WO2003022462A1 - Surfaces autonettoyantes a l'aide d'une composition de revetement de polysiloxane presentant des proprietes photocatalytiques - Google Patents

Surfaces autonettoyantes a l'aide d'une composition de revetement de polysiloxane presentant des proprietes photocatalytiques Download PDF

Info

Publication number
WO2003022462A1
WO2003022462A1 PCT/US2002/028570 US0228570W WO03022462A1 WO 2003022462 A1 WO2003022462 A1 WO 2003022462A1 US 0228570 W US0228570 W US 0228570W WO 03022462 A1 WO03022462 A1 WO 03022462A1
Authority
WO
WIPO (PCT)
Prior art keywords
titanium
substrate
silane
coating
formula
Prior art date
Application number
PCT/US2002/028570
Other languages
English (en)
Inventor
John B. Schutt
Original Assignee
Adsil Lc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Adsil Lc filed Critical Adsil Lc
Publication of WO2003022462A1 publication Critical patent/WO2003022462A1/fr

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • B01J35/39
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/46Coating 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
    • C04B41/49Compounds 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
    • C04B41/4905Compounds 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
    • C04B41/4922Compounds 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 monomers, i.e. as organosilanes RnSiX4-n, e.g. alkyltrialkoxysilane, dialkyldialkoxysilane
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/60After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
    • C04B41/61Coating or impregnation
    • C04B41/62Coating or impregnation with organic materials
    • C04B41/64Compounds having one or more carbon-to-metal of carbon-to-silicon linkages
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/48Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/58Metal-containing linkages
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D183/00Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/14Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0201Oxygen-containing compounds
    • B01J31/0211Oxygen-containing compounds with a metal-oxygen link
    • B01J31/0212Alkoxylates
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20Resistance against chemical, physical or biological attack
    • C04B2111/2038Resistance against physical degradation
    • C04B2111/2061Materials containing photocatalysts, e.g. TiO2, for avoiding staining by air pollutants or the like
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20Resistance against chemical, physical or biological attack
    • C04B2111/2038Resistance against physical degradation
    • C04B2111/2069Self cleaning materials, e.g. using lotus effect
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2222/00Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/20Use of solutions containing silanes

