WO2002049980A1 - Substrates with a self-cleaning surface, a process for their production and their use - Google Patents
Substrates with a self-cleaning surface, a process for their production and their use Download PDFInfo
- Publication number
- WO2002049980A1 WO2002049980A1 PCT/EP2001/014168 EP0114168W WO0249980A1 WO 2002049980 A1 WO2002049980 A1 WO 2002049980A1 EP 0114168 W EP0114168 W EP 0114168W WO 0249980 A1 WO0249980 A1 WO 0249980A1
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- WO
- WIPO (PCT)
- Prior art keywords
- substrate
- self
- glass
- forming
- layer
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B17/00—Methods preventing fouling
- B08B17/02—Preventing deposition of fouling or of dust
- B08B17/06—Preventing deposition of fouling or of dust by giving articles subject to fouling a special shape or arrangement
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B17/00—Methods preventing fouling
- B08B17/02—Preventing deposition of fouling or of dust
- B08B17/06—Preventing deposition of fouling or of dust by giving articles subject to fouling a special shape or arrangement
- B08B17/065—Preventing deposition of fouling or of dust by giving articles subject to fouling a special shape or arrangement the surface having a microscopic surface pattern to achieve the same effect as a lotus flower
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- 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
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- 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
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
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- 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
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/42—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating of an organic material and at least one non-metal coating
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- 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
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
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- 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
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
- C03C8/20—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing titanium compounds; containing zirconium compounds
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
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- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23C—COATING 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
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
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- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23C—COATING 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
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
- C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
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- 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
- C03C2205/00—Compositions applicable for the manufacture of vitreous enamels or glazes
- C03C2205/04—Compositions applicable for the manufacture of vitreous enamels or glazes for self-cleaning enamels or glazes
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- 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
- C03C2217/45—Inorganic continuous phases
- C03C2217/452—Glass
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- 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
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/76—Hydrophobic and oleophobic coatings
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/77—Coatings having a rough surface
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- 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
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/2038—Resistance against physical degradation
- C04B2111/2069—Self cleaning materials, e.g. using lotus effect
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
- Y10T428/24364—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.] with transparent or protective coating
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
- Y10T428/24372—Particulate matter
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
- Y10T428/24372—Particulate matter
- Y10T428/2438—Coated
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/256—Heavy metal or aluminum or compound thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/258—Alkali metal or alkaline earth metal or compound thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/259—Silicic material
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- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
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- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31609—Particulate metal or metal compound-containing
- Y10T428/31612—As silicone, silane or siloxane
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- Y10T428/31663—As siloxane, silicone or silane
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- Y10T428/31652—Of asbestos
- Y10T428/31667—Next to addition polymer from unsaturated monomers, or aldehyde or ketone condensation product
Definitions
- the invention relates to a substrate with at least one self-cleaning surface, the substrates being in particular a substrate of glass, ceramic, plastic or metal or a glazed or enamelled substrate.
- the self-cleaning surface located on the substrate is based on a coating with structure- forming particles which is located on the substrate, resulting in a surface structure of elevations and depressions; the surface is at least partly hydrophobic.
- the invention also relates to a composition for the production of a substrate according to the invention with at least one self-cleaning surface.
- the invention also relates to a process for the production of the substrate with at least one self-cleaning surface, which comprises coating the substrate with the abovementioned composition.
- the invention also relates to the use of the substrates according to the invention with a self-cleaning surface .
- US 3, 354,022 discloses water-repellent surfaces, the surface having a micro-rough structure with elevations and depressions and being formed from a hydrophobic material, in particular a fluorine-containing polymer.
- a surface with a self-cleaning effect can be applied to ceramic brick or to glass by coating the substrate with a suspension which comprises glass beads with a diameter in the range from 3 to 12 ⁇ m and a fluorocarbon wax based on a fluoroalkyl ethoxymethacrylate polymer.
- a suspension which comprises glass beads with a diameter in the range from 3 to 12 ⁇ m and a fluorocarbon wax based on a fluoroalkyl ethoxymethacrylate polymer.
- Their low abrasion resistance and moderate self-cleaning effect are a disadvantage of such coatings.
- the doctrine of EP 0 909 747 Al is a process for producing a self-cleaning property of surfaces, in particular roof tiles.
- the surface has hydrophobic elevations with a height of 5 to 200 ⁇ m.
- Such a surface is produced by application of a dispersion of powder particles of an inert material in a siloxane solution and subsequent curing.
- the structure-forming particles are not fixed on the surface of the substrate in an abrasion-stable manner.
