WO2012110513A1 - Procede de fabrication de feuille de verre decoree - Google Patents
Procede de fabrication de feuille de verre decoree Download PDFInfo
- Publication number
- WO2012110513A1 WO2012110513A1 PCT/EP2012/052514 EP2012052514W WO2012110513A1 WO 2012110513 A1 WO2012110513 A1 WO 2012110513A1 EP 2012052514 W EP2012052514 W EP 2012052514W WO 2012110513 A1 WO2012110513 A1 WO 2012110513A1
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- WIPO (PCT)
- Prior art keywords
- functional coating
- glass sheet
- manufacturing
- oxide
- coating
- Prior art date
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Classifications
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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
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C5/00—Processes for producing special ornamental bodies
- B44C5/04—Ornamental plaques, e.g. decorative panels, decorative veneers
- B44C5/0407—Ornamental plaques, e.g. decorative panels, decorative veneers containing glass elements
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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
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide 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
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3429—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
- C03C17/3435—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising a nitride, oxynitride, boronitride or carbonitride
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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
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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
- C03C17/3618—Coatings of type glass/inorganic compound/other inorganic layers, at least one layer being metallic
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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
- C03C17/3644—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 metal being 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
- C03C17/3657—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 having optical properties
- C03C17/366—Low-emissivity or solar control coatings
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/0041—Digital printing on surfaces other than ordinary paper
- B41M5/0047—Digital printing on surfaces other than ordinary paper by ink-jet printing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/0041—Digital printing on surfaces other than ordinary paper
- B41M5/007—Digital printing on surfaces other than ordinary paper on glass, ceramic, tiles, concrete, stones, etc.
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
- B41M7/009—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using thermal means, e.g. infrared radiation, heat
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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
- C03C2217/78—Coatings specially designed to be durable, e.g. scratch-resistant
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/15—Deposition methods from the vapour phase
- C03C2218/154—Deposition methods from the vapour phase by sputtering
- C03C2218/156—Deposition methods from the vapour phase by sputtering by magnetron sputtering
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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
Definitions
- the field of the invention is that of processes for manufacturing decorated glass sheet coated with a functional coating conferring low emissive, antisolar, protective or electrical conductivity properties. More specifically, the invention relates to a method of manufacturing decorated glass sheet coated with a functional coating conferring low emissivity or antisolar properties, the functional coating being deposited on said face of the glass sheet provided with the decorative pattern and covering at less partially said decorative pattern.
- the decorated glass sheet When the decorated glass sheet is intended to be used as a facade element of a building, it is essential that in addition to its decorative function, the glass sheet has an energy function.
- energy function By the term “energy function” is meant the fact that the decorated glass sheet also reduces the heat exchange on both sides thereof. The reduction of the heat exchange through the decorated glass sheet is obtained by depositing a low emissive or antisolar coating.
- the functional coating must not, by its position, alter the color of the pattern, in other words the color of the pattern seen through the glass sheet should not be influenced by the functional coating.
- the low emissive or sunscreen coating may be disposed between the glass sheet and the decorative pattern or above said decorative pattern.
- Such a process requires, necessarily, the preliminary dimensioning of the glass sheet before any printing of the decorative pattern. This prior cutting operation induces less flexibility of the process. Furthermore, the deposition of the functional coating is carried out by pyrolysis, which excludes the possibility of using low-emissive or sunscreen functional coatings based on metallic silver obtained by sputtering magnetron type.
- an object of the invention in at least one of its embodiments, is to provide a method of manufacturing decorated glass sheet coated with a functional coating, said method having a greater flexibility.
- Another objective of the invention in at least one of its embodiments, is to implement a method making it possible to work on large format glass sheets of PLF or DLF format that can be cut to size. thereafter.
- the invention in at least one of its embodiments, is also intended to provide a method for obtaining a decorated glass sheet covered with a functional coating conferring low emissive or antisolar properties or coated with a protective coating based on oxide or nitride or covered with an electrically conductive coating based on at least one doped oxide, said sheet having a pleasing aesthetic in that the appearance of the decorative pattern is not impaired by the deposition of said functional coating.
- the invention relates to a method of manufacturing a decorated glass sheet covered with a functional coating comprising the following successive steps:
- such a method also comprises magnetron sputtering deposition of the functional coating at least partially covering said decorative pattern.
