WO2021185614A1 - Method for obtaining an enamelled panel - Google Patents

Method for obtaining an enamelled panel Download PDF

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Publication number
WO2021185614A1
WO2021185614A1 PCT/EP2021/055780 EP2021055780W WO2021185614A1 WO 2021185614 A1 WO2021185614 A1 WO 2021185614A1 EP 2021055780 W EP2021055780 W EP 2021055780W WO 2021185614 A1 WO2021185614 A1 WO 2021185614A1
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WO
WIPO (PCT)
Prior art keywords
enamel
miti
panel
acid
layer
Prior art date
Application number
PCT/EP2021/055780
Other languages
French (fr)
Inventor
Matthieu GSELL
Benoit Kolheb
Original Assignee
Schott Vtf
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Schott Vtf filed Critical Schott Vtf
Publication of WO2021185614A1 publication Critical patent/WO2021185614A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/001—General methods for coating; Devices therefor
    • C03C17/002—General methods for coating; Devices therefor for flat glass, e.g. float glass
    • 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
    • C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
    • C—CHEMISTRY; METALLURGY
    • 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
    • C03C17/02—Surface treatment of glass, not in the form of fibres or filaments, by coating with glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
    • C03C2217/44—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the composition of the continuous phase
    • C03C2217/45—Inorganic continuous phases
    • C03C2217/452—Glass
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to a method of obtaining an enamel panel having a silky feel and a matt appearance, to such a panel, and to its use for making a decorative panel for household appliances.
  • Such panels are generally obtained by depositing, on the glass support, an opaque and colored enamel composition, in the form of a paste, which is then vitrified by the action of heat.
  • the enamel panel can be either a matte appearance and a rough feel, the upper surface of the enamel coating comprising asperities or surface irregularities, or a shiny appearance and a smooth feel. , in this case the upper surface substantially does not include any roughness.
  • Document WO2016 / 008752 describes a decorative glass panel for household appliances, one or both sides of which are covered with a coating based on glass powder and glass particles, vitroceramics or ceramics, which are spherical, and which protrude from the coating, the panel having non-stick properties and a shiny appearance.
  • the coating has a thickness of 0.5 to 5 miti and has a profilometric roughness, in which the difference in height, between the highest point of the protruding particle and the lowest between two particles, is between 3 and 35. miti.
  • the panel is obtained by heating the coating composition to a powder softening temperature of glass, which is lower than the melting temperature of the spherical particles, namely between 500 and 1000 ° C.
  • Document EP 2 592 056 describes a glass panel covered with a coating of 1 to 50 miti thick, having a velvety or rough feel, the coating comprising protruding glass particles, and has a profilometric roughness , wherein the average height difference between the lowest point between two particles and the highest point on one of the particles is between 4 and 10 miti.
  • the coating is obtained by covering, by screen printing, a glass substrate with a paste based on a glass frit and glass particles, by drying the composition, then by vitrifying it at a temperature between 400 and 1000 ° vs.
  • an enamel panel having both a matte visual appearance, with a sensation under the fingers, a touch, which is silky or satin.
  • the present invention aims to provide a method of manufacturing an enamel panel, an enamel panel, and a method of producing a decorative panel for household appliances, which does not have the drawbacks of the state of the art .
  • the present invention aims to provide an alternative to existing state of the art solutions.
  • the present invention aims to provide a method of obtaining an enameled panel, having a matte visual appearance and a silky or satin feel.
  • the present invention relates to a method of making an enamel panel having a silky feel and a matt appearance, comprising the steps of taking a rigid support comprising at least one surface, of taking or preparing at least one composition of enamel comprising a vitrifiable material and silica particles, to deposit the enamel composition on all or part of the at least one surface of the support, to form an enamel layer, having an upper face from which the silica particles protrude, forming a surface roughness made of bumps and pits, to dry the enamel layer, vitrify the enamel layer by the action of heat, then chemically resurfacing the surface top of the enamel layer.
  • the method of making the panel according to the invention comprises at least one, or any suitable combination, of the following characteristics:
  • the chemical surfacing step is carried out by the action of an acid
  • the chemical surfacing step is carried out using sulfamic acid, formic acid, citric acid, acetic acid, benzene sulfonic acid, phosphoric acid, or a mixture thereof,
  • the chemical surfacing step is carried out at room temperature for one to ten minutes
  • the step of vitrification of the enamel layer is carried out at a temperature between 650 ° C and 750 ° C, for a period of between six seconds and five minutes, followed by a cooling step, lasting between thirty seconds and five minutes, in which the temperature rises from 650 ° C to 60 ° C,
  • the thickness of the enamel layer (5), after the vitrification step, is between 3 and 10 miti
  • the surface roughness, after the vitrification step has a height value Sz, between the top of the highest bump and the deepest hollow, between 12 miti and 18 miti
  • the surface roughness, after the vitrification step has a root mean square height value Sq, between 660 and 990 nm
  • the enamel composition comprises silica particles having a size in three dimensions between 0.9 miti and 50 miti,
  • the enamel composition comprises a mattifying agent chosen from wollastonite (CaSi0 3 ), zirconium dioxide, calcined alumina, feldspar, and their mixture,
  • the support comprises two surfaces, and comprises a step of depositing the enamel composition on all or part of the two surfaces, or a step of taking or preparing several enamel compositions and a step of depositing the compositions on all or part of one or both surfaces, in order to form an enamel layer, continuous or discontinuous.
  • the present invention relates to an enameled panel obtained by the method according to the invention, comprising at least one surface, covered with a layer of enamel, based on a composition of a vitrifiable material and particles of silicas, having a thickness after vitrification of between 3 miti and 10 miti, and comprising an upper face, from which said silica particles protrude, and having a surface roughness having a height value Sz, between the top of the bump la highest and the deepest trough, which is between 12 miti and 18miti.
  • the enamel panel according to the invention may have a surface roughness, the root mean square height value Sq, which is between 660 and 990 nm.
  • the present invention also relates to a method of producing a decorative panel for a household appliance comprising the step of taking an enamel panel according to the invention, or the step of producing an enamel panel by implementing the method according to the invention.
  • Figure 1 is a schematic representation of a cross sectional view of a panel according to the invention.
  • Figure 2 is a graph showing the change over time of the roughness of the upper face of the enamel layer of the panel according to the invention during surfacing.
  • Figure 3 is a graph showing the roughness of the upper face of the enamel layer of the panel according to the invention during 20 minutes surfacing with different acids.
  • the method of obtaining an enamel panel comprises a first step of taking, or making, a support 2, which is rigid, substantially inflexible, and which has mechanical resistance to stresses of bending and / or torsion, sufficient not to deform under the action of a bending and / or torsional force.
  • the support 2 is substantially planar, and comprises at least one first surface 3, continuous and substantially planar, preferably at least one second surface 4, continuous and substantially planar, opposite to said first surface 3 (FIG. 1).
  • the support 2 has a shape, thickness and dimensions adequate and adapted, or compatible, with the end use of the panel 1, or elements which include such a panel 1.
  • the support 2 has a cross section, vertical, in the XY plane and / or a longitudinal section, horizontal, in the plane formed by the surface 3 or the surface 4, in the XZ plane, of circular shape , elliptical, polygonal, trapezoidal or else of a quadrilateral, advantageously a rhombus, square or rectangular section.
  • the support 2 is made of an inert material, preferably at least thermally inert, advantageously also physically and chemically inert to the material (s) of which one or both of these surfaces 2 and 3 is / are covered or in contact.
  • the support 2 is made of, or comprises, plastic, glass, a crystalline or semi-crystalline material, a ceramic or a glass ceramic.
  • the support 2 is glass, preferably a screen-printing glass, advantageously a transparent soda-lime glass or tinted in the mass, optionally with various layers, such as anti-bacterial, anti reflective, for example of the type known under the trademark Matelux, chrome-plated, with low emissivity, for example of the type known under the name of Planibel Clear or of Planibel low-E IsoComfort, marketed by the company AGC, or a known borosilicate for example under the trademark Borofloat ® 33.
  • the glass has a high Si0 2 content, a content advantageously between 69% and 81% by weight and with a light transmission which can range up to 90%.
  • the glass may optionally have previously undergone a heat treatment of the hardening, annealing, tempering or bending type.
  • the support 2 is preferably transparent, or semi-transparent, but it can also be opaque, or else partially transparent, semi-transparent or opaque, or include one or more portions which are. It can be sandblasted and / or screen printed and / or colored.
  • the method comprises the step of taking or preparing at least one enamel composition, preferably several enamel compositions, and the step of depositing it or them, preferably directly, without the use of a bond layer, on the whole, part or parts, adjacent or distant, superimposed or not, of at least one surface 3 or 4 of the support 2, or on at least the two surfaces 3 and 4 of the support 2, in order to obtain at least one enamel layer 5, continuous or discontinuous, comprising at least one upper face 6.
  • compositions or of the enamel compositions, can be done by any suitable method, for example, by coating, by screen printing, by pad printing, by offset, by digital printing or by inkjet.
  • the enamel layer 5 according to the invention is based on a vitrifiable material and silica particles, particles which have the advantage of giving it a mattifying effect.
  • the vitrifiable material is any suitable material or mixture of materials, to form an enamel, preferably it is a frit or mixture of glass frits, advantageously suitable for application on a flat glass, preferably a zinc-based material, which has the advantage of giving the enamel layer 5 increased resistance to the action of bases.
  • the vitrifiable material preferably represents between 55 and 75% of the total weight of the composition, all the other components representing the amount sufficient to reach 100% by weight.
  • the silica particles have a size in three dimensions between 0.9 and 50 miti, preferably they have a size of about 10 miti. Preferably, the silica particles represent between 10 and 15% of the total weight of the composition.
