧化钛及10～35质量%的氧化锆而形成。氧化钛优选67.5～85质量%，更优选70～80质量%。氧化锆优选15～32.5质量%，更优选20～30质量%。
卫生陶器
卫生陶器坯料
根据本发明的卫生陶器的陶器坯料没有特别限定，可以是通常的卫生陶器坯料。另外，也可以在最表层的具有上述表面性状的瓷釉层的下面设置成为中间层的瓷釉层。
制造方法
根据本发明的卫生陶器可以优选通过以下所述的方法进行制造。即，首先，将以硅砂、长石、粘土等作为原料而制备的卫生陶器坯料泥浆采用利用了吸水性模具的浇注成形从而形成适合形状的陶器坯料。然后，在干燥的成形体表面上，将上述瓷釉原料适宜地选择喷雾涂布、浸渍涂布、旋转涂布、辊涂等的一般的方法从而进行涂布。接着将所得到的表面瓷釉层的前躯层形成的成形体进行烧成。烧成温度优选烧结陶器坯料且软化瓷釉的1000℃以上、1300℃以下的温度。
瓷釉
根据本发明的生成卫生陶器的瓷釉层的瓷釉只要可以实现上述表面性状，则其组成没有限定。在本发明中，一般地说，瓷釉原料定义为硅砂、长石、石灰石等天然矿物粒子的混合物。而且，所谓颜料例如为钴化合物、铁化合物等，所谓乳浊剂例如为硅酸锆、氧化锡等。非晶质瓷釉是指将由如上所述的天然矿物粒子等混合物组成的瓷釉原料在高温下熔融后，使其急速冷却呈玻璃化的瓷釉，例如，可以适当地利用玻璃瓷釉。
根据本发明的优选形态，优选的瓷釉组成为，例如长石10wt%～30wt%、硅砂15wt%～40wt%、碳酸钙10wt%～25wt%、刚玉、滑石、白云石、氧化锌分别在10wt%以下，乳浊剂及颜料合计在15wt%以下。
制造方法
本发明涉及的卫生陶器，可以通过以下步骤进行制造，在具有瓷釉层的卫生陶器上，应用含有烷氧基钛与烷氧基锆而形成的溶液，即涂层液，优选进行涂布，然后进行烧成。
在涂层液中除烷氧基钛及烷氧基锆之外，还可以添加以下那样的成分。例如，为了提高光触媒层的均匀性可列举流平剂等的表面活性剂。
另外，作为涂层液的溶剂，可列举乙醇、异丙醇、正丁醇等的醇类、甲基溶纤剂、丁基溶纤剂等的溶纤剂类、甲苯、二甲苯等的芳香族烃类、醋酸乙酯、醋酸丁酯等的酯类，但是只要是溶解烷氧基钛及烷氧基锆的溶剂就没有特别限定。
涂层液向卫生陶器的应用优选通过毛刷涂布、滚涂、喷涂、辊涂、浇涂、浸渍涂布、流涂、网版印刷等一般广泛使用的方法进行即可。在向卫生陶器将涂层液涂布后，进行烧成。烧成的温度及时间只要在上述的范围内进行即可。
实施例
虽然基于以下例子对本发明进行具体说明，但是本发明不限定于这些例子。
另外，由于关于在卫生陶器表面形成的光触媒层对于水的耐久性（耐水性）评价与耐碱性的试验显示出大致相同的趋势，因此在本实施例中使用以下所述的耐碱性试验来进行评价。
用于形成光触媒层的涂布液的制备
将烷氧基钛（二异丙氧基钛双(乙酰丙酮酸盐)、NDH－510C、日本曹达株式会社制）与烷氧基锆（三丁氧基锆单乙酰丙酮酸盐、Orgatix ZC－540，日本Matsumoto Fine Chemical株式会社制）能够使烧成后的固体成分的重量比按下述表所述的比例混合。接着，将该混合物用2-丙醇（80%）与甲基溶纤剂（20%）的混合溶剂稀释，使烧成后的固体成分成为1%，将稀释液用搅拌机混合。将所得到的混合液放置1小时以上，将其作为涂布液。
陶器瓷砖的制作
将陶器原料浇注成形从而得到坯料，在该坯料的表面上使用手喷枪（F100日本明治机械制作所株式会社制）涂布瓷釉。接下来，使其通过缓慢升温及降温用24小时在最高温度设定为1180℃的隧道窑中通过进行烧成，从而得到陶器瓷砖。
光触媒层的形成
使用手喷枪（F100日本明治机械制作所株式会社制）在上面得到的陶器瓷砖表面上将上面得到的涂布液控制在烧成后的膜厚成为100nm的涂布量进行涂覆。接着，用最高温度设定为770℃的高温电炉（FUH732DA日本ADVANTEC株式会社制）通过缓慢升温及降温进行24小时烧成，从而得到光触媒涂层瓷砖。
亲水性试验
对所得到的光触媒涂层瓷砖，使用紫外灯（FL20SBLB-A日本东芝照明技术株式会社制）使紫外线照度计（光触媒用光功率计（C9536-01，H9958）日本滨松光子学株式会社制）的测定值成为0.2±0.01mW／cm2而进行5小时照射。接着，在瓷砖表面喷洒蒸馏水，并确认水膜的形成，及测定水膜破坏为止的时间。其结果用以下的基准进行评价。