- the general principle of the invention is based on the magnetron sputtering deposition of the functional coating on at least a portion of the decorative pattern after printing and drying said pattern.
- the invention is based on a completely new and inventive approach.
- the inventors have in fact determined that, surprisingly, it is possible to deposit a functional coating by magnetron cathode sputtering after a simple drying of the printed decorative pattern without having a degradation of said pattern by degassing during the evacuation of the installation of sputtering and thus a contamination of said installation.
- drying is meant a heat treatment process whose conditions in terms of temperatures and processing time are lower than those used in the context of the baking of said pattern.
- the inventors have also surprisingly determined that a functional coating obtained by cathodic sputtering, although having a much thinner thickness than the coatings obtained by pyrolysis, do not present a discontinuity problem at the "step". created by the difference in level between the surface of the glass sheet and the surface of the printed decorative pattern, this discontinuity of the functional coating being revealed by the presence of halos.
- the invention thus makes it possible to provide a process for manufacturing decorated glass sheet covered with a functional coating that offers greater flexibility in the logistics of the glasses produced. Indeed, different decorations can be united on the same glass sheet, said sheet being transported to a final transformer which can subsequently cut and die. In addition, the aesthetics of the decorated glass sheet is retained after the deposition of the functional coating.
- glass sheet is meant an inorganic glass sheet. Glass can belong to various categories.
- the glass may be a soda-lime type glass, a boron glass, an aluminosilicate glass, a glass comprising one or more additives homogeneously distributed in its mass, such as, for example, at least one inorganic dye, an oxidizing compound, a viscosity regulating agent and / or a melt facilitating agent.
- the glass is of the soda-lime type.
- the glass of the invention may be a float glass, a drawn glass or a textured glass. It can be clear, extra-clear, sandblasted and / or matte.
- sida-lime glass is used here in its broad sense and refers to any glass that contains the following basic components (expressed as percentages by total weight of glass):
- Extraclear glass means a glass whose composition comprises less than 0.06% by weight of total iron, expressed in the form of Fe 2 O 3 , and preferably less than 0.02% by weight of total iron, expressed in the form of Fe 2 O 3 .
- glass sheet is also meant a glass sheet with a thickness of at least 0.5 mm and at most 20.0 mm, preferably at least 4.0 mm and at most 10.0 mm.
- the term "decorative pattern” denotes a single pattern or a plurality of disjoint, juxtaposed or superimposed patterns. When there is a plurality of patterns, these may be of the same shape or of different shapes.
- the pattern (s) can be of simple geometrical shape (round, quadrilateral, polygons, ...) or complex (drawings, logo, lettering, label, ).
- the decorative motif can be a single color (white, black, blue, red, green, ...) or multicolored.
- said decorative pattern may be opaque or translucent.
- the thickness of the decorative pattern may be less than or equal to 30 ⁇ , preferably less than or equal to 15 ⁇ .
- the printing composition of said decorative pattern is enamel-based, which is incorporated in a ceramic toner, a ceramic ink or a ceramic paste.
- enamel is meant a vitreous substance composed in particular of silica, feldspar, kaolin and metal oxides.
- the drying conditions of the printed decorative pattern depend on the nature of the printing composition. The role of drying is the elimination of organic compounds that may, on the one hand, contaminate the magnetron sputtering system during the operation of deposition of the functional coating and, on the other hand, degassing during the subsequent phase of cooking. quenching with the effect of deterioration of the functional coating. These compounds correspond to the organic matrix in which the enamels are incorporated.
- this matrix is more or less liquid and the drying makes it possible to stiffen and fix the enamel on the glass.
- the matrix is solid and the role of the drying is also to stiffen and fix the toner on the glass after application thereof, to avoid dispersion of the powder constituting said toner in the magnetron sputtering system. Drying conditions will depend on the type of print composition of the pattern chosen decorative (ink, paste or ceramic toner).
- a decorative pattern having a ceramic paste or ceramic toner printing composition requires drying at a temperature of at least 500 ° C, preferably at least 550 ° C, the duration of this treatment being conditioned by the thickness of the glass sheet on which the enamel-based printing composition incorporated in a ceramic toner or ceramic paste is applied.