- EP Patent 0 772 514 is self-cleaning surfaces of objects with a synthetic surface structure of elevations and depressions, the distance between the elevations being in the range from 5 to 200 ⁇ m and the height of the elevations being in the range from 5 to 100 ⁇ m and the structure comprising hydrophobic polymers or materials which have been hydrophobized in a stable manner.
- Etching and embossing processes, and furthermore coating processes are suitable for formation of the structures. If necessary, the formation of the structure is followed by a hydrophobization, for example a so-called silanization.
- structured surfaces with hydrophobic properties are the doctrine of EP 0 933 388 A2.
- the surface has elevations with an average height of 50 nm to 10 ⁇ m and an average separation of between 50 nm to 10 ⁇ m, and a surface energy of the non-structured material of 10 to 20 mN/m.
- the structured surface comprises fluorine-containing polymers or has been treated using alkylfluorosilanes. Indications of also using coating processes, instead of the shaping processes disclosed here, for structuring the surface are not to be obtained from this document.
- the doctrine of DE Patent Application 100 16 485.4 is glass, ceramic and metal substrates with a self-cleaning surface based on a structured and at least partly hydrophobized coating.
- the coating comprises a glass flux and structure-forming particles with an average particle diameter in the range from 0.1 to 50 ⁇ m.
- the glass flux and structure-forming particles are present in a volume ratio in the range from 0.1 to 5 and the micro-rough surface structure has a ratio of average profile height to average distance between adjacent profile peaks in the range from 0.3 to 10.
- the self-cleaning surface has a higher abrasion resistance than self-cleaning surfaces of roof tiles according to the EP 0 909 747 Al acknowledged above.
- the object of the invention is to provide substrates, in particular substrates of glass, ceramic, plastic and metal and glazed and enamelled substrates, with at least one self-cleaning surface which not only have a low roll-off angle or high contact angle and therefore a good self- cleaning effect, but furthermore are transparent.
- the self- cleaning surface should have a very high contact angle with respect to water, preferably a contact angle of about/above 150°.
- the transparency of a transparent substrate, such as glass or plastic should as far as possible not be reduced.
- a decoration under the self-cleaning surface should remain clearly detectable.
- TJ 3 TJ Ci ⁇ PJ PJ 1 cr ⁇ N H> 0 ⁇ ) D- ra H H ⁇ rt ⁇ ra ⁇ o
- the structure-forming particles can be organic or inorganic substances.
- the inorganic substances which may be mentioned are: metal oxides, mixed oxides, silicates, sulfates, phosphates, borates, metal sulfides, oxosulfides, selenides and sulfoselenides, metal nitrides and oxide- nitrides and metal powders .
- the organic structure-forming particles which may be mentioned are carbon blacks and nanoscale organic polymeric particles, and among these fluorine-containing polymers. Many structure-forming particles with the particle diameter according to the claims, such as, in particular, 5 to less than 50 nm, are commercially obtainable.
- the structure- forming particles are particularly preferably metal oxides from the series consisting of silica (Si0 2 ) , titanium dioxide (Ti0 2 ) , aluminium oxide (A1 2 0 3 ) , zirconium dioxide (Zr0 2 ) and tin dioxide (Sn0 2 ) .
- These oxides are particularly preferably pyrogenically prepared oxides, and among these in particular silica.
- Pyrogenic silicas are commercially obtainable with an average primary particle size in the range from about 7 to 40 nm.
- the self- cleaning surface of substrates according to the invention comprises a layer-forming material, which can be an inorganic or organic material.
- the layer-forming material either forms a homogeneous layer in which the structure- forming particles are fixed in the form of their primary particles and/or agglomerates, or the structure-forming particles are fixed on the substrate by means of the layer- forming material.
- the glazing/enamel layer and optionally additionally the structure-forming particles during the firing.
- coating materials with Me-O-Me* structural elements are those systems such as are formed from organometallic compounds of the elements boron, silicon, aluminium, titanium and zirconium which have at least two hydrolysable groupings during alcoholysis/hydrolysis with a subsequent condensation reaction and optionally subsequent firing.
- the structured coating comprises structure-forming particles with an average diameter of less than 100 nm, in particular in the range from 5 nm to less than 50 nm, and a layer-forming inorganic or organic material in a weight ratio in the range from 100 : 1 to 1 : 2, in particular 20 : 1 to 1 : 1.
- a ratio outside the limits mentioned is indeed possible, but if the content of layer-forming material is too low, a possibly inadequate fixing of the structure-forming particles is the consequence. In the case of too high a content of the layer-forming material, the self-cleaning effect decreases because the structure- forming particles may be sunk too low in the layer-forming material .
