US20130040116A1 - Method for producing a pane with a patterned surface, and pane having a patterned surface - Google Patents
Method for producing a pane with a patterned surface, and pane having a patterned surface Download PDFInfo
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- US20130040116A1 US20130040116A1 US13/521,824 US201113521824A US2013040116A1 US 20130040116 A1 US20130040116 A1 US 20130040116A1 US 201113521824 A US201113521824 A US 201113521824A US 2013040116 A1 US2013040116 A1 US 2013040116A1
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- Prior art keywords
- sol
- pane
- gel layer
- layer
- substrate
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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
- C03C17/36—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 being a metal
- C03C17/3602—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 being a metal the metal being present as a layer
- C03C17/3607—Coatings of the type glass/inorganic compound/metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44F—SPECIAL DESIGNS OR PICTURES
- B44F7/00—Designs imitating three-dimensional effects
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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
- 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
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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
- C03C17/36—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 being a metal
- C03C17/3602—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 being a metal the metal being present as a layer
- C03C17/3636—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 being a metal the metal being present as a layer one layer at least containing silicon, hydrogenated silicon or a silicide
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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
- C03C17/36—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 being a metal
- C03C17/3602—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 being a metal the metal being present as a layer
- C03C17/3649—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 being a metal the metal being present as a layer made of metals other than silver
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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
- C03C17/36—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 being a metal
- C03C17/3602—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 being a metal the metal being present as a layer
- C03C17/3684—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 being a metal the metal being present as a layer the multilayer coating being used for decoration purposes
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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
- C03C17/36—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 being a metal
- C03C17/3602—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 being a metal the metal being present as a layer
- C03C17/3686—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 being a metal the metal being present as a layer the multilayer coating being used for ovens
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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
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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
- C03C2217/465—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase having a specific shape
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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
- C03C2217/478—Silica
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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
- C03C2217/48—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase having a specific function
- C03C2217/485—Pigments
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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
- C03C2217/72—Decorative 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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- 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.]
- Y10T428/24479—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness
- Y10T428/24521—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness with component conforming to contour of nonplanar surface
- Y10T428/24545—Containing metal or metal compound
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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.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
- Y10T428/24851—Intermediate layer is discontinuous or differential
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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.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
- Y10T428/24893—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material
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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.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
- Y10T428/24926—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including ceramic, glass, porcelain or quartz layer
Definitions
- the invention relates to a method for producing a pane, in particular a pane for a household appliance or a viewing window for an oven or an architectural glass. Furthermore, the invention relates to such a pane.
- glass surfaces are patterned by an etching process using hydrofluoric acid. This process is complex, dangerous, and the variety of shapes is limited due to the etching process.
- document EP 0 493 202 B1 shows manufacturing of a patterned glass using a roller which embosses the pattern into the still viscous glass.
- a roller which embosses the pattern into the still viscous glass.
- the method is not suitable to produce exact pattern depths in a range below 500 ⁇ m, since due to the viscosity of the glass a rounding of the embossed shapes occurs.
- An object of the invention is to provide a method which permits to produce a pane, in particular a pane of a household appliance or the viewing window of an oven or an architectural glass with a haptically perceptible pattern in an simple manner.
- the pattern should exhibit good durability.
- the object of the invention is already achieved by a method for producing a pane, and by a pane of a household appliance or piece of furniture according to any of the independent claims.
- the invention on the one hand, relates to a method for producing a pane which especially is a part of a household appliance or a viewing window of an oven.
- the pane is intended for use as a viewing window or control panel for so-called “white goods” such as cooker extraction hoods, ovens, steam cookers, microwave ovens, kitchen fronts, splash guards in kitchens, and small electrical appliances such as toasters, or for cooktops.
- the pane may likewise be provided as a fireplace viewing window or for architectural glazing applications and picture framing. It may also be used in elevators, as a door, or in furniture.
- the pane is intended for building glazing applications in the interior and outside.
- flooring or wall or ceiling surface or partition wall for example in wet areas.
- Use thereof in the automotive, shipbuilding or aviation sector for example as an instrument panel, or in the field of consumer electronics such as for mobile phones, computers, monitors, or television sets is also being considered.
- a substrate is provided.
- the substrate is transparent.