Definitions

  • the present invention relates to metallic and non-metallic surfaces which are rendered self-cleaning. More particularly, this invention relates to the use of certain polysiloxane coating compositions for protecting surfaces, such as cement, concrete and brick walkways and building structures, from forming permanent stains when exposed to organic substances, such as foods, beverages, gasoline spills, oil spills, and the like.
  • this invention relates to photocatalytically active silane-based, coating compositions of the type disclosed in my prior copending application, SN 09/778,921, the disclosure of which is incorporated herein, in its entirety, by reference thereto, particularly, namely, those compositions containing compounds of titanium alcoholates incorporated into the coating layer. Discussion of the Prior Art
  • R 2 is a lower alkyl group; and n is a number of 1 or 2;
  • compositions may further include one or more of (C) ethylortho- silicate, ethylpolysilicate or colloidal silica dispersed in lower alkanol; (D) boric acid, optionally dissolved in lower alkanol; (E) ⁇ -glycidyloxypropyltrimethoxysilane; (F) finely divided solid lubricant.
  • Staining is often particularly acute in high traffic areas, such as in and near amusement parks, sports and entertainment stadium, railroad stations, downtown city streets, and the like.
  • the only effective means of removing such stains is often by hosing with high-pressure water sprays.
  • high-pressure water will significantly accelerate the degradation of the concrete, cement, brick, etc., substrate.
  • PHOTOCATALYTIC ACTIVITY U.S, 5,811,192 to K. Takahama, et al; U.S. 6,013,372 to M. Hayakawa, et al; U.S. 6,027,766 to C.B. Greenberg, et al; U.S. 6,027,797 to T. Watanabe, et al; U.S. 6,054,227 to C. B. Greenberg, et al; U.S. 6,090,489 to M. Hayakawa, et al; U.S. 6,139,803 to T. Watanabe, et al; U.S. 6,154,311 to F. L.
  • the photocatalytically active catalysts generally semiconductor metal oxides, including especially titanium oxides, are present in the crystalline form, preferably the rutile or anatase form.
  • the starting material which in some cases, is a TiO precursor, for example, titanyl sulfate, titanium alkoxides, and the like, and whether the form of titanium oxide, is TiO , or hydrated titanium oxide, hydrous titanium oxide, metatitanate, orthotitatanate, or titanium hydroxide (see, e.g., column 4, of U.S. 6,277,346B1).
  • the photoconductive catalyst layers generally include high concentrations of the titanium oxide photocatalyst particles, even if the layer itself is very thin.
  • the coating compositions of my prior application which contain a titanium compound, in which titanium oxide is present in copolymerized form, chemically integrated into a polymer backbone, are effective in as self-cleaning coatings, wherein the titanium oxide is still able to function effectively as a photocatalyst, in the presence of ultraviolet (UV) light.
  • UV ultraviolet
  • Ti ⁇ O Ti O + uv light Ti + — — 0 "2+ ⁇ (charge transfer excitation)
  • the presented invention was completed on the basis of this discovery. Accordingly, it is an object of the invention to provide a method for coating porous, non-metallic architectural and construction materials, such as concrete, whereby the coated concrete is self-cleaning, e.g., resistant to the formation of permanent stains caused by contact with organic substances.
  • this invention provides a method for protecting porous and non-porous, metallic and non-metallic, materials against staining by organic substances.
  • this invention provides a method for providing a protective and self- cleaning coating on concrete and masonry surfaces, such as concrete and brick walkways, external concrete, brick and cinder block building structures, and other such materials which are subject to exposure to natural (e.g., sunlight) or artificial (e.g., fluorescent) UV irradiation.
  • natural e.g., sunlight
  • artificial e.g., fluorescent
  • the self-cleaning protective coatings of this invention are applied in the interior spaces of buildings, such as, for example, manufacturing and processing plants and facilities, hospitals, apartment building and family dwellings, and the like, including, for example, floors and walls, as well as to any structures and/or appliances, therein and especially those surfaces expected or likely to come into contact with organic debris, e.g., food and/or beverages, blood products, and the like, such as, equipment, food handling surfaces, and the like
  • the protective and self-cleaning coating compositions applied to the surface to be protected in the method of the present invention include silane coating compositions having Ti-O groups bonded in the siloxane matrix.
  • the protective coating composition is formed by admixing the at least one silane of formula (1) [component (A)], a titanium alcoholate of formula (2) [component (B)], silane condensation catalyst, which is, preferably, one or both of (i) acid compound [component (C)] and/or (ii) basic compound [component (D)], and water [component (E)].
  • the protective coating composition is formed by admixing and applying to the substrate
  • R 1 is a lower alkyl group, a phenyl group or a functional group, including at least one of vinyl, acrylic, amino, mercapto, or vinyl chloride functional group; and R 2 is a lower alkyl group;
  • silane condensation catalyst which comprises base component and/or boric acid and/or aluminum isopropoxide; and (D) water.
  • the protective coating is formed from an aqueous coating composition containing mixed valence silane condensation catalysts.
  • an aqueous coating composition is formed by admixing (A) at least one silane of formula (1) given above; (B) titanium alcoholate, especially of formula Ti(OR 3 ) , where R 3 represent a lower alkyl group, (C) (i) trivalent boric acid or derivative thereof, (ii) aluminum isopropoxide and/or (iii) at least one divalent metal silanol condensation catalyst compound, preferably, an hydroxide and/or carbonate of a divalent metal, such as calcium or magnesium hydroxide or carbonate; and (D) water; and, optionally, one or more of (E) ethyl polysiloxane; and (H) lower alkanol solvent.
  • the invention also provides the novel coated articles obtained by coating the surface as described herein.
  • the present invention provides a method for providing self cleaning surfaces, including, for example, architectural and structural materials, such as, concrete and similar materials, including, in particular, walkways, building exteriors, work surfaces, concrete tanks and storage vessels, and similar structures from other masonry materials, including, for example, brick, mortar, concrete, cement, blocks, limestone, stone, and other generally hard, porous, architectural building and construction materials; and metal and plastic materials, including, for example, manufacturing equipment and appliances.