  • the silica particles are also intended to make, and protrude, for at least some of them, on the upper face 6 of the enamel layer 5 ( Figure 1), to form a roughness, surface irregularities, a relief formed by bumps and hollows.
  • the roughness of a surface can be defined, in accordance with the ISO 25178 standard, by various physical measurements, such as for example the parameter "Sq”, defined as being the value of the root mean square height, namely the arithmetic mean , in absolute value, of the difference in height of each vertex with respect to the mean plane of the surface, this value Sq being able to be considered as being the equivalent of the standard deviation of the heights of the vertices of the roughness, and by the parameter "Sz”, defined as being the total height of the surface, or the sum of the value of the height of the highest peak and the depth of the deepest trough.
  • the composition of the enamel layer 5 according to the invention may comprise one or more mattifying agents, which are, or comprise, mineral powders, of micrometric size, for example between 0.9 and 60 miti, powders immiscible with the vitrifiable material used. It can be wollastonite (CaSi0 3 ), zirconium dioxide, calcined alumina or feldspar.
  • the matting agent or agents preferably represent between 10 and 15% of the total weight of the composition.
  • composition of the enamel layer 5 according to the invention further comprises one or more additives, such as for example one or more pigments, microspheres, preferably ceramic microspheres, and mixtures thereof.
  • additives such as for example one or more pigments, microspheres, preferably ceramic microspheres, and mixtures thereof.
  • the additive (s) preferably represent between 1 and 10% of the total weight of the composition.
  • the enamel layer 5 is then dried, by any suitable means.
  • the enamel layer 5 is then to be vitrified under the action of heat, during a quenching step, which is carried out by heating for example at a temperature between 650 ° C and 750 ° C, for a period of between six seconds and five minutes, preferably between two and five minutes, followed by rapid cooling, between thirty seconds and five minutes, at a temperature passing in this time lapse from 650 ° C to 60 ° C.
  • a quenching step which is carried out by heating for example at a temperature between 650 ° C and 750 ° C, for a period of between six seconds and five minutes, preferably between two and five minutes, followed by rapid cooling, between thirty seconds and five minutes, at a temperature passing in this time lapse from 650 ° C to 60 ° C.
  • the total thickness of the enamel layer (s) 5 is between 10 and 17 miti, before vitrification, and between 3 and 10 miti after vitrification.
  • This step has the advantage of smoothing the surface roughness of the enamel layer 5, of homogenizing the roughness over the entire surface of the enamel layer 5.
  • the surfacing is a chemical surfacing, advantageously an acid attack, in order to give the upper face 6 a silky feel, without however modifying the matt visual appearance.
  • silky touch is meant a sensation which is the same or similar to the touch of a silk fabric, namely a sensation of a smooth surface.
  • the acid attack is carried out by any suitable means, preferably by soaking, in an acidic aqueous solution, having a pH of between 0.5 and 1.5, the acid being chosen from l sulfamic acid, citric acid, acetic acid, benzene sulfonic acid, phosphoric acid, or a mixture thereof.
  • the surfacing using acid is carried out at room temperature, for 1 minute to 14 hours, or between 1 minute and 1 hour, or between 1 minute and 20 minutes, or between 1 minute and 10 minutes, or between 1 minute and 5 minutes, or between 1 minute and 2 minutes.
  • the surfacing is done with sulfamic acid for two minutes.
  • the upper face 6 of the enamel layer 5 according to the invention has an Sq value between 660 and 990 nm, preferably between 664 and 729 nm, or between 849 and 914 nm, and a Sz value between 12 miti and 18 miti, preferably between 12 miti and 13 miti, or between 15 miti and 17 miti.
  • the upper face 6 of the enamel layer 5 has a Gloss value, measured with a KSJ hg268-f2 gloss meter, in Gloss Unit (UB), at an angle of 60 °, between 2.5 and 3.2 BU.
  • the invention also relates to the use of the method of producing an enameled panel according to the invention to produce a decorative panel, preferably of a household appliance, which is, or forms part, for example of a control panel of a household appliance, for example, an oven, a hob.
  • the enamelled panel 1 according to the invention obtained by the method according to the invention, has a matte visual appearance and a silky feel. It comprises a support 2, of which at least one surface 3 or 4, preferably the two surfaces 3 and 4, or advantageously all of these surfaces, are covered, partially or completely, with one or more enamel compositions, in order to form a layer of enamel 5, continuous or discontinuous, conferring this matt visual appearance and this silky touch.
  • panels 1 according to the invention have been produced, comprising a support 2 made of soda-lime glass, of which only one of the two surfaces 3 and 4 has been covered with an enamel composition Zinc-based comprising, by weight relative to the total weight of the composition, 48.75% of enamel sold under the reference 104001 by the company Ferro, 1.25% of enamel sold under the reference 778110 by the company Prince Minerai Inc , 12.5% of enamel marketed under the reference 1T3015-654-63 by the company Johnson Matthey, 9% of DuoDesign additive from the company Schott AG, which comprises the medium marketed under the reference 801022 by the company Ferro, a black pigment and ceramic microspheres, marketed under the reference N1200 by the company Zeeospheres Ceramic, having a diameter of between 2.8 and 58 miti, 12.5% of silica powder marketed under the reference SS1402 by the company Industrial Powder, having sizes of partic ules between 0.9 and 8 miti, 1% of zirconium dioxide Z3
  • the thickness of the enamel layer 5 is determined by acquiring scanning electron microscopy images of the cross section of the samples, the panels 1 having been covered beforehand with a layer platinum of about 5 nm.
  • the roughness measurements of the upper face 6 of the enamel layer 5 were carried out by white light interferometry at different magnifications (5.5X and 20X), using a phase shift interferometer, marketed by the company ZYGO , comprising an interferometric objective and a precise positioning unit, a piezoelectric actuator, making it possible to move the interference objective vertically.
  • the chemical composition of the upper face 6 of the enamel layer 5 was analyzed by time-of-flight secondary ion mass spectrometry, or TOF-SIMS analysis, after decontamination of the upper face 6 of the samples and a measurement by negative polarity, and a flight time of approximately 0.4nm / s.
  • the values of Sq therefore of the average height of the peaks of the roughness, decrease from 6 to 9% between sample 1, which has not undergone chemical surfacing, and sample B, which has undergone attack acid.
  • the chemical composition of sample B, having undergone the chemical surface step comprises a chemical modification of the upper face 6 of the enamel layer 5.
  • the enamel layer 5 shows a decrease in the amount of ions: Li, B, Na, Al, K and Zn, and an increase in ions: Mg, H, C, F, Si, S, Cl, Ca and N, which indicates that ion exchange took place during the surfacing step.
  • Example 1 Other panels 1 were produced in accordance with Example 1, without chemical surfacing (sample 1) or with chemical surfacing (samples 2 to 9). The thickness of their enamel layer 5, its roughness, and the analysis of its ionic composition, were analyzed for different acids and different processing times. The results are given in Tables 2 and 3.
  • the thickness determinations of the enamel layer 5, and their roughness, are done in the same way as those described for Example 1.
  • the determination of the ionic compositions is done both by ray spectrometry.
  • EDX energy dispersive
  • time-of-flight secondary ion mass spectrometry or TOF-SIMS analysis.
  • EDX energy dispersive X-ray spectrometry
  • a panel 1 according to the invention (sample C) was produced, according to Example 1. It comprises a support 2, made of soda-lime glass, of which only one of the two surfaces 3 and 4 has been covered with a enamel composition according to Example 1 or 2. Its resistance to various organic compounds, representative of the compounds which could come into contact with the panel 1 during its use as part of a household appliance, were tested and compared to a same panel 1 not having undergone chemical surfacing (sample D).
  • Detergent 1 is marketed under the factory name AJAX ® window cleaner.
  • Detergent 2 comprises sodium alkyl benzene sulphonate, sodium carbonate of 2 (2-Butoxyethoxy) ethanol; it is marketed under the brand name Cif ® cream.
  • Detergent 3 comprises sodium hypochlorite and Amines, C12-14-alkyldimethyl, N-oxides; it is marketed under the brand name Cilit bang ® powerful cleaner with bleach.
  • Detergent 4 comprises sodium hydroxide and Ammonium hydroxide; it is marketed under the brand name Destop ® .
  • the panel 1 according to the invention has an aesthetic surface appearance which appears much less degraded than the control sample, after coming into contact with various organic acids, such as vinegar and vinegar. lemon, and as insensitive to detergents as the control sample.

Abstract

The present invention relates to a method for obtaining an enamelled panel (1) having a silky feel and a matt appearance, comprising the steps of taking a rigid support (2) comprising at least one surface (3, 4), taking or preparing at least one enamel composition comprising a vitrifiable material, and silica particles, depositing the enamel composition on all or part of said at least one surface (3, 4) of the support (2), in order to form an enamel layer (5), having an upper face (6) from which the silica particles protrude, forming a surface roughness made of bumps and recesses, drying the enamel layer (5), vitrifying the enamel layer (5) through the action of heat, and chemically surfacing the upper surface (6).

Description

METHODE D’OBTENTION D’UN PANNEAU EMAILLE METHOD OF OBTAINING AN ENAMEL PANEL
Objet de l’invention Object of the invention
[0001] La présente invention a trait à une méthode d’obtention d’un panneau émaillé possédant un touché soyeux et un aspect mat, à un tel panneau, et à son utilisation pour réaliser un panneau décoratif pour des appareils électroménagers. The present invention relates to a method of obtaining an enamel panel having a silky feel and a matt appearance, to such a panel, and to its use for making a decorative panel for household appliances.
