WO2005082810A1 - COMPOSITION FOR USE NOx REMOVING TRANSLUCENT COATING - Google Patents
COMPOSITION FOR USE NOx REMOVING TRANSLUCENT COATING Download PDFInfo
- Publication number
- WO2005082810A1 WO2005082810A1 PCT/IB2004/000226 IB2004000226W WO2005082810A1 WO 2005082810 A1 WO2005082810 A1 WO 2005082810A1 IB 2004000226 W IB2004000226 W IB 2004000226W WO 2005082810 A1 WO2005082810 A1 WO 2005082810A1
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- WIPO (PCT)
- Prior art keywords
- particles
- composition according
- composition
- anyone
- photocatalytic
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 56
- 238000000576 coating method Methods 0.000 title claims abstract description 28
- 239000011248 coating agent Substances 0.000 title claims abstract description 24
- 239000002245 particle Substances 0.000 claims abstract description 58
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 56
- 230000001699 photocatalysis Effects 0.000 claims abstract description 26
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 17
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 15
- 230000000694 effects Effects 0.000 claims abstract description 9
- 239000002210 silicon-based material Substances 0.000 claims abstract description 9
- 239000004035 construction material Substances 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 19
- -1 polysiloxane Polymers 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 9
- 229920001296 polysiloxane Polymers 0.000 claims description 9
- 239000000356 contaminant Substances 0.000 claims description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 3
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 2
- 150000007514 bases Chemical class 0.000 claims description 2
- 239000011667 zinc carbonate Substances 0.000 claims description 2
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 2
- 235000004416 zinc carbonate Nutrition 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 229910002089 NOx Inorganic materials 0.000 description 13
- 239000007789 gas Substances 0.000 description 11
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 8
- JCXJVPUVTGWSNB-UHFFFAOYSA-N Nitrogen dioxide Chemical compound O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 7
- 239000010408 film Substances 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- 229910052911 sodium silicate Inorganic materials 0.000 description 4
- 241000894007 species Species 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920004482 WACKER® Polymers 0.000 description 3
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229940071826 hydroxyethyl cellulose Drugs 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000010186 staining Methods 0.000 description 2
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 239000004368 Modified starch Substances 0.000 description 1
- 239000005041 Mylar™ Substances 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 241001074085 Scophthalmus aquosus Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 229910052601 baryte Inorganic materials 0.000 description 1
- 239000010428 baryte Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 239000002772 conduction electron Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- 229920000591 gum Polymers 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000006254 rheological additive Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 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
- 239000000080 wetting agent Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Classifications
-
- 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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/006—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels to produce glass through wet route
- C03C1/008—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels to produce glass through wet route for the production of films or coatings
-
- 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
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
-
- 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
- C04B41/49—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes
- C04B41/4905—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon
- C04B41/495—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as oligomers or polymers
- C04B41/4961—Polyorganosiloxanes, i.e. polymers with a Si-O-Si-O-chain; "silicones"
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1618—Non-macromolecular compounds inorganic
-
- 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
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/212—TiO2
-
- 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
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/213—SiO2
-
- 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
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/28—Other inorganic materials
-
- 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
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/29—Mixtures
-
- 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
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/44—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the composition of the continuous phase
- C03C2217/445—Organic continuous phases
-
- 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
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
- C03C2217/47—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase consisting of a specific material
- C03C2217/475—Inorganic materials
- C03C2217/477—Titanium oxide
-
- 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
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/113—Deposition methods from solutions or suspensions by sol-gel processes
-
- 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
Definitions
- the present invention relates to compositions having photocatalytic self- cleaning properties for use as translucent coating on construction material surfaces.
- the pollution of the environment raises a serious problem of contamination of exterior materials for buildings and outdoor buildings. Dust and particles floating in the air deposit on the roof and the outer wall of buildings in fine weather. Upon exposure to rainfall, the deposits flow together with rainwater and flow down along the outer wall of the building. As a result, the contaminant adheres along the course of the rainwater. As the surface dries, soil appears in a stripe pattern.
- said coating furthermore exhibits photocatalytic self-cleaning properties towards atmospheric contaminants.
- titanium oxide photocatalytic coatings are disclosed in EP 0 901 991, WO 97/07069, WO 97/10186 and WO 98/41480. More specifically, titanium dioxide (TiO ) which is a semiconductor, converts
- UV radiation for example from UV light
- Typical atmospheric contaminants are for example, nitrogen oxides, ozone and organic pollutants adsorbed on the coated surface of the materials. This is particularly advantageous in built- up areas, for example, in city streets, where the concentration of organic contaminants may be relatively high, especially in intense sunlight, but where the available surface area of materials is also relatively high.