- This drying time is in the time range of from 40 to 90 seconds per millimeter of thickness of the glass sheet, preferably this drying time is equal to 60 seconds per millimeter of thickness of the glass sheet.
- an ink then requires drying at a temperature of at least 150 ° C. for a time of at least 320 seconds.
- the inventors have also determined that the drying is carried out when at least 90%, preferably at least 95% of the organic materials which constitute the printing composition are evaporated, whatever the nature of this composition: toner, paste or ceramic ink.
- This evaporation rate is measured by a standard measurement of thermogravimetry, a technique known to those skilled in the art, which also makes it possible to precisely determine the temperature necessary to evaporate the amount of organic required.
- the drying step also conditions the enamel-based printing composition of the decorative pattern used: ceramic toner, ceramic ink or ceramic paste.
- printing compositions comprising organic solvents evaporating at a temperature of less than or equal to 300 ° C. are preferred.
- ceramic inks more particularly the ceramic inks used by the "Dip Tech" ink jet printer, are preferred.
- the use of enamel-based printing composition comprising solvents with higher evaporation temperatures is not excluded, these enamels requiring drying temperatures of at least 500 ° C., preferably from minus 550 ° C.
- a size cut of the decorated glass sheet is performed, directly or not, after the deposition of the functional coating.
- the invention makes it possible to work large sheets of glass that can have a format of the type PLF (Full Width of Sheet) or DLF (Half Width of Sheet)
- a heat treatment of the decorated glass sheet is carried out, directly or not, after the deposition of the functional coating, said heat treatment corresponding to a baking of the enamel-based printing composition of the pattern decorative.
- This firing has the effect of solidifying the decorative pattern by sintering or sintering and it also allows to remove any organic compounds remaining after drying.
- Sintering or sintering is understood to denote a process which evolves by heat treatment a system consisting of individual particles (or a porous agglomerate), in the absence of external pressure exerted or under the effect of such pressure, so that this evolution leads to a significant (if not complete) decrease in the initial porosity.
- the firing temperatures of the enamel-based printing compositions are generally in the range of 650 ° C to 700 ° C.
- the heat treatment corresponds to a quenching heat treatment of the decorated glass sheet when said sheet is intended to be a glass to be quenched.
- the temperatures necessary to effect the thermal quenching of the glass sheet are at most of the order of 700 ° C. These temperatures are preferably at most of the order of 690 ° C., more preferably at most of the order of 670 ° C.
- the heat treatment of the decorated glass sheet corresponds to a bending thermal treatment of said glass sheet.
- the temperatures necessary to effect the thermal bending of the glass sheet are at least greater than 605 ° C.
- the heat treatment corresponds to a bending heat treatment followed by a quenching heat treatment.
- the printing of the decorative pattern is performed by at least one of the printing means selected from the screen printing, the laser printer or the ink jet printer.
- the printing means such as the laser printer or the ink jet printer are preferred.
- digital printing or digital printing means make it possible to include in the drawing the targets for a subsequent cutting without the process becoming complex.
- serigraphy is advantageously used.
- the manufacturing method according to the invention is such that the functional coating is a low emissive, sunscreen, protective and / or electrical conductive coating based on at least one doped oxide.
- functional coating is meant any type of coating.
- coating in the sense of the present invention, it is meant that said coating may consist of a layer of single material or a plurality of layers each of a different material.
- the functional coating may thus be a protective coating having, for example, sufficient durability to withstand transport, an electrically conductive coating based on at least one doped oxide, preferably selected from tin-doped indium oxide, zinc oxide doped by at least a doping element selected from aluminum, gallium or their mixture and / or a coating of low emissive or antisolar type.
- an electrically conductive coating based on at least one doped oxide, preferably selected from tin-doped indium oxide, zinc oxide doped by at least a doping element selected from aluminum, gallium or their mixture and / or a coating of low emissive or antisolar type.
- the functional coating is of low emissivity type
- said coating comprises a layer based on silver, preferably a single layer of silver.
- the functional coating is of the antisolar type
- said coating comprises at least one silver-based layer, preferably at least two silver-based layers and / or said antisolar coating comprises at least one oxide-based layer.