- Preferred substrates have a coating which substantially comprises structure-forming particles and a layer-forming inorganic material, but the coating can additionally comprise adhesion promoters or those compounds such as are formed from auxiliary substances present and/or precursors of the layer-forming material during the production of the coating, including a heat treatment step which may be necessary or firing.
- TJ rt Di Hi O TJ TJ O PJ ⁇ ⁇ 3 O r-3 P ra TJ ⁇ J Oi M TJ CO J ⁇ TJ ⁇ -3 ri CO CT cr o cr 3 ⁇ J O p, ⁇ 0 p, 3 cr O PJ ti cr o 3 PJ tr 0J P- O ⁇ J 3 ⁇ cr O P cr ⁇ rt PJ ⁇ ⁇ ti P CQ ⁇ ⁇ 3 rt tQ ⁇ o tr P. 0 ⁇ ⁇ J O p. ⁇ ⁇ ⁇ 3 o ⁇ 3 ri ⁇ ! Oi p. P- ⁇ 3 ⁇ 03 ⁇ ⁇ J 3 rt ⁇ PJ 03 rt ⁇ : ⁇ 3 ft O O TJ Pi ⁇ J 3 P- ri
- this comprises inorganic layer-forming materials or at least precursors thereof.
- Most glass-forming substances are contained in the composition in particulate form.
- Alkali metal oxides and alkali metal silicates are expediently contained in the composition in the form of aqueous alkali solution or in the form of water-glass (sodium silicate solution) .
- compositions according to the invention comprise an organometallic compound of one or more of the elements boron, silicon, aluminium, titanium and zirconium as the layer-forming material.
- organometallic compounds are preferably those which contain alkoxy groups, acetyl groups or acetylacetonate groupings, so that Me-0-Me % structural elements are formed by a condensation reaction, wherein Me and Me can be identical or different and represent the elements mentioned.
- the structure-forming particles and the layer-forming material are usually contained in the .composition according to the invention in a weight ratio of 100 : 1 to 1 : 2; the weight ratio is preferably in the range from 20 : 1 to 1 : 1.
- Pulverulent compositions according to the invention can be applied to the substrate by dusting or by electrostatic coating.
- a preferred embodiment of the composition according to the invention also comprises, in addition to the layer-forming ⁇ t to P 1 P> en o c ⁇ o en o c ⁇
- 03 03 ⁇ J 3 3 € 0- cr P- tr « P- 3 O ⁇ J • ⁇ ; rt O ft rt ⁇ N 03 03 ⁇ 3 TJ ⁇ o rt 3 03 3 P. ri P- 1 cr P- ⁇ 03 P- 3 ⁇ ti 3 P- X r cr X P- ⁇ 3 CD ri ⁇ ⁇ ra cr P ⁇ ⁇ P- rr O ⁇ rt 3 ⁇ Pi ⁇ J O J ⁇ ⁇ 0J 3 0 p. ⁇ ⁇ J p, P-
- CD PJ 03 Ul P 1 0 P. ⁇ ri 03
- structure-forming particles substantially only particles with a particle diameter of less than 100 nm, preferably less than 50 nm, to be baked and then to be hydrophobized.
- the hydrophobization can be carried out by application of a hydrophobic lacquer or by polymerization of monomers on the micro-rough surface.
- Suitable polymeric lacquers are solutions or dispersions of e.g. polyvinylidene fluoride.
- a hydrophobization can also be carried out by plasma polymerization of completely or partly fluorinated vinyl compounds .
- the hydrophobization is particularly expediently carried out using reactive alkyl- or, preferably, fluoroalkylsilanes and oligomeric alkyl- or fluoroalkylsiloxanes.
- the silanes or siloxanes preferably contain one or more alkoxy or acetyl groups, such as ethoxy groups, as the reactive group.
- Crosslinking of the hydrophobizing agent and also chemical bonding thereof to a silicatic surface containing silanol groups is possible by means of these functional groups.
- Silanizing agents which are particularly preferably to be used are tridecafluorooctyltriethoxysilane and oligomers thereof.
- Such products can be applied to the surface to be hydrophobized in the form of dilute organic, in particular alcoholic, aqueous-organic and aqueous solutions, for example by dipping, spraying or brushing.
- the substrate After application of a solution comprising a fluorine- containing silane or siloxane to the substrate, the substrate is dried and cured, preferably at a temperature of up to 500 °C, for example for 30-60 min at about 150 °C, 10-15 min at 250 to 300 °C or 1 min at about 500 °C.
- the optimum of the after-treatment with heat in respect of highest abrasion resistance is at a temperature in the range from 200 to 300 °C.