- a glass or glass-ceramic substrate may be used which is particularly suitable for use at higher temperatures.
- the invention may also be used for plastic substrates, in particular transparent plastic substrates such as polycarbonates, polyacrylates, polyolefins, in particular cyclo-olefin copolymers.
- a sol-gel layer is applied onto the substrate.
- sol-gel layer using a printing technique.
- Particularly suitable are in particular screen printing or ink jet printing techniques.
- a partial coating which for example may comprise graphic elements, such as letters, borders, etc. may be applied in a very simple manner using a printing process, in particular by screen printing.
- a haptically perceptible pattern is embossed into the sol-gel layer using an embossing tool.
- the embossing tool can be formed as a stamp or as a roller, for example.
- a haptically perceptible pattern in the present context, is to be understood as a pattern, which due to the spacing of the individual pattern elements and due to the depth of the pattern can be felt by a person who touches it and thus clearly differs from a smooth layer.
- anti-slip grip surfaces are contemplated, or textures of wood, natural stone, and/or regular geometric shapes such as regular three-dimensional bodies, especially diamonds, prisms, or cylinders.
- sol-gel layer is cured and forms the surface or at least the pattern-defining layer within a layer system on the surface of the substrate.
- Curing of the sol may be accomplished for example by simple drying, the sol, as the case may be, curing by chemical reactions.
- the sol-gel layer may be fired by a thermal treatment, in particular to produce temperature-resistant haptic layers.
- organic constituents of the sol-gel layer, if present, may be burned out, at least partially.
- Sol-gel layers may be provided with such a temperature resistance that they resist a tempering process, for example. As such, firing of the layer may be accomplished during a tempering process, for example, so that no further process step is required.
- One preferred embodiment of the invention contemplates to produce the pattern of the embossing tool by molding the pattern from a master. This especially permits to transfer textures of other materials to a glass or glass ceramic substrate.
- etched textures such as for example those of etched metal or glass to the substrate.
- a surprising impression of an etched metal pattern may thus be created on a glass or glass-ceramic substrate, wherein in case an only partial coating the metallic appearance seamlessly merges into a transparent pane.
- sol-gel layer on a pane which has two different patterns. So, two areas with a different appearance may be produced in a very simple way.
- the substrate preferably has a thickness from 0.5 and 10 mm.
- coloring and/or opaque particles are added to the sol-gel layer, or the sol-gel layer is coated with a further layer, especially a metallic-looking lacquer or a metal layer.
- a haptically perceptible pattern which is embossed regularly, at least in sections has a pitch from 0.1 ⁇ m to 10 mm, preferably from 1 ⁇ m to 2 mm.
- Pitch herein means the space between the center of a structural element and that of another, similar structural element.
- the invention permits to provide patterns in which the individual pattern elements are relatively large and considerably spaced from one another. So, for example, it is conceivable to create textures which resemble the surface of carbon fiber reinforced plastics.
- the composite material producible and in particular produced according to invention is particularly suitable as a pane of a household appliance, a piece of furniture, a picture glazing, or an architectural glass.
- the invention furthermore relates to a pane of a household appliance or piece of furniture.
- It may for example be formed as a viewing window or a control panel and comprises a glass or glass-ceramic substrate with a patterned sol-gel layer which has a haptically perceptible pattern.
- the pane has been produced by the method described above.
- organic constituents of the sol-gel layer have been burned out, so as to achieve better temperature resistance.
- a sol-gel layer in the context of the invention is also understood as a layer in which the organic constituents of a sol, for example a hybrid sol, have been removed.
- the sol-gel layer may be dyed, for example by means of a dye or by means of coloring particles such as metal or carbon black particles.
- the pattern depth of the sol-gel layer preferably ranges from 100 nm to 1 mm in order to produce clearly perceptible haptic properties of the layer.
- a further layer is disposed on the sol-gel layer.
- This layer follows the pattern of the sol-gel layer and provides for the desired opacity, the desired gloss, and/or the desired color.
- the sol-gel layer comprises particles for matting the layer.
- particles for matting the layer By adding larger particles, in particular particles having a size of more than 100 nm, a matte surface may be obtained in addition to the pattern, since the surface due to the particles has a roughness which reduces light reflections.