- so-formed oxidized species like HNO 3 formed from the reaction of NO and NO with TiO 2 /UV light in the presence of water and oxygen, is their absorption on the coated surface of the material which they may cause problems of stains and/or corrosion.
- an object of the present invention is to provide a composition which, when applied as a coating on a surface of a material, exhibits improved NO x and optionally VOC x (i.e. Volatile Organic Content like xylene and benzene) removing properties.
- Another object of the present invention is to provide a composition which can impart such properties without sacrificing the translucency of the coating.
- Still another object of the present invention is to provide a composition which, when applied as a coating on the surface of a material, can easily release the contaminant therefrom in particular by rainfall or by washing with water.
- the composition when applied to the surface of a substrate to form a film, enables a contaminant or derivative thereof adhered onto the surface to be easily washed away by water.
- the instant invention is directed to a NO x removing composition for use as a translucent coating on construction material surfaces, comprising at least: a) photocatalytic titanium dioxide particles having at least a de-NO x activity, b) particles having a de-HNO 3 activity, and c) a silicon based-material, in which are dispersed said particles, wherein said photocatalytic particles have a crystalline size ranging from 1 to 50 nm and particles a) and b) are present in an amount lower than 20% by weight of the total weight of said composition.
- the instant invention relates to a method for imparting self-cleaning properties towards atmospheric contaminants at the surface of a material, said method comprising at least the steps of: applying a composition according to the invention onto the surface of a material, and - drying or curing the said composition to provide a translucent coating system.
- Photocatalytic titanium dioxide particles The composition according to the present invention comprises at least dispersed photocatalytic titanium dioxide particles having at least a de-NO x activity with NO x meaning NO and/or NO 2 . According to a specific embodiment, said photocatalytic particles also exhibit a de-VOC activity.
- de-NO x and/or de-VOC activity refers to an ability to transform NO x and/or VOC species to their respective oxidized species like HNO 3 for NO x .
- the term "photocatalytic particles” used herein refers to particles based on a material which, when exposed to light (excitation light) having higher energy (i.e., shorter wavelength) than the energy gap between the conduction band and the valence band of the crystal, can cause excitation (photoexcitation) of electrons in the valence band to produce a conduction electron and a valence hole.
- the photocatalytic titanium dioxide particles contained in the composition according to the present invention basically include anatase and rutile forms of titanium oxide and mixtures thereof although anatase-type titanium oxide is especially preferred for its high photoactivity.
- the nature of the particle is, preferably, predominantly the anatase crystalline form.
- Predominantly means that the level of anatase in the titanium dioxide particles of the coating composition is greater than 50% by mass.
- the particles of the coating composition preferably exhibit a level of anatase of greater than 80%.
- the degree of crystallization and the nature of the crystalline phase are measured by X-ray diffraction.
- the crystalline titanium dioxide particles incorporated in the coating exhibit a mean size ranging from 1 to 150 nm, preferably ranging from 2 to 30 nm, more preferably still from 5 to 20 nm.
- the diameters are measured by transmission electron microscopy (TEM) and also XRD.
- the preferred photocatalyst particles have a high surface area per gram, e.g., higher than 30 m /g, preferably above 50 m /g and most preferably greater than about 100 m 2 /g as measured by the BET method.
- the surface area per gram of conventional TiO 2 pigments i.e. having photocatalytic properties is about 1-30 m 2 /g.
- the difference in the much smaller particles and crystallites of the photocatalyst particles gives rise to a much higher surface area.
- Particularly convenient for the invention are the photocatalytic TiO 2 sold sold under the name S5-300B by Millennium Inorganic Chemicals Ltd.
- the particles having a photocatalytic activity are added in an amount of 0.1 to 15, preferably 1 to 12, and most preferably 2 to 10, by weight (expressed in dry matter) of the total weight of said composition.
- the composition according to the invention includes at least 5% by weight of photocatalytic particles.
- photocatalytic particles may also exhibit a de-VOC removing property.
- the photocatalytic titanium dioxide particles may be used as a sol prepared by dispersion in water, as a water- or solvent-containing paste, or as a powder.
- Preferred examples of the dispersant used to prepare a sol include water, alcohols such as methanol, ethanol, isopropanol, n-butanol and isobutanol, and ketones such as methyl ethyl ketone and methyl isobutyl ketone.