Etat de la technique State of the art
[0002] Dans le domaine de l’électroménager, grand publique ou professionnel, il est connu d’employer des panneaux comprenant un support en verre recouvert d’un émail, pour décorer la face avant d’appareils électroménagers, ou bien comme élément d’un bandeau de commande de fonctionnement de tels appareils. In the field of household appliances, general public or professional, it is known to use panels comprising a glass support covered with an enamel, to decorate the front face of household appliances, or as an element of a control panel for the operation of such devices.
[0003] De tels panneaux sont généralement obtenus par la dépose, sur le support en verre, d’une composition d’émail opaque et colorée, sous la forme d’une pâte, qui est ensuite vitrifiée par l’action de la chaleur. [0003] Such panels are generally obtained by depositing, on the glass support, an opaque and colored enamel composition, in the form of a paste, which is then vitrified by the action of heat.
[0004] Quel que soit leur usage final, de tels panneaux émaillés décoratifs se doivent d’avoir, pour l’usager, un aspect visuel et un touché agréable. [0004] Whatever their end use, such decorative enamel panels must have, for the user, a visual appearance and a pleasant feel.
[0005] En fonction de la composition de l’émail, le panneau émaillé peut être soit un aspect mat et un touché rugueux, la surface supérieure du revêtement en émail comprenant des aspérités ou irrégularités de surface, soit un aspect brillant et un touché lisse, dans ce cas la surface supérieure ne comprend sensiblement pas d’aspérités. [0005] Depending on the composition of the enamel, the enamel panel can be either a matte appearance and a rough feel, the upper surface of the enamel coating comprising asperities or surface irregularities, or a shiny appearance and a smooth feel. , in this case the upper surface substantially does not include any roughness.
[0006] Le document WO2016/008752 décrit un panneau décoratif en verre pour appareils électroménagers, dont une ou les deux faces sont recouvertes d’un revêtement à base de poudre de verre et de particules de verre, vitrocéramiques ou céramiques, qui sont sphériques, et qui font saillies du revêtement, le panneau ayant des propriétés anti adhérentes et un aspect brillant. Le revêtement a une épaisseur de 0,5 à 5 miti et présente une rugosité profilométrique, dans laquelle la différence de hauteur, entre le point le plus haut de la particule en saillie et le plus bas entre deux particules, est comprise entre 3 et 35 miti. Le panneau est obtenu par chauffage de la composition de revêtement, à une température de ramollissement de la poudre de verre, qui est inférieure à la température de fusion des particules sphériques, à savoir entre 500 et 1000°C. [0006] Document WO2016 / 008752 describes a decorative glass panel for household appliances, one or both sides of which are covered with a coating based on glass powder and glass particles, vitroceramics or ceramics, which are spherical, and which protrude from the coating, the panel having non-stick properties and a shiny appearance. The coating has a thickness of 0.5 to 5 miti and has a profilometric roughness, in which the difference in height, between the highest point of the protruding particle and the lowest between two particles, is between 3 and 35. miti. The panel is obtained by heating the coating composition to a powder softening temperature of glass, which is lower than the melting temperature of the spherical particles, namely between 500 and 1000 ° C.
[0007] Le document EP 2 592 056 décrit un panneau en verre recouvert d’un revêtement de 1 à 50 miti d’épaisseur, ayant un touché velouté ou rugueux, le revêtement comprenant des particules de verre faisant saillie, et présente une rugosité profilométrique, dans laquelle la différence de hauteur moyenne entre le point le plus bas entre deux particules et le point le plus élevé sur l’une des particules est comprise entre 4 et 10 miti. Le revêtement est obtenu en recouvrant, par sérigraphie, un substrat en verre d’une pâte à base d’une fritte de verre et des particules de verre, en séchant la composition, puis en la vitrifiant à une température comprise entre 400 et 1000 ° C. [0007] Document EP 2 592 056 describes a glass panel covered with a coating of 1 to 50 miti thick, having a velvety or rough feel, the coating comprising protruding glass particles, and has a profilometric roughness , wherein the average height difference between the lowest point between two particles and the highest point on one of the particles is between 4 and 10 miti. The coating is obtained by covering, by screen printing, a glass substrate with a paste based on a glass frit and glass particles, by drying the composition, then by vitrifying it at a temperature between 400 and 1000 ° vs.
[0008] Toutefois, il peut être avantageux d’avoir un panneau émaillé ayant tout à la fois un aspect visuel mat, avec une sensation sous les doigts, un touché, qui soit soyeux ou satin. [0008] However, it may be advantageous to have an enamel panel having both a matte visual appearance, with a sensation under the fingers, a touch, which is silky or satin.
Buts de l’invention Aims of the invention
[0009] La présente invention vise à fournir une méthode de fabrication d’un panneau émaillé, un panneau émaillé, et une méthode de réalisation d’un panneau décoratif pour appareils électroménagers, qui ne présentent pas les inconvénients de l’état de la technique. The present invention aims to provide a method of manufacturing an enamel panel, an enamel panel, and a method of producing a decorative panel for household appliances, which does not have the drawbacks of the state of the art .
[0010] La présente invention vise à fournir une alternative aux solutions de l’état de la technique existantes. The present invention aims to provide an alternative to existing state of the art solutions.
[0011] La présente invention vise à fournir une méthode d’obtention d’un panneau émaillé, ayant un aspect visuel mat et un touché soyeux ou satin. The present invention aims to provide a method of obtaining an enameled panel, having a matte visual appearance and a silky or satin feel.
Résumé de l’invention Summary of the invention
[0012] La présente invention porte sur une méthode de réalisation d’un panneau émaillé ayant un touché soyeux et un aspect mat, comprenant les étapes de prendre un support rigide comprenant au moins une surface, de prendre ou préparer au moins une composition d’émail comprenant un matériau vitrifiable et des particules de silices, de déposer la composition d’émail sur tout ou partie de la au moins une surface du support, pour former une couche d’émail, ayant une face supérieure depuis laquelle les particules de silice font saillie, formant une rugosité de surface faite de bosses et de creux, de sécher la couche d’émail, de vitrifier la couche d’émail par l’action de la chaleur, puis de surfacer chimiquement la surface supérieure de la couche d’émail. The present invention relates to a method of making an enamel panel having a silky feel and a matt appearance, comprising the steps of taking a rigid support comprising at least one surface, of taking or preparing at least one composition of enamel comprising a vitrifiable material and silica particles, to deposit the enamel composition on all or part of the at least one surface of the support, to form an enamel layer, having an upper face from which the silica particles protrude, forming a surface roughness made of bumps and pits, to dry the enamel layer, vitrify the enamel layer by the action of heat, then chemically resurfacing the surface top of the enamel layer.
[0013] Selon des modes préférés de l’invention, la méthode de réalisation du panneau selon l’invention comprend au moins une, ou une combinaison quelconque appropriée, des caractéristiques suivantes : [0013] According to preferred embodiments of the invention, the method of making the panel according to the invention comprises at least one, or any suitable combination, of the following characteristics:
- l’étape de surfaçage chimique est mise en œuvre par l’action d’un acide, - the chemical surfacing step is carried out by the action of an acid,
- l’étape de surfaçage chimique est réalisée à l’aide d’acide sulfamique, d’acide formique, d’acide citrique, d’acide acétique, d’acide benzène sulfonique, d’acide phosphorique, ou de leur mélange, - the chemical surfacing step is carried out using sulfamic acid, formic acid, citric acid, acetic acid, benzene sulfonic acid, phosphoric acid, or a mixture thereof,
- l’étape de surfaçage chimique est réalisée à température ambiante pendant une à dix minutes, - the chemical surfacing step is carried out at room temperature for one to ten minutes,
- l’étape de vitrification de la couche d’émail est réalisée à une température comprise entre 650°C et 750°C, pendant une période comprise entre six secondes et cinq minutes, suivie par une étape de refroidissement, durant entre trente secondes et cinq minutes, dans laquelle la température passe de 650°C à 60°C, - the step of vitrification of the enamel layer is carried out at a temperature between 650 ° C and 750 ° C, for a period of between six seconds and five minutes, followed by a cooling step, lasting between thirty seconds and five minutes, in which the temperature rises from 650 ° C to 60 ° C,
- l’épaisseur de la couche d’émail (5), après l’étape de vitrification, est comprise entre 3 et 10 miti, la rugosité de surface, après l’étape de vitrification, a une valeur de hauteur Sz, entre le sommet de la bosse la plus haute et le creux le plus profond, comprise entre 12 miti et 18miti, - the thickness of the enamel layer (5), after the vitrification step, is between 3 and 10 miti, the surface roughness, after the vitrification step, has a height value Sz, between the top of the highest bump and the deepest hollow, between 12 miti and 18 miti,
- la rugosité de surface, après l’étape de vitrification, a une valeur de hauteur moyenne quadratique Sq, comprise entre 660 et 990 nm, - the surface roughness, after the vitrification step, has a root mean square height value Sq, between 660 and 990 nm,
- la composition d’émail comprend des particules de silices ayant une taille dans les trois dimensions comprise entre 0,9 miti et 50 miti, - the enamel composition comprises silica particles having a size in three dimensions between 0.9 miti and 50 miti,
- la composition d’émail comprend un agent matifiant choisi parmi la wollastonite (CaSi03), le dioxyde de zirconium, l’alumine calciné, le feldspath, et leur mélange,- the enamel composition comprises a mattifying agent chosen from wollastonite (CaSi0 3 ), zirconium dioxide, calcined alumina, feldspar, and their mixture,
- le support comprend deux surfaces, et comprend une étape de déposer la composition d’émail sur tout ou partie des deux surfaces, ou une étape de prendre ou préparer plusieurs compositions d’émail et une étape de déposer les compositions sur tout ou partie d’une ou des deux surfaces, afin de former une couche d’émail, continue ou discontinue. - the support comprises two surfaces, and comprises a step of depositing the enamel composition on all or part of the two surfaces, or a step of taking or preparing several enamel compositions and a step of depositing the compositions on all or part of one or both surfaces, in order to form an enamel layer, continuous or discontinuous.