  • architectural and structural materials such as, concrete and similar materials, including, in particular, walkways, building exteriors, work surfaces, concrete tanks and storage vessels, and similar structures from other masonry materials, including, for example, brick, mortar, concrete, cement, blocks, limestone, stone, and other generally hard, porous, architectural building and construction materials
  • metal and plastic materials including, for example, manufacturing equipment and appliances.
  • the surfaces to be protected are outdoor surfaces, such as walkways, e.g., streets, roads, pathways, pavement, sidewalks, etc., and outside (external) building structures, e.g., walls of building, window casings, bridge abutments, above ground concrete or metal tanks and other storage structures, and the like.
  • outdoor surfaces e.g., streets, roads, pathways, pavement, sidewalks, etc.
  • outside building structures e.g., walls of building, window casings, bridge abutments, above ground concrete or metal tanks and other storage structures, and the like.
  • effective self-cleaning also takes place under irradiation with artificial UV light, e.g., from indoor or outside mercury or fluorescent lighting fixtures, generally, any light source providing light having a wavelength of about 400 microns or lower. Accordingly, both indoor and outdoor surfaces may be protected by the method of the present invention.
  • the term "self-cleaning,” means that although stains may not be prevented from forming on the substrates treated according to the present invention, any such stains, especially those based on organic matter, e.g., carbohydrates, such as sugars, proteins, starches, and the like, will be "spontaneously” removed, that is, by exposure to sunlight or artificial UV irradiation, or combination of sunlight and artificial lighting.
  • organic matter e.g., carbohydrates, such as sugars, proteins, starches, and the like
  • the process of self-cleaning under irradiation by UV light is a photocatalytic oxidation reaction, as described above, and may require several to many hours, up to, for example, up to 1 or more days, e.g., about 1,2 or 3 days, for essentially complete stain removal, depending on, for example, severity and nature of the stain, the particular coating, including the amount of the Ti-O groups, the intensity and duration of UV exposure, and the like.
  • the stains which may be effectively prevented/removed, according to the present invention include, for example, organic based stains, such as, for example, proteins, carbohydrates, e.g., sugars, starches, oils, gasoline and other organic substances, i.e., compounds containing carbon and hydrogen as the major and essential elements, often with nitrogen and/or oxygen.
  • organic based stains such as, for example, proteins, carbohydrates, e.g., sugars, starches, oils, gasoline and other organic substances, i.e., compounds containing carbon and hydrogen as the major and essential elements, often with nitrogen and/or oxygen.
  • stains caused by proteinaceous or starchy food products, or sugar based food and condiment products including often difficult or hard to remove materials, such as ketchup, mustard, mayonnaise, blood, and the like
  • beverages such as, for example, soft drinks, alcoholic beverages, juices, and the like.
  • Oily and gasoline spills are another major source of staining on, especially, roadways and walkways, especially near or in the vicinity of grassy areas or construction sites, as well as on the floors, walls and equipment, of manufacturing plants, warehouses, etc. where machinery oils and fuels are subject to leaking and spilling. All of these types of stains may be effectively prevented from permanently staining substrates treated with the silane based Ti-O coating compositions of the present invention.
  • alkoxides of other transition metal oxides e.g., zirconium and hafnium
  • the oxides of Zr and Hf require even shorter wavelength irradiation, e.g., blue, light, such as light of wavelength of about 300 microns or lower, therefore, would not be as effective or efficient under most circumstances as the preferred coatings based on Ti-O incorporated into the siloxane coating matrix, as titanium alkoxides.
  • the effectiveness and efficiency of the photocatalytically induced oxidation reaction results, at least in part, by the chemical incorporation of the Ti ⁇ O groups in the polysiloxane matrix of the cured coatings, such as, for example, is believed to be the case where the Ti ⁇ O groups are derived from titanium alcoholate.
  • the incorporation of the Ti ⁇ O groups in the polysiloxane matrix is, furthermore, believed to include chemical bonding of the Ti atom to two adjacent silanol groups, as in a titanyl structure, such that, the vacant valencies of Ti +4 are filled as either TiO or Ti(OH) 2 .
  • titania e.g., pigment or UV absorber
  • the silane of the coating will attach to the titania particles and may, therefore, facilitate the absorption of UV light and, therefore, promote the photocatalytic activation of the Ti ⁇ O in the polysiloxane matrix.
  • silanes of formula (1) wherein R 1 is an alkyl group or aryl group
  • R 1 is a functional group
  • the expression "functional group” is intended to include any group, other than hydroxyl, (including alkoxy, aryloxy, etc.), which is hydrolyzable to provide, in situ, a reactive group (e.g., reactive hydrogen) which will react, in other than a condensation reaction, with the substrate (e.g., metal), itself, or other reactive components in or from the coating composition.
  • a reactive group e.g., reactive hydrogen
  • the functional groups in addition to the hydroxyl group (by hydrolysis of the (OR ) groups), tend to form three-dimensional or cross-linked structure, as well known in the art. Moreover, in the various embodiments of the invention, it is often preferred to use mixtures of two or more silane compounds of formula (1). Mixtures of at least phenyltrimethoxysilane and methyltrimethoxysilane are often especially preferred.
  • total amounts of silane compounds of formula (1) will fall within the range of from about 40 to about 90 percent by weight, preferably from about 50 to about 85 percent by weight, based on the total weight of silanes, acid component and water.
  • composition may additionally include a bis-trifunctional aminosilane, such as represented by the following formula (4):
  • silane compounds of formula (4) function as a less active basic catalyst, not requiring acidic passivation and, when used, are usually from about 1 to about 10 parts, preferably, from about 2 to about 8 parts, of compound of formula (4) per 100 parts of silane compound(s) of formula (1).