- De-HNOi particles The composition according to the present invention comprises dispersed particles for removing the oxidized species HNO 3 , formed photocatalytically from NOx particles. These second type of particles are called "HNO 3 removing particles" or de-HNO 3 particles.
- HNO 3 removing particles include basic compounds, in particular any insoluble carbonates and for example calcium carbonate, zinc carbonate, magnesium carbonate and mixtures thereof. Especially, preferred examples of such compounds include calcium carbonate. No particular limitation is imposed on its amount which should be sufficient to achieve the transformation of HNO 3 to its alkaline salt and, secondary, compatible with the coating including it.
- An amount of 0.05 to 15, in particular of 0.1 to 2, by weight (expressed in dry matter) of the total weight of said composition may be particularly convenient.
- the ratio de-HNO 3 particles/photocatalytic particles may vary from 0.05 to 2, in particular from 0.1 to 1 and more particularly from 0.2 to 0.8.
- Said particles i.e. de-HNO 3 particles and photocatalytic particles are included in the composition according to the invention in an amount lower than 20% by weight (expressed in dry matter), in particular lower than 15% by weight, and more particularly lower than 12% by weight of the total weight of the composition.
- Silicon-based component The composition of the present invention contains a silicon-based component wherein at least previously disclosed particles are entrapped.
- the term "silicon-based material” used herein refers to any material based on silica or mixture thereof, which is able to provide a silicon based-film convenient for coating.
- the silicon based-material advantageously provides a polysiloxane polymer film.
- the silicon based-material includes at least one polysiloxane derivative and in particular having the formula R, wherein n has a value to provide an aqueous dispersion of polysiloxane having weight percentage solid ranging from 40 - 70%, and Rj and R 2 are alkyl radicals of 1 to 20 carbon atoms or an aryl group such as phenyl. Typically, the value of n ranges from about 50 to 2000.
- Rj and R 2 radicals are alkyl groups (e.g., methyl, ethyl, propyl, butyl, 2-ethylbutyl, octyl), cycloaklyl groups (e.g., cyclohexyl, cyclopentyl), alkenyl groups (e.g., vinyl, hexenyl, allyl), aryl groups (e.g., phenyl, tolyl, xylyl, naphthyl, diphenyl) aralkyl groups (e.g., benzyl, phenylethyl), any of the foregoing groups in which some or all of the hydrogens bonded to the carbons have been substituted (such as with halogen atoms or cyano), or groups substituted with or containing, for example, amino groups, ether groups ( — O — ), carbonyl groups ( — CO — ), carboxyl groups ( — CO
- the composition according to the present invention may include at least a solvent.
- solvents usable herein include water, an organic solvent, and a mixed solvent composed of water and an organic solvent. Water, and alcohol is particularly preferred.
- the composition according to the present invention may contain optional components provided that such an addition does not compromise the shelflife, UV durability, translucency or non-staining properties.
- additional compounds include filler(s) like quartz, calcite, clay, talc, barite and/or Na-Al-silicate; pigments like TiO 2 , lithopone, and other inorganic pigments; dispersants like polyphosphates, polyacrylates, phosphonates, naphthene and lignin sulfonates; wetting agents like anionic, cationic, amphoteric and non-ionic surfactants; defoamers like silicon emulsions, hydrocarbons, long-chain alcohols, ...; stabilizers like mostly cationic compounds; coalescents agents like alkali-stable esters, glycols, hydrocarbons; rheological additives like cellulose derivatives (CMC, HEC), xanthane gum, polyurethane, polyacrylate, modified starch, bentone and other lamellar silicates; water repellents like alkyl siliconates, siloxanes, wax emulsion, fatty acid Li salts and
- the composition of the present invention may be applied onto the surface of the material by any suitable method, and examples of suitable methods include spray coating, dip coating, flow coating, spin coating, roll coating, brush coating, and sponge coating.
- the composition after the application onto the surface of the substrate is then dried or cured to form a thin film.
- dried or cured used herein means that the silicon based-material contained in the composition according to the present invention is converted to a silicon film. Therefore, drying may be performed by either air drying or heat drying. Alternatively, ultraviolet irradiation or the like may be conducted to cause polymerization so far as the precursor is converted to a silicon film.
- the composition according to the present invention may be applied on the surface of a high variety of materials.
- the material is not particularly limited, and examples thereof include metals, ceramics, glasses, plastics, woods, stones, cements, concretes, fibers, woven fabrics, and combinations of the above materials and laminates of the above materials.
- Specific examples to which the composition may be applied include housings, building materials; exterior of the buildings; interior of the buildings; sashes; windowpanes; structural materials; exterior of machineries and articles; dustproof covers and coatings; and films, sheets and seals.