- the pane is designed to be transparent in sections thereof and simultaneously opaque in other sections.
- sol-gel layer in a colored and/or opaque form.
- the invention permits to obtain embossed patterns on rigid or brittle material, such as glass or glass ceramic, in a simple manner and with a variety of appearances and haptics.
- plastics of all kinds, polymers, metals, etc. may likewise be coated.
- the invention provides for temperature resistant, corrosion resistant, non-yellowing, weather and scratch resistant coatings.
- a master which has the desired pattern, as mentioned above.
- this may be an appropriately etched surface, and when regular geometric shapes are desired, this may be a metal structure on which regular geometric patterns had been provided using an etching process or mechanical processes, in particular machining, grinding, or sand blasting.
- the master template is preferably cleaned so as to be free of grease and lint.
- a polymer mass is poured onto the clean master template, in particular a two-component silicone molding compound, and cured. Curing may be accomplished, for example, by heating. Especially complex patterns may include bubbles which may be removed by applying a vacuum. The cured polymer stamps are released from the master template and are then ready to be used for embossing purposes.
- the stamps may be cleaned, for example using an alcohol or alkaline cleaning agents, and may be reused.
- the embossing tool may be provided in particular in form of a transparent foil on which a lacquer had been applied which was embossed using a roller with the corresponding pattern.
- the sol-gel layer may be applied on glass, glass ceramic or on another substrate using an inexpensive liquid coating process.
- the sol-gel layer may comprise amorphous and/or crystalline particles as well as organic/inorganic sol-gel hybrid polymer particles, as is known in the art.
- the refractive index of the sol-gel layer may be adapted to that of the substrate and/or to that of a layer optionally arranged above.
- high or low refractive index particles may be added to the sol.
- the refractive index of the particles ranges from 1.3 to 2.9
- An advantageous method for applying the sol is screen printing, in particular for larger substrates.
- a screen printing process in particular allows to apply the sol only in sections of the substrate.
- areas which are not to be patterned may be excluded from being coated, and in free areas which for example serve as a viewing window or as a display or control panel, an inspection for layer roughnesses, inhomogeneities, and contaminations may be dispensed with.
- the sol-gel coating may be precured, in particular in case of hybrid polymers which for example can be precured using electromagnetic waves such as UV radiation, or by heat.
- the sol-gel layer is embossed using a polymer stamp, in continuous or static manner.
- This embossing stamp may likewise be provided with a sol-gel layer.
- the layer is cured under a defined pressure of the embossing stamp, thermally and/or photochemically.
- photochemical curing is envisaged in which the sol-gel layer is cured through a UV radiation transparent stamp while still being in contact with the stamp.
- no pressure is required, since the sol is automatically drawn into the pattern of the stamp. This may be caused by capillary forces and/or the own weight of the stamp and may also be a result of the selected viscosity and the high plasticity of the lacquer.
- the lacquers preferably exhibit a low thixotropy which promotes the process of ‘automatically being drawn into the pattern’. Furthermore, the lacquers exhibit a rather Newtonian behavior which means that the shear stress is proportionally related to the shear rate.
- Typical viscosities of the employed lacquers range from 50 mPas to 2500 mPas, preferably from 75 mPas to 500 mPas, more preferably from 100 mPas to 300 mPas. All values were determined at a shear stress of 85 N/m 2 .
- bubbles are eliminated either manually, using a roller, or by applying a negative pressure.
- a patterned, thin sol-gel layer which preferably has a thickness from 10 nm to 1 mm, more preferably from 50 nm to 100 ⁇ m.
- the patterns of this layer are defined by the pattern of the embossing stamp.
- Possible patterns are both periodic and random patterns, in particular lines of a brushed surface and/or brushed and/or emerized and/or polished surface, light-scattering layers, etched surfaces, punched surfaces, three-dimensional shapes such as pyramids, inverted pyramids, etc.
- the pattern depth preferably varies in a range from 50 nm to 1 mm, more preferably from 50 nm to 100 ⁇ m.
- the pattern of the sol-gel layer defines the pattern of optional additional layers, in particular metal layers or metallic shining lacquers, as is the case in one embodiment of the invention.
- a luster color as an additional layer.
- Such color usually comprises dissolved metal resinates which, at higher temperatures, form a thin metal oxide layer with a colored or metallic appearance.