  • the coating compositions contain, as well known in the field of siloxane and silicone coatings, a silanol condensation catalyst (C), which may be a base component, for example,- an inorganic base, such as, for example, calcium hydroxide, aluminum hydroxide or zinc hydroxide, or mixture thereof; or an organic base component, such as, for example, aminosilane.
  • a silanol condensation catalyst C
  • the amount of the base component is generally, up to about 2%, such as, for example, from about 0.1 to 2.0%, by weight of the composition, especially, from about 0.2 to 1.6%.
  • an acid as the silanol condensation catalyst (C) is not preferred in the present invention because acids tend to quench the reaction, therefore, conventionally known acid condensation catalysts, such as, lower alkanoic acids or ortho-phosphorous acid (H 3 PO 3 ), are not preferably used.
  • conventionally known acid condensation catalysts such as, lower alkanoic acids or ortho-phosphorous acid (H 3 PO 3 ) are not preferably used.
  • boric acid may be used an acidic silanol condensation catalyst component may be advantageously used as condensation catalyst in the present invention.
  • the boric acid when used, may be added as free acid or as inorganic salt thereof, such as zinc borate, alkaline earth metal (e.g., calcium) borate, or ammonium borate, or organic derivative, e.g., boron methoxide.
  • total amounts of the boric acid component will fall within the range of from about 0.3 to about 4 percent by weight, preferably from about 0.5 to about 3%, preferably, from about 0.5 to about 2.5 percent by weight, based on the total weight of silanes, acid component and water.
  • silanol condensation catalyst which may be used by itself, or in combination with either or both of the basic catalyst and boric acid component, is aluminum isopropoxide.
  • the amounts of aluminum isopropoxide when present, may be the same as the amounts specified above for the boric acid component.
  • the total amounts will generally fall within the ranges noted above, namely, between about 0.3 to about 4 percent by weight, preferably, from about 0.5 to about 3% by weight, such as, from about 0.5 to 2.5 percent by weight, based on the total weight of silanes and condensation catalyst(s) and water.
  • coating compositions of this invention are most effective at neutral or slightly basic pH's, it is often preferred, especially when boric acid, or other acidic groups are included in the composition, to incorporate a basic aminosilane condensation catalyst, generally in an amount to maintain a pH in the range of from about 6.8 to about 8.0, preferably, from about 7.0 to 7.9.
  • aminoethyl-triethoxysilane beta-amino-ethyltrimethoxysilane, beta-aminoethyl-triethoxysilane, beta-amino-ethyl-tributoxysilane, beta-aminoethyltripropoxysilane, alpha-aminoethyl-trimethoxysilane, alpha-aminoethyl-triethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropyl-triethoxysilane, gamma-aminopropyl-tributoxysilane, gamma-amino-propyltripropoxysilane, beta-aminopropyl-trimethoxysilane, beta-aminopropyl-triethoxysilane, beta-aminopropyl-triethoxysilane, beta-amino
  • N-aminomethyl-beta-aminoethyl-trimethoxysilane N-aminomethyl-beta-aminoethyl-triethoxysilane
  • N-aminomethyl-gamma-aminopropyl-tripropoxysilane N-aminomethyl-beta-aminopropyl-trimethoxysilane
  • N-aminopropyltripropoxysilane N-aminopropyl-trimethoxysilane
  • N-(beta-aminoethyl)-gamma-aminopropyl-triethoxysilane N-(beta-aminoethyl)-gamma-aminopropyl-tripropoxysilane, N-(beta-aminoethyl)-gamma-aminopropyl-trimethoxysilane, N-(beta-aminoethyl)-beta-aminopropyl-triethoxysilane, N-(beta-aminoethyl)-beta-aminopropyl-tripropoxysilane,
  • N-(gamma-aminopropyl)-beta-aminoethyl-tripropoxysilane N-methyl aminopropyl trimethoxysilane, beta-aminopropyl methyl diethoxysilane, gamma-diethylene triaminepropyltriethoxysilane, and the like.
  • 3-(2-aminoethylamino)propyltrimethoxy silane also known as N-(2- aminoethyl)-3-aminopropyltrimethoxysilane]
  • 3-aminopropyltrimethoxy silane are especially preferred.
  • Aminosilanes of formula (4), above, may also be used.
  • the total amount of water will usually fall within the range of from about 10 to about 60 percent by weight, preferably from about 10 to about 45 percent by weight, based on the total weight of silanes, acid component and water.
  • water may be provided by other components, e.g., aqueous solution of boric acid (about 5% by weight of H 3 BO 3 ).
  • the water is distilled or de-ionized water.
  • the coating to be applied to the concrete, etc., substrate includes a titanium oxy group, e.g., Ti ⁇ O group, (where the " ⁇ " bond connotes bonding occurring because the Ti has donated two electrons to the same oxygen atom); or Ti-O (where the "-" bond connotes an oxygen obtaining its electrons from neighboring cations), derived from a titanium alcoholate, which also functions as a polymerization catalyst for the silanol condensation reaction and, therefore, assists in film formation (this is the function envisioned for the metal alcoholates in the copending application SN 09/778,921).
  • Ti ⁇ O group where the " ⁇ " bond connotes bonding occurring because the Ti has donated two electrons to the same oxygen atom
  • Ti-O where the "-” bond connotes an oxygen obtaining its electrons from neighboring cations
  • Preferred metal alcoholates are those of the formula Ti(OR 3 ) 5 where R 3 is a lower alkyl group, e.g., C ⁇ -C 6 straight or branched chain alkyl group, preferably C -C 4 alkyl group, most preferably, isopropyl, isobutyl or n-butyl.
  • the excitation process driving the photocatalysis involves UV excited transfer of an electron from oxygen into a titanium oxy electron transfer orbital for momentary storage in the vacant d-orbital structure on titanium, or the creation of an electron hole pair, when a molecular matrix is present in which, a band structure at some level may be postulated.
  • This process may be represented, for example, as follows:
  • the coating compositions of this invention tend to be water repellant.
  • Ti 4+ incorporated in the coated films have empty d-orbitals, trace water molecules tend to be attracted to the surface, such that water vapor and oxygen molecules may penetrate into the surface layer.
  • Amounts of titanium alkoxide (as TiO 2 ) as low as about 0.25%, by weight, of the coating, preferably, from about 0.5 to 2%, more preferably, from about 0.6 to about 1.4%, especially, from about 0.7 to about 1.2%, by weight, should be effective to provide the desired photocatalytic activity.
  • substantially all of the titanium oxy groups are copolymerized in the polysiloxane matrix and effectively distributed throughout the coated film.
  • none or substantially none of the Ti is bonded to the substrate.