形成水膜且保持30秒以上：○
形成水膜但不能保持30秒以上：△
没有形成水膜：×
光触媒活性
依照JIS（日本工业标准）R1703－2用亚甲基蓝分解指数评价了光触媒涂层瓷砖的光触媒活性。其结果用以下的基准进行评价。
分解指数为10以上：○
大于5小于10：△
分解指数小于5：×
耐碱性试验（耐水性评价）
将光触媒涂层瓷砖浸渍于保持在30℃的5%氢氧化钠（试剂特级日本和光纯药工业株式会社制）水溶液中。在浸渍规定的时间后，基于JISK5600－5－6实施胶带剥离试验。其结果用以下的基准进行评价。
浸渍80小时无剥离：○
浸渍小于80小时产生剥离：△
浸渍小于40小时产生剥离：×
耐滑动性试验
使用摩擦测试器（日本太平理化工业株式会社制）实施光触媒涂层瓷砖的耐滑动性试验。将磨擦布（SS－72K日本住友3M株式会社制）切成2.24cm方形，使用双面胶带以使无纺布的部分接触滑动面的方式粘接在摩擦头上后，用蒸馏水润湿。接着，放上250g的锤（载重条件：5kPa）滑动规定的次数，目视确认表面是否有划伤。聚氨酯海绵每滑动1000次后替换为新的聚氨酯海绵。结果用以下的基准进行评价。
滑动2000次后无可目视确认的划伤：○
滑动1000次后无可目视确认的划伤：△
滑动1000次后存在可目视确认的划伤：×
以上的结果如下表所示。
表1
Claims (16)
1.一种卫生陶器，其为由具有瓷釉层与在其上设置的光触媒层而形成的卫生陶器，其特征为，
所述光触媒层为同时烧成氧化钛的前体与氧化锆的前体而得到的氧化物被膜，且含有氧化钛65～90质量%及氧化锆10～35质量%。
2.根据权利要求1中所述的卫生陶器，其特征为，所述光触媒层中的氧化钛量为65～85质量%，氧化锆量为15～35质量%。
3.根据权利要求1或2中所述的卫生陶器，其特征为，所述光触媒层具有5以上的亚甲基蓝分解指数。
4.根据权利要求1～3中任意一项所述的卫生陶器，其特征为，所述光触媒层的膜厚为50～200nm。
5.根据权利要求1～4中任意一项所述的卫生陶器，其特征为，所述烧成在700～800℃下进行。
6.根据权利要求1～5中任意一项所述的卫生陶器，其特征为，所述氧化钛的前体为烷氧基钛或钛螯合物。
7.根据权利要求1～6中任意一项所述的卫生陶器，其特征为，所述烷氧基钛以通式：Ti（OR）4进行表示，在此，OR表示C1-6烷氧基、乙酰丙酮酸盐或乙酰乙酸乙酯。
8.根据权利要求7中所述的卫生陶器，其特征为，所述烷氧基钛为选自四乙氧基钛、四异丙氧基钛、四n-丙氧基钛、四丁氧基钛、四甲氧基钛、二异丙氧基钛双（乙酰丙酮酸盐）及二异丙氧基钛双（乙酰乙酸乙酯）中的一种或它们的混合物。
9.根据权利要求6中所述的卫生陶器，其特征为，所述钛螯合物为四乙酰丙酮酸钛。
10.根据权利要求1～9中任意一项所述的卫生陶器，其特征为，所述氧化锆的前体为烷氧基锆或锆螯合物。
11.根据权利要求1～10中任意一项所述的卫生陶器，其特征为，所述烷氧基锆以通式：Zr（OR）4进行表示，在此，OR表示C1-6烷氧基、乙酰丙酮酸盐或乙酰乙酸乙酯。
12.根据权利要求10中所述的卫生陶器，其特征为，所述烷氧基锆为选自四乙氧基锆、四异丙氧基锆、四丁氧基锆、三丁氧基锆单乙酰丙酮酸盐、二丁氧基锆双（乙酰乙酸乙酯）及单丁氧基锆乙酰丙酮酸盐双（乙酰乙酸乙酯）的一种或它们的混合物。
13.根据权利要求10中所述的卫生陶器，其特征为，所述锆螯合物为四乙酰丙酮酸锆。
14.根据权利要求1～13中任意一项所述的卫生陶器，其特征为，为大便器、小便器、便器的滤网、便器水箱、洗脸台的洗脸盆或洗手盆。
15.一种制造方法，其为根据权利要求1～14中任意一项所述的卫生陶器的制造方法，其特征为，
至少含有以下工序，将至少含有氧化钛的前体与氧化锆的前体的溶液应用于所述卫生陶器表面，然后进行烧成来作为光触媒层。
16.根据权利要求15中所述的制造方法，其特征为，所述烧成在700～800℃的温度下进行。