- the embossability of the layer is adjusted through the chemical composition of the sol, the degree of hydrolysis, and/or the pH-value, and/or the content of nanoparticles.
- the ratio of water to hydrolyzable groups is below 0.5.
- the solvent content of the starting lacquer ranges from 50 to 25 mass-%, more preferably from 45 to 35 mass-%, in order to ensure screen printability.
- the solvent fraction has been determined after drying at 100° C. for 2 h using IR radiation.
- the embossability of the layer is adjusted through the chemical composition of the sol and the degree of hydrolysis.
- the ratio of water to hydrolyzable groups is below 0.5.
- the embossability of the layer may be adjusted via the proportion of organic functional groups and/or the content of inorganic nanoparticles and/or the morphology and/or the type of material of the nanoparticles and/or the pH of the lacquer and/or the type of shielding or the chemical stabilization of the nanoparticles.
- the mass ratio of hydrolyzed UV cross-linkable component and nanoparticles preferably is between 90:10 and 40:60, more preferably between 70:30 and 50:50.
- the mass fraction of UV cross-linking monomers should not be smaller than 10%.
- the organic content should not be selected too high, in particular an organic content from 5 to 80 mass-%, preferably from 10 to 50 mass-% is envisaged.
- burning out of the organics and layer compaction result in a reactive bonding to the substrate and/or formation of a transition zone in which for example an ion exchange occurred. This contributes to an improved mechanical stability of the layer and improved adhesion of the layer.
- This transition zone may have a thickness from 0.5 nm to 10 ⁇ m, preferably from 5 nm to 500 nm.
- sintering or densification additives may be added to the embossing lacquer.
- these may include for example ions, salts, alkoxides, and/or metal oxides of the alkali and/or alkaline earth elements and/or transition elements.
- such compounds may diffuse from the substrate into the applied layer and/or may be introduced from the nanoparticles and/or via a second coating or by infiltration.
- the embossed layer according to the invention includes at least two, preferably three or more different metal cations, for example Si, and/or K, and/or Na, and/or Mg, and/or Na, and/or Ca, and/or Li, and/or Ba, and/or Zn, and/or Bi, and/or B, and/or Zr, and/or Ti, and/or Al, and/or Ce.
- metal cations for example Si, and/or K, and/or Na, and/or Mg, and/or Na, and/or Ca, and/or Li, and/or Ba, and/or Zn, and/or Bi, and/or B, and/or Zr, and/or Ti, and/or Al, and/or Ce.
- Such layers and/or layer systems preferably exhibit a scratch resistance of more than 300 g, preferably more than 700 g in the BSH test. In the pencil hardness test, they preferably exhibit a hardness of more than 1H, more preferably of more than 3H.
- the sol-gel layers may be cured at a temperature from 50 to 1000° C., preferably from 100 to 900° C., most preferably from 400 to 730° C. The pattern is maintained, even if the organic components are almost completely burned out.
- the pattern depth may decrease by 0 to 60% as compared to the master pattern. If necessary, this may be compensated for by using a master pattern with a greater pattern depth.
- hydrolyzed and condensed epoxy- and/or methacrylate-functionalized, and/or ally- and/or vinyl-functionalized alkoxysilanes, which are filled with amorphous and/or crystalline nanoparticles and which are added as an alcoholic dispersion, are used as a sol-gel precursor. In this way, shrinking between 0 and 25% may be achieved.
- irregularly shaped fibrous particles are used, especially SiO 2 particles, in particular with a diameter from 5 to 15 nm and a length from 5 to 150 nm.
- Other embodiments use mixtures of spherical particles of different sizes ranging from 5 to 125 nm.
- Such fibrous particles are obtained, for example, by stringing together individual spherical particles.
- Especially the mechanical strength of the patterned layer may be adjusted via the chemical composition of the inorganic constituents (molecularly disperse sol-gel components and inorganic nanoparticles).
- Preferred materials are those that are sintered easily.
- both amorphous and crystalline compositions of molecularly dispersed silicon oxide in the sol-gel precursor and crystalline and/or amorphous inorganic nanoparticles may be used.
- a composition may be adjusted which corresponds to a low temperature sintered multicomponent glass, such as for example used for enamel coatings.