  • An amount of titanium alkoxide to provide a ratio of 1 Ti0 2 molecule per from about 42 to about 83 silanol molecules provides effective self- cleaning property.
  • compositions of this embodiment may further include one or more additional additives for functional and/or esthetics effects, such as, for example, silicates, organic solvents and co-solvents, UV absorbers, metal catalysts and the like.
  • additional additives for functional and/or esthetics effects such as, for example, silicates, organic solvents and co-solvents, UV absorbers, metal catalysts and the like.
  • silicate component examples include ethyl or methyl orthosilicate or ethyl polysilicate. These silicates may be hydrolyzed, for example, from about 28% to about 52% silica. Especially preferred in this regard is tetraethylsilicate (TEOS) which has been subjected to controlled hydrolysis, providing a mixture of TEOS and, from about 20% to about 60% polydiethoxysilane oligomers. For example, a 50% hydrolysis product may be referred to herein as "polydiethoxysilane (50%).”
  • TEOS tetraethylsilicate
  • total amounts of silicate component when used, will fall within the range of from 0 to about 45 percent by weight, preferably from 0 to about 25 percent by weight, based on the total weight of silanes, acid component and water.
  • mono-lower alkyl ether of alkylene (e.g., ethylene) glycol mention may be made of mono- -C ⁇ -alkyl ethers of ethylene glycol, such as, for example, monomethyl ether, monoethyl ether, monopropyl ether, monobutylether, monopentylether or monohexylether, preferably monoethyl ether of ethylene glycol.
  • total amounts of the mono-lower alkyl ether of ethylene glycol when used, will fall within the range of from 0 to about 15 percent by weight, preferably from 0 to about 6 percent by weight, based on the total weight of silanes, boric acid and water.
  • ultra-violet light absorber As an example of ultra-violet light absorber, mention may be made of titanium dioxide in finely powdered form, e.g., having an average particle diameter of about 20 nm.
  • total amounts of the ultra-violet light absorber when used, will fall within the range of from 0 to about 10 percent by weight, preferably from 0 to about 5 percent by weight, more preferably not more than about 1 percent by weight, based on the total weight of silanes, silanol condensation catalyst component(s) and water.
  • organic solvents examples include lower alkanol, e.g., C -C alkanols, preferably isopropanol.
  • organic solvents such as, for example, acetone, methyl ethyl ketone, ethyl acetate, and the like may also be used.
  • total amounts of organic solvent such as, lower alkanol
  • organic solvent such as, lower alkanol
  • metal catalysts other than the titanium alkoxides, mention may be made of for example, colloidal aluminum hydroxide (e.g., from aluminum isopropoxide), and other metal alkoxides, such as, for example, hafnium alkoxides and zirconium alkoxides.
  • the silane component (A) may be used in an amount of from about 15 to about 25 parts by weight, preferably as a mixture of from about 15 to about 20 parts by weight of methyltrimethoxysilane and from about 1 to about 5 parts by weight of phenyltrimethoxysilane;
  • the titanium alkoxide (B) is present in the range of from about 0.05 to 1 part by weight, preferably, from about 0.1 to 0.8 part by weight, such as about 0.25 or 0.30 part by weight, the base component (C)(i), when present, is used in an amount of from about 0.1 to 3 weight percent, preferably from about 0.2 to 2.5 weight percent;
  • the present coating composition may be formed by mixing the above-noted components and allowing them to react.
  • a suitable reaction time is typically from about 30 minutes to about 12 hours, more usually, from about 60 minutes to about 2 hours. If no lower alkanol is present, frequent shaking may be necessary to achieve a shorter reaction time.
  • the coating composition may be provided as a two or three container system, e.g., the silane component and any silicate component, if present, being provided in a first container and all other components being provided in a second or second and third container.
  • the water may be provided separately from the other components.
  • the contents of the two or three containers may be mixed shortly prior to use and allowed to react for an appropriate reaction time, as noted above.
  • the mixed multivalent catalyst may include a divalent metal compound, such as hydroxide or carbonate of calcium, magnesium or other alkaline earth metal; a trivalent metal compound, such as, for example, boric acid or other compound of boron or aluminum; and the titanium alkoxide, as a tetravalent metal catalyst.
  • a divalent metal compound such as hydroxide or carbonate of calcium, magnesium or other alkaline earth metal
  • a trivalent metal compound such as, for example, boric acid or other compound of boron or aluminum
  • titanium alkoxide as a tetravalent metal catalyst.
  • the proportions of the respective catalysts may be selected based on the desired properties but generally in terms of metal ions, weight ratios of M +2 :M +3 :M +4 of from about 0.1-1:0.05-1:0.1-2, preferably from about 0.4-1:0.2-1:0.5-1, provide good results.
  • the multivalent catalyst system may be used with any of the coating compositions described herein.
  • the self-cleaning and protective coating compositions of this invention may be applied to a wide range of metallic and non-metallic surfaces.
  • metallic and non-metallic surfaces For example, mention may be made of generally porous architectural building and construction materials, such as cement, concrete, limestone and other stone materials, as well as, e.g., siliceous, ceramic, vitreous substrates.
  • the coating compositions may also be applied to plastic substrates, for example, and not by way of limitation, , e.g., polyolefins, polyesters, polyamides, polyimides, polycarbonates, polyetherimides, polysulfones, and the like, glass, alkali metal silicates, and the like.
  • the coatings also adhere well to and may be used to coat metal surfaces, e.g., steel, stainless steel, aluminum, and the like. Also, any of the substrates may be painted or, otherwise, colored or pigmented, without adversely affecting adherence of the coating to the paint coating.
  • the self-cleaning and protective coating compositions of this invention when applied to a substrate will readily penetrate even narrow and microscopic crevices or pores of the substrate, to form strong adherent bonds with the substrate.
  • the coating compositions contemplated herein may be formulated as solventless, aqueous or non-aqueous systems (although, in most cases, at least a catalytic amount of water is eventually added, directly or taken from the atmosphere).