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|---|---|---|---|
| JP2011074621A JP5472182B2 (ja) | 2011-03-30 | 2011-03-30 | 衛生陶器 |
| JP2011-074621 | 2011-03-30 | ||
| PCT/JP2012/058114 WO2012133523A1 (ja) | 2011-03-30 | 2012-03-28 | 衛生陶器 |
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| CN103429555A true CN103429555A (zh) | 2013-12-04 |
| CN103429555B CN103429555B (zh) | 2015-04-01 |
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| US (2) | US20140017425A1 (zh) |
| EP (1) | EP2692713A4 (zh) |
| JP (1) | JP5472182B2 (zh) |
| KR (1) | KR101406831B1 (zh) |
| CN (1) | CN103429555B (zh) |
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| JP6028495B2 (ja) | 2012-09-27 | 2016-11-16 | Toto株式会社 | 光触媒部材 |
| JP6750348B2 (ja) | 2015-09-15 | 2020-09-02 | Toto株式会社 | 光触媒層を有する衛生陶器 |
| US11094208B2 (en) * | 2016-09-30 | 2021-08-17 | The Boeing Company | Stereo camera system for collision avoidance during aircraft surface operations |
| JP7317071B2 (ja) * | 2021-06-01 | 2023-07-28 | シノスチール ルオナイ マテリアルズ テクノロジー コーポレーション | 高温耐摩耗セラミック釉薬、高温耐摩耗セラミック塗布層プリフォーム及びその製造方法、使用 |
| KR102593723B1 (ko) * | 2021-06-01 | 2023-10-25 | 시노스틸 루오나이 머티리얼즈 테크놀로지 코퍼레이션 | 고온 내마모성 세라믹 유약, 고온 내마모성 세라믹 코팅층 프리폼 및 그 제조방법과 응용 |
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| EP2692713A1 (en) | 2014-02-05 |
| TWI549748B (zh) | 2016-09-21 |
| US20140017425A1 (en) | 2014-01-16 |
| KR20130116940A (ko) | 2013-10-24 |
| TW201238656A (en) | 2012-10-01 |
| JP5472182B2 (ja) | 2014-04-16 |
| JP2012206907A (ja) | 2012-10-25 |
| US20160023958A1 (en) | 2016-01-28 |
| WO2012133523A1 (ja) | 2012-10-04 |
| EP2692713A4 (en) | 2014-09-24 |
| CN103429555B (zh) | 2015-04-01 |
| KR101406831B1 (ko) | 2014-06-13 |
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