- Paints were prepared by using the following materials: - TiO 2 (24%o w/w): TiO 2 S5-300B from Millennium Inorganic Chemicals, Sodium silicate: Sodium silicate soln.Grade Crytal 79 from Ineos.
- the TiO 2 sol is diluted with water to which is then added the sodium silicate, calcium carbonate followed by the hydroxyethylcellulose and antifoam.
- the components are mixed under high shear.
- the water is added to the polysiloxane polymer and the pH of this is then adjusted to 10.0 followed by the addition of the sodium silicate.
- Part A is then mixed with part B under high shear mixing.
- Texanol is added.
- Table I The compositions of so-prepared paints are listed in Table I.
- the NO x that is used is NO at 30 ppm.
- the paint films were irradiated with 55 W/m 2 UV in the range of 300 to 400 nm range for 18 hours using a filtered Xenon light source.
- the samples are irradiated with a UV fluorescent tube which emits 10 W/m 2 UV in the range of 300 to 400 nm.
- the equipment, products and methods used for determining of NO/NO removal by coating are as follows: 1. Equipment Nitrogen Oxides Analyser SIGNAL 4000 UV Lamp Model VL-6LM 365 & 312 nanometer wavelength - ex BDH Air-tight sample chamber 3 channel gas mixer - ex Brooks Instruments, Holland
- Method The method of measure is as follows: 1. Switch on Analyser and exhaust pump. Ensure exhaust pipe goes to atmosphere. 2. Allow to warm-up. Several internal components need to reach operating temperature before the analyser will begin operation. The process will, typically, take 60 mins from cold start and the message START-UP SEQUENCE ACTIVE will be displayed until operating conditions are met. 3. After warm-up turn on air and test gas supply to the gas mixer. 4. Calibrate the Analyser on the Test gas supply only, (turn the air channel to zero on the gas mixer), according to the manufacturer's instructions 5. After calibration turn OFF the test gas supply at the gas mixer. 6. Place test sample in the test chamber and seal chamber. 7.
Abstract
Description
Claims
Priority Applications (12)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNB200480042302XA CN100519485C (en) | 2004-01-30 | 2004-01-30 | Composition for NOx removing translucent coating |
MXPA06008478A MXPA06008478A (en) | 2004-01-30 | 2004-01-30 | COMPOSITION FOR USE NOx. |
PCT/IB2004/000226 WO2005082810A1 (en) | 2004-01-30 | 2004-01-30 | COMPOSITION FOR USE NOx REMOVING TRANSLUCENT COATING |
BRPI0418475-0B1A BRPI0418475B1 (en) | 2004-01-30 | 2004-01-30 | nox removal composition for use as a translucent coating on a building material surface, and method for imparting self-cleaning properties to atmospheric contaminants on the surface of a material |
ES04706742.6T ES2459197T3 (en) | 2004-01-30 | 2004-01-30 | Composition for using a translucent coating that removes NOx |
EP04706742.6A EP1706360B1 (en) | 2004-01-30 | 2004-01-30 | COMPOSITION FOR USE NOx REMOVING TRANSLUCENT COATING |
JP2006550314A JP4633742B2 (en) | 2004-01-30 | 2004-01-30 | Composition used for NOx-removable translucent coating |
US10/587,339 US20070155622A1 (en) | 2004-01-30 | 2004-01-30 | Composition for use nox removing translucent coating |
AU2004316444A AU2004316444B2 (en) | 2004-01-30 | 2004-01-30 | Composition for use NOx removing translucent coating |
TW094102757A TW200536808A (en) | 2004-01-30 | 2005-01-28 | Composition for use NOx as removing translucent coating |
MYPI20050348A MY145563A (en) | 2004-01-30 | 2005-01-28 | Composition for use nox as removing translucent coating |
ARP050100318A AR047868A1 (en) | 2004-01-30 | 2005-01-28 | A NOX ELIMINATING COMPOSITION TO USE AS TRANSFER COATED ON THE SURFACE OF CONSTRUCTION MATERIALS |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/IB2004/000226 WO2005082810A1 (en) | 2004-01-30 | 2004-01-30 | COMPOSITION FOR USE NOx REMOVING TRANSLUCENT COATING |
Publications (1)
Publication Number | Publication Date |