[0014] La présente invention porte sur un panneau émaillé obtenu par la méthode selon l’invention, comprenant au moins une surface, recouverte d’une couche d’émail, à base d’une composition d’un matériau vitrifiable et des particules de silices, ayant une épaisseur après vitrification comprise entre 3 miti et 10 miti, et comprenant une face supérieure, depuis laquelle lesdites particules de silice font saillie, et ayant une rugosité de surface ayant une valeur de hauteur Sz, entre le sommet de la bosse la plus haute et le creux le plus profond, qui est comprise entre 12 miti et 18miti. The present invention relates to an enameled panel obtained by the method according to the invention, comprising at least one surface, covered with a layer of enamel, based on a composition of a vitrifiable material and particles of silicas, having a thickness after vitrification of between 3 miti and 10 miti, and comprising an upper face, from which said silica particles protrude, and having a surface roughness having a height value Sz, between the top of the bump la highest and the deepest trough, which is between 12 miti and 18miti.
[0015] Le panneau émaillé selon l’invention peut présenter une rugosité de surface dont la valeur de hauteur moyenne quadratique Sq, qui est comprise entre 660 et 990 nm. The enamel panel according to the invention may have a surface roughness, the root mean square height value Sq, which is between 660 and 990 nm.
[0016] La présente invention porte aussi sur une méthode de réalisation d’un panneau décoratif pour un appareil électroménager comprenant l’étape de prendre un panneau émaillé selon l’invention, ou l’étape de réaliser un panneau émaillé en mettant en œuvre la méthode selon l’invention. The present invention also relates to a method of producing a decorative panel for a household appliance comprising the step of taking an enamel panel according to the invention, or the step of producing an enamel panel by implementing the method according to the invention.
Brève description des figures Brief description of the figures
[0017] La figure 1 est une représentation schématique d’une vue d’une coupe transversale d’un panneau selon l’invention. [0017] Figure 1 is a schematic representation of a cross sectional view of a panel according to the invention.
[0018] La figure 2 est un graphique représentant l’évolution dans le temps de la rugosité de la face supérieure de la couche d’émail du panneau selon l’invention lors d’un surfaçage. [0018] Figure 2 is a graph showing the change over time of the roughness of the upper face of the enamel layer of the panel according to the invention during surfacing.
[0019] La figure 3 est un graphique représentant la rugosité de la face supérieure de la couche d’émail du panneau selon l’invention lors d’un surfaçage de 20 minutes avec différents acides. [0019] Figure 3 is a graph showing the roughness of the upper face of the enamel layer of the panel according to the invention during 20 minutes surfacing with different acids.
Description détaillée de l'invention Detailed description of the invention
[0020] Dans la suite de la description et des revendications, les termes « haut », « bas », « supérieur », « inférieur », « vertical » ou « horizontal » font référence à la position horizontale du panneau 1 selon l’invention, comme représenté à la figure 1. [0021] La méthode d’obtention d’un panneau émaillé, selon l’invention, comprend une première étape de prendre, ou réaliser, un support 2, qui est rigide, sensiblement inflexible, et qui présente une résistance mécanique, à des sollicitations de flexion et/ou de torsion, suffisante pour ne pas se déformer sous l’action d’une force de flexion et/ou de torsion. Le support 2 est sensiblement plan, et comprend au moins une première surface 3, continue et sensiblement plane, de préférence au moins une seconde surface 4, continue et sensiblement plane, opposée à ladite première surface 3 (figure 1). In the remainder of the description and of the claims, the terms "top", "bottom", "upper", "lower", "vertical" or "horizontal" refer to the horizontal position of the panel 1 according to the invention, as shown in Figure 1. The method of obtaining an enamel panel, according to the invention, comprises a first step of taking, or making, a support 2, which is rigid, substantially inflexible, and which has mechanical resistance to stresses of bending and / or torsion, sufficient not to deform under the action of a bending and / or torsional force. The support 2 is substantially planar, and comprises at least one first surface 3, continuous and substantially planar, preferably at least one second surface 4, continuous and substantially planar, opposite to said first surface 3 (FIG. 1).
[0022] Le support 2 a une forme, une épaisseur et des dimensions adéquates et adaptées, ou compatibles, avec l’utilisation finale du panneau 1, ou des éléments qui comprennent un tel panneau 1. The support 2 has a shape, thickness and dimensions adequate and adapted, or compatible, with the end use of the panel 1, or elements which include such a panel 1.
[0023] De préférence, le support 2 a une section transversale, verticale, dans le plan X-Y et/ou une section longitudinale, horizontale, dans le plan formé par la surface 3 ou la surface 4, dans le plan X-Z, de forme circulaire, elliptique, polygonale, trapézoïdale ou bien d’un quadrilatère, avantageusement une section losange, carrée ou rectangulaire. Preferably, the support 2 has a cross section, vertical, in the XY plane and / or a longitudinal section, horizontal, in the plane formed by the surface 3 or the surface 4, in the XZ plane, of circular shape , elliptical, polygonal, trapezoidal or else of a quadrilateral, advantageously a rhombus, square or rectangular section.
[0024] Le support 2 est fait d’un matériau inerte, de préférence au moins inerte thermiquement, avantageusement également inerte physiquement et chimiquement au(x) matériau(x) dont l’une ou les deux de ces surfaces 2 et 3 est/sont recouverte(s) ou en contact. The support 2 is made of an inert material, preferably at least thermally inert, advantageously also physically and chemically inert to the material (s) of which one or both of these surfaces 2 and 3 is / are covered or in contact.
[0025] De préférence, le support 2 est fait de, ou comprend, du plastique, du verre, une matière cristalline ou semi-cristalline, une céramique ou une vitrocéramique. [0026] Dans un mode de réalisation préféré de l’invention, le support 2 est du verre, de préférence un verre sérigraphiable, avantageusement un verre sodocalcique transparent ou teinté dans la masse, éventuellement à couches diverses, telles que anti-bactériennes, anti-réfléchissantes, par exemple du type connu sous la marque Matelux , chromées, à faible émissivité, par exemple du type connu sous le nom de Planibel Clear ou de Planibel low-E IsoComfort, commercialisé par la société AGC, ou un borosilicate par exemple connu sous la marque Borofloat® 33. De préférence, le verre est à forte teneur en Si02, une teneur avantageusement comprise entre 69 % et 81 % en poids et avec une transmission lumineuse pouvant aller jusqu’à 90 %. Le verre peut avoir éventuellement préalablement subi un traitement thermique du type durcissement, recuit, trempe, bombage. Preferably, the support 2 is made of, or comprises, plastic, glass, a crystalline or semi-crystalline material, a ceramic or a glass ceramic. In a preferred embodiment of the invention, the support 2 is glass, preferably a screen-printing glass, advantageously a transparent soda-lime glass or tinted in the mass, optionally with various layers, such as anti-bacterial, anti reflective, for example of the type known under the trademark Matelux, chrome-plated, with low emissivity, for example of the type known under the name of Planibel Clear or of Planibel low-E IsoComfort, marketed by the company AGC, or a known borosilicate for example under the trademark Borofloat ® 33. Preferably, the glass has a high Si0 2 content, a content advantageously between 69% and 81% by weight and with a light transmission which can range up to 90%. The glass may optionally have previously undergone a heat treatment of the hardening, annealing, tempering or bending type.
[0027] Le support 2 est de préférence transparent, ou semi-transparent, mais il peut également être opaque, ou bien partiellement transparent, semi-transparent ou opaque, ou comprendre une ou plusieurs portions qui le sont. Il peut être sablé et/ou sérigraphie et/ou coloré. The support 2 is preferably transparent, or semi-transparent, but it can also be opaque, or else partially transparent, semi-transparent or opaque, or include one or more portions which are. It can be sandblasted and / or screen printed and / or colored.
[0028] La méthode comprend l’étape de prendre ou préparer au moins une composition d’émail, de préférence plusieurs compositions d’émail, et l’étape de la ou les déposer, de préférence directement, sans l’emploi d’une couche d’accroche, sur la totalité, une partie ou des parties, adjacentes ou distantes, de façon superposée ou non, d’au moins une surface 3 ou 4 du support 2, ou sur au moins les deux surfaces 3 et 4 du support 2, afin d’obtenir au moins une couche d’émail 5, continue ou discontinue, comprenant au moins une face supérieure 6. The method comprises the step of taking or preparing at least one enamel composition, preferably several enamel compositions, and the step of depositing it or them, preferably directly, without the use of a bond layer, on the whole, part or parts, adjacent or distant, superimposed or not, of at least one surface 3 or 4 of the support 2, or on at least the two surfaces 3 and 4 of the support 2, in order to obtain at least one enamel layer 5, continuous or discontinuous, comprising at least one upper face 6.
[0029] L’application de la composition, ou des compositions d’émail, peut se faire par toute méthode adéquate, par exemple, par enduction, par sérigraphie, par tampographe, par offset, par impression digitale ou par jet d’encre. The application of the composition, or of the enamel compositions, can be done by any suitable method, for example, by coating, by screen printing, by pad printing, by offset, by digital printing or by inkjet.
[0030] La couche d’émail 5 selon l’invention est à base d’un matériau vitrifiable et des particules de silice, des particules qui présentent l’avantage de lui procurer un effet matifiant. The enamel layer 5 according to the invention is based on a vitrifiable material and silica particles, particles which have the advantage of giving it a mattifying effect.