- At least one element selected from titanium, zirconium, tin or mixed oxides of at least two of them, preferably the titanium zirconium mixed oxide and / or a nitride-based layer of at least one selected from the group consisting of silicon and aluminum, the products sold under the name "Stopsol Phoenix" by the company AGC and / or said functional coating comprise at least one layer based on an example of a non-sunscreen functional coating without a silver layer; of semi-metals selected from tungsten, chromium or nickel-chromium mixture, said semi-metal layer being protected on both sides by at least one oxide-based layer, preferably substantially based on titanium oxide, zirconium oxide, tin oxide or titanium zirconium or nitride-based mixed oxide, preferably based on at least one element selected from silicon, aluminum.
- the low emissivity or sunscreen functional coating comprises a silver-based layer
- the silver is present in pure form or alloyed with another metal, the pure form being preferred, said silver layer being protected by and else by at least one layer based on oxide or nitride.
- the other metal preferably comprises at least palladium and / or gold, more preferably palladium.
- the functional coating is a low-emissive or sunscreen functional coating comprising at least one silver-based layer
- said coating also comprises a set of dielectric layers disposed on either side of said silver-based layer.
- the silver layer has a geometric thickness of at least 5.0 nm, preferably at least 9.0 nm.
- the silver layer has a geometric thickness of at most 25.0 nm, preferably at most 18.0 nm, more preferably at most 14.0 nm. Most preferably, the silver layer has a thickness equal to 12.5 nm.
- the low emissive or antisolar coating may comprise several silver-based layers, said layers being separated by dielectric layers making the decorated glass sheet covered with a functional coating according to the antireflective invention in part of the spectrum of solar radiation, especially without the visible range of lengths.
- An example of a sunscreen functional coating is the products marketed under the name of "Stopray" by AGC and as an example of low-emitting coating products marketed under the term "TopN, TopN +, TopN + T" by the same company.
- the manufacturing method according to the invention is such that the functional coating is a functional protective coating comprising at least one oxide of an element selected from titanium, zirconium, vanadium, niobium, tantalum, aluminum, zinc, silicon, tin, bismuth, indium, mixtures of two or more of them, or mixed oxides of at least two of them and / or a nitride of an element selected from titanium, zirconium, aluminum, silicon or mixtures of at least two of them or the mixed nitrides of at least two of them.
- a functional protective coating comprising at least one oxide of an element selected from titanium, zirconium, vanadium, niobium, tantalum, aluminum, zinc, silicon, tin, bismuth, indium, mixtures of two or more of them, or mixed oxides of at least two of them and / or a nitride of an element selected from titanium, zirconium, aluminum, silicon or mixtures of at least two of them or the mixed nitri
- the protective coating is a coating based on silicon nitride and / or based on titanium oxide, said titanium oxide being associated with at least one other oxide of high hardness selected from the group comprising niobium oxide, silicon oxide, chromium oxide, zirconium oxide, preferably selected from the group consisting of silicon oxide, chromium oxide, zirconium oxide.
- the respective proportions of titanium oxide and other oxides can cover a wide range.
- the additional oxide (s) must represent at least 5% by weight of the assembly and preferably at least 10%.
- titanium oxide represents at least 50% by weight, preferably at least 55% by weight of the mixed oxide.
- zirconium oxide is particularly preferred because of its very high hardness. It is advantageously present in a proportion of 15 to 50% by weight of the protective layer.
- the protective layer may also contain additional oxides substantially indissociable with the preceding oxides. This is particularly the case for lanthanides such as yttrium oxide or hafnium oxide. When these additional oxides are present, their content remains relatively limited and does not exceed 8% by weight of the whole and most often remains less than 5%.
- the manufacturing method according to the invention is such that the functional coating is a low emissive or antisolar type coating comprising at least one silver-based layer, said coating also comprises a set of layers. dielectrics arranged on either side of said silver-based layer.
- the manufacturing method according to the invention is such that the low emissive or sunscreen functional coating comprises at least one physical protection means.
- physical protection is meant to designate a protection against mechanical wear, by friction, with the claw, ... Since the magnetron sputtering layers are so-called soft layers, it is necessary to protect them against any physical deterioration.
- the protection means include, for example, a plastic sheet, a magnetron layer of high hardness such as a titanium zirconium mixed oxide layer, a carbon layer, said physical protection means being deposited on the low emissive functional coating or sunscreen.