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WO2005082810A1 true WO2005082810A1 (en) | 2005-09-09 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/IB2004/000226 WO2005082810A1 (en) | 2004-01-30 | 2004-01-30 | COMPOSITION FOR USE NOx REMOVING TRANSLUCENT COATING |
Country Status (12)
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US (1) | US20070155622A1 (en) |
EP (1) | EP1706360B1 (en) |
JP (1) | JP4633742B2 (en) |
CN (1) | CN100519485C (en) |
AR (1) | AR047868A1 (en) |
AU (1) | AU2004316444B2 (en) |
BR (1) | BRPI0418475B1 (en) |
ES (1) | ES2459197T3 (en) |
MX (1) | MXPA06008478A (en) |
MY (1) | MY145563A (en) |
TW (1) | TW200536808A (en) |
WO (1) | WO2005082810A1 (en) |
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GB2425075A (en) * | 2005-04-15 | 2006-10-18 | Marley Eternit Ltd | Concrete roof tile or wall cladding element |
WO2008048765A3 (en) * | 2006-10-18 | 2008-11-06 | Millennium Inorganic Chem | Improved depolluting coating composition |
EP2237899A1 (en) * | 2008-01-30 | 2010-10-13 | Millennium Inorganic Chemicals, Inc. | Photocatalytic coating compositions |
EP2281684A1 (en) * | 2008-05-27 | 2011-02-09 | Toto Ltd. | Object with photo-catalyst coating |
EP2300548A2 (en) * | 2008-05-06 | 2011-03-30 | Millennium Inorganic Chemicals, Inc. | De-polluting and self-cleaning epoxy siloxane coating |
US8906460B2 (en) | 2004-01-30 | 2014-12-09 | Cristal Usa Inc. | Composition for use as NOx removing translucent coating |
US9126145B2 (en) | 2007-08-31 | 2015-09-08 | Cristal USA, Inc. | Photocatalytic coating |
WO2018146364A1 (en) * | 2017-02-09 | 2018-08-16 | Primlab Global, Sl | Composition for mineralising carbon dioxide and nitrogen oxide gases and uses of same |
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WO2005083013A1 (en) * | 2004-01-30 | 2005-09-09 | Millennium Chemicals | Coating composition having surface depolluting properties |
EP2393763A1 (en) * | 2009-02-04 | 2011-12-14 | Said S.p.a. | Composition and process for sealing the surface of building materials |
US8545796B2 (en) | 2009-07-31 | 2013-10-01 | Cristal Usa Inc. | Silica-stabilized ultrafine anatase titania, vanadia catalysts, and methods of production thereof |
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JP6914927B2 (en) | 2015-10-21 | 2021-08-04 | トロノックス エルエルシー | Coatings that reduce NOx and methods for reducing NOx by the coating |
CN114832803A (en) * | 2022-04-08 | 2022-08-02 | 重庆城市综合交通枢纽(集团)有限公司 | Film-forming composition, preparation method thereof and application of composite photocatalyst |
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EP2281684A4 (en) * | 2008-05-27 | 2011-11-16 | Toto Ltd | Object with photo-catalyst coating |
EP2281684A1 (en) * | 2008-05-27 | 2011-02-09 | Toto Ltd. | Object with photo-catalyst coating |
WO2018146364A1 (en) * | 2017-02-09 | 2018-08-16 | Primlab Global, Sl | Composition for mineralising carbon dioxide and nitrogen oxide gases and uses of same |
EP3581267A4 (en) * | 2017-02-09 | 2020-12-16 | Primlab Global, SL | Composition for mineralising carbon dioxide and nitrogen oxide gases and uses of same |
US11338268B2 (en) | 2017-02-09 | 2022-05-24 | Primlab Global, Sl | Composition for mineralizing carbon dioxide and nitrogen oxide gases and uses thereof |
Also Published As
Publication number | Publication date |
---|---|
BRPI0418475B1 (en) | 2013-08-06 |
EP1706360B1 (en) | 2014-01-22 |
AU2004316444B2 (en) | 2010-07-01 |
BRPI0418475A (en) | 2007-06-19 |
MXPA06008478A (en) | 2007-11-23 |
US20070155622A1 (en) | 2007-07-05 |
MY145563A (en) | 2012-02-29 |
CN1953949A (en) | 2007-04-25 |
ES2459197T3 (en) | 2014-05-08 |
JP4633742B2 (en) | 2011-02-16 |
EP1706360A1 (en) | 2006-10-04 |
JP2007522923A (en) | 2007-08-16 |
AR047868A1 (en) | 2006-03-01 |
AU2004316444A1 (en) | 2005-09-09 |
TW200536808A (en) | 2005-11-16 |
CN100519485C (en) | 2009-07-29 |
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