[0031] Le matériau vitrifiable est tout matériau adéquat ou mélange de matériaux, pour former un émail, de préférence il s’agit d’une fritte ou mélange de frittes de verre, avantageusement adapté à une application sur un verre plat, de préférence un matériau à base de zinc, ce qui présente l’avantage de conférer à la couche d’émail 5 une résistance accrue à l’action de bases. The vitrifiable material is any suitable material or mixture of materials, to form an enamel, preferably it is a frit or mixture of glass frits, advantageously suitable for application on a flat glass, preferably a zinc-based material, which has the advantage of giving the enamel layer 5 increased resistance to the action of bases.
[0032] Le matériau vitrifiable représente de préférence entre 55 et 75% du poids total de la composition, tous les autres composants représentant la quantité suffisante pour atteindre 100% en poids. The vitrifiable material preferably represents between 55 and 75% of the total weight of the composition, all the other components representing the amount sufficient to reach 100% by weight.
[0033] Les particules de silice ont une taille dans les trois dimensions comprise entre 0,9 et 50 miti, de préférence, elles ont une taille d’environ 10 miti. De préférence, les particules de silice représentent entre 10 et 15% du poids total de la composition. [0034] Les particules de silice sont en outre destinées à faire, et font, saillie, pour au moins certaines d’entre elles, sur la face supérieure 6 de la couche d’émail 5 (figure 1), pour former une rugosité, des irrégularités de surface, un relief formé de bosses et de creux. The silica particles have a size in three dimensions between 0.9 and 50 miti, preferably they have a size of about 10 miti. Preferably, the silica particles represent between 10 and 15% of the total weight of the composition. The silica particles are also intended to make, and protrude, for at least some of them, on the upper face 6 of the enamel layer 5 (Figure 1), to form a roughness, surface irregularities, a relief formed by bumps and hollows.
[0035] La rugosité d’une surface peut être définie, conformément à la norme ISO 25178, par différentes mesures physiques, comme par exemple le paramètre « Sq », défini comme étant la valeur de la hauteur moyenne quadratique, à savoir la moyenne arithmétique, en valeur absolue, de la différence de hauteur de chaque sommet par rapport au plan moyen de la surface, cette valeur Sq pouvant être considérée comme étant l’équivalent de l'écart type des hauteurs des sommets de la rugosité, et par le paramètre « Sz », défini comme étant comme la hauteur totale de la surface, ou la somme de la valeur de la hauteur du sommet le plus haut et la profondeur du creux le plus profond. The roughness of a surface can be defined, in accordance with the ISO 25178 standard, by various physical measurements, such as for example the parameter "Sq", defined as being the value of the root mean square height, namely the arithmetic mean , in absolute value, of the difference in height of each vertex with respect to the mean plane of the surface, this value Sq being able to be considered as being the equivalent of the standard deviation of the heights of the vertices of the roughness, and by the parameter "Sz", defined as being the total height of the surface, or the sum of the value of the height of the highest peak and the depth of the deepest trough.
[0036] La composition de la couche d’émail 5 selon l’invention peut comprendre un ou plusieurs agents matifiants, qui sont, ou comprennent, des poudres minérales, de taille micrométrique, par exemple comprise entre 0,9 et 60 miti, des poudres non miscibles au matériau vitrifiable utilisé. Il peut s’agit de wollastonite (CaSi03), de dioxyde de zirconium, d’alumine calciné ou de feldspath. De préférence, l’agent ou les agents matifiants représentent de préférence entre 10 et 15 % du poids total de la composition. The composition of the enamel layer 5 according to the invention may comprise one or more mattifying agents, which are, or comprise, mineral powders, of micrometric size, for example between 0.9 and 60 miti, powders immiscible with the vitrifiable material used. It can be wollastonite (CaSi0 3 ), zirconium dioxide, calcined alumina or feldspar. Preferably, the matting agent or agents preferably represent between 10 and 15% of the total weight of the composition.
[0037] La composition de la couche d’émail 5 selon l’invention comprend en outre un ou plusieurs additifs, comme par exemple un ou plusieurs pigments, des microsphères, de préférence des microsphères de céramiques, et leurs mélange. Le ou les additifs représentent de préférence entre 1 et 10 % du poids total de la composition. The composition of the enamel layer 5 according to the invention further comprises one or more additives, such as for example one or more pigments, microspheres, preferably ceramic microspheres, and mixtures thereof. The additive (s) preferably represent between 1 and 10% of the total weight of the composition.
[0038] La couche d’email 5 est ensuite séchée, par tous moyens adéquats. The enamel layer 5 is then dried, by any suitable means.
[0039] La couche d’émail 5 est ensuite être vitrifiée sous l’action de la chaleur, lors d’une étape de trempe, qui est réalisée par chauffage par exemple à une température comprise entre 650°C et 750°C, pendant une période comprise entre six secondes et cinq minutes, de préférence entre deux et cinq minutes, puis par un refroidissement rapide, entre trente secondes et cinq minutes, à une température passant dans ce lapse de temps de 650°C à 60°C. Cette étape permet de figer définitivement cette couche d’émail 5. The enamel layer 5 is then to be vitrified under the action of heat, during a quenching step, which is carried out by heating for example at a temperature between 650 ° C and 750 ° C, for a period of between six seconds and five minutes, preferably between two and five minutes, followed by rapid cooling, between thirty seconds and five minutes, at a temperature passing in this time lapse from 650 ° C to 60 ° C. This step allows this layer of enamel to be fixed definitively 5.
[0040] L’épaisseur totale de la ou des couches d’émail 5 est comprise entre 10 et 17 miti, avant vitrification, et entre 3 et 10 miti après vitrification. The total thickness of the enamel layer (s) 5 is between 10 and 17 miti, before vitrification, and between 3 and 10 miti after vitrification.
[0041] Après le séchage de la couche d’émail 5 et sa vitrification, sa face supérieure 6 est soumise à une étape de surfaçage. Cette étape présente l’avantage de lisser la rugosité de surface de la couche d’émail 5, d’homogénéiser la rugosité sur toute la surface de la couche d’émail 5. After the enamel layer 5 has dried and its vitrification, its upper face 6 is subjected to a surfacing step. This step has the advantage of smoothing the surface roughness of the enamel layer 5, of homogenizing the roughness over the entire surface of the enamel layer 5.
[0042] De préférence, le surfaçage est un surfaçage chimique, avantageusement une attaque acide, afin de conférer à la face supérieure 6 un touché soyeux, sans pour autant modifier l’aspect visuel mat. Preferably, the surfacing is a chemical surfacing, advantageously an acid attack, in order to give the upper face 6 a silky feel, without however modifying the matt visual appearance.
[0043] On entend par touché soyeux, une sensation qui est identique ou similaire au touché d’un tissu de soie, à savoir une sensation d’une surface lisse. [0043] By silky touch is meant a sensation which is the same or similar to the touch of a silk fabric, namely a sensation of a smooth surface.
[0044] De préférence, l’attaque acide est mise en œuvre par tous moyens adéquats, de préférence par trempage, dans une solution aqueuse acide, ayant un pH compris entre 0,5 et 1,5, l’acide étant choisi parmi l’acide sulfamique, l’acide citrique, l’acide acétique, l’acide benzène sulfonique, l’acide phosphorique, ou leur mélange. Preferably, the acid attack is carried out by any suitable means, preferably by soaking, in an acidic aqueous solution, having a pH of between 0.5 and 1.5, the acid being chosen from l sulfamic acid, citric acid, acetic acid, benzene sulfonic acid, phosphoric acid, or a mixture thereof.
[0045] Le surfaçage à l’aide d’acide se réalise à température ambiante, pendant 1 minutes à 14 heures, ou entre 1 minute et 1 heure, ou entre 1 minute et 20 minutes, ou entre 1 minute et 10 minutes, ou entre 1 minute et 5 minutes, ou entre 1 minute et 2 minutes. The surfacing using acid is carried out at room temperature, for 1 minute to 14 hours, or between 1 minute and 1 hour, or between 1 minute and 20 minutes, or between 1 minute and 10 minutes, or between 1 minute and 5 minutes, or between 1 minute and 2 minutes.
[0046] De préférence, le surfaçage se fait avec de l’acide sulfamique pendant deux minutes. Preferably, the surfacing is done with sulfamic acid for two minutes.
[0047] La face supérieure 6 de la couche d’émail 5 selon l’invention a une valeur Sq comprise entre 660 et 990 nm, de préférence entre 664 et 729 nm, ou entre 849 et 914 nm, et une valeur Sz comprise entre 12 miti et 18 miti, de préférence entre 12 miti et 13 miti, ou entre 15 miti et 17 miti. The upper face 6 of the enamel layer 5 according to the invention has an Sq value between 660 and 990 nm, preferably between 664 and 729 nm, or between 849 and 914 nm, and a Sz value between 12 miti and 18 miti, preferably between 12 miti and 13 miti, or between 15 miti and 17 miti.
[0048] La face supérieure 6 de la couche d’émail 5 a une valeur de Gloss, mesurée avec un gloss mètre KSJ hg268-f2, en Unité de Brillant (UB), sous un angle de 60°, comprise entre 2,5 et 3,2 UB. The upper face 6 of the enamel layer 5 has a Gloss value, measured with a KSJ hg268-f2 gloss meter, in Gloss Unit (UB), at an angle of 60 °, between 2.5 and 3.2 BU.