- the manufacturing method according to the invention is such that the low emissive or sunscreen functional coating comprising a silver-based layer also comprises at least one means. for chemically protecting said silver layer.
- chemical protection is intended to denote protection against any phenomenon of chemical degradation of silver (oxidation, diffusion of alkaline ions from the glass sheet, diffusion of silver during quenching heat treatment) .
- these means for example:
- At least one barrier layer said barrier layer being, with respect to the glass sheet, the first layer constituting the low emissive or antisolar functional coating.
- the material constituting the barrier layer being selected from titanium oxide, zinc oxide, silicon nitride, silicon oxynitride, silicon oxycarbide, silicon oxycarbonitride, aluminum nitride, aluminum oxynitride, aluminum oxide, this barrier layer being optionally doped or alloyed with tin.
- the barrier layer has a geometric thickness of at least 3.0 nm, preferably at least 10.0 nm, more preferably at least 30.0 nm, even more preferably at least 50.0 nm.
- the barrier layer has a thickness of at most 100 nm.
- At least one sacrificial layer the sacrificial layer being located on at least one face of the silver-based layer.
- sacrificial layer is meant a layer that can be oxidized in whole or in part. This layer makes it possible to avoid deterioration of the silver layer, in particular by oxidation.
- the sacrificial layer comprises at least one compound chosen from metals, nitrides, oxides and sub-stoichiometric oxygen oxides.
- the metals, nitrides, oxides and sub-stoichiometric metal oxides comprise at least one element selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn, Al.
- the sacrificial layer comprises at least Ti, TiO x (with x 2 2), NiCr.
- the thickness of the layer sacrificial is at least 0.5 nm.
- the thickness of the sacrificial layer is at most 6.0 nm. More preferably, the thickness is equal to 2.5 nm.
- a sacrificial layer is deposited on the face of the silver-based layer layer furthest from the glass sheet.
- the manufacturing method according to the invention is such that the low emissive or antisolar functional coating comprising a silver-based layer comprises a barrier layer comprising at least one compound selected from silicon nitride , silicon oxynitride, aluminum nitride, aluminum oxynitride, aluminum oxide, preferably the barrier layer is made of silicon oxide. Said layer blocking the diffusion of silver when the decorated glass sheet coated with said layer is subjected to a quenching heat treatment.
- the manufacturing method according to the invention is such that a base layer is deposited on the glass sheet prior to application by printing at least one decorative pattern on at least a portion one side of the glass sheet.
- Said primer comprises at least one compound selected from titanium oxide, zirconium oxide, niobium oxide, zinc oxide, tin oxide, mixed oxides of at least two of them, silicon nitride, silicon oxynitride, silicon oxycarbide, silicon oxycarbonitride, aluminum nitride, aluminum oxynitride, aluminum oxide, this layer bottom being optionally doped or alloyed with tin.
- the materials constituting the base layer may also contain of the order of 10% or even 15% atomic percentage of additional elements such as silicon.
- the primer layer has a geometric thickness of at least 10.0 nm, preferably at least 30.0 nm, even more preferably at least 50.0 nm.
- the bottom layer has a thickness of at most 100 nm.
- the basecoat comprises at least one compound selected silicon nitride, silicon oxynitride, aluminum nitride, aluminum oxynitide, aluminum oxide, more preferably the bottom layer is silicon oxide.
- This primer has a dual role, on the one hand, it also acts as a barrier to diffusion through the enamel, money coming from the functional coating comprising a silver layer and secondly, it generally allows for better enamel membership.
- a low emissivity or sunscreen functional coating comprising a silver-based layer poses a problem of diffusion of the silver through the enamel during the quenching heat treatment, resulting in a yellowing, or a browning, of the glass sheet and therefore the glass sheet coated with the decorative pattern.
- the manufacturing method according to the invention is such that the printing composition of the enamel-based decorative pattern contains elements that block the diffusion of silver when the functional coating is a coating.
- Low emissive or sunscreen comprising a silver-based layer.
- the emulsion advantageously contains zinc oxide in an amount of 15 to 70% by weight, silicon dioxide in an amount of 15 to 40% by weight, boron trioxide in an amount of 5 to 25% by weight and from 0.05% to 15% mole% sulfur and / or sulfides, preferably zinc sulfide, said sulfides being dissociated at least in part.