  • the solventless systems may contain a mixture of methyltrimethoxysilane and phenyltrimethoxysilane and, catalyst, such as, for instance, tetrabutoxytitanate.
  • the self-cleaning coating composition may be applied in conventional manner, preferably by dipping, wiping, brushing or spraying, however, especially when applied to outside pre-existing structures, e.g., sidewalks, building exteriors and the like, it is apparent that brushing or spraying, most preferably spraying, will be used.
  • the coating compositions of the present invention are effective when applied to a coating (film) thickness (after cure) in the range of from about 5 to about 150 millionths of an inch, however, if desired to provide even superior corrosion protection, thicker films, up to about several mil, e.g., up to about 5/1000 inch (5 mil), preferably, up to about 2 mil, may be applied. Moreover, multiple applications of the coating composition may be applied to achieve thicker coatings, including, particularly, covering any pinholes which may existing when only a single coating application is used.
  • a polysiloxane coating will not accept (e.g., adhere) another polysiloxane coating layer. Accordingly, it is a distinct advantage of the coatings of the present invention that multiple layers may be provided and this is an important and useful feature of the present invention.
  • the ability of the coatings of this invention to accept multiple layers provides the additional advantage that, even if photocatalytic activity diminishes with time, it is a simple matter to reapply the coating composition without any special treatment of the substrate, although, it is usually preferred to remove loose dirt or other loose residues before re-coating the substrate.
  • the old surface should be cleaned, usually with an aqueous surfactant solution, then rinsed and dried, before applying additional or new layer of the subject coating composition.
  • the so-formed liquid mixture may be applied by wiping, foam brushing, conventional brushing or spraying to concrete, cement, limestone, and other architectural, building or construction material substrates and will dry to a tack-free condition in about 60 minutes or less. After the coating becomes tack-free, it may be overcoated with additional liquid mixture to build-up the final thickness. The resulting coating becomes insensitive to isopropyl alcohol and impervious to gasoline, in less than four hours.
  • methyltrimethoxysilane To 15 parts methyltrimethoxysilane, there is added, while stirring, 5 parts propyltrimethoxysilane or 5 parts phenyltrimethoxysilane. To this mixture, 0.3 parts boric acid is added followed by addition of 0.2 to 0.3 parts tetrabutoxytitanate. The mixture is allowed to clear. Then, 10 to 13 parts of water is added slowly to avoid excessive heat build-up. The resulting composition may be applied to a substrate while it is still warm or after further heating by reaction. Alternatively, the composition may be stored and applied after as long as about 6 days after water addition. Application may be by spraying, wiping, brushing, etc.
  • an organic-solvent free self-cleaning coating composition a mixture of 15 parts methyltrimethoxysilane and 5 parts phenyltrimethoxysilane is combined with 0.2 to 0.35 parts of tetrabutoxytitanate. While stirring, 2.4 parts water is added. After about 15 minutes the resulting composition is ready to be applied to cement or other substrate.
  • composition may also be advantageously applied for the protection of interior and exterior building materials from, for example, deposition and growth of mildew or infectious organisms, especially in salt air environments, such as coastlines, industrial areas and the like.
  • the composition may be used to coat ceramic roofing tiles, concrete, galvanized steel, duct works (e.g., interior surfaces), etc.
  • phenyltrimethoxysilane 5 parts are added to a container containing 15 parts methyltrimethoxysilane. While mixing, 0.3 part of tetrabutoxy titanate are added, along with 2 parts of polydiethylsiloxane (approx. 50%), and 15 parts of isopropyl alcohol. After mixing, 10 parts of an aqueous 3% boric acid solution are added and, after waiting eight hours, the resulting coating composition may be applied, by brushing or spraying. The cured compositions will be corrosion resistant and self-cleaning.
  • EXAMPLE 4 10 parts of a 3% boric acid solution are placed in a first container. 20 parts of methyltrimethoxysilane, 10 parts of isopropyl alcohol and 0.5 part of tetrabutoxy titanate are mixed in a second container. The contents of the two containers can then be mixed together and allowed to react to form a self-cleaning coating composition.
  • a silane-alcohol mixture (Pot A) is prepared by mixing 15 parts of methyltrimethoxysilane, 5 parts of isobutyltrimethoxysilane and 1.1 parts of polydiethylsiloxane (-50%) to form a homogeneous silane-alcohol solution.
  • a mixture obtained by combining 11.3 parts of a 3% solution of boron methoxide in isopropyl alcohol, 2 parts of polydiethoxysiloxane ( ⁇ 50% solids), 0.4 parts of tetrabutoxytitanate, and 2 parts of methyl-trimethoxysilane.
  • the mixture in Pot B is allowed to react for 24 hours and is then added to the silane-alcohol solution in Pot A.
  • the resulting mixture may be sprayed on concrete walkways.
  • This example shows a two part mixed valence catalyst system for silane catalyzation.
  • tetrabutoxy titanate Ti+4
  • B+3 boric acid
  • This composition even without addition of a stabilizer, has a pot life of about 2 days.
  • the resulting composition is sprayed onto a cement slab which is located outdoors in Palm Coast, Florida.
  • a non-diet cola drink is poured on the treated concrete and on a non- treated concrete slab.
  • the treated and non-treated concrete slabs are left with dark stains from the soft drink. Both slabs are left outdoors, with equal daytime exposure to the sunlight and, after 2 days, the stain completely disappears from the treated slab but no change is observed in the non-treated slab.
  • methyltrimethoxysilane Twenty parts of methyltrimethoxysilane are combined with 5 part of phenyltrimethoxysilane in a container to which is added 4 parts of a polydiethylsiloxane hydrolyzed to about 50% solids. To this mixture is added 0.3 parts boric acid. The mixture is stirred until the boric acid is dissolved. Next, 0.5 parts of tetrabutoxytitanate are added, while stirring is continued. Finally, 6.7 parts of water are slowly added to avoid a color change. After the catalyzed reaction proceeds for about two hours, the mixture may be applied, by spraying, on the substrate to be protected. The coating will cure under ambient conditions in about one week. The resulting coating can withstand immersion in HCl bath for a minimum of two hours.