[0049] L’invention porte également sur l’utilisation de la méthode de réalisation d’un panneau émaillé selon l’invention pour réaliser un panneau décoratif, de préférence d’un appareil électroménager, qui est, ou fait partie, par exemple d’un bandeau de commande d’un appareil électroménager, par exemple, un four, une plaque de cuisson. The invention also relates to the use of the method of producing an enameled panel according to the invention to produce a decorative panel, preferably of a household appliance, which is, or forms part, for example of a control panel of a household appliance, for example, an oven, a hob.
[0050] Le panneau 1 émaillé selon l’invention, obtenu par la méthode selon l’invention, comprend un aspect visuel mat et un touché soyeux. Il comprend un support 2, dont au moins une surface 3 ou 4, de préférences les deux surfaces 3 et 4, ou avantageusement toutes ces surfaces, sont recouvertes, partiellement ou complètement, d’une ou plusieurs compositions d’émail, afin de former une couche d’émail 5, continue ou discontinue, conférant cet aspect visuel mat et ce touche soyeux. The enamelled panel 1 according to the invention, obtained by the method according to the invention, has a matte visual appearance and a silky feel. It comprises a support 2, of which at least one surface 3 or 4, preferably the two surfaces 3 and 4, or advantageously all of these surfaces, are covered, partially or completely, with one or more enamel compositions, in order to form a layer of enamel 5, continuous or discontinuous, conferring this matt visual appearance and this silky touch.
Exemples Exemples 1 Examples Examples 1
[0051] A titre d’exemples non limitatifs, des panneaux 1 selon l’invention ont été réalisés, comprenant un support 2 fait de verre sodocalcique, dont seule une des deux surfaces 3 et 4 a été recouverte d’une composition d’émail à base de Zinc comprenant, en poids par rapport au poids total de la composition, 48,75% d’émail commercialisé sous la référence 104001 par la société Ferro, 1.25% d’émail commercialisé sous la référence 778110 par la société Prince Minerai Inc, 12.5 % d’émail commercialisé sous la référence 1T3015-654-63 par la société Johnson Matthey, 9% d’additif DuoDesign de la société Schott AG, qui comprend le médium commercialisé sous la référence 801022 par la société Ferro, un pigment noir et des microsphères de céramique, commercialisées sous la référence N1200 par la société Zeeospheres Ceramic, ayant un diamètre compris entre 2,8 et 58 miti, 12.5% de poudre de silice commercialisée sous la référence SS1402 par la société Industrial Powder, ayant des tailles de particules comprise entre 0,9 et 8 miti, 1% de poudre de dioxyde de zirconium Z3 de la société Auer-Remy des tailles de particules comprise entre 0,9 et 41 miti, et 15% d’un fluidifiant, commercialisé sous la référence 801022 par la société Ferro. By way of nonlimiting examples, panels 1 according to the invention have been produced, comprising a support 2 made of soda-lime glass, of which only one of the two surfaces 3 and 4 has been covered with an enamel composition Zinc-based comprising, by weight relative to the total weight of the composition, 48.75% of enamel sold under the reference 104001 by the company Ferro, 1.25% of enamel sold under the reference 778110 by the company Prince Minerai Inc , 12.5% of enamel marketed under the reference 1T3015-654-63 by the company Johnson Matthey, 9% of DuoDesign additive from the company Schott AG, which comprises the medium marketed under the reference 801022 by the company Ferro, a black pigment and ceramic microspheres, marketed under the reference N1200 by the company Zeeospheres Ceramic, having a diameter of between 2.8 and 58 miti, 12.5% of silica powder marketed under the reference SS1402 by the company Industrial Powder, having sizes of partic ules between 0.9 and 8 miti, 1% of zirconium dioxide Z3 powder from the company Auer-Remy with particle sizes between 0.9 and 41 miti, and 15% of a thinner, marketed under the reference 801022 by the company Ferro.
[0052] La rugosité de la couche d’émail 5, son épaisseur et sa composition ionique, ont été analysées, sans surfaçage chimique (échantillon A) ou avec surfaçage chimique (échantillon B) de deux minutes dans de l’acide sulfamique, à 110g/L et un pH de 0,5. Les résultats sont donnés dans le tableau 1. The roughness of the enamel layer 5, its thickness and its ionic composition, were analyzed, without chemical surfacing (sample A) or with surfacing chemical (sample B) for two minutes in sulfamic acid, at 110g / L and a pH of 0.5. The results are given in Table 1.
Tableau 1 : Mesure de rugosité et d’épaisseur par imagerie électronique
Figure imgf000012_0001
Table 1: Roughness and thickness measurement by electronic imaging
Figure imgf000012_0001
[0053] La détermination de l’épaisseur de la couche d’émail 5 se fait par l’acquisition d’images de microscopie électronique à balayage, de la section transversale des échantillons, les panneaux 1 ayant été recouverts au préalable d’une couche de platine d’environ 5 nm. Les mesures de rugosité de la face supérieure 6 de la couche d’émail 5 ont été effectuées par interférométrie en lumière blanche à différents grossissements (5,5X et 20X), mettant en œuvre un interféromètre à décalage de phase, commercialisé par la société ZYGO, comprenant un objectif interférométrique et une unité de positionnement précis, un actionneur piézoélectrique, permettant de déplacer l’objectif interférentiel verticalement. La composition chimique, de la face supérieure 6 de la couche d’émail 5, a été analysée par spectrométrie de masse à d’ions secondaires à temps de vol, ou analyse TOF-SIMS, après décontamination de la face supérieure 6 des échantillons et une mesure par polarité négative, et un temps de vol d’environ 0,4nm/s. The thickness of the enamel layer 5 is determined by acquiring scanning electron microscopy images of the cross section of the samples, the panels 1 having been covered beforehand with a layer platinum of about 5 nm. The roughness measurements of the upper face 6 of the enamel layer 5 were carried out by white light interferometry at different magnifications (5.5X and 20X), using a phase shift interferometer, marketed by the company ZYGO , comprising an interferometric objective and a precise positioning unit, a piezoelectric actuator, making it possible to move the interference objective vertically. The chemical composition of the upper face 6 of the enamel layer 5 was analyzed by time-of-flight secondary ion mass spectrometry, or TOF-SIMS analysis, after decontamination of the upper face 6 of the samples and a measurement by negative polarity, and a flight time of approximately 0.4nm / s.
[0054] Des mesures présentées dans le tableau 1, il apparaît que l’étape de surfaçage acide ne modifie pas l’épaisseur de la couche d’émail 5. Des particules d’un diamètre d’environ 12 miti sont visibles sur les images de microscopie électronique à balayage, qui semblent correspondre aux particules de silice faisant saillie sur la face supérieure 6 de la couche d’émail 5. From the measurements presented in Table 1, it appears that the acid surfacing step does not modify the thickness of the enamel layer 5. Particles with a diameter of approximately 12 miti are visible in the images. scanning electron microscopy, which appear to correspond to the silica particles protruding from the top face 6 of the enamel layer 5.
[0055] Les valeurs de Sq, donc de la hauteur moyenne des sommets de la rugosité, diminuent de 6 à 9% entre l’échantillon 1, n’ayant pas subi de surfaçage chimique, et l’échantillon B, ayant subi une attaque acide. [0056] La composition chimique de l’échantillon B, ayant subi l’étape de surface chimique comprend une modification chimique de la face supérieure 6 de la couche d’émail 5. Sur entre 100 et 300 nm, la couche d’émail 5 présente une diminution de la quantité des ions: Li, B, Na, Al, K et Zn, et une augmentation des ions: Mg, H, C, F, Si, S, Cl, Ca et N, ce qui indique qu’un échange d’ions a eu lieu durant l’étape de surfaçage. The values of Sq, therefore of the average height of the peaks of the roughness, decrease from 6 to 9% between sample 1, which has not undergone chemical surfacing, and sample B, which has undergone attack acid. The chemical composition of sample B, having undergone the chemical surface step, comprises a chemical modification of the upper face 6 of the enamel layer 5. On between 100 and 300 nm, the enamel layer 5 shows a decrease in the amount of ions: Li, B, Na, Al, K and Zn, and an increase in ions: Mg, H, C, F, Si, S, Cl, Ca and N, which indicates that ion exchange took place during the surfacing step.
Exemples 2 Examples 2
[0057] D’autres panneaux 1 ont été réalisés conformément à l’exemple 1, sans surfaçage chimique (échantillon 1) ou avec surfaçage chimique (échantillons 2 à 9). L’épaisseur de leur couche d’émail 5, sa rugosité, et l’analyse de sa composition ionique, ont été analysées pour différents acides et différents temps de traitement. Les résultats sont donnés dans les tableaux 2 et 3. [0057] Other panels 1 were produced in accordance with Example 1, without chemical surfacing (sample 1) or with chemical surfacing (samples 2 to 9). The thickness of their enamel layer 5, its roughness, and the analysis of its ionic composition, were analyzed for different acids and different processing times. The results are given in Tables 2 and 3.
Tableau 2 : Mesure d’épaisseur de la couche d’émail par imagerie électronique
Figure imgf000013_0001
Figure imgf000014_0002
Table 2: Measurement of the thickness of the enamel layer by electronic imaging
Figure imgf000013_0001
Figure imgf000014_0002
Tableau 3 : Mesure de Rugosité par imagerie électronique
Figure imgf000014_0001
Table 3: Roughness measurement by electronic imaging
Figure imgf000014_0001
[0058] Les déterminations d’épaisseur de la couche d’émail 5, et de leur rugosité, se font de la même manière que celles décrites pour l’exemple 1. La détermination des compositions ioniques se fait à la fois par spectrométrie de rayons X à dispersion d'énergie (EDX) et par spectrométrie de masse d’ions secondaires à temps de vol, ou analyse TOF-SIMS. The thickness determinations of the enamel layer 5, and their roughness, are done in the same way as those described for Example 1. The determination of the ionic compositions is done both by ray spectrometry. X energy dispersive (EDX) and time-of-flight secondary ion mass spectrometry, or TOF-SIMS analysis.