- hydrophobic layers accessible using reactive fluoroalkylsilanes or -siloxanes are distinguished by a similarly good hydrophobicity and oleophobicity, so that substrates according to the invention contaminated with hydrophobic dirt particles can also easily be cleaned with water.
- the invention also relates to the use of a substrate according to the invention with a self-cleaning surface.
- a substrate according to the invention with a self-cleaning surface.
- examples are glass panes for vehicles and windows, construction glass, ceramic tiles, roof tiles, covers on photovoltaic solar cells, metal profiles and lacquered substrates, such as car lacquers.
- the substrates according to the invention with a self- cleaning surface are distinguished by a very high efficiency of the self-cleaning property.
- the contact angle of preferred substrates according to the invention with respect to water is in general about and often above 150°.
- a particularly outstanding feature of substrates according to the invention is the transparency of the nanostructured coating.
- Transparent substrates of plastic and glass and glazed or enamelled substrates are accordingly particularly suitable for being provided with a transparent coating according to the invention and therefore for obtaining high-quality self-cleaning surfaces which are themselves transparent and therefore also clearly reveal underlying decorations .
- Essential advantages of compositions according to the invention are their easy accessibility and range of variation in respect of composition. The compositions can therefore be used for coating the most diverse substrates and producing good self-cleaning properties.
- the stages of the process according to the invention are based closely on those process stages such as are used, for example, for decoration purposes in the glass and ceramics industry, but are also conventional in the lacquering of metallic substrates with stoving lacquers.
- the devices and technologies known to the expert can therefore be used.
- the composition comprised 0.5 wt . % boric acid (B 2 0 3 ) and 4 wt . % pyrogenic silica in a screen printing medium (no. 80858 from dmc 2 AG) .
- the pyrogenic silica had an average diameter of the primary particles of 12 nm.
- the printing medium was a water-friendly medium.
- the screen printing was carried out using a 100 T screen. After drying, the coating was shock-fired at 660°C in the course of 4 min.
- the hydrophobization of the structured stoved surface was carried out using a fluoroalkylsilane formulation, that is to say an ethanolic solution of tridecafluorooctyltriethoxysilane.
- the solution was introduced over the surface, and curing was then carried out at elevated temperature .
- Example 1 was repeated with the only difference that the composition comprised 0.5 wt . % diammonium hydrogen phosphate ((NH) 2 HP0 4 ) [sic] instead of boric acid as the layer-forming material. After the hydrophobization, the glass coating showed outstanding self-cleaning properties .
- Substrate was degreased V4A high-grade steel .
- a composition with 4 wt.% pyrogenic silica (d 12 nm) and diammonium hydrogen phosphate in an amount of (a) 0.25 wt.%, (b) 0.5 wt.% and (c) 1.0 wt . % in screen printing medium 80858 was used for the coating.
Abstract
Description
Claims
Priority Applications (5)
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KR20037008037A KR20030069186A (en) | 2000-12-21 | 2001-12-04 | Substrates with a self-cleaning surface, a process for their production and their use |
AU2002235752A AU2002235752A1 (en) | 2000-12-21 | 2001-12-04 | Substrates with a self-cleaning surface, a process for their production and their use |
EP01985843A EP1347948A1 (en) | 2000-12-21 | 2001-12-04 | Substrates with a self-cleaning surface, a process for their production and their use |
CA002429866A CA2429866A1 (en) | 2000-12-21 | 2001-12-04 | Substrates with a self-cleaning surface, a process for their production and their use |
JP2002551485A JP2004516216A (en) | 2000-12-21 | 2001-12-04 | Substrate with self-cleaning surface, method of making the same and use thereof |
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DE10063739.6 | 2000-12-21 | ||
DE10063739A DE10063739B4 (en) | 2000-12-21 | 2000-12-21 | Substrates with self-cleaning surface, process for their preparation and their use |
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US (1) | US6800354B2 (en) |
EP (1) | EP1347948A1 (en) |
JP (1) | JP2004516216A (en) |
KR (1) | KR20030069186A (en) |
CN (1) | CN1481342A (en) |
AU (1) | AU2002235752A1 (en) |
CA (1) | CA2429866A1 (en) |
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Also Published As
Publication number | Publication date |
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KR20030069186A (en) | 2003-08-25 |
DE10063739B4 (en) | 2009-04-02 |
CN1481342A (en) | 2004-03-10 |
DE10063739A1 (en) | 2002-06-27 |
EP1347948A1 (en) | 2003-10-01 |
US6800354B2 (en) | 2004-10-05 |
AU2002235752A1 (en) | 2002-07-01 |
CA2429866A1 (en) | 2002-06-27 |
US20020142150A1 (en) | 2002-10-03 |
JP2004516216A (en) | 2004-06-03 |
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