- amorphous, substantially spherical silicon oxide nanoparticles with a mean particle size from 300 to 600 nm or platelet-shaped inorganic particles or irregularly shaped particles with an mean size from 100 to 1000 nm may be used. These particles may be produced by flame pyrolysis, for example.
- the patterned sol-gel layer has an intrinsic color, for example due to absorption or due to interference effects. Absorption may be adjusted through the choice of the molecularly dispersed sol-gel precursor and/or by adding absorbent nanoparticles or pigments. In particular inorganic nanoparticles absorbing in the visible and/or infrared wavelength range may be used, such as CuO, Co 2 O 3 , C, TiC, ZrC, TiN, ZrN, Ag, Al, Fe 2 O 3 , SiN, BN.
- the thickness of the sol-gel layer preferably ranges from 0.05 to 3 ⁇ m.
- the layer material preferably comprises amorphous or hybrid polymeric silicon oxide, optionally with fractions of amorphous or nanocrystalline oxide and/or non-oxide metal compounds such as TiO 2 , MgF 2 , MgO x F y , CaF 2 , CaO x F y , CaO, K 2 O, MgO, Li 2 O, Na 2 O, ZrO 2 , Yttrium-stabilized ZrO 2 , Ca-stabilized ZrO 2 , Mg-stabilized ZrO 2 , Ce-stabilized ZrO 2 , Si-stabilized ZrO 2 , Al 2 O 3 , CeO 2 , Gd 2 O 3 , Bi 2 O 3 , B 2 O 3 , ZnO, ITO, SiN, SiON, SiC, SiOC, TiN, TiC, TiON, TiOC, ZrC, ZrN, ZrON, Z
- the coating solution may comprise amorphous or crystalline molecularly or colloidally dispersed or hybrid polymeric sol-gel precursors of silicon, titanium, boron, bismuth, sodium, lithium, potassium, calcium, zirconium, phosphorus, niobium, hafnium, yttrium, aluminum, zinc, magnesium, tin (e.g.
- the particles in the sol-gel precursor preferably have a particle size ranging from of 0.05 to 200 nm, more preferably from 1 to 100 nm.
- a preferred embodiment of the invention comprises UV light curable hybrid polymers, in particular in form of a hydrolyzed and condensed alkoxysilane precursor, such as glycidyloxypropyltriethoxysilane, glycidyloxypropyltrimethoxysilane, methacryloxytrimethoxysilane, methacryloxytriethoxysilane, allylsilane, vinylsilane.
- a hydrolyzed and condensed alkoxysilane precursor such as glycidyloxypropyltriethoxysilane, glycidyloxypropyltrimethoxysilane, methacryloxytrimethoxysilane, methacryloxytriethoxysilane, allylsilane, vinylsilane.
- This precursor constitutes the binder for silicon oxide nanoparticles which are added to the sol.
- silicon oxide nanoparticles are used which are fixed with a sol whose degree of condensation is greater than 60%.
- the volume fraction of the silicon oxide nanoparticles is greater than 20%, more preferably greater than 40%.
- the porosity may range from 1 to 50% (open porosity).
- a temperature treatment at 500° C. results in pores with a pore diameter from 0.4 to 15 nm. These pores preferably have a bottleneck-shaped geometry and are distinguished by a pore diameter that is larger than the pore outlet or the connection of the pores. In a preferred embodiment of the invention, the pore diameter ranges from 3 to 10 nm, and the size of the pore outlet ranges from 1 to 6 nm.
- a methacrylic acid complexed sol-gel precursor may be used as the UV-crosslinking component, in particular titanium alkoxide and/or zirconium alkoxide, reacted with methacrylic acid.
- sol-gel precursors with a low solvent content are preferably used.
- Preferred solvents exhibit a vapor pressure of less than 2 bars, an evaporation number of more than 35, and/or a boiling point above 120° C.
- a solvent exchange of highly volatile alcohols may be accomplished for ethylene glycol monoethyl ether and/or ethylene glycol monoisopropyl ether and/or 4-hydroxy-4-methyl-2-pentanone and/or terpineol and/or diethylene glycol monoethyl ether and/or tripropylene glycol monomethyl ether.