[0059] D’après les images de microscopie électronique à balayage prises de six portions aléatoires de sections transversales des échantillons 1 à 9, il apparaît qu’il n’y a pas de changement significatif de l’épaisseur de la couche d’émail 5 entre un échantillon n’ayant pas subi de surfaçage chimique (échantillon 1) et les échantillons ayant subi un surfaçage à différents temps de trempe et avec différents acides (échantillons 2 à 9). Il n’y a donc pas de dissolution de la couche d’émail 5. Toutefois, les images montrent un changement de morphologie de la couche d’émail, avec l’apparition de fissures, qui sont plus importantes à mesure que le temps de traitement est élevé. Les fissures les plus importantes, en largeur et profondeur, sont obtenues avec un surfaçage à l’aide sulfamique et l’acide phosphorique, alors qu’avec un mélange acide sulfonique / acide formique ou avec l’acide acétique, les fissures sont moins nombreuses et moins profondes. From the scanning electron microscopy images taken of six random portions of cross sections of samples 1 to 9, it appears that there is no significant change in the thickness of the enamel layer 5 between a sample not having undergone chemical surfacing (sample 1) and the samples having undergone a surfacing at different quenching times and with different acids (samples 2 to 9). There is therefore no dissolution of the enamel layer 5. However, the images show a change in morphology of the enamel layer, with the appearance of cracks, which are more important with the time of. processing is high. The largest cracks, in width and depth, are obtained with surfacing using sulfamic acid and phosphoric acid, while with a sulfonic acid / formic acid mixture or with acetic acid, the cracks are less numerous. and shallower.
[0060] Le surfaçage par l’action d’un acide permet de diminuer les valeurs de Sq, donc de diminuer la rugosité moyenne de la surface de la couche d’émail 5 d’environ 6 à environ 13 %, tout en maintenant des valeurs de Sz constantes, et donc tout en maintenant sensiblement constante l’amplitude des rugosités. Surfacing by the action of an acid makes it possible to reduce the values of Sq, therefore to reduce the average roughness of the surface of the enamel layer 5 from about 6 to about 13%, while maintaining constant values of Sz, and therefore while maintaining substantially constant the amplitude of the roughness.
[0061] Les résultats du surfaçage par un acide varient en fonction du temps de contact avec l’acide (figure 2). Toutefois, un temps de traitement court, environ deux minutes, permet de modifier la rugosité de surface de façon plus importante que des temps de réaction plus long. L’analyse d’un surfaçage de 20 minutes avec différents acides (figure 3), montre que l’acide acétique présente l’influence la plus grande sur la rugosité, suivi du mélange acide sulfamique / acide formique, de l’acide phosphorique, de l’acide citrique puis de l’acide sulfamique. The results of surfacing with an acid vary depending on the contact time with the acid (Figure 2). However, a short treatment time, around two minutes, allows the surface roughness to change more significantly than longer reaction times. The analysis of a 20-minute surfacing with different acids (figure 3), shows that acetic acid has the greatest influence on roughness, followed by the sulfamic acid / formic acid mixture, phosphoric acid, citric acid then sulfamic acid.
[0062] L’analyse de la composition ionique de l’échantillon 1, faite par spectrométrie de rayon X à dispersion d'énergie (EDX), montre la présence d’éléments tels que Si, Al, Na, K qui sont caractéristiques du support 2 en verre, et la présence d’élément tels que, Ti, Cr, Zn, Fe, Mg, Bi qui sont caractéristiques de la couche d’émail 5. The analysis of the ionic composition of sample 1, made by energy dispersive X-ray spectrometry (EDX), shows the presence of elements such as Si, Al, Na, K which are characteristic of the glass support 2, and the presence of elements such as Ti, Cr, Zn, Fe, Mg, Bi which are characteristic of the enamel layer 5.
[0063] Il apparaît que plus long est le surfaçage acide, plus la surface supérieure 6 de la couche d’émail 5 perd des éléments basiques, ce qui pourrait expliquer la présence des fissures qui ont été observées. L’analyse TOF-SIMS montre une diminution des ions Li, Na, K, B, Al, F et Zn et en enrichissement en Si, ce qui indique qu’une couche de silice se forme sur la surface supérieure 6 de la couche d’émail 5, une couche de silice qui semble protéger la surface supérieure 6 de la couche d’émail 5 d’une attaque acide supplémentaire, ce qui explique que l’épaisseur de la couche d’émail 5 ne diminue pas avec l’augmentation du temps de surfaçage. Cela pourrait également expliquer la variation dans le temps de la rugosité qui a été observée (figure 2), qui dans un premier temps diminue suite à une dissolution des ions basiques, pour ensuite augmenter probablement à la suite de la formation de la couche de silice. Une augmentation de Cu, Fe, Ni, Cr et Bi peut également être observée. De telles évolutions d’ions sont observées quel que soit l’acide utilisé, seules les intensités de diminution ou d’augmentation diffèrent. It appears that the longer the acid surfacing, the more the upper surface 6 of the enamel layer 5 loses basic elements, which could explain the presence of the cracks which were observed. TOF-SIMS analysis shows a decrease in Li, Na, K, B, Al, F and Zn ions and in Si enrichment, indicating that a silica layer is forming on the top surface 6 of the d layer. 'enamel 5, a layer of silica which appears to protect the upper surface 6 of the enamel layer 5 from further acid attack, which explains why the thickness of the enamel layer 5 does not decrease with the increase in the surfacing time. This could also explain the variation over time of the roughness which was observed (figure 2), which initially decreases following a dissolution of the basic ions, and then probably increases following the formation of the silica layer. . An increase in Cu, Fe, Ni, Cr and Bi can also be observed. Such ion evolutions are observed whatever the acid used, only the intensities of decrease or increase differ.
Exemples 3 Examples 3
[0064] Un panneau 1 selon l’invention (échantillon C) a été réalisé, selon l’exemple 1. Il comprend un support 2, fait de verre sodocalcique, dont seule une des deux surfaces 3 et 4 a été recouverte d’une composition d’émail selon l’exemple 1 ou 2. Sa résistance à différents composés organiques, représentatifs des composés qui pourraient entrer en contact avec le panneau 1 lors de son utilisation comme élément d’un appareil électroménager, ont été testés et comparés à un même panneau 1 n’ayant pas subi de surfaçage chimique (échantillon D). A panel 1 according to the invention (sample C) was produced, according to Example 1. It comprises a support 2, made of soda-lime glass, of which only one of the two surfaces 3 and 4 has been covered with a enamel composition according to Example 1 or 2. Its resistance to various organic compounds, representative of the compounds which could come into contact with the panel 1 during its use as part of a household appliance, were tested and compared to a same panel 1 not having undergone chemical surfacing (sample D).
[0065] Les échantillons sont mis en contact avec les composés organiques pendant 120 min à température ambiante, puis un nettoyage à l’aide de d’eau chaude et de liquide vaisselle et d’un chiffon WYPALL* X60 - Pliés 1/4 / Bleu, afin d’évaluer leur aspect esthétique de surface. Pour l’échantillon C, six cycles de mise en contact et nettoyage sont effectués. La présence de taches ou d’ombres, est ensuite évalué à l’œil nu, comparativement à un panneau 1 témoin n’ayant pas été au contact avec ces produits organiques. Une note de « 0 » est attribuée lorsqu’il n’y a de changement visible après une observation intense sous différent angles, une note de « 1 » lorsqu’il y a un léger changement sous certains angles d’observation, une note de « 2 » lorsqu’il y a un changement visible sous différents angles d’observation et une note de « 3 » lorsque qu’il y a un changement visible sous tous les angles d’observation. Les résultats sont donnés dans le tableau 4. Tableau 4 : Aspect esthétique de surface après un contact avec des matières organiques
Figure imgf000017_0001
The samples are brought into contact with the organic compounds for 120 min at room temperature, then cleaning using hot water and washing up liquid and a WYPALL * X60 cloth - Folded 1/4 / Blue, in order to assess their aesthetic surface appearance. For sample C, six cycles of contacting and cleaning are carried out. The presence of spots or shadows is then evaluated with the naked eye, compared to a control panel 1 which has not been in contact with these organic products. A score of "0" is given when there is no visible change after intense observation from different angles, a score of "1" when there is a slight change from certain viewing angles, a score of “2” when there is a visible change from different viewing angles and a score of “3” when there is a visible change from all viewing angles. The results are given in Table 4. Table 4: Aesthetic surface appearance after contact with organic materials
Figure imgf000017_0001
[0066] Le détergent 1 est commercialisé sous le nom de fabrique AJAX® nettoyant vitre Le détergent 2 comprend de l’alkyle benzène sulphonate de sodium, du carbonate de sodium du 2(2-Butoxyéthoxy)éthanol ; il est commercialisé sous le nom de fabrique Cif® crème. Le détergent 3 comprend de l’hypochlorite de sodium et des Amines, C12-14-alkyldimethyl,N-oxides ; il est commercialisé sous le nom de fabrique Cilit bang® nettoyant surpuissant avec Javel. Le détergent 4 comprend de l’hydroxyde de sodium et de l’hydroxyde d’Ammonium ; il est commercialisé sous le nom de fabrique Destop®. Detergent 1 is marketed under the factory name AJAX ® window cleaner. Detergent 2 comprises sodium alkyl benzene sulphonate, sodium carbonate of 2 (2-Butoxyethoxy) ethanol; it is marketed under the brand name Cif ® cream. Detergent 3 comprises sodium hypochlorite and Amines, C12-14-alkyldimethyl, N-oxides; it is marketed under the brand name Cilit bang ® powerful cleaner with bleach. Detergent 4 comprises sodium hydroxide and Ammonium hydroxide; it is marketed under the brand name Destop ® .