Abstract

Des tâches d'aliments, de boissons, d'huile et de pétrole et d'autres tâches à base organique sur divers matériaux de construction et de pavage, comme le béton, le ciment et autres matériaux de maçonnerie peuvent disparaître spontanément sous l'action d'une oxydation induite par voie photocatalytique, lors de l'exposition à une lumière ultraviolette naturelle ou artificielle. Dans cette réaction, le substrat est recouvert d'une composition de revêtement à base de silane autonettoyante, dans laquelle le Ti-O amorphe est lié chimiquement dans le squelette de polysiloxane. Le revêtement autonettoyant constitue également un revêtement durable et résistant à la corrosion sur des surfaces non métalliques. Une composition typique peut comprendre un silane, ou un mélange de silanes, tels que du méthyltriméthoxysilane et du phényltriméthoxysilane. Les compositions de revêtement peuvent être formulées avec des catalyseurs acide ou basique. Les trottoirs en béton traités avec ces compositions de revêtement en silane auto-nettoyantes ne nécessitent pas de lavage à l'eau sous haute pression pour retirer les tâches d'aliments, de boissons, d'huile ou d'essence.
PCT/US2002/028570 2001-09-10 2002-09-09 Surfaces autonettoyantes a l'aide d'une composition de revetement de polysiloxane presentant des proprietes photocatalytiques WO2003022462A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US31797101P 2001-09-10 2001-09-10
US60/317,971 2001-09-10

Publications (1)

Publication Number Publication Date
WO2003022462A1 true WO2003022462A1 (fr) 2003-03-20

Family

ID=23236060

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2002/028570 WO2003022462A1 (fr) 2001-09-10 2002-09-09 Surfaces autonettoyantes a l'aide d'une composition de revetement de polysiloxane presentant des proprietes photocatalytiques

Country Status (1)

Country Link
WO (1) WO2003022462A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1524249A1 (fr) * 2003-10-16 2005-04-20 Global Engineering and Trade S.r.L. Peinture de ciment
EP1652827A1 (fr) * 2004-10-27 2006-05-03 Eurovia Système dépolluant pour espaces confinés
WO2006070395A1 (fr) * 2004-12-28 2006-07-06 Council Of Scientific And Industrial Research Procédé d’autonettoyage photocatalytique de taches
WO2009055055A1 (fr) * 2007-10-26 2009-04-30 Gimvang Bo H Revêtement résistant à l'abrasion et à la corrosion
US8075679B2 (en) 2007-10-26 2011-12-13 Xurex, Inc. Corrosion and abrasion resistant coating
RU2444540C1 (ru) * 2010-10-21 2012-03-10 Общество с ограниченной ответственностью "Пента-91" Способ получения полиметаллосилоксанов
CN115895004A (zh) * 2022-11-10 2023-04-04 江苏凯伦建材股份有限公司 一种自清洁卷材及其制备方法和应用

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4552941A (en) * 1981-08-20 1985-11-12 Union Carbide Corporation Polysiloxanes from acyloxysilanes using organo metallic catalyst
US4753827A (en) * 1986-10-03 1988-06-28 Ppg Industries, Inc. Abrasion-resistant organosiloxane/metal oxide coating
US5623030A (en) * 1994-12-01 1997-04-22 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Curable composition and process for producing molded articles using the same
EP0857770A2 (fr) * 1997-02-06 1998-08-12 Shin-Etsu Chemical Co., Ltd. Compositions de revêtement, films hydrophiles et articles revêtus d'un film hydrophile
US6013369A (en) * 1994-11-21 2000-01-11 Ube Nitto Kasei Co., Ltd. Process for the production of titanium oxide coated particles
US6037289A (en) * 1995-09-15 2000-03-14 Rhodia Chimie Titanium dioxide-based photocatalytic coating substrate, and titanium dioxide-based organic dispersions
US6072018A (en) * 1996-09-30 2000-06-06 Virginia Tech Intellectual Properties, Inc. High abrasion resistant coating material
WO2001064804A1 (fr) * 2000-02-28 2001-09-07 Adsil, Lc Compositions de revetement a base de silane articles a revetement obtenus avec ces compositions et utilisations de ceux-ci

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4552941A (en) * 1981-08-20 1985-11-12 Union Carbide Corporation Polysiloxanes from acyloxysilanes using organo metallic catalyst
US4753827A (en) * 1986-10-03 1988-06-28 Ppg Industries, Inc. Abrasion-resistant organosiloxane/metal oxide coating
US6013369A (en) * 1994-11-21 2000-01-11 Ube Nitto Kasei Co., Ltd. Process for the production of titanium oxide coated particles
US5623030A (en) * 1994-12-01 1997-04-22 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Curable composition and process for producing molded articles using the same
US6037289A (en) * 1995-09-15 2000-03-14 Rhodia Chimie Titanium dioxide-based photocatalytic coating substrate, and titanium dioxide-based organic dispersions
US6072018A (en) * 1996-09-30 2000-06-06 Virginia Tech Intellectual Properties, Inc. High abrasion resistant coating material
EP0857770A2 (fr) * 1997-02-06 1998-08-12 Shin-Etsu Chemical Co., Ltd. Compositions de revêtement, films hydrophiles et articles revêtus d'un film hydrophile
WO2001064804A1 (fr) * 2000-02-28 2001-09-07 Adsil, Lc Compositions de revetement a base de silane articles a revetement obtenus avec ces compositions et utilisations de ceux-ci