- the embossing lacquer comprises a high proportion of polysiloxane.
- polysiloxane In particular branched or linear methyl and/or phenylpolysiloxanes may be used.
- polysiloxanes may be provided with UV-crosslinking organic functional groups.
- Polysiloxanes having a high inorganic solids content are preferably used.
- curing during the embossing process is exclusively accomplished by UV light.
- a final thermal curing is performed in a temperature range from 100 to 1000° C., in particular between 450 and 740° C.
- the duration of thermal curing may range from 2 min to 180 min, preferably from 3 min to 60 min.
- the contact pressure of the stamp during embossing is preferably adjustable between 0.01 and 5 bars.
- compounds having a dewetting or wetting effect may be added to the lacquer system comprising the sol.
- These may be for example fluoro-organosilane compounds.
- the substrate Prior to coating, the substrate may be treated with a primer, or the surface may be preconditioned before applying the embossing lacquer, for example by a plasma treatment.
- the master pattern and/or the embossing stamp are coated with solutions which form a monolayer that has a wetting or dewetting effect.
- a multi-component lacquer system in particular a two- or three-component lacquer system may be used.
- a two-component system is used.
- One component thereof is the hydrolyzed organically functionalized silane, for example a solvent-reduced hydrolyzate of tetraalkoxysilane and glycidylpropyltrialkoxysilane.
- Another, second component comprises the metal oxide and/or semi-metal oxide nanoparticles with a photoinitiator in a high-boiling solvent.
- the two components are mixed in an appropriate ratio and can then be used for more than 24 h.
- FIGS. 1 to 6 The invention will now be explained in more detail with reference to the drawings of FIGS. 1 to 6 :
- FIG. 1 schematically illustrates a master pattern 1 which in this embodiment is a metal plate that has an etched periodic pattern with diamonds as pattern elements 2 .
- the spacing of these pattern elements 2 is referred to as pitch t.
- a curable polymer mass is applied thereto to produce a stamp 3 .
- a stamp 3 has been created which comprises impressions of the pattern elements 2 . So the pitch t is identical.
- FIG. 4 shows how a glass substrate 4 is coated with a sol-gel layer 5 . Coating is accomplished by a screen printing process during which only a section of the glass substrate 4 , here the edge region, is printed.
- stamp 3 is pressed onto sol-gel layer 5 .
- Stamp 3 may also be pressed onto areas of the glass substrate 4 which are not coated.
- the dimension of the patterned layer is defined by the screen printing process.
- FIG. 6 schematically shows the final product, namely a household appliance 6 which comprises a pane 9 produced according to the invention, as a front pane.
- Pane 9 has the patterned sol-gel layer 5 in its upper surface area. In this case it is provided as a haptic pattern, i.e. to achieve a specific tactile effect when touched. Furthermore, the household appliance 6 has a handle 8 for opening and a display field 7 in which patterned sol-gel layer 5 is omitted.
- a patterned layer may be produced as follows, for example:
- GPTES glycidyloxypropyltriethoxysilane
- TEOS tetraethoxysilane
- PTSA p-toluenesulfonic acid
- the nanoparticles have a fibrous shape, for example, with a diameter from 5 to 15 nm and a length from 30 to 150 nm.
- 15 g of tripropylene glycol monomethyl ether is added to this solution, and the highly volatile solvent is removed in a rotary evaporator at 100 mbar and 50° C. bath temperature.
- 0.6 g of the cationic photoinitiator Irgacure® 250 in 1 g of ethylene glycol isopropyl ether is added to the embossing sol.
- This lacquer system allows to apply layers to one side of a soda lime glass by screen printing using a 180 mesh.
- a patterned silicone stamp (PDMS) is applied, and then curing is accomplished through the stamp using a UV lamp.
- PDMS patterned silicone stamp
- the layers are now thermally cured at temperatures of 670° C. for 4 min.
- the final thickness of the layer ranges from 2.5 to 3 ⁇ m.
- a stainless steel layer is applied by a sputtering process in a thickness of at least 100 nm.
- a layer may be applied as follows:
- GPTES glycoloxypropyltriethoxysilane
- TEOS tetraethoxysilane
- MTEOS methyltriethoxysilane
- This lacquer system allows to apply layers to one side of a soda lime glass by screen printing using a 180 mesh.