[0067] Il apparaît, de façon générale, que le panneau 1 selon l’invention a un aspect esthétique de surface qui apparaît bien moins dégradé que l’échantillon témoin, après la mise en contact avec différents acides organiques, comme le vinaigre et le citron, et aussi peu sensible à des détergents que l’échantillon témoin. It appears, in general, that the panel 1 according to the invention has an aesthetic surface appearance which appears much less degraded than the control sample, after coming into contact with various organic acids, such as vinegar and vinegar. lemon, and as insensitive to detergents as the control sample.

Claims

REVENDICATIONS
1. Méthode de réalisation d’un panneau (1) émaillé ayant un touché soyeux et un aspect mat, comprenant les étapes de : 1. Method for producing an enamelled panel (1) having a silky feel and a matt appearance, comprising the steps of:
- prendre un support (2) rigide comprenant au moins une surface (3, 4), - take a rigid support (2) comprising at least one surface (3, 4),
- prendre ou préparer au moins une composition d’émail comprenant un matériau vitrifiable et des particules de silices, - take or prepare at least one enamel composition comprising a vitrifiable material and silica particles,
- déposer ladite composition d’émail sur tout ou partie de ladite au moins une surface (3, 4) dudit support (2), pour former une couche d’émail (5), ayant une face supérieure (6), depuis laquelle lesdites particules de silice font saillie, formant une rugosité de surface, faite de bosses et de creux, - depositing said enamel composition on all or part of said at least one surface (3, 4) of said support (2), to form an enamel layer (5), having an upper face (6), from which said silica particles protrude, forming a surface roughness, made of bumps and pits,
- sécher ladite couche d’émail (5), - dry said enamel layer (5),
- vitrifier ladite couche d’émail (5) par l’action de la chaleur, - vitrify said layer of enamel (5) by the action of heat,
- surfacer chimiquement ladite surface supérieure (6). - chemically surfacing said upper surface (6).
2. La méthode selon la revendication 1, dans laquelle, l’étape de surfaçage chimique est mise en œuvre par l’action d’un acide. 2. The method of claim 1, wherein the chemical surfacing step is carried out by the action of an acid.
3. La méthode selon l’une quelconque des revendications précédentes, dans laquelle l’étape de surfaçage chimique est réalisée à l’aide d’acide sulfamique, d’acide formique, d’acide citrique, d’acide acétique, d’acide benzène sulfonique, d’acide phosphorique, ou de leur mélange. 3. The method according to any one of the preceding claims, wherein the chemical surfacing step is carried out using sulfamic acid, formic acid, citric acid, acetic acid, acid. benzene sulfonic acid, phosphoric acid, or a mixture thereof.
4. La méthode selon l’une quelconque des revendications précédentes, dans laquelle l’étape de surfaçage chimique est réalisée à température ambiante, pendant une à dix minutes. 4. The method according to any one of the preceding claims, wherein the chemical surfacing step is carried out at room temperature for one to ten minutes.
5. La méthode selon l’une quelconque des revendications précédentes, dans laquelle l’étape de vitrification de la couche d’émail est réalisée à une température comprise entre 650°C et 750°C, pendant une période comprise entre six secondes et cinq minutes, suivie par une étape de refroidissement, durant entre trente secondes et cinq minutes, dans laquelle la température passe de 650°C à 60°C. 5. The method according to any one of the preceding claims, in which the step of vitrifying the enamel layer is carried out at a temperature between 650 ° C and 750 ° C, for a period of between six seconds and five seconds. minutes, followed by a cooling step, lasting between thirty seconds and five minutes, in which the temperature goes from 650 ° C to 60 ° C.
6. La méthode selon l’une quelconque des revendications précédentes, dans laquelle l’épaisseur de la couche d’émail (5), après l’étape de vitrification, est comprise entre 3 et 10 miti. 6. The method according to any one of the preceding claims, in which the thickness of the enamel layer (5), after the vitrification step, is between 3 and 10 miti.
7. La méthode selon l’une quelconque des revendications précédentes, dans laquelle la rugosité de surface, après l’étape de vitrification, a une valeur de hauteur Sz, entre le sommet de la bosse la plus haute et le creux le plus profond, comprise entre 12 miti et 18miti. 7. The method according to any one of the preceding claims, in which the surface roughness, after the vitrification step, has a height value Sz, between the top of the highest bump and the deepest hollow, between 12 miti and 18miti.
8. La méthode selon l’une quelconque des revendications précédentes, dans laquelle, la rugosité de surface, après l’étape de vitrification, a une valeur de hauteur moyenne quadratique Sq, comprise entre 660 et 990 nm. 8. The method according to any one of the preceding claims, wherein the surface roughness after the vitrification step has a root mean square height value Sq of between 660 and 990 nm.
9. La méthode selon l’une quelconque des revendications précédentes, dans laquelle, la composition d’émail comprend des particules de silices ayant une taille dans les trois dimensions comprise entre 0,9 miti et 50 miti. 9. The method according to any one of the preceding claims, wherein the enamel composition comprises silica particles having a three-dimensional size between 0.9 miti and 50 miti.
10. La méthode selon l’une quelconque des revendications précédentes, dans laquelle, la composition d’émail comprend un agent matifiant choisi parmi la wollastonite (CaSi03), le dioxyde de zirconium, l’alumine calciné, le feldspath, et leur mélange. 10. The method according to any one of the preceding claims, in which the enamel composition comprises a mattifying agent chosen from wollastonite (CaSi0 3 ), zirconium dioxide, calcined alumina, feldspar, and their mixture. .
11. Le méthode selon l’une quelconque des revendications précédentes, dans laquelle le support (2) comprend deux surfaces (3, 4), et comprend une étape de déposer la composition d’émail sur tout ou partie desdites deux surfaces (3, 4), ou une étape de prendre ou préparer plusieurs compositions d’émail et une étape de déposer lesdites compositions sur tout ou partie d’une ou des deux surface (3, 4), afin de former une couche d’émail (5), continue ou discontinue. 11. The method according to any one of the preceding claims, wherein the support (2) comprises two surfaces (3, 4), and comprises a step of depositing the enamel composition on all or part of said two surfaces (3, 4). 4), or a step of taking or preparing several enamel compositions and a step of depositing said compositions on all or part of one or both surfaces (3, 4), in order to form an enamel layer (5) , continuous or discontinuous.
12. Panneau émaillé obtenu par la méthode selon l’une quelconque des revendications 1 à 11, comprenant au moins une surface (3, 4), recouverte d’une couche d’émail (5), à base d’une composition d’un matériau vitrifiable et des particules de silices, ayant une épaisseur après vitrification comprise entre 3 miti et 10 miti, et comprenant une face supérieure (6), depuis laquelle lesdites particules de silice font saillie, et ayant une rugosité de surface ayant une valeur de hauteur Sz, entre le sommet de la bosse la plus haute et le creux le plus profond, qui est comprise entre 12 miti et 18miti 12. Enamelled panel obtained by the method according to any one of claims 1 to 11, comprising at least one surface (3, 4), covered with a layer of enamel (5), based on a composition of a vitrifiable material and particles of silica, having a thickness after vitrification of between 3 miti and 10 miti, and comprising an upper face (6), from which said silica particles protrude, and having a surface roughness having a value of height Sz, between the top of the highest bump and the deepest hollow, which is between 12 miti and 18miti
13. Panneau émaillé selon la revendication 12, dans lequel la rugosité de surface a une valeur de hauteur moyenne quadratique Sq, qui est comprise entre 660 et 990 nm. 13. The enamel panel of claim 12, wherein the surface roughness has a root mean square height value Sq which is between 660 and 990 nm.
14. Méthode de réalisation d’un panneau décoratif pour un appareil électroménager, comprenant l’étape de prendre un panneau émaillé selon l’une quelconque des revendications 12 ou 13, ou l’étape de réaliser un panneau émaillé en mettant en œuvre la méthode selon l’une quelconque des revendications 1 à 11 . 14. Method of producing a decorative panel for a household appliance, comprising the step of taking an enamel panel according to any one of claims 12 or 13, or the step of producing an enamel panel by implementing the method. according to any one of claims 1 to 11.
PCT/EP2021/055780 2020-03-20 2021-03-08 Method for obtaining an enamelled panel WO2021185614A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2592056A1 (en) 2011-10-10 2013-05-15 Schott AG Coated glass or glass ceramic substrate with haptic characteristics
WO2016008752A1 (en) 2014-07-16 2016-01-21 Schott Ag Method for producing a coated substrate, planar substrate, comprising at least two layers applied by means of heating, and the use of the coated substrate
WO2018145017A1 (en) * 2017-02-06 2018-08-09 Schott Gemtron Corporation Thermally insulating glass laminates with a plurality of glass spacers submerged in a coating layer to form a sealed cavity of gas molecules

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2592056A1 (en) 2011-10-10 2013-05-15 Schott AG Coated glass or glass ceramic substrate with haptic characteristics
WO2016008752A1 (en) 2014-07-16 2016-01-21 Schott Ag Method for producing a coated substrate, planar substrate, comprising at least two layers applied by means of heating, and the use of the coated substrate
WO2018145017A1 (en) * 2017-02-06 2018-08-09 Schott Gemtron Corporation Thermally insulating glass laminates with a plurality of glass spacers submerged in a coating layer to form a sealed cavity of gas molecules

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