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1524249A1 (fr) * 2003-10-16 2005-04-20 Global Engineering and Trade S.r.L. Peinture de ciment
US6972048B2 (en) 2003-10-16 2005-12-06 Global Engineering And Trade S.R.L. Cement paint
AU2004220711B2 (en) * 2003-10-16 2008-07-10 Global Engineering And Trade S.R.L. Cement paint
EP1652827A1 (fr) * 2004-10-27 2006-05-03 Eurovia Système dépolluant pour espaces confinés
WO2006070395A1 (fr) * 2004-12-28 2006-07-06 Council Of Scientific And Industrial Research Procédé d’autonettoyage photocatalytique de taches
JP2008525188A (ja) * 2004-12-28 2008-07-17 カウンシル オブ サイエンティフィック アンド インダストリアル リサーチ 光触媒による汚れの自動洗浄工程
KR101231894B1 (ko) * 2004-12-28 2013-02-08 카운슬 오브 사이언티픽 앤드 인더스트리얼 리서치 얼룩을 광촉매작용에 의해 자동 세정하는 방법
WO2009055055A1 (fr) * 2007-10-26 2009-04-30 Gimvang Bo H Revêtement résistant à l'abrasion et à la corrosion
US8075679B2 (en) 2007-10-26 2011-12-13 Xurex, Inc. Corrosion and abrasion resistant coating
RU2444540C1 (ru) * 2010-10-21 2012-03-10 Общество с ограниченной ответственностью "Пента-91" Способ получения полиметаллосилоксанов
CN115895004A (zh) * 2022-11-10 2023-04-04 江苏凯伦建材股份有限公司 一种自清洁卷材及其制备方法和应用
CN115895004B (zh) * 2022-11-10 2023-12-08 江苏凯伦建材股份有限公司 一种自清洁卷材及其制备方法和应用

Similar Documents

Publication Publication Date Title
AU2001251679B2 (en) Silane-based, coating compositions, coated articles obtained therefrom and methods of using same
KR100487968B1 (ko) 농무및오염방지유리제품
EP1960482B1 (fr) Composition de revetement stable au stockage permettant de produire des surfaces inorganiques lisses resistantes a l'abrasion et stables aux intemperies presentant des proprietes de nettoyage facile
AU2001297867B2 (en) Non-aqueous coating compositions formed from silanes and metal alcoholates
EP0987317A1 (fr) Procede de traitement prealable de surface avant formation d'une pellicule hydrophile photocatalytique, detergent et composition de sous-couche mis en application dans ce procede
WO2000018504A1 (fr) Article photocatalyseur, article protege contre l'encrassement et le voilement, et procede de production d'un article protege contre l'encrassement et le voilement
EP1749066A1 (fr) Compositions hydrophiles, procedes de production associes, et substrats revetus par lesdites compositions
KR20080022577A (ko) 내알칼리성 졸―겔 코팅제
EP1765936A1 (fr) Revetements a couches multiples et procedes associes
JP3797037B2 (ja) 光触媒性親水性コーティング組成物
JP4287695B2 (ja) 光触媒体
WO2003022462A1 (fr) Surfaces autonettoyantes a l'aide d'une composition de revetement de polysiloxane presentant des proprietes photocatalytiques
JP2005138059A (ja) 速硬化性光触媒体
JP2006131917A (ja) 光触媒性親水性コーティング組成物
JP4086055B2 (ja) 防曇防汚ガラス物品
JP2000303055A (ja) 光触媒性親水性被膜の親水性回復剤
JP2003183634A (ja) ゾル組成物、その製造方法、硬化体および基材の撥水処理方法
JP2002080782A (ja) 光触媒性塗膜形成組成物
JP2002285088A (ja) コーティング材組成物、塗装品、鏡、風呂の壁
EP0883035A1 (fr) Support pour electrophotographie et revelateur utilisant un tel support
AU2001251679A1 (en) Silane-based, coating compositions, coated articles obtained therefrom and methods of using same
ZA200206708B (en) Silane-based, coating compositions, coated articles obtained therefrom and methods of using same.
MXPA99010818A (en) Method for surface pretreatment before formation of photocatalytic hydrophilic film, and detergent and undercoat composition for use in the same

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 BY BZ CA CH CN CO CR CU CZ DE DM DZ EC EE ES FI GB GD GE GH HR HU ID IL IN IS JP KE KG KP KR LC LK LR LS LT LU LV MA MD MG MN MW MX MZ NO NZ OM PH PL PT RU SD SE SG SI SK SL TJ TM TN TR TZ UA UG US UZ VN YU ZA ZM

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ UG ZM ZW AM AZ BY KG KZ RU TJ TM AT BE BG CH CY CZ DK EE ES FI FR GB GR IE IT LU MC PT SE SK TR BF BJ CF CG CI GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP

WWW Wipo information: withdrawn in national office

Country of ref document: JP