- the method according to the invention comprises following the steps of applying by printing at least one decorative pattern on at least a part of a face of the glass sheet, drying of the printed decorative pattern, deposition by magnetron sputtering of the functional coating, the following successive additional steps: transport to ariosdier or "processor", storage, cutting to size of the glass sheet, quenching cut sheets.
- ariosdier or processor mean a person implementing a at least steps of storage, cutting to size of the glass sheet, quenching of the cut sheets
- Another object of the invention relates to a decorated glass sheet covered with a functional coating obtained using the manufacturing method according to the invention.
- the invention also relates to the use of a decorated glass sheet covered with the functional coating obtained by a manufacturing method according to the invention as a facade element and a facade comprising at least one decorated glass sheet. covered with a functional coating obtained according to a manufacturing method according to the invention.
- Other uses of this type of decorated glass sheet covered with a functional coating obtained by a manufacturing method according to the invention are however possible, for example we can mention the products that make it possible to reduce heat transfer or heat transfer.
- FIG. 1 schematically represents the various steps of a preferred embodiment of the method of manufacturing a decorated glass sheet covered with a functional coating according to the invention comprising successively the steps of application by printing of the minus a decorative pattern on at least a portion of a face of the glass sheet (1), drying of the printed decorative pattern (2), magnetron sputtering deposition of the functional coating (3), transport to a facade or "processor” (4) , storage (5), size cutting of the glass sheet (6), quenching of the cut sheets (7).
- Fig. 2 shows an example of a decorated glass sheet structure covered with a functional coating comprising the glass sheet (1), a decorative pattern (2) and a functional coating (3).
- Example 1 A 30x40 cm sample is cut from a glass sheet covered with a SiO 2 layer 30 nm thick. It is washed and printed on this sample 6 squares of different colors using a "Dip tech" ink jet printer. The ink used is a ceramic ink marketed by the supplier of the machine. Once printed, the sample passes into a dryer. The length of the dryer is 8 m, its speed is 1.5 m / min and its set temperature is 150 ° C. The sample then passes into the coater where a "double silver” sunscreen coating, marketed under the name “Stopray” coating by AGC, is applied. The sample thus produced is transported to the quenching plant where it is quenched according to the usual conditions for quenching a glass covered with an antisolar coating.
- a "double silver” sunscreen coating marketed under the name “Stopray” coating by AGC
- a 30x30 cm sample is cut from a 6mm thick glass sheet. He is lapped and washed. A black 5 cm edge is printed on this sample by serigraphy, which ends with a marie-louise towards the inside of the glass and the logo of a car make.
- the paste used is a ceramic paste marketed by the Jonhson Matthey company and including agents blocking the dissemination of money.
- the sample passes into a dryer. In this case the drying temperature is 550 ° C and the drying time is 360s.
- the sample then passes into the coater where a low-emissive "silver single" type coating marketed under the name "TopN + T" coating by AGC is applied.