- a patterned silicone stamp (PDMS) is applied, and then the layer is cured through the stamp using a UV lamp.
- the stamp is removed the pattern of the stamp had been transferred into the nanoparticle-functionalized coating.
- the layers are now thermally cured at temperatures from 300 to 500° C.
- a preferred heating rate is 3 K/min, with a holding time of 1 h at 500° C.
- the final thickness of the layer is 2.5 ⁇ m.
- the invention permits to provide specific haptics and appearances on almost any substrates in a very economical way.
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Applications Claiming Priority (3)
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DE102010004741.4A DE102010004741B4 (de) | 2010-01-14 | 2010-01-14 | Verfahren zur Herstellung eines Verbundmaterials sowie Küchengerät |
DE102010004741.4 | 2010-01-14 | ||
PCT/EP2011/000142 WO2011085997A1 (fr) | 2010-01-14 | 2011-01-14 | Procédé de fabrication d'une vitre à surface texturée et vitre à surface texturée |
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US20130040116A1 true US20130040116A1 (en) | 2013-02-14 |
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US13/521,824 Abandoned US20130040116A1 (en) | 2010-01-14 | 2011-01-14 | Method for producing a pane with a patterned surface, and pane having a patterned surface |
US14/635,074 Active US9388070B2 (en) | 2010-01-14 | 2015-03-02 | Glass or glass-ceramic composite material and method for producing same |
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EP (3) | EP2523917A1 (fr) |
JP (1) | JP2013517196A (fr) |
CN (2) | CN102712517A (fr) |
DE (1) | DE102010004741B4 (fr) |
ES (1) | ES2613500T3 (fr) |
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US20150144613A1 (en) * | 2012-06-21 | 2015-05-28 | Eurokera S.N.C. | Glass-ceramic article and manufacturing process |
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US20160068431A1 (en) * | 2013-04-18 | 2016-03-10 | Agc Glass Europe | Process for enamelling a glass sheet |
US10265726B2 (en) * | 2014-12-30 | 2019-04-23 | Seb S.A. | Method for decorating a kitchen item by mechanical treatment |
US10239782B2 (en) | 2015-02-26 | 2019-03-26 | Corning Incorporated | Method for controlling surface features on glass-ceramic articles and articles formed therefrom |
US10067267B2 (en) * | 2015-02-26 | 2018-09-04 | Schott Ag | Coated glass or glass ceramic article |
US20160252656A1 (en) * | 2015-02-26 | 2016-09-01 | Schott Ag | Coated glass or glass ceramic article |
US10473829B2 (en) | 2016-01-18 | 2019-11-12 | Corning Incorporated | Enclosures having an improved tactile surface |
US10928561B2 (en) | 2016-01-18 | 2021-02-23 | Corning Incorporated | Enclosures having an improved tactile surface |
RU2770201C1 (ru) * | 2021-07-02 | 2022-04-14 | Автономная некоммерческая организация высшего образования «Белгородский университет кооперации, экономики и права» | Способ матирования объемных изделий из стекла |
Also Published As
Publication number | Publication date |
---|---|
DE102010004741B4 (de) | 2023-02-23 |
US20120295081A1 (en) | 2012-11-22 |
US9388070B2 (en) | 2016-07-12 |
EP2523916B1 (fr) | 2017-08-23 |
EP2523915A1 (fr) | 2012-11-21 |
CN102712518A (zh) | 2012-10-03 |
EP2523915B1 (fr) | 2017-01-11 |
CN102712517A (zh) | 2012-10-03 |
WO2011085997A1 (fr) | 2011-07-21 |
CN102712518B (zh) | 2016-08-03 |
WO2011085996A1 (fr) | 2011-07-21 |
ES2613500T3 (es) | 2017-05-24 |
EP2523917A1 (fr) | 2012-11-21 |
EP2523916A1 (fr) | 2012-11-21 |
US8999445B2 (en) | 2015-04-07 |
US20150191392A1 (en) | 2015-07-09 |
WO2011085995A1 (fr) | 2011-07-21 |
DE102010004741A1 (de) | 2011-07-21 |
US20130183487A1 (en) | 2013-07-18 |
JP2013517196A (ja) | 2013-05-16 |
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