- the sample thus produced is transported to the quenching plant where it is quenched according to the usual conditions for tempering a glass covered with a low emissive coating.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2012800089349A CN103391904A (zh) | 2011-02-15 | 2012-02-14 | 用于制造装饰玻璃片材的方法 |
EA201391177A EA201391177A1 (ru) | 2011-02-15 | 2012-02-14 | Способ производства листа декорированного стекла |
BR112013020834A BR112013020834A2 (pt) | 2011-02-15 | 2012-02-14 | método para fabricação de uma folha de vidro de decorado |
EP12703556.6A EP2675761A1 (fr) | 2011-02-15 | 2012-02-14 | Procede de fabrication de feuille de verre decoree |
US13/985,730 US20130323477A1 (en) | 2011-02-15 | 2012-02-14 | Method for manufacturing a decorated glass sheet |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BE2011/0098A BE1020114A3 (fr) | 2011-02-15 | 2011-02-15 | Procede de fabrication de feuille de verre decoree. |
BEBE2011/0098 | 2011-02-15 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012110513A1 true WO2012110513A1 (fr) | 2012-08-23 |
Family
ID=45581904
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2012/052514 WO2012110513A1 (fr) | 2011-02-15 | 2012-02-14 | Procede de fabrication de feuille de verre decoree |
Country Status (7)
Country | Link |
---|---|
US (1) | US20130323477A1 (fr) |
EP (1) | EP2675761A1 (fr) |
CN (1) | CN103391904A (fr) |
BE (1) | BE1020114A3 (fr) |
BR (1) | BR112013020834A2 (fr) |
EA (1) | EA201391177A1 (fr) |
WO (1) | WO2012110513A1 (fr) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8993104B2 (en) | 2013-03-12 | 2015-03-31 | Guardian Industries Corp. | Method of making a coated article and/or glazing for automobiles and/or the like |
US9499435B2 (en) | 2013-06-17 | 2016-11-22 | Guardian Industries Corp. | Heat treatable article with screen and/or inkjet printed coating thereon, and/or method of making the same |
US9499433B2 (en) | 2013-06-17 | 2016-11-22 | Guardian Industries Corp. | Heat treatable article with printed coating thereon, and/or method of making the same |
US9567258B2 (en) | 2013-03-12 | 2017-02-14 | Guardian Industries Corp. | Picture frame with glass mat, and/or method of making the same |
IT201900009783A1 (it) * | 2019-06-21 | 2020-12-21 | Omni Decor S R L | Lastra di vetro decorato e suo metodo di fabbricazione |
CN112573808A (zh) * | 2020-12-24 | 2021-03-30 | 宝丰大博瓷画文化创意有限公司 | 一种无龙骨超薄墙板的制作方法 |
WO2021254766A1 (fr) | 2020-06-18 | 2021-12-23 | Saint-Gobain Glass France | Procédé de fabrication d'une vitre de véhicule incurvée et revêtue comportant un revêtement supérieur opaque et un revêtement transparent |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
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CN104843978A (zh) * | 2015-02-10 | 2015-08-19 | 江苏繁华玻璃股份有限公司 | 一种小曲率半径玻璃制品的生产工艺 |
CN106995282B (zh) * | 2017-04-28 | 2020-06-05 | 江苏秀强玻璃工艺股份有限公司 | 金属质感的金黄色图案印刷装饰玻璃及其制备方法 |
BR112020007193A2 (pt) | 2017-11-30 | 2020-09-29 | Saint-Gobain Glass France | método para produzir um painel revestido impresso |
DE102018109102A1 (de) * | 2018-04-17 | 2019-10-17 | Schott Ag | Bedruckte Gerätekomponente |
CN109734328A (zh) * | 2018-11-30 | 2019-05-10 | 江苏福坤玻璃有限公司 | 一种低辐射镀膜中空玻璃的制备方法 |
KR102602111B1 (ko) * | 2019-04-24 | 2023-11-13 | 쌩-고벵 글래스 프랑스 | 유리 프릿, 이로부터 형성된 흑색 에나멜 코팅을 포함하는 코팅 물품, 및 코팅 물품의 제조 방법 |
DE102021110208A1 (de) * | 2020-04-28 | 2021-10-28 | Schott Ag | Abdeckplatte, Verfahren zu deren Herstellung sowie deren Verwendung |
FR3117106B1 (fr) * | 2020-12-07 | 2023-08-25 | Saint Gobain | Procédé d’obtention de vitrages munis d’un revêtement d’émail et de motifs électroconducteurs |
US11926112B1 (en) | 2022-11-01 | 2024-03-12 | Shay Alsaid LLC | Tattoo artist practice tool system, method and article |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB822842A (en) * | 1956-02-16 | 1959-11-04 | Manufacturers Des Glaces Et Pr | Improvements relating to the manufacture of metal coated enamelled tempered glass sheets |
DE202004012958U1 (de) * | 2004-08-18 | 2004-11-11 | Schott Ag | Dekorblende mit metallischer Anmutung |
FR2878844A1 (fr) * | 2004-12-06 | 2006-06-09 | Saint Gobain | Structure decoree et a couche |
FR2889182A1 (fr) * | 2005-07-29 | 2007-02-02 | Saint Gobain | Vitrage muni d'un empilement de couches minces agissant sur le rayonnement solaire |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2652037B1 (fr) * | 1989-09-18 | 1992-04-03 | Saint Gobain Vitrage Int | Vitrage feuillete chauffant. |
DE19718303C1 (de) * | 1997-04-30 | 1998-07-16 | Ver Glaswerke Gmbh | Verfahren zum Herstellen einer mit einem farbigen Bild oder Dekor versehenen Glasscheibe |
FR2829723B1 (fr) * | 2001-09-14 | 2004-02-20 | Saint Gobain | Vitrage de securite fonctionnalise |
FR2835205B1 (fr) * | 2002-01-25 | 2007-02-16 | Saint Gobain | Traitement de pollution organique sur un substrat inorganique |
FR2852553B1 (fr) * | 2003-03-21 | 2005-06-17 | Saint Gobain | Procede pour deposer des films fonctionnels sur des substrats tels que des plaques de verres, et machine de pelliculage pour la mise en oeuvre de ce procede |
-
2011
- 2011-02-15 BE BE2011/0098A patent/BE1020114A3/fr not_active IP Right Cessation
-
2012
- 2012-02-14 EP EP12703556.6A patent/EP2675761A1/fr not_active Withdrawn
- 2012-02-14 WO PCT/EP2012/052514 patent/WO2012110513A1/fr active Application Filing
- 2012-02-14 CN CN2012800089349A patent/CN103391904A/zh active Pending
- 2012-02-14 US US13/985,730 patent/US20130323477A1/en not_active Abandoned
- 2012-02-14 EA EA201391177A patent/EA201391177A1/ru unknown
- 2012-02-14 BR BR112013020834A patent/BR112013020834A2/pt active Search and Examination
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB822842A (en) * | 1956-02-16 | 1959-11-04 | Manufacturers Des Glaces Et Pr | Improvements relating to the manufacture of metal coated enamelled tempered glass sheets |
DE202004012958U1 (de) * | 2004-08-18 | 2004-11-11 | Schott Ag | Dekorblende mit metallischer Anmutung |
FR2878844A1 (fr) * | 2004-12-06 | 2006-06-09 | Saint Gobain | Structure decoree et a couche |
WO2006061541A2 (fr) | 2004-12-06 | 2006-06-15 | Saint-Gobain Glass France | Structure decoree et a couche et sa fabrication |
FR2889182A1 (fr) * | 2005-07-29 | 2007-02-02 | Saint Gobain | Vitrage muni d'un empilement de couches minces agissant sur le rayonnement solaire |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8993104B2 (en) | 2013-03-12 | 2015-03-31 | Guardian Industries Corp. | Method of making a coated article and/or glazing for automobiles and/or the like |
US9567258B2 (en) | 2013-03-12 | 2017-02-14 | Guardian Industries Corp. | Picture frame with glass mat, and/or method of making the same |
US9499435B2 (en) | 2013-06-17 | 2016-11-22 | Guardian Industries Corp. | Heat treatable article with screen and/or inkjet printed coating thereon, and/or method of making the same |
US9499433B2 (en) | 2013-06-17 | 2016-11-22 | Guardian Industries Corp. | Heat treatable article with printed coating thereon, and/or method of making the same |
IT201900009783A1 (it) * | 2019-06-21 | 2020-12-21 | Omni Decor S R L | Lastra di vetro decorato e suo metodo di fabbricazione |
WO2020255068A1 (fr) * | 2019-06-21 | 2020-12-24 | Omni Decor S.R.L. | Feuille de verre décorée et son procédé de fabrication |
WO2021254766A1 (fr) | 2020-06-18 | 2021-12-23 | Saint-Gobain Glass France | Procédé de fabrication d'une vitre de véhicule incurvée et revêtue comportant un revêtement supérieur opaque et un revêtement transparent |
CN112573808A (zh) * | 2020-12-24 | 2021-03-30 | 宝丰大博瓷画文化创意有限公司 | 一种无龙骨超薄墙板的制作方法 |
Also Published As
Publication number | Publication date |
---|---|
US20130323477A1 (en) | 2013-12-05 |
EP2675761A1 (fr) | 2013-12-25 |
CN103391904A (zh) | 2013-11-13 |
BE1020114A3 (fr) | 2013-05-07 |
BR112013020834A2 (pt) | 2016-10-04 |
EA201391177A1 (ru) | 2014-02